Platinum Metals Review - Johnson Matthey …E-mail: [email protected] Platinum Metals Rev., 2008, 52, (4), 208–214 208 The L1 2 intermetallic compounds based on irid-ium (Ir 3 X)

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VOLUME 52 NUMBER 4 OCTOBER 2008

E-ISSN 1471–0676

PLATINUM METALS REVIEWA Quarterly Survey of Research on the Platinum Metals and

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VOL. 52 OCTOBER 2008 NO. 4

ContentsThermophysical Properties of L12 Intermetallic 208

Compounds of IridiumBy Yoshihiro Terada

Platinum Group Metal Chemistry of Functionalised Phosphines 215

By Martin B. Smith

EuropaCat VIII: “From Theory to Industrial Practice” 222A conference review by Emma Schofield, Nadia Acerbi and Cristian Spadoni

“Catalysis for Renewables: From Feedstock to Energy Production” 229

A book review by John Birtill

Platinum Group Metals Patent Analysis and Mapping 231By Richard Seymour

Creep 2008: 11th International Conference on Creep and Fracture 241of Engineering Materials and Structures

A conference review by J. Preußner, R. Völkl and U. Glatzel

Global Release Liner Industry Conference 2008 243A conference review by Andrew J. Holwell

“The Periodic Table: Its Story and Its Significance” 247A book review by Michael Laing

John Ward Jenkins 249A tribute by S. E. Golunski

Abstracts 251

New Patents 254

Indexes to Volume 52 256

Acting Editor: David Jollie; Editorial Assistant: Sara Coles; Senior Information Scientist: Keith White

Platinum Metals Review, Johnson Matthey PLC, Orchard Road, Royston, Hertfordshire SG8 5HE, U.K.E-mail: [email protected]

Platinum Metals Rev., 2008, 52, (4), 208–214 208

The L12 intermetallic compounds based on irid-ium (Ir3X) have been pursued as the nextgeneration of high-temperature structural materials(1–6). The advantages of Ir3X are summarised asfollows. Firstly, the melting points are between 600and 1000 K higher than those of nickel-basedsuperalloys (7). Secondly, an L12 crystal structureoffers the possibility of enhanced ductility as aresult of the large number of possible slip systems.Finally, the two-phase γ/γ' type microstructureformed in Ni-based superalloys can also be pro-duced in Ir-based alloys (8–10).

Thermal conductivity and thermal expansionare key parameters to evaluate the suitability ofmetallic materials for high-temperature structuralapplications (11, 12). Rapid heat transfer affordedby high thermal conductivity enables efficientcooling, which suppresses the appearance of life-limiting heat-attacked spots (6). A smaller thermalexpansion is desirable to avoid thermal fatigue bycyclic thermal conditions, since thermal stressdepends directly on the magnitude of the thermalexpansion. However, no data on the thermal prop-erties of Ir3X are available in the literature.

The Ir-based compounds Ir3X form an L12

crystal structure when the partner component Xbelongs to Group 4 or 5 of the Periodic Table

(13–15). The present study was conducted toprovide the data for thermal conductivity andthermal expansion of Ir3X (X = Ti, Zr, Hf, V, Nbor Ta) which serve to evaluate the suitability ofthe compounds for high-temperature structuralapplications. The alloy compositions prepared inthis study are given in Table I, together with thecompositional range of the L12 phase at thehomogenised temperature (1573 K) (7). The sto-ichiometric composition was chosen for eachcompound except Ir3Hf. Note that the composi-tion close to stoichiometry with L12 single phasewas selected for Ir3Hf, since an L12 singlephase is not achieved at the stoichiometriccomposition.

Thermal conductivity measurements were per-formed by the laser flash method in vacuum in thetemperature range between 300 and 1100 K, usinga disc specimen of diameter 10 mm and thickness2 mm (16). A short duration laser pulse is emittedfrom a ruby rod onto the surface of the disc spec-imen. The temperature change on the other side ofthe specimen was measured over time by both aninfrared detector and a type R thermocouple.From the temperature-time profile, thermal con-ductivity was obtained (17). Thermal expansionmeasurements were made using a dilatometer

DOI: 10.1595/147106708X361321

Thermophysical Properties of L12

Intermetallic Compounds of IridiumTHERMAL CONDUCTIVITY AND THERMAL EXPANSION OF Ir3X FOR ULTRA HIGH-TEMPERATUREAPPLICATIONS

By Yoshihiro TeradaDepartment of Materials, Physics and Energy Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan;

E-mail: [email protected]

Thermal conductivity and thermal expansion for the intermetallic compounds Ir3X (X = Ti,Zr, Hf, V, Nb or Ta) were measured in the temperature range between 300 and 1100 K. Thethermal conductivities of Ir3X are distributed in the range from 41 to 99 W m–1 K–1 at 300 K,while the difference of thermal conductivities becomes less emphasised at higher temperatures.The coefficient of thermal expansion (CTE) values of Ir3X are insensitive to temperature,and fall around 8 × 10–6 K–1 at 800 K. The Ir3X intermetallic compounds with X = Ti, Zr, Hf,Nb or Ta are suitable for ultra high-temperature structural applications due to their higherthermal conductivities and smaller CTE values.

which consists of an alumina pushrod driving alinear voltage differential transformer (LVDT)(18). Dilatometer specimens were normally 3 mmsquare and 8 mm long. Thermal expansion testswere conducted over the temperature range from300 to 1100 K at a heating rate of 10 K min–1 in anargon atmosphere.

Thermal ConductivityFigure 1 shows the thermal conductivities of

Ir3X compounds as a function of temperature.The thermal conductivity tends to decrease with

increasing temperature for Ir3Nb and Ir3Ta,which have thermal conductivities above80 W m–1 K–1 at 300 K. Conversely, a continuousincrease in thermal conductivity with increasingtemperature is observed for Ir3V, which has asmaller thermal conductivity at 300 K. The ther-mal conductivities of Ir3Ti, Ir3Zr and Ir3Hf arerather insensitive to temperature. The thermalconductivities of Ir3X at 300 K are widely distrib-uted in the range from 41 to 99 W m–1 K–1, whilethe difference becomes less emphasised at highertemperatures.

Platinum Metals Rev., 2008, 52, (4) 209

Table I

Chemical Composition of the Ir3X Compounds Used in ThisInvestigation, Together with the Composition Range of the L12 Phaseat the Homogenised Temperature (1573 K) (7)

Compound Nominal composition, Composition range of L12 phaseat.% at 1573 K, at.%

Ir3Ti Ir-25.0Ti 23.6–26.7TiIr3Zr Ir-25.0Zr 22.2–25.5ZrIr3Hf Ir-24.4Hf 23.5–24.5HfIr3V Ir-25.0V 22.6–36.1VIr3Nb Ir-25.0Nb 24.0–32.0NbIr3Ta Ir-25.0Ta 24.6–27.2Ta

100

50

0 500 1000 1500Temperature, K

Ther

mal

con

duct

ivity

, λ, W

m–1

K–1

Ir3Nb

Ir3Ta

Ir3Zr

Ir3Ti

Ir3Hf

Ir3V

Fig. 1 Thermalconductivityversustemperature forIr3X (X = Ti, Zr,Hf, V, Nb or Ta).Note that thevalue of Ir3Hf isthe off-stoichiometricdata

The temperature coefficient of thermal conduc-tivity, k, in the temperature range between 300 and1100 K can be estimated from Equation (i):

k = (1/λ300 K)(dλ/dT)

≈ (1/λ300 K){(λ1100 K–λ300 K)/(1100–300)} (i)where λ300 K and λ1100 K are the thermal conductivi-ties at the temperature indicated by the subscript.The temperature coefficients of Ir3X are plottedagainst the thermal conductivity at 300 K inFigure 2, together with the plots for pure metals(19–21) and intermetallic compounds (22–24).

As a general rule, the thermal conductivity andthe temperature coefficient are inversely correlated

in pure metals and intermetallic compounds. Allthe Ir3X compounds other than Ir3V are charac-terised by larger thermal conductivities and smallertemperature coefficients. In particular, the thermalconductivities of Ir3Nb and Ir3Ta are nearly equalto that of NiAl, which is widely recognised as ahigh thermal conductivity compound (17, 25).

The thermal conductivity of an intermetalliccompound is quantitatively correlated with thoseof the constituents of the compound thoughNordheim’s relation (26). The high thermal con-ductivities of Ir3X may be partly due to the highthermal conductivity of pure Ir, whose thermalconductivity at 300 K is 147 W m–1 K–1.


3 5 7 10 20 30 50 70 100 200 300 500 700 1000Thermal conductivity at 300 K, λ300 K, W m–1 K–1

25

20

15

10

5

0

–5

–10

Tem

pera

ture

coe

ffici

ent o

f the

rmal

con

duct

ivity

, k, 1

04K

–1

34.1

CoGa

Pt3Ge NiTi

NiGaRh3Ti

Ni2Al3

Pt3Ga

Rh3Hf

Pt3Ti

FeAl

Ni3Al Ir3V

HfTi

Zr NiAl3CoAlCoTi

VNi3Ge Rh3V NbPd

Ni3Ga

TaIr3Ti Os

Ir3ZrNiAl

Ru MoRh

Ir

WRh3NbCrRh3Ta

Rh3ZrRe

BeFeTi

Ir3TaNi3Ti

Pt

AuAg

Cu

Ir3Nb

Ir3Hf

Ir3X

f.c.c.b.c.c.h.c.p.L12B2Other crystal structures

Fig. 2 Correlation between thermal conductivity at 300 K and temperature coefficient for Ir3X. The data for puremetals (19–21) and intermetallic compounds (22–24) are also indicated

Thermal ExpansionResults of the thermal expansion measure-

ments (ΔL/L) are shown in Figure 3. Thedilatation curves for all the Ir3X compounds aresmooth functions of temperature exhibiting nosudden changes in slope. The curves in Figure 3reveal that the thermal expansion of Ir3Ta isslightly smaller than that of either Ir3V or Ir3Nbover the temperature range between 300 and1100 K. Also, the data indicate the smaller ther-mal expansion of Ir3Ti in comparison with thoseof Ir3Zr and Ir3Hf.

The slope of the curve of ΔL/L vs. temperatureis the CTE. The relatively flat dilatation curve foreach compound indicates that the CTE of Ir3X areinsensitive to temperature in the range 300 to1100 K. The CTE of Ir3X compounds at 800 Kare summarised in Table II. All the values of CTEare concentrated around 8 × 10–6 K–1. The largestCTE is found in Ir3V with 8.4 × 10–6 K–1, whileIr3Ti shows the smallest at 7.5 × 10–6 K–1.

Figure 4 shows the correlation between theCTE at 800 K and the melting point for Ir3X,together with the plots for pure metals (21, 27) andintermetallic compounds (22, 28). It is found that

all the plots of pure metals and intermetallic com-pounds including Ir3X are arranged by a universalcurve, irrespective of crystal structure. The CTEof Ir3X are approximately equal to that of pure Irand one half those of conventional intermetalliccompounds such as Ni3Al and NiAl. The smallerCTE values of Ir3X correlate well with the highermelting points of the compounds.

The interatomic force in metallic materials ischaracterised by cohesive energy, Ecoh, defined asthe difference between the potential energy ofatoms in the gas state and that in a crystal of the


Table II

Coefficient of Thermal Expansion of Ir3XCompounds at 800 K

Compound Coefficient of thermal expansionat 800 K, K–1

Ir3Ti 7.5 × 10–6

Ir3Zr 8.2 × 10–6

Ir3Hf* 8.2 × 10–6

Ir3V 8.4 × 10–6

Ir3Nb 8.0 × 10–6

Ir3Ta 7.6 × 10–6

*Note that the value of Ir3Hf is the off-stoichiometric data

1.0

0.5

0

300 400 500 600 700 800 900 1000 1100Temperature, K

1.0

0.5

0

ΔL/L

, %

ΔL/L, %

Ir3Hf

Ir3TiIr3Zr

Ir3V

Ir3TaIr3Nb

Fig. 3 Thermalexpansion of Ir3X duringheating from 300 to1100 K. The heating rateis 10 K min–1. Note thatthe curve of Ir3Hf is theoff-stoichiometric data.Left-hand axis: Ir3V,Ir3Ta, Ir3NbRight-hand axis: Ir3Hf,Ir3Ti, Ir3Zr

material. The cohesive energy in intermetalliccompounds is expressed as the sum of the subli-mation energy of the alloy, Esub, and the heat offormation of ordered structure, ΔH (29),Equation (ii):

Ecoh = Esub + ΔH (ii)

Table III summarises the Ecoh, Esub and ΔH valuesfor the Ir3X compounds, where Esub was obtainedfrom the data source (30) and ΔH was calculatedfrom Miedema’s formula (31, 32). The data forNi3Al and NiAl are also indicated in Table III. Itcan be seen that the cohesive energy of intermetal-lic compounds originates mostly from thesublimation energy rather than the heat of forma-

tion of ordered structure. The cohesive energy forIr3X is located around 700 kJ mol–1, which is 1.7times larger than that of Ni3Al and NiAl. The larger cohesive energy of Ir3X would result in thehigher melting point and in the smaller CTE of thecompounds.

ConclusionsThermal conductivity and thermal expansion of

Ir3X (X = Ti, Zr, Hf, V, Nb or Ta) were surveyedin the temperature range between 300 and 1100 K.The thermal conductivity and the temperaturecoefficient are inversely correlated for Ir3X. All theIr3X compounds other than Ir3V have larger ther-mal conductivities and smaller temperature


40

30

20

10

Coe

ffici

ent o

f the

rmal

exp

ansi

on, α

, 10–6

K–1

0 1000 2000 3000 4000 5000Melting point, Tm, K

MgAl

CoHfRh3Nb

Rh3VRh3Zr

CoNi3GeNi3Si

FeTiNiTiCoTi

Rh3Ti

CoAlNi3AlNiAlNiNi3In

Ni3Ga

Ni3SnNiGaCoGa Be

Cu FeAl

Ag

AgMg

MoW

Os

ReTa

Ir3Zr

Au

PdY

Fe

Ti

Pt

Zr

VCrRh

Rh3Hf

Ir3Nb

Ir3VIr3Hf

HfRh3Ta

Ir3Ti IrIr3Ta

Ir3Xf.c.c.b.c.c.h.c.p.L12B2D019

Fig. 4 Correlation between coefficient of thermal expansion at 800 K and melting point for Ir3X. The data for puremetals (21, 27) and intermetallic compounds (22, 28) are also indicated

coefficients. The CTE of Ir3X compounds areinsensitive to temperature, and fall around 8 × 10–6

K–1 at 800 K. The smaller CTE of Ir3X are wellcorrelated with the higher melting points of the

compounds. The L12 intermetallic compoundsIr3X with X = Ti, Zr, Hf, Nb and Ta are charac-terised by larger thermal conductivity and smallerthermal expansion.


Table III

Cohesive Energy, Sublimation Energy and Heat of Formation for Ir3X,Ni3Al and NiAl

Compound Cohesive energy, Sublimation energy*, Heat of formation**,Ecoh, kJ mol–1 Esub, kJ mol–1 ΔH, kJ mol–1

Ir3Ti 675 620 55Ir3Zr 732 653 79Ir3Hf 728 658 70Ir3V 662 631 31Ir3Nb 737 685 52Ir3Ta 749 698 51Ni3Al 436 403 33NiAl 426 378 48

*Sublimation energy is obtained from the data source (30) **Heat of formation is calculated from Miedema’s formula (31, 32)

1 R. L. Fleischer, J. Met., 1985, 37, (12), 162 R. L. Fleischer, J. Mater. Sci., 1987, 22, (7), 22813 S. M. Bruemmer, J. L. Brimhall and C. H. Henager,

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Massalski, ASM International, Materials Park, OH,U.S.A., 1990

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9 Y. Yamabe-Mitarai, Y. Ro, T. Maruko and H.Harada, Metall. Mater. Trans. A, 1998, 29, (2), 537

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1993, 24, (1), 4313 W. B. Pearson, “A Handbook of Lattice Spacings

and Structures of Metals and Alloys”, Vol. 2,Pergamon Press, Oxford, 1967

14 S. Miura, K. Ohkubo, Y. Terada, Y. Kimura, Y.Mishima, Y. Yamabe-Mitarai, H. Harada and T.Mohri, J. Alloys Compd., 2005, 393, (1–2), 239

15 S. Miura, K. Ohkubo, Y. Terada, Y. Kimura, Y.Mishima, Y. Yamabe-Mitarai, H. Harada and T.Mohri, J. Alloys Compd., 2005, 395, (1–2), 263

16 W. J. Parker, R. J. Jenkins, C. P. Butler and G. L.

Abbott, J. Appl. Phys., 1961, 32, (9), 167917 Y. Terada, K. Ohkubo, K. Nakagawa, T. Mohri and

T. Suzuki, Intermetallics, 1995, 3, (5), 34718 T. Honma, Y. Terada, S. Miura, T. Mohri and T.

Suzuki, Proceedings of the 1998 InternationalSymposium on Advanced Energy Technology,Centre for Advanced Research of EnergyTechnology, Hokkaido University, Sapporo, 1998,p. 699

19 Y. S. Touloukian, R. W. Powell, C. Y. Ho and P. G.Klemens, “Thermal Conductivity, Metallic Elementsand Alloys”, Plenum, New York, 1970

20 C. Y. Ho, R. W. Powell and P. E. Liley, ‘Thermalconductivity of the elements: A comprehensivereview’, J. Phys. Chem. Ref. Data, 1974, 3, Suppl. (1)

21 “Tables of Physical and Chemical Constants”, 16thEdn., eds. G. W. C. Kaye and T. H. Laby, Longman,Harlow, Essex, 1995

22 Y. Terada, K. Ohkubo, S. Miura and T. Mohri,Platinum Metals Rev., 2006, 50, (2), 69

23 Y. Terada, K. Ohkubo, T. Mohri and T. Suzuki,Mater. Sci. Eng. A, 1997, 239–240, 907

24 Y. Terada, T. Mohri and T. Suzuki, Proceedings ofthe Third Pacific Rim International Conference onAdvanced Materials and Processing (PRICM-3),Honolulu, Hawaii, 12th–16th July, 1998, eds. M. A.Imam, R. DeNale, S. Hanada, Z. Zhong and D. N.Lee, TMS, Warrendale, Pennsylvania, U.S.A., 1998,p. 2431

25 R. Darolia, J. Met., 1991, 43, (3), 4426 Y. Terada, K. Ohkubo, T. Mohri and T. Suzuki,

Mater. Sci. Eng. A, 2000, 278, (1–2), 29227 Y. S. Touloukian, R. K. Kirby, R. E. Taylor and P.

References

D. Desai, “Thermal Expansion, Metallic Elementsand Alloys”, Plenum, New York, 1975

28 T. Honma, M.Sc. Thesis, Hokkaido University,Sapporo, Japan, 1998

29 T. Mohri, Mater. Jpn., 1994, 33, (11), 141630 C. Kittel, “Introduction to Solid State Physics”, John

Wiley & Sons, New York, 195331 A. R. Miedema, P. F. de Châtel and F. R. de Boer,

Physica B+C, 1980, 100, (1), 132 F. R. de Boer, R. Boom, W. C. M. Mattens, A. R.

Miedema and A. K. Niessen, “Cohesion in Metals,Transition Metal Alloys”, Elsevier, Amsterdam,1988


The AuthorYoshihiro Terada is an Associate Professor in theDepartment of Materials, Physics and EnergyEngineering, Nagoya University, Japan. His mainactivities are in the thermal and mechanicalproperties in metallic materials for high-temperatureapplications. His major field of present interest is thecreep mechanisms of heat resistant magnesiumalloys.

Tertiary phosphines arguably remain the linch-pin of much of our understanding aboutcoordination chemistry, catalysis and other appli-cations using metal complexes. Their extremeflexibility originates from the ease with which theirsteric and electronic properties, bite angle, solubil-ity and chirality can be regulated in a precise andcontrolled way. Trivalent phosphorus ligands havefrequently been used in coordination andorganometallic chemistry as a means of stabilisingthe metal centre, typically a pgm. Tertiary phos-phines can dictate the coordination number of ametal centre. For example, low-coordinate linearor trigonal planar geometries can be stabilised bybulky ligands such as tricyclohexylphosphine(PCy3) and tri(tert-butyl)phosphine (P(tBu)3).Furthermore the electronic properties, and hencereactivity, of the metal centre can be influenced bysubstituents bound to the phosphorus donoratom. In our research group at LoughboroughUniversity, we have been interested in phosphorus

ligands for over a decade. In this article, some ofour recent achievements are reviewed, along withcontributions from others, in this stimulating fieldof pgm chemistry.

The preparative strategy for ligands 1 and 2,illustrated in Scheme I, relies on an establishedvariant of the classic Mannich condensation reac-tion (1). In our work, many ligands of both typeshave been synthesised in high yields by a singlestep procedure, using a phosphorus-basedMannich condensation (PBMC) reaction.Adaptation of this simple methodology to non-symmetric ditertiary phosphines will also bediscussed. Our initial contribution to this fieldstemmed from reports (2, 3) that diphenyl-2-pyridylphosphine (Ph2P(2-C5H4N)) could be used,in conjunction with simple palladium(II) salts anda strong acid, typically p-toluenesulfonic acid (p-MeC6H4SO3H), as an efficient homogeneousalkyne carbonylation catalyst system. Drent et al.(2) proposed that the 2-pyridyl (2-C5H4N) group is


Platinum Group Metal Chemistryof Functionalised PhosphinesPROPERTIES AND APPLICATIONS OF THEIR COORDINATION COMPLEXES

By Martin B. SmithDepartment of Chemistry, Loughborough University, Loughborough, Leicestershire LE11 3TU, U.K.;


Tertiary phosphines are a large class of fascinating ligands commonly used in platinum groupmetal (pgm) coordination chemistry. They play an important role in areas ranging fromhomogeneous catalysis to selective metal extraction chemistry and to therapeutic applications.In this article, pgm-containing complexes of new functionalised mono-, di- and polytertiaryphosphines, derived from straightforward condensation reactions, are reviewed. Thesephosphines have been used as building blocks in supramolecular chemistry and for constructingnovel hexanuclear pgm complexes, as ligands for bridging homo- and heterobimetallic latetransition metals, and in the field of precious metal-based catalysis.

DOI: 10.1595/147106708X361493

N

H

R

H

N

H

R

CH2

PR2 N

CH2

R

CH2

PR2R2P

- H2O - H2O

HO

H2C

PR2 HO

H2C

PR2

(1) (2)1 2

– –

Scheme I Synthetic approaches to new aminophosphine ligands 1 and 2

necessary for two reasons. Firstly, it facilitates thecarbonylation of alkynes by accessing differentcoordination capabilities of Ph2P(2-C5H4N), usingthe phosphorus and/or nitrogen donor atoms.Secondly, it acts as a ‘proton messenger’ throughan intermediate Pd(II) species bearing a pendantpyridinium group. We have prepared new func-tionalised pyridylphosphines and investigated theirligating properties to pgms (4). As will be shown,hydrogen bonding, invariably using the secondaryamine group, was a key aspect. Its action was characterised through crystallographic solid-statestudies. Using the PBMC approach illustrated inScheme I, the first ligand synthesised was 3a.Phosphine 3a and its derivatives 3b and 3c exhib-ited a plethora of coordination modes(monodentate, chelating, bridging) when com-plexed to an array of pgms such as ruthenium(II),rhodium(III), iridium(III) and platinum(II).

Recently, phosphine 3d was shown to bridgetwo dichloropalladium(II) (Cl2Pd(II)) metal centresin a head-to-tail fashion (Figure 1), affording the12-membered metallocycle 4 (5, 6). One feature weroutinely observed when closely relatedpyridylphosphines were studied by single-crystalX-ray diffraction (XRD) was the presence of

intermolecular H-bonded dimer pairs involving thesecondary amine (–NH) group (7). These earlyfindings prompted us to probe in more detail thesesecondary interactions with other pgm complexesof functionalised tertiary and ditertiary phosphines.In particular, the ability of carboxylic acids to asso-ciate through H-bonding led us to design andsynthesise new ligands for supramolecular chem-istry and crystal engineering.

Crystal EngineeringGiven the versatility of tertiary phosphines, we

were intrigued to find that their use in supramole-cular chemistry is often reserved to that ofspectator or ancillary ligand (8). Our efforts tostudy the solid-state packing behaviour of an iso-meric series of metal complexes containingphosphorus-based ligands were thwarted by a lackof suitable examples in the literature. With this inmind, and identifying commercially available iso-meric amines with hydroxyl/carboxylic acidgroups as attractive reagents, a range of highlyfunctionalised ditertiary phosphines were synthe-sised using a PBMC route (Scheme I). These wereisolated in good to high yields and complexed toafford an isomeric series of seven square-planardichoropalladium(II) compounds. Crystallographicstudies showed that these complexes H-bond in amanner highly dependent on the disposition of thefunctional groups on the N-arene ring. Some ofthe isomers are shown in Figure 2. Solid-statestructures are formed, composed of 20-membereddimer pairs, 5a, 1D-polymeric chains, 5b, or lad-ders, 5c, containing 38-membered rings (9).

More strikingly, changing the labile Pd(II)source from PdCl2(cod) to Pd(CH3)Cl(cod) (cod =cycloocta-1,5-diene) afforded the novel self-assem-bled hexameric Pd compound 6 in high yield (10).In this example, the ligand bridges two Pd(II)metal centres via an unusual P2O-tridentate coordi-nation mode to give a large 48-memberedmetallocycle possessing a unique hexagonalarrangement. Other hexameric analogues, ofnanometre dimensions, have also been reported(10). Self-assembly, using a range of H-bondinginteractions, have also been studied in lineargold(I) complexes (11) and half-sandwich


N

HN

PPh2

X

X = OHX = OP(O)Ph2X = OPPh2X = H

(3a)(3b)(3c)(3d)

3a3b3c3d

4

Fig. 1 Single crystal X-ray structure of palladium(II)phosphine complex 4

organometallic Ru(II) complexes (12) using ourisomeric phosphine ligands. This area of pgm ter-tiary phosphine chemistry, coupled withcontrolled H-bonding capabilities, coincides withnew interest in supramolecular-based pgm catalysts (13).

Mixed Metal ComplexesSymmetric diphosphines are normally known to

use both phosphorus donor sites for coordination,thereby forming a classic chelate ring. We wereinterested in investigating whether, by manipulatingthe ligand structure, it would be possible tosequentially coordinate a metal centre at one P-donorsite, then add a second metal centre to the remainingnoncoordinated position (14). To accomplish this,our PBMC approach was modified such that twosterically dissimilar P-based groups (P1 and P2) couldbe introduced in two consecutive steps (SchemeII, Steps (a) and (b)). By choosing suitable pgmprecursors, for example dichloro(p-cymene)ruthenium(II) dimer [RuCl2(p-cymene)]2, or a dichloropentamethylcyclopentadienyl metaldimer [MCl2(Cp*)]2 (M = Rh, Ir), novel

organometallic ‘piano-stool’ complexes wereobtained (Scheme II, Step (c)). These ‘metalloligands’were used to prepare heterobimetallic complexes(Scheme II, Step (d)) with distinct metalcombinations such as Ru(II)/Au(I) or Ir(III)/Au(I),7. A recent extension to this work, using a newnonsymmetric ligand incorporating –PPh2 and –PAdgroups (PAd = phosphaadamantane), allowed us toprepare Ru2Pd and Ru2Pt trinuclear complexes, inwhich the square-planar PdCl2 or PtCl2 metal centreshave two bulky phosphaadamantane cages trans toeach other (15).

Supported P–C–N–C–P CatalystsComplexes of the pgms are extremely valuable

as catalysts for many homogeneous catalysed reac-tions in the chemical and pharmaceuticalindustries. While homogeneous catalysis offersmany rewards over heterogeneous catalysis, itsmajor handicap is the requirement to separate thecatalyst from (by)products and unused reactants.This has important industrial implications, affect-ing the economic viability of a process.Modification of the skeletal P–C–N–C–P frame-


N

P

P

Pd Cl

O

N

P PPd

ClClN

PPPd

Cl ClN

P

PPd

Cl

Cl

N

P

P

PdCl

Cl

OH

OOH

O

OHHO

OHO

O HN

P

PPd

Cl

ClN

P

PPd

Cl

Cl

OHO

O HOH

O HO

OH

OO

H

N

P

P

Pd Cl

Cl

OH

O O

H

N

P

P

PdCl

Cl

OH

OO

H

N

P

P

Pd Cl

Cl

OH

O O

H

N

P

P

PdCl

Cl

OH

OO

H

N

P

P

Pd Cl

Cl

OH

O O

H

OH

O

NP

PPd

ClO

HO

O

O

N

P

PPdCl

HO

O

N

P

P

PdCl

O

OH

O

NP

P Pd

ClO

OH

O

O

N

P

P

PdCl

OH

O

(5a)

(5b)

(5c) (6)

5a

5b

5c 6

O O

Fig. 2 Structural motifs of different square-planar palladium(II) phosphine complexes 5a–5c and 6. Phenyl groups onphosphorus (pink) are omitted for clarity and dashed lines indicate hydrogen-bonding contacts

work of ligand 2, shown in Scheme I, has enabledphosphines to be studied in homogeneous cataly-sis, and allowed the development of new methodsfor the separation of the pgm catalyst. The varietyof these ligands will be illustrated later in this arti-cle, and hinges on the tunability of the R group onthe central N atom, rather than on the P donoratoms as discussed previously. This facilitatesattachment to different solid supports. The follow-ing examples serve to illustrate some recentlypublished approaches, and highlight the impor-tance of using chelating diphosphines to aid

catalyst stability. Lu and Alper (16) showed howthe recovery and recycling of catalysts could berealised using dendrimers peripherally decoratedwith catalytically active Pd(II) metal centres, sup-ported on silica gel. The preparation of dendrimercomplexes on silica, such as 8, involved first syn-thesising the diphosphine by reaction of theappropriate primary amine with (hydroxymethyl)-diphenylphosphine (Ph2PCH2OH), thencomplexing using the labile Pd(II) complexPdCl2(PhCN)2. These Pd-based dendrimers wereused for the intramolecular cyclocarbonylation of


Scheme II Cartoon illustration showing the synthesis of mixed metal dinuclear phosphine complexes (P1 and P2 are P-based groups). The insert shows an X-ray structure of the heterobimetallic phosphine complex 7

NH2

P1 P2

P1R NH P1 N

R

P2

P1 N

R

P2

[M]

P1 N

R

P2

[M][M`]

[M]

[M`]

R

(7)

(a) (b)

(c )

(d)

(a)

(c)

(d)

(b)

7

Ir(1)

Cl(2)Cl(3)

P(2)C(18)

C(19)C(25)

C(11)

C(12)

C(1)C(4)O(1)

O(2)

O(3)

P(1)

Cl(1)

Au(1)

N(1)[M´]

[M´]

Silica support O

O

O

Si (CH2)3 N

N

N

Ph2P

PPh2

PPh2

PPh2

Pd

Cl

Cl

PdCl

Cl

N

R2P

PR2

PdOAc

OAcPh

R = Ph, Cy

N

Cy2P

PCy2

PdOAc

OAc

N

Cy2P

PCy2

PdOAc

OAc

(CH3)4 N

N

Cy2P

PCy2

PdAcO

AcO

N

Cy2P

PCy2

PdAcO

AcO

N

(8) (9) (Pd4-10)(Pd8 and Pd16 not shown)

8 9 Pd4-10(Pd8 and Pd16 not shown)

R = Ph, Cy

Ph2

Cy2

(CH2)4Cy2 Cy2

Cy2

iodinated aryl amines and various 12- to 18-mem-bered ring macrocycles were generated.Dendrimer complexes such as 8 attached to silicagel permitted simple filtration and reuse (up toeight times) without any significant diminution incatalytic activity.

On a similar theme, the monomeric complex 9and metallodendrimer Pd4-10, along with twohigher generations related to Pd4-10, were foundto be efficient catalysts for Suzuki coupling reac-tions of chloro- and bromoarenes (17). Recoveryand reuse was possible with the dendrimer-basedPd catalysts, while recovery of the single metal sitecomplex 9 was hampered by rapid decomposition,affording a catalytically inactive black precipitate.

Two independent research groups (18, 19)have prepared the silica-supported P–C–N–C–Pdiphosphine catalyst 11 using the PBMC ligandsynthesis strategy shown in Scheme I. Long andcoworkers (18) loaded the supported catalyst 11into standard teflon tubing and performed car-bonylative cross-coupling reactions with differentaryl halides and benzylamine. The microtube reac-tor permitted catalyst reuse for a number ofcycles. 11CO radiolabelled amides could also besynthesised by this method. Uozumi and Nakai(20) prepared a supported diphosphine fromArgoGelTM-NH2 (from Argonaut TechnologiesInc, now owned by Biotage AB) and

Ph2PCH2OH, and characterised the product bygel-phase 31P magic angle spinning nuclear mag-netic resonance (MAS NMR) spectroscopicstudies. Reacting the diphosphine with the allyl-palladium dimer [PdCl(η3-C3H5)]2 in toluene at25ºC for 15 min gave complex 12. In aqueouspotassium carbonate, complex 12 was an effectivecatalyst for the Suzuki-Miyaura coupling of arylhalides and aryl- or vinylboronic acids and couldbe reused up to three times. Employing the sametactic for attachment to solid supports, treatmentof the commercially available ArgoGelTM amineresin with diphenylphosphine/paraformaldehyde(Ph2PH/(CH2O)n), followed by addition of[Ru6C(CO)17], gave compound 13 as dark redbeads (21). No catalytic data was reported for 13;however, phosphine-free [Ru6C(CO)17] variantswere shown to be promising hydrogenation cata-lysts for cyclohexene.

Related phosphine-modified ArgoGelTM

amine-based compounds, in this instance con-taining the pentaruthenium cluster [Ru5C(CO)15],were shown to act as gas sensors for hydrogensulfide (H2S), carbon monoxide (CO) and sulfurdioxide (SO2) (22). Changes were monitored byFourier transform infrared (FTIR) spectroscopyand by colour changes of the beads prior to andafter gas addition. Furthermore theArgoGelTM-NH2 resin was used to prepare sup-


Silica support

O

OSi N

Ph2P

PPh2

Pd

Cl

ClOEt

O N

Ph2P

PPh2

PdO+

C l−

(11) (12)

n

ArgoGelres in

11 12

+n

Cl–

Et

N

Ph2P

PPh2

OArgoGelresin (CH2)2 [Ru6C(CO)17]

n

(13)

N

Ph2P

PPh2

ArgoGelresin Ru N

Ph2P

PPh2

ArgoGelresin

Cl

Cl

N

Ph2P

PPh2

ArgoGelresin

RuH

PPh3

H

PPh3

(14)

(15)

Cl

ClRu

PCy3

PCy3

Ph

(16)

13 14

15 16

nPh2 Ph2 Ph2

Ph2

resin

ported octahedral Ru(II) diphosphine complexes14 and 15 as brown and yellow beads respectively(23). Both compounds were shown to hydro-genate supercritical carbon dioxide in thepresence of dimethylamine (HN(CH3)2) to givedimethylformamide (DMF, HCON(CH3)2). Thecatalysts could be reused up to four times, afterdecantation and drying under vacuum, with someloss in catalytic activity. Polymer-based phosphineresins have recently been shown to act as scav-engers for removal of Grubbs’ catalyst, 16, fromreaction mixtures, and could be separated by sim-ple filtration delivering > 95% Ru-free reactionproducts (24).

Conclusions and Future Work The PBMC approach continues to be an attrac-

tive, yet simple, preparative method for accessingnew trivalent phosphorus(III) ligands. Phosphinesoffer important insights into how structural ligandmodifications can be made, allowing different lig-ating modes to be adopted at pgm centres.Furthermore, careful incorporation of highly polarfunctional groups can lead to diverse solid-state

structures. The ease of using the PBMC approachto target late transition metal-based catalysts, withrecyclable properties, offers practical alternativesin the field of homogeneous catalysis.

Unpublished recent work from our group hastaken us back to some earlier studies reviewed inPlatinum Metals Review (25). We are usingtetrakis(hydroxymethyl)phosphonium chloride(THPC), itself a precursor used to preparetris(hydroxymethyl)phosphine (THP), as a startingreagent for the preparation of neutral and cationicphosphorus-containing ligands. The pgm coordi-nation chemistry of these new ligands has providedus with some interesting results that will be pub-lished shortly (26).

Acknowledgements The author would like to acknowledge those

involved in supporting our research activities,especially Johnson Matthey PLC. Many thanks toall group members, past and present, who havemade valuable contributions in the areas of pgmchemistry with phosphorus-based ligands, catalysisand supramolecular chemistry.


1 M. Tramontini and L. Angiolini, “Mannich Bases,Chemistry and Uses”, CRC Press, Boca Raton,Florida, 1994

2 E. Drent, P. Arnoldy and P. H. M. Budzelaar, J.Organomet. Chem., 1993, 455, (1–2), 247

3 M. L. Clarke, D. J. Cole-Hamilton, D. F. Foster, A.M. Z. Slawin and J. D. Woollins, J. Chem. Soc., DaltonTrans., 2002, (8), 1618

4 S. E. Durran, M. B. Smith, A. M. Z. Slawin and J. W.Steed, J. Chem. Soc., Dalton Trans., 2000, (16), 2771

5 S. E. Durran, M. B. Smith, S. H. Dale, S. J. Coles, M.B. Hursthouse and M. E. Light, Inorg. Chim. Acta,2006, 359, (9), 2980

6 H.-B. Song, Z.-Z. Zhang and T. C. W. Mak, J. Chem.Soc., Dalton Trans., 2002, (7), 1336

7 S. J. Coles, S. E. Durran, M. B. Hursthouse, A. M. Z.Slawin and M. B. Smith, New J. Chem., 2001, 25, (3),416

8 B. J. Holliday and C. A. Mirkin, Angew. Chem. Int.Ed., 2001, 40, (11), 2022

9 M. B. Smith, S. H. Dale, S. J. Coles, T. Gelbrich, M.B. Hursthouse, M. E. Light and P. N. Horton,CrystEngComm, 2007, 9, (2), 165

10 M. R. J. Elsegood, M. B. Smith and P. M. Staniland,Inorg. Chem., 2006, 45, (17), 6761

11 M. B. Smith, S. H. Dale, S. J. Coles, T. Gelbrich, M.

J. Hursthouse and M. E. Light, CrystEngComm, 2006,8, (2), 140

12 S. E. Dann, S. E. Durran, M. R. J. Elsegood, M. B.Smith, P. M. Staniland, S. Talib and S. H. Dale, J.Organomet. Chem., 2006, 691, (23), 4829

13 T. Šmejkal and B. Breit, Angew. Chem. Int. Ed., 2008,47, (2), 311

14 G. M. Brown, M. R. J. Elsegood, A. J. Lake, N. M.Sanchez-Ballester, M. B. Smith, T. S. Varley and K.Blann, Eur. J. Inorg. Chem., 2007, (10), 1405

15 T. J. Cunningham, M. R. J. Elsegood, P. F. Kelly, M.B. Smith and P. M. Staniland, Eur. J. Inorg. Chem.,2008, (14), 2326

16 S.-M. Lu and H. Alper, Chem. Eur. J., 2007, 13, (20),5908

17 J. Lemo, K. Heuzé and D. Astruc, Org. Lett., 2005, 7,(11), 2253

18 P. W. Miller, N. J. Long, A. J. de Mello, R. Vilar, H.Audrain, D. Bender, J. Passchier and A. Gee, Angew.Chem. Int. Ed., 2007, 46, (16), 2875

19 T. Posset and J. Blümel, J. Am. Chem. Soc., 2006, 128,(26), 8394

20 Y. Uozumi and Y. Nakai, Org. Lett., 2002, 4, (17),2997

21 C. M. G. Judkins, K. A. Knights, B. F. G. Johnson,Y. R. de Miguel, R. Raja and J. M. Thomas, Chem.

References

Commun., 2001, (24), 262422 C. M. G. Judkins, K. A. Knights, B. F. G. Johnson

and Y. R. de Miguel, Polyhedron, 2003, 22, (1), 323 Y. Kayaki, Y. Shimokawatoko and T. Ikariya, Adv.

Synth. Catal., 2003, 345, (1–2), 17524 M. Westhus, E. Gonthier, D. Brohm and R.

Breinbauer, Tetrahedron Lett., 2004, 45, (15), 3141

25 P. G. Pringle and M. B. Smith, Platinum Metals Rev.,1990, 34, (2), 74

26 A. T. Ekubo, M. R. J. Elsegood, A. J. Lake and M.B. Smith, manuscript in preparation


The AuthorMartin Smith was born in Royston, Hertfordshire, U.K., and grew up inthe neighbouring village of Melbourn. He was awarded a B.Sc. inChemistry at the University of Warwick, U.K., and completed his Ph.D.at Bristol University in the group of Professor Paul Pringle. Afterpostdoctoral positions and a Royal Society Fellowship with ProfessorsTony Deeming (University College London), Brian James (University ofBritish Columbia, Canada) and Derek Woollins (LoughboroughUniversity) he took up a Lectureship at Loughborough University in1997. He was promoted to Senior Lecturer in 2008. His research

interests are focused on pgm phosphine complexes and their applications in catalysis.


This biennial European Federation of CatalysisSocieties (EFCATS) conference took place on the26th to 31st August 2007, in the town of Turku onthe southwestern coast of Finland, and was hostedby the Nordic Catalysis Society (1). It was attend-ed by 1350 scientists from Asia, the U.S.A. andEurope, of whom 65% were men, with an indus-trial representation of 40%. The oral presentationsincluded seven plenary lectures, one or morekeynote lectures for each session, 180 oral presen-tations in four parallel sessions and 750 posters.The significance of this conference was highlight-ed by the fact that there were up to ninetysubmissions for a session from which only ten pre-sentations could be selected. Presentations weredivided into eighteen topic areas:– Catalysis from first principles– Nanotechnology in catalysis, novel catalytic

materials– Surface science in catalysis– New experimental approaches and characterisa-

tion under reaction conditions (combinatorialmethods included)

– Catalysis for pharma and fine chemistry (homo-and heterogeneous catalysis)

– Catalysis by enzymes– Polymerisation– Electro-catalysis and catalysis related to fuel

cells– Catalysis in oil refining– Natural gas conversion (GTL, MTO, methanol,

etc.)– The Hydrogen Society (hydrogen production

and storage)– Catalysis in the conversion of renewable

resources (biofuels, catalysis for sustainabledevelopments)

– Catalysis for pollution control (stationary)

– Catalysis for pollution control (mobile)– Catalysis for bulk and specialty chemicals– Catalytic reaction engineering (novel reactor

systems and novel reaction media included)– Photocatalysis– Catalyst deactivation, regeneration and recyclingThere was also a workshop entitled “Towards100% Selectivity in Catalytic Oxidation overNanostructured Metal Oxides” (VIII EuropeanWorkshop on Selective Oxidation ISO 2007, host-ed by EuropaCat VIII).

Platinum group metals (pgms) featured in mostof these sessions, and retain their pivotal roles infuel cell catalysis, automotive applications, surfacescience and photocatalysis.

The Berzelius LectureAmong the plenary lectures of the conference

was the Berzelius Lecture, resurrected by theEuropaCat committee in honour of the Swedishscientist who, in a report in 1836, highlighted the“significance of reactions which take place in thepresence of some substance which remains unaf-fected” (2). This year, this prestigious lecture wasgiven by Nobel Laureate R. H. Grubbs (CaliforniaInstitute of Technology, U.S.A.) after whom isnamed the homogeneous Grubbs’ catalyst. Thiscatalyst is an efficient, selective catalyst for olefinmetathesis which works under mild reaction con-ditions that tolerate the presence of a range ofother functionalities. More than fifty Grubbs’ cat-alysts have been synthesised. Grubbsdemonstrated that, by tuning the N-heterocycliccarbene ligands on the ruthenium centre, the cata-lyst can be made more reactive or more stable,water soluble or enantioselective. Recent work hasfocused on increasing the barrier to decompositionby hindering the ligand rotation which is the initial

DOI: 10.1595/147106708X363437

EuropaCat VIII: “From Theory toIndustrial Practice”PLATINUM GROUP METALS RETAIN FUNDAMENTAL ROLE IN CATALYSIS

Reviewed by Emma Schofield*, Nadia Acerbi and Cristian Spadoni Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.; *E-mail: [email protected]

step in this pathway. The consequences of modify-ing the catalyst ligands by a single methyl groupwere further illustrated in ethanolysis, in whichthis structural refinement resulted in a decrease inreaction times from 20 h to 1 h, maintaining thehigh selectivity. For larger scale applications, aGrubbs’ catalyst is being explored for conversionof seed oils – corn and soy bean – into value addedchemicals. In these clean, solvent-free reactions,the functionalities already present in the oils areretained at high turnover numbers.

Catalysis from First PrinciplesJ. A. van Bokhoven (ETH Zurich, Switzerland)

gave a well-attended and inspirational talk on theways in which oxide supported nanoparticles ofgold are different from bulk metal or crystals. Thecatalysts discussed were prepared by base deposi-tion precipitation from hydrogen tetrachloroaurate(HAuCl4) on a range of supports: alumina (Al2O3),silica (SiO2), ceria (CeO2), titania (TiO2), zirconia(ZrO2) or niobium oxide (Nb2O5). Independent ofthe support, as the size of Au particles decreases,melting point, coordination number and bondlengths to adjacent atoms all decrease. The reasonis that smaller particles have a different electronicstructure. This was explained in terms of the factthat the d-band narrows and shifts up in energytowards the Fermi level as particle size decreases.The consequence is that the particles are catalyti-cally reactive where the bulk metal is not. UsingX-ray techniques – X-ray absorption near edgestructure (XANES), extended X-ray absorptionfine structure (EXAFS) – and in particular by theuse of hard X-rays for high resolution, vanBokhoven showed that nanosized Au interactswith H2 and O2 and demonstrated that, for thehydrogenation of cinamaldehyde, smaller particlesexhibit a higher selectivity. The issue of supporteffects was raised in the questions; the point wasreiterated that, while support effects are clearlyimportant in catalysis on Au, they did not influ-ence the electronic particle properties underdiscussion.

Novel phenomena related to Au clustersdeposited on ultra-thin oxide films were discussedby G. Pacchioni (Università degli Studi di Milano-

Bicocca, Italy). He showed by means of densityfunctional theory (DFT) calculations how oxidethin films may exhibit special properties which dif-fer from the bulk oxide. He considered a system inwhich a thin layer of magnesium oxide (MgO) isgrown on a metal, in this case silver or molybde-num. Subsequently Au particles are deposited onthe metal oxide support. The formation of ametal/oxide interface can change the chemicalproperties of the oxide support and the systemwork function. When the supporting metal is Mo,what results is the charging of the supported metalatoms and clusters by direct tunneling of electronsfrom the metal substrate to the supported metal;this is not observed when Ag is used. The reasonfor this electronic behaviour is that the Fermi levelof Ag is lower in energy than the Au 6s orbital, sospontaneous electron tunneling is not allowed; incontrast the Fermi level of Mo lies at higher energy than the Au 6s.

This fundamental approach to the behaviour ofcatalytic metal particles was taken further by J. K.Nørskov (Technical University of Denmark) whodiscussed the reactivity of catalysts in terms of thegeometrical and electronic structure of metalnanoparticles. Having discussed the correlationsbetween the energy of d-states and the reactivity ofa catalyst, he illustrated the practical applicationsof the theoretical principles in the synthesis ofammonia on 11% Ru on a MgAl spinel. On the Runanoparticle surface in this catalyst there are close-packed regions, on which there is a large barrier todissociation, and steps, where the barrier is muchlower and where the catalysis occurs. The questionis then how many step sites there are on thenanoparticles, which can be modelled from trans-mission electron microscope (TEM) images.Around 2–3 nm, the required steps are no longerpossible, hence the optimal nanoparticle size is >3 nm. Although these are simple examples, theyserve to illustrate the enormous potential of com-putational chemistry in predicting useful catalyststructures.

Surface ScienceInvestigating the surface science of platinum

and palladium, T. Visart de Bocarmé (Université


Libre de Bruxelles, Belgium) illustrated the useful-ness of field ion microscopy to elucidate the activesites and chemical species relevant to a catalyticreaction. Observing the reaction between H2 andNO on a Pt tip showed that an oscillatory reactionoccurs with local oxide reduction by H2 during theoscillating cycles. The reaction occurs on the kinksurfaces of the (012) planes where there are [001]zones. For Pd in contrast, there are no plane-spe-cific effects and hysteresis rather than oscillation isobserved; here reduction of oxides is only possibleat high pressures of H2.

Extending the scope of his studies to all thepgms, M. Johansson (Technical University ofDenmark) measured splitting coefficients and desorption rates in the hydrogen–deuteriumexchange reaction with and without added carbonmonoxide on a range of pgms in 1 bar H2 at temperatures between 40 and 200ºC. Surprisingly,in the absence of CO, Ru and Rh proved to havethe highest sticking probabilities: the order fol-lowed: Ru > Rh >> Pd ~ Pt > Ir. The addition ofCO slows the reaction for all the metals, in partic-ular Pt and iridium.

Pd was the focus of the talk by W. T. Tysoe(University of Wisconsin-Milwaukee, U.S.A.). Heused deuterium-labelling to investigate the reactionmechanism of the industrially significant vinylacetate monomer (VAM) reaction on, in this case,a Pd(111) surface, in which ethene reacts oxida-tively with acetic acid. Using an elegantcombination of variable temperature infrared (IR)and temperature-programmed desorption (TPD)spectroscopy, he showed that changing thelabelled ethenes – CHD=CHD or CH2=CD2 –gave different rates of reaction. The conclusionthat the reaction on Pd proceeds via the Samanospathway (3) was substantiated by DFT, which pre-dicts that the Samanos pathway is energeticallymore favourable. In the subsequent discussion thepossibility was raised that the pathway may be dif-ferent on a PdAu alloy.

S. Schauermann (Fritz-Haber-Institut der Max-Planck-Gesellschaft, Germany) demonstrated theactive role played by the support iron oxide(Fe2O3) in the decomposition of methanol. In amodel system in which crystalline particles of Pd

were prepared on an Fe2O3 film deposited on aPt(111) surface, at T > 450 K she showed that O2

was chemisorbed on metallic Pd. At T > 500 K,layers of PdO formed at the particle–support inter-face, leading to the coexistence of PdO and Pdmetal. At T > 600 K, there was nearly completeoxidation of the particle. The consequences of thedecomposition of MeOH are that a reservoir ofpredissociated methoxy species build up on theFe2O3 support which spill over onto the Pd parti-cles in order to react. On the theme of reactions ofMeOH, R. Blume (Fritz-Haber-Institut der Max-Planck-Gesellschaft, Germany) showed that in theoxidation of MeOH to formaldehyde on oxidic Rusurfaces, different precatalysts evolve into thesame catalytically active surface. The amount oftransition surface oxide in the first few layersproved to be the parameter which determineswhich catalytic pathway is followed rather than theamount of RuO2.

Alcohols also featured in the investigation of N.Bion (Université de Poitiers, France) into thesteam reforming of bioethanol overRh/MgAl2O4/Al2O3 to generate H2. In crudebioethanol there are a range of impurities whichdeactivate this reaction. Each impurity was testedindividually and it was shown that there is a strongpoisoning effect of acetic acid – although there areonly low levels of acetic acid in bioethanol – andno inhibition by diethylamine. Of a series of alco-hols, the order of poisoning was: branched > linear> other functional groups. This was thought to bedue partly to coke deposition and partly influencedby the hydrophobicity of the alcohol, where the C4and C5 alcohols hinder water activation. Followingthe ethanol theme, W. Shen (Dalian Institute ofChemical Physics, Chinese Academy of Sciences)proposed an Ir/CeO2 catalyst for steam reformingof ethanol. He showed that, while there was onlylimited sintering of Ir during the 60 h test reaction,there was significant growth and morphologicalchanges of the ceria particles, although this did notinfluence the catalytic activity noticeably.

New Experimental ApproachesIn situ techniques, which can be used to study

the structural modification of catalysts under real-


life reaction conditions, are of critical importanceto any scientist who is trying to understand how acatalyst really behaves. J.-D. Grunwaldt (ETHZurich, Switzerland) presented 2D mapping ofsupported pgm catalysts under operational condi-tions in order to investigate the variation of thecatalyst structure that can occur inside a catalyticreactor as a result of prominent temperature orconcentration gradients. The catalytic systemsstudied were alumina supported pgms (Rh/Al2O3,Pt-Rh/Al2O3, Pt/Al2O3, Pt-Ru/Al2O3, Pd/Al2O3)prepared by flame-spray pyrolysis and the reactionstudied was the total oxidation of methane. X-Rayabsorption spectroscopy (XAS), recorded with amicro-focused beam scanning over the samplecoupled with a 2D-area detector, is particularlyeffective for in situ studies since it requires shorteracquisition times. The temperature profile wasanalysed using an IR thermography camera andthe catalytic performance by means of mass spec-trometry. It was shown that the structure of acatalyst during partial oxidation of methane variesstrongly along the axial coordinate of a tubular catalytic microreactor. There are considerablestructural differences between the pgm particles ofless than 100 μm diameter, and a strong depen-dence on the reaction conditions (temperature,space velocity). This talk highlighted the impor-tance of 2D-spectroscopic studies underoperational reaction conditions.

A. Tompos (Chemical Research Center,Institute of Surface Chemistry and Catalysis,Hungarian Academy of Sciences) used catalystscombinatorially designed for methane total oxida-tion in order to understand the role of Pt and Auon the performance of trimetallic Pt-Pd-Au/CeO2

catalysts. Ceria was obtained by the urea precipita-tion route and subsequently impregnated with thethree metals. By X-ray photoelectron spectroscopy,in situ Fourier transform infrared (FTIR) spec-troscopy, TPD of H2 and CO chemisorptionmeasurements, direct evidence was found foralloying of Pt with Pd. The conclusion was that theimproved catalytic properties of multimetallic Pt-Pd-Au/CeO2 catalysts over the monometallic Pdanalogues are due to: (a) the increase of the number of Pd(0)–PdO dual-type active sites,

(b) stronger methane adsorption at the Pd(0)–PdOboundary, (c) a higher accessible metallic area inthe working catalyst, (d) suppression of the reduc-tion of Ce(IV), and (e) suppression of theconcentration of ionic Pd(II).

Novel Catalytic MaterialsThe pgms are the first port of call for scientists

in search of new catalytic materials. Pd featured inthe talk by G. L. Chiarello (Università degli Studidi Milano, Italy). He compared 0.5% Pd/LaCoO3

catalysts made by flame-spray pyrolysis with moreconventional catalysts prepared by impregnationin the reaction in which small amounts of H2 inexhaust gases are used to reduce NO. In theflame-made catalyst, the Pd(II) partially replacesCo in the perovskite structure. When this catalystis calcined at 800ºC and reduced at 300ºC in 5%H2/He, Pd segregates to the catalyst surface. Incontrast, reduction at 600ºC leads to the formationof a PdCo alloy. A further feature of the flame-made catalyst is that at temperatures over 500ºC,EXAFS evidence suggested that the Pd redissolvesin the perovskite framework instead of sintering,putting this in the class of so-called ‘intelligent catalysts’ which redisperse following sintering. Theflame-based preparation route gave a clear advan-tage in catalyst performance over the impregnationmethod; the catalyst yielded 100% conversion at160ºC along with 78% selectivity to nitrogen andafter 100 h there was no deactivation of the flame-made catalyst.

Encapsulated pgm nanoparticles are the novelapproach to preventing sintering described by M.Paul (Max-Planck-Institute for Coal Research,Germany). He proposed encapsulating Au or Ptnanoparticles in hollow metal oxide spheres. Inthis way the nanoparticles are physically separateand sintering is prevented at high temperatures. Bythis method a colloidal nanoparticle is encapsulat-ed in a silica shell, which is then coated withzirconia or titania and calcined at 900ºC.Subsequently the silica core is leached out by treat-ment with sodium hydroxide. TEM imagesshowed the effective encapsulation. Using the COoxidation reaction, it was shown that hollowsphere encapsulation does stabilise the catalyst


against sintering while causing no mass-transferlimitation and thus retaining catalytic activity.

As a catalytic element, Au has proved a particu-larly popular subject of study since Haruta’s workin the 1980s (4). In this meeting, S. Carrettin(Instituto de Tecnología Química, CSIC, Spain)gave a pioneering example of a heterogeneous Aucatalyst used for a carbon–carbon bond formation,namely the isomerisation of ω-alkynylfurans tophenols. The 1.8% Au on ceria catalyst was pre-pared using HAuCl4 and nanocrystalline ceria. Thenanocrystalline support seems to stabilise thecationic species Au(I) and Au(III): the presence ofthese species on the surface was established byobserving CO probe molecules by FTIR spec-troscopy. The hypothesis that the Au cationicspecies is the active site was challenged during thediscussion, and the question remained as towhether FTIR is a sufficiently sensitive techniqueto allow Au(I) and Au(III) differentiation.

Well known in the field of Au catalysis, G. J.Hutchings (Cardiff University, U.K.) presented anew synthetic approach to supports for highlyactive oxidation catalysts. Au supported on ceriaprepared using supercritical antisolvent (scCO2)precipitation was demonstrably more active andmore stable for CO oxidation than comparablenanoparticles supported on conventional ceriaderived from the direct calcination of cerium(III)acetylacetonate. In search of new industrial usesfor Au catalysts J. McPherson (Project AuTEK,South Africa) deposited Au on hopcalite with theaim of improving the stability of this filter materi-al to water. Despite extremely efficient depositionof Au, Au/ZnO and Au/TiO2 proved more activefor aspirator applications.

Automotive CatalysisAs ever, pgms played a starring role in the sec-

tion on automotive catalysis. In the section onNOx traps E. C. Corbos (Université de Poitiers,France) elegantly illustrated the redispersion of Pton ceria-containing supports at temperaturesgreater than 800ºC in an oxidising atmosphere.The techniques used were in situ time-resolvedturbo XAS in fluorescence mode and in situ TEM.In a cycling regime of 3% H2/He (60 s) followed

by 20% O2/He (60 s), the particles which start at7 nm decrease in size to 5 nm within 30 s and to3 nm within 1000 s. The hypothesis was that theoxidised atoms migrate. In the discussion the question was raised concerning the influence ofwater on these process, which is yet to be studied.

H. Grönbeck (Chalmers University ofTechnology, Sweden) approached NOx storagefrom a computational perspective, using super-cellcalculations to examine the adsorption of NO2 onlayers of barium oxide(100) on Pt(100). Theadsorption energy of BaO (Ea = 1.04) is enhancedby a factor of 2 (Ea = 2.38) when two layers ofBaO are arranged on the Pt surface and there is anoticeable effect even up to 5 layers, 16 Å, of BaObetween the Pt and the NO2. It was proposed thata similarly substantial effect would be observed onPt supported MgO(100) (Ea = 1.65) with chargingof the NO2 molecule induced by the Pt–MgOinteraction.

The theme of the talk by R. Burch (Universityof Belfast, Northern Ireland) was the importanceof scientific rigour, in particular in not theorisingbeyond the available data. This is particularlyimportant in studying non-steady state processes.In order to study NOx storage on 1% Pt/17.5%Ba/γ-alumina, Burch uses fast transient kineticsapparatus with very short residence times and a fullgas mixture. The conclusion was that NH3 is onlyobserved in large quantities over a Pt catalyst whenH2 alone is used as the reductant. With the typical3:1 CO:H2 mixture, CO inhibits the formation(release) of NH3.

Among the talks devoted to catalytic combus-tion, A. Baylet (Université de Poitiers, France) andP. Gélin (Université de Lyon, France) shared atheme of catalytic combustion of natural gas oversupported PdO. Since metallic Pd is much lessreactive than its oxide, and reoxidation of Pd maybe the rate limiting step in the reaction, differentapproaches were taken to increase the PdO:Pdratio. A. Baylet doped highly thermally stable hexa-aluminate supports (La0.2Sr0.3Ba0.5)(MnAl11)O19 with1% Pd; the most effective catalyst proved to be ahexaaluminate/alumina mixture. The approach ofP. Gélin was to vary the support in order toincrease the PdO–Pd transition temperature,


achieving the highest activity on Pd/YSZ in theabsence of sulfur. Only Pd/Al2O3 was not poisoned by sulfur.

The theme of catalytic combustion was contin-ued by A. de Lucas-Consuegra (Universidad deCastilla-La Mancha, Spain) who discussed the useof solid electrolytes to make conducting electroac-tive catalyst supports for use in the catalyticcombustion of hydrocarbons, exemplified bypropane. Promoting 1% Pt/β-Al2O3 with potassi-um ions gives a catalyst that operates, both innear-stoichiometric and O2 rich conditions, atlower temperatures – around 200ºC – well withinthe 190–310ºC working exhaust temperature.

Fuel CellsFor some time a lot of scientific effort has been

devoted to decreasing the amount of pgm requiredfor efficient operation of a fuel cell. M. Tada(University of Tokyo, Japan) used an impressiverange of in situ XAS techniques to study the mech-anism of the O2 reduction reaction at the cathodeon a Pt/C catalyst under realistic operating condi-tions. Two in situ time-resolved techniques wereused: time-gated EXAFS (TG-EXAFS), with atime resolution of 1 s and in situ time-resolvedenergy-dispersive EXAFS (DXANES), with a resolution of 4 ms. Having estimated all kineticparameters for the reaction, she concluded thatthere are eight elementary steps involved, andthere is a significant time lag between electrontransfer and structural changes in the Pt catalyst.Since the Pt–Pt bond dissociation rate and thePtO bond formation rate constants are similar, itwas shown that at higher potentials than the opencircuit voltage oxygen atoms break in to the sub-surface of the Pt nanoparticles.

N. Tsiouvaras (Universidad de la Laguna,Spain) gave a controversial presentation on ternarycatalysts for direct methanol fuel cells in which Mohad been introduced to PtRu/C at loadings ofbetween 2 and 12 wt.% for an overall 30% metalloading. Pt crystallite sizes of 2–5 nm wereobserved; there was no evidence of alloying.Although the catalyst displayed high metal losseson electrochemical cycling – mostly of Mo – theCO stripping potentials were lower than the com-

mercial 30% PtRu/C standard. Using differentialelectrochemical mass spectrometry, the gases produced during electrochemical processes wereanalysed demonstrating that the onset of CO2

production was at lower potentials than observedfor commercial catalysts. Similarly, by carrying outin situ FTIR on the electrochemical cell, itappeared that qualitatively a small quantity of COpoisoned the ternary catalyst surface. Finally, testsfor activity in MeOH oxidation again gave highercurrent densities than the commercial standard.

PhotocatalysisA. Kudo (Tokyo University of Science, Japan)

demonstrated an exciting system for solar H2 pro-duction from water. Ru/SiTiO3 doped with Rhwas the catalyst for H2 generation; this proved better than the Pt analogue because the presenceof Ru effectively suppresses the back reaction. Bypreparing the catalyst by a hydrothermal ratherthan solid state route, an improvement in quantumyield to 3.9% from 0.3% resulted. The improve-ment was thought to be due to the bettercrystallinity, smaller particle size and decrease ingrain boundaries in the hydrothermally preparedcatalyst, providing fewer sites where recombina-tion could occur. The optimal system combinedRu/SiTiO3:Rh for H2 generation with BiVO4 forO2 generation, using Fe(III) as the couple media-tor, and gave a system responsive up to 520 nm.

Selective OxidationA. Pashkova (DECHEMA, Germany)

presented a new approach for the synthesis ofhydrogen peroxide directly from H2 and O2.Single channel asymmetric membranes were usedas the support for the active Pd or Pd-Ag alloyspecies. The selectivity for H2O2 could beincreased from 20% to 80% by changing the con-centration profiles of O2 and H2 fromcountercurrent to equicurrent profiles.

The selective generation of propylene oxide byepoxidation of propylene was the subject of apaper by N. Mimura (Research Institute forInnovation in Sustainable Chemistry, Japan). Theepoxidation was carried out using a mixture of H2

and O2 over titania supported Au nanoparticles


prepared by deposition precipitation.Characterisation showed that the nanoparticleshad deposited only on the four-coordinate titani-um sites. The problem of the explosion limit wassolved by feeding in H2 and O2 in two separatestreams and using a membrane in the catalyst area.Similarly good performances were obtained withAu on titanium silicalite-1 (TS-1) and with Mooxide on silica for epoxidation by molecular O2.

ConclusionEuropaCat VIII proved to be a key conference

for any researcher studying the behaviour andcharacterisation of catalysts. An impressive selec-tion of oral and written presentations generatedwhat was certainly high quality if occasionallysomewhat heated discussion both in and out of theconference venue. The high industrial representa-

tion attested to the significance of the conferenceto the wider commercial world. It was clear thatpgms retain their fundamental role in manybranches of catalysis and, despite or perhaps as aresult of all efforts at substitution and thrifting, willcontinue to be the focus of considerable catalystresearch activity for the foreseeable future.

EuropaCat IX: “Catalysis for a SustainableWorld” will take place in Salamanca, Spain, from30th August to 4th September 2009 (5).

References 1 EuropaCat VIII: http://www.europacat.org/ 2 Berzelius, Ann. Chim. Phys. (Paris), 1836, 61, 1463 B. Samanos, P. Boutry and R. Montarnal, J. Catal.,

1971, 23, (1), 194 M. Haruta, T. Kobayashi, H. Sano and N. Yamada,

Chem. Lett., 1987, 16, (2), 4055 EuropaCat IX: http://www.europacat2009.eu/


After her Ph.D. in CoordinationChemistry in Basel, Switzerland (1999),Emma Schofield spend two years as apost-doctoral researcher in Strasbourg,France, before taking up a Lectureship inInorganic Chemistry at Trinity College inDublin, Ireland. In 2004 she moved toJohnson Matthey in the U.K. where she

specialises in developing new synthetic routes to heterogeneouscatalysts.

Cristian Spadoni graduated from theFacoltà di Chimica Industriale, Universitàdi Bologna, Italy, with a specialisation inheterogeneous catalysis. He started hisPh.D. in Chemical Engineering withJohnson Matthey in the framework of theMarie Curie Actions and in collaborationwith the University of Bath, U.K. Hisresearch has been focused on ‘Direct

Synthesis of Hydrogen Peroxide from Oxygen and Hydrogen’.

After specialising in heterogeneouscatalysis applied to environmentaltechnology at the UniversidadComplutense de Madrid, Spain, andgraduating from the Università diUrbino, Italy, Nadia Acerbi started herPh.D. with Johnson Matthey in theframework of the Marie Curie Actions

and in collaboration with the University of Oxford, U.K. Herresearch is focused on ‘Novel Nano-Coated Catalysts forSelective Oxidation of Hydrocarbons’.

The Reviewers

The drive for renewable feedstocks and fuels isa hot topic for scientists and governments, andcatalysis is a key enabling technology for the development of new and improved processes.Hence, the appearance of this book is well timed. Iam not sure about the publisher’s claim that “thiswill be a white book in the field”. The sixteenchapters are mostly reviews, and some of themhave overlapping content. As with any type ofboom, this research field is prone to exaggeratedclaims and false trails. Competition between foodand biofeedstocks is likely in due course to dis-courage the use of food crops, but agricultural(lignocellulosic) waste products and targeted cropsfrom marginal land have long-term potential.

The content originated in a workshop,“Catalysis for Renewables”, held in theNetherlands in 2006, and organised within the EUsponsored ‘IDECAT’ (Integrated Design ofCatalytic Nanomaterials for a SustainableProduction) framework (1). The editors of thebook were members of the Organising Committee.The aim was to define “new directions and oppor-tunities for catalytic research in this field byintegrating industrial, governmental and academicpoints of view”. The authors are mostly academicand government scientists from the Netherlandsand Italy, with a few more from France andFinland. There are very few industrial scientists.Hence, although the subject matter is of globalgeopolitical and industrial significance, the contentreflects the views of attendees at this regional, academic workshop. However, the reviews cover awide range of literature, and so the book serves asa useful source of information.

Each chapter clearly stands alone as the work ofits authors, suggesting a light editorial touch. Most

of the reviews are informative, and a few are excel-lent. I liked the overall perspective on renewablecatalytic technologies in the early chapters and theroadmap in the final chapter. Various controversialpoints are well described, regarding the magnitudeof environmental challenges and the effectivenessof proposed solutions. However, the lists of acad-emic studies of catalytic reactions in chapters onchemical transformations are not very helpfulwithout some critical appraisal of their true poten-tial for application (cost, robustness, effectiveness).The early chapters cover the biomass conversionchain, from the biorefinery to fuels and chemicalproducts. The ordering of later chapters seemsmore random. Chapter 8, which describes com-bustion modelling, appears to be in the wrongbook. There are further chapters on bioethanolproduction and upgrading, the conversion of glycerol to diesel components, other chemicals andsyngas (carbon monoxide and hydrogen), and themethodology of cascade catalysis. The chapters onhydrogen production and fuel cells, and the techno-commercial and environmental case forhydrogen in transportation are loosely linked to thetitle theme, but are relevant for strategic reasons.The production of hydrogen by solar photocataly-sis is the biggest challenge for the future.

In general, there is little novel catalysis in thisbook. The production chain from the biorefineryis based on catalytic unit operations familiar tothe chemical industry. Hence, processes such asreforming, hydrogenation, oxidation, hydrolysisand etherification appear throughout the book.New catalytic requirements do appear, for example, in the selective deoxygenation of cer-tain intermediates. There is an interestingroadmap in the final chapter for priorities in


“Catalysis for Renewables: FromFeedstock to Energy Production”EDITED BY GABRIELE CENTI (University of Messina, Italy) and RUTGER A. VAN SANTEN (Eindhoven University of Technology,

The Netherlands), Wiley-VCH, Weinheim, Germany, 2007, 448 pages, ISBN 978-3-527-31788-2, £105.00, €141.80, U.S.$200.00

Reviewed by John Birtill15 Portman Rise, Guisborough, Cleveland TS14 7LW, U.K.; E-mail: [email protected]

DOI: 10.1595/147106708X364922

catalysis research into renewable raw materialsand sources of energy.

Not surprisingly, there are many passing refer-ences throughout the book to supported and/orbifunctional platinum group metal catalysts, forexample hydrogenation (palladium, platinum,ruthenium, rhodium, iridium), hydrogenolysis(Pd), dehydrogenation (Pd), oxidation (Pt, Pd),homogeneous telomerisation (Pd), homogeneoushydrogenation (Rh), steam reforming (Pt), aqueousreforming (Ru, Pt, Pd) and electrocatalysis (Pt).However, many of these references have not beenincluded in the index. The practical conversion ofbiofeedstocks is certain to place new demands onthe robustness of catalysts, but this aspect is hardly mentioned by the mainly academic authors.A chapter on new challenges for catalyst designmight have been useful, but I suppose that no-onetalked about this at the IDECAT workshop.Besides the lack of industrial experience of biopro-cessing, other notable omissions include thepotential use of marine harvests and municipalwaste.

In conclusion, this book will be useful to any-one who wants an academic, strategic perspective

on the potential contributions from various cat-alytic technologies to this field of research. Thelack of industrial perspective is its most seriousweakness. The price will limit its purchase mainlyto libraries. It will be read by academic and indus-trial scientists, research students seeking a widerperspective, and those concerned with science policy. For instance, the issues of food competi-tion and poor overall effectiveness attached to useof some food crops as industrial feedstocks arewell explained, and it is surprising that these issueshave only recently become politically controversial.Anyone interested in detailed catalytic science willfind texts dedicated to the respective catalytic tech-nologies to be more useful; for a general source,see for example Reference (2).

References1 IDECAT Conference Series, Catalysis for

Renewables Conference: http://idecat.unime.it/index.php?pag=CatForRen

2 C. H. Bartholomew and R. J. Farrauto,“Fundamentals of Industrial Catalytic Processes”,2nd Edn., Wiley-Interscience, Weinheim, Germany,2006


The ReviewerJohn Birtill is a consultant in industrialcatalytic technology, an Honorary ResearchFellow at the University of Glasgow, U.K.,and Secretary of the Royal Society ofChemistry Applied Catalysis Group. See hiswebsite at: www.catalyst-decay.com formore information.

Previous articles in this Journal have describedthe importance of patents as a key source of techni-cal and commercial intelligence (1, 2). The use ofpatent mapping to visualise large sets of patent dataand to identify trends contained within that data hasalso been demonstrated (2). The present paper fur-ther develops these themes by examining the patentliterature on pgms published since 1983, in particu-lar that on the minor metals iridium and ruthenium.

Searching – What and Where?I will begin by thinking about search strategy. In

this case, the initial objective is to create a large setof patents relating to the pgms, which will later beanalysed and refined. The choice of keywords istherefore straightforward: platinum, palladium,rhodium, iridium, osmium and ruthenium. In thepatent literature it is unlikely that the names ofthese metals would be used in other contexts.However, this might be a difficult problem if wewere searching the news or business press, wherethe names of the pgms are associated with manybrand names – for example there would probablybe many hits on topics such as platinum creditcards or iridium satellite communication systems,and strategies for removing such material wouldneed to be found.

Perhaps a more important question to ask iswhich patent collections to use to search for thesewords? The software package used at the Johnson

Matthey Technology Centre is Aureka® (a productavailable from Thomson Reuters) (3), whichincludes patent data sets from the PatentCooperation Treaty (PCT) and European Patentoffices, plus a range of national patent collectionsincluding those of the U.S.A., Japan, the U.K.,France and Germany. With the exception of Japan,these collections contain full-text patent docu-ments, available either as PDF or HTML files. Inthe case of Japanese patents, a text version of theEnglish-language title, abstract and other frontpage details is available, together with a PDF file ofthe full specification in Japanese.

It must be borne in mind that using the Frenchand German collections would require us to searchin French or German respectively, and of coursethe results obtained would also be in French orGerman. The patent collections of other countries,for example China and India, are not currentlyavailable in Aureka. However at this stage we arelooking for the big picture. The detail can followlater if necessary, for example by adding Chinesepatent documents retrieved from other patentdatabases.

We also need to think about where in thepatent document we might wish to search forinformation on pgms. This is an important ques-tion and to understand the various possibilitiesand their implications we first need to think aboutthe structure of a typical patent:


Platinum Group Metals Patent Analysisand MappingA REVIEW OF PATENTING TRENDS AND IDENTIFICATION OF EMERGING TECHNOLOGIES

By Richard SeymourJohnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.; E-mail: [email protected]

The patent literature contains a wealth of detailed information about existing and new usesfor the platinum group metals (pgms). While excellent searching tools have existed for manyyears for identifying patents relating to specific topics, it is only relatively recently that ithas been feasible to map the complete archive of patent literature to identify importanttrends relating to potential new applications. This paper summarises the results of such anexercise for the pgms carried out in early 2008 and shows that one such ‘hot spot’ relates toorganic light emitting diodes (OLEDs).

DOI: 10.1595/147106708X362735

– Title: often deliberately rather vague and non-specific.

– Abstract: a short summary of the invention, inperhaps 100 to 200 words.

– Claims: the claims of a patent govern its legaleffect, that is, the areas of technology that are tobe monopolised. Generally it can be said that afeature is not protected unless that feature isclaimed or covered by the general language inthe claims. So these are key – get the claimswrong and your invention may be seriouslycompromised.

Then, depending on the particular country, theremay also be sections on:– Background: provides details on the context of

the invention, current technology, and whyexisting solutions may be inadequate.

– Description: a detailed description of the inven-tion and possible variants thereof.

– Examples: worked examples, covering aspectssuch as how the invention is made. Scientistssometimes wrongly concentrate on the exam-ples just as they would read the experimentalsections of scientific papers.Now let us suppose we are searching for patents

in which a new pgm chemical or material is dis-closed, or in which the use of a pgm is a key part ofthe invention. In this case restricting the search toterms in the title or abstract, and possibly also theclaims, will be adequate. Clearly if the word ‘plat-inum’ appears in any of these sections then it islikely to be a very important part of the invention.

But what about the case when the name of thepgm appears somewhere in the rest of the patent,but not in the title, abstract or claims? Can thesepatents safely be ignored? An example of suchpatents might be the use of a standard palladiumon carbon hydrogenation catalyst in a multi-stageorganic synthesis route. The novelty is in the end-product, not the catalyst used, and therefore theterm ‘palladium’ is unlikely to occur in the title,abstract or claims. However it may well come up inthe examples. While we can probably ignore suchpatents for the purpose of identifying key newapplication areas, important information may nevertheless be obtained from them. For example,they may provide valuable intelligence on sales

opportunities for suppliers of catalysts, the cus-tomer being the owner of the patent.

Table I illustrates the wide variation in the num-ber of retrieved patents obtained according towhere in the patent the search is performed. Thetable clearly shows that choosing which part of thepatent document to search is critical. If we searchin the patent title, abstract and claims then weretrieve over five times as many patents as exactlythe same search restricted to just title and abstract.If we search in the full text of the patent then weretrieve five times as many again.

Table II shows the top fifteen assignees foreach set of results in Table I. It shows that wemight expect to obtain quite different results forthe various searches, even though the keyword isthe same in each case. Apart from MicronTechnology Inc, which heads up each list, there aresome very significant differences. Engelhard (nowBASF Catalysts) comes in at number five in the‘title or abstract’ search but does not appear in the‘title, abstract or claims’ or full-text searches. Onthe other hand, the Semiconductor EnergyLaboratory, while it does not appear in the ‘title orabstract’ search, and only reaches number twelvein the ‘title, abstract or claims’ search, comes in atnumber two in the full-text search.

Pfizer is another good example. LikeSemiconductor Energy Laboratory, this company


Table I

Searches on the Term ‘Platinum’ Conducted inthe U.S. Granted Patent Collection, for PatentsPublished between 1st January 2001 and 31stDecember 2007

Criteria Number of ‘hits’

‘Platinum’ in the patent 1611 title or abstract

‘Platinum’ in the patent 8878 title, abstract or claims

‘Platinum’ in the patent 44,541full-text

‘Platinum’ in the patent 35,663full-text but not title, abstract or claims

only appears in the top assignees from the full-textsearch. One would expect Pfizer’s main interest inplatinum to be as a user of catalysts in pharmaceu-tical manufacturing, rather than as a developer ofnew pgm-based technologies. Manual inspection ofselected Pfizer patents confirms this to be the case.

The Results List and InitialAnalysis

For the remainder of this paper we will be con-sidering the results of searches based on the namesof the pgms in the patent title or abstract. We haveundertaken the search in the U.S., European andPCT patent collections, for patent applications orgranted patents published in the period from 1stJanuary 1983 to 31st December 2007. The searchresults have then been ‘deduplicated’ to exclude

patent family members filed in different geograph-ical regions, to leave one patent per invention. Thefinal document list contains just over 13,540patents.

Figure 1 shows a basic breakdown of thesepatents by metal and by five-year timeslices.Overall growth in pgm patents in the period from1983 to 2007 is about 6% per annum. In the lastseven years, this growth rate has been nearly 13%.However, growth in the number of patents byindividual metal is not completely uniform. Therehas been somewhat higher growth for platinum,ruthenium and iridium patents, and slightly lowergrowth for palladium and rhodium, as shown inTable III.

A comparison between the pgm patent pictureand that for a number of other metals (gold, silver,


Table II

Search Results by Top Fifteen Assignees for Patents in the U.S. Granted Patent Collection, Published between 1st January 2001 and 31st December 2007

Rank ‘Platinum’ in patent title ‘Platinum’ in patent title, abstract ‘Platinum’ in patent full-text or abstract (1611 patents) or claims (8878 patents) but not title, abstract or claims

(35,663 patents)

1 Micron Technology Inc Micron Technology Inc Micron Technology Inc

2 General Electric General Electric Semiconductor Energy Laboratory

3 Shin-Etsu Chemical Co IBM Fuji Photo Film Co Ltd

4 UOP LLC Samsung Electronics Co Ltd Eastman Kodak

5 Engelhard Corporation1 Advanced Micro Devices Inc Canon KK

6 Dow Corning Matsushita Electric Industrial Matsushita Electric IndustrialCo Ltd Co Ltd

7 Matsushita Electric Industrial Shin-Etsu Chemical Co General ElectricCo Ltd

8 Texas Instruments Inc Intel Corp 3M Innovative Properties Co

9 Dow Corning Toray Silicone Infineon Technologies AG IBM

10 IBM Hitachi Ltd NGK Insulators Ltd

11 Advanced Cardiovascular Institut Francais du Petrole Seiko EpsonSystems

12 Samsung Electronics Co Ltd Semiconductor Energy Laboratory Medtronic Inc

13 Honeywell International Inc UOP LLC Pfizer

14 Infineon Technologies AG Texas Instruments Inc Sony Corp

15 BASF Hewlett-Packard Development Co Hitachi Ltd

1Now BASF Catalysts

nickel and cobalt) is shown in Figure 2. The num-ber of patents on all these metals has increased.However the rate of increase for pgms and gold isconsiderably higher than that for nickel, cobalt andsilver. This is illustrated in Table IV by looking atthe earliest (1983–1987) and latest (2003–2007)time periods.

Figure 3 shows the importance of these metalsin selected technology areas. The analysis wasbased on selected International PatentClassification (IPC) codes (4).

Patent MappingThe Aureka ThemeScapeTM tool (3) was used to

create a visualisation of the pgm document listdescribed above. The results are shown in Figure 4.The resulting map looks like a mountainous island

surrounded by sea. The visualisation is helpfulbecause ThemeScape groups together similar doc-uments and labels these groups according tofrequently used key terms found within thosegroups. The more documents contained withineach group, the higher the ‘mountain’ appears. Theautomatic labelling sometimes produces meaning-ful headings (e.g. silicone, rubber, polysiloxane),but sometimes these are less obviously meaningful(compounds, preparation, reaction). Where neces-sary these can be edited following an inspection ofdocuments contained within the groups.

The grey dots represent sample documents – inthis set of 13,540 documents only a small propor-tion are shown in this view, but more (or all)documents will be shown when specific areas aremagnified. Clicking on specific dots will display the


7000

6000

5000

4000

3000

2000

1000

0

Num

ber o

f pat

ents

pub

lishe

d

Osmium

Iridium

Ruthenium

Rhodium

Palladium

Platinum

1983–1987

2003–2007

1998–2002

1993–1997

1988–1992Time period

Fig. 1 PGMpatents bymetal –numberpublished infive-year timeperiods

Table III

PGM Patents by Metal: Number and Proportion of Patents Containing Specific PGMsPublished in Early (1983–1987) and Recent (2003–2007) Time Periods

Metal Patents containing specific pgms Patents containing specific pgmsvs. total pgm patents, 1983–1987 vs. total pgm patents, 2003–2007

Number Proportion, % Number Proportion, %

Platinum 840 46 2265 52Palladium 659 36 1452 33Rhodium 408 22 689 16Ruthenium 349 19 1024 23Iridium 184 10 613 14Osmium 56 3 189 4

Total1 18331 – 43921 –

1This is not the arithmetic sum as more than one pgm can appear in any given document


Table IV

PGM Patents vs. Other Metals: Number and Proportion of Patents Containing SpecificMetals Published in Early (1983–1987) and Recent (2003–2007) Time Periods

Metal Patents containing specific metals Patents containing specific metalsvs. total metal patents, 1983–1987 vs. total metal patents, 2003–2007

Number Proportion, % Number Proportion, %

PGMs 1833 28 4392 31Gold 646 10 2152 15Silver 2009 31 4062 28Nickel 2200 34 4626 32Cobalt 1279 20 2441 17

Total1 65361 – 14,2931 –

200001800016000140001200010000

8000600040002000

0

Num

ber o

f pat

ents

pub

lishe

d

Cobalt

Nickel

Silver

Gold

PGM

1983–1987

2003–2007

1998–2002

1993–1997


Fig. 2Comparison ofpgms withselected othermetals –number ofpatentspublished infive-year timeperiods

1This is not the arithmetic sum as more than one pgm can appear in any given document

Fig. 3 Relative importance of various metals in selected technology areas, by IPC code, for the time periodbetween 1st January 2003 and 31st December 2007

PGM

Gold

Silver

Nickel

Cobalt

Heterogeneous catalysts

Semiconductors or Electronics

Homogeneous catalysts

Fuel cells and batteries

Coated products

Alloys

Medical

Tech

nolo

gy a

rea

0 500 1000 1500 2000Number of patents

original document. The contour lines enclosingparticular areas can be used to select groups ofdocuments for inspection or further analysis.

In Figure 5, we have further processed the basicmap shown in Figure 4 in two ways. Firstly, to cre-ate a timeslice covering documents published onlyin the period January 2003 to December 2007; sec-ondly, to show patents on platinum as red dots andpatents on palladium as green dots. Where specif-ic documents cover both platinum and palladium,these are shown as white dots.

The reason for this exercise is to show the rela-tive importance of particular metals in specifictechnology areas. For example, the ‘silicone, rub-ber, organopolysiloxane’ and ‘fuel cell, fuel,electrode’ areas are dominated by red dots, indicat-ing that platinum is the preferred metal in theseapplications. The ‘plating, deposited, substrate’region is dominated by green dots, confirming theimportance of palladium in electronic applications.

The ‘exhaust, engine, oxide’ area contains manyred, green and white dots, indicating that both met-als may be used in emission control applications.

Figure 6 is a similar image showing the minormetals rhodium, ruthenium, iridium and osmium.Of particular interest here are the two boxedareas, the first just left of centre, the second cen-tre right. These contain a cluster of mainly lightblue dots (ruthenium) and dark blue dots (iridi-um), respectively. Comparison of the number ofdots with the same areas in Figure 7, covering the1993 to 1997 timeslice, shows a marked increasein the numbers of iridium and ruthenium patentspublished in 2003–2007. These are examples ofemerging technologies. Magnification of one ofthese areas (see Figure 8) shows that this areaincludes many patents on organic light emittingdiodes (OLEDs), which is an important potentialnew application for iridium-based fluorescent orphosphorescent dopants. OLEDs (see also


Fig. 4 PGM patent map covering granted patents or patent applications published between 1st January 1983 and 31stDecember 2007

References (5, 6)) are solid-state devices com-posed of thin films of organic molecules thatcreate light with the application of an electric cur-rent. Compared with conventional light-emittingdiodes (LEDs) or liquid crystal displays (LCDs),OLEDs provide brighter, crisper displays whichrequire less power. It has been discovered that insome iridium complexes, strong spin-orbit cou-pling leads to singlet-triplet mixing, ideal forhighly efficient electrophosphorescence requiredfor future OLEDs. Companies with pgm patentsin the OLED area currently include DuPont(U.S.A.), Samsung (Korea), LG Electronics(Korea), Idemitsu Kosan (Japan) and KonicaMinolta (Japan).

Further analysis of the map shows that ruthe-nium-based interconnects and electrodes,iridium-based capacitor materials, new magneticmaterials containing iridium or ruthenium, ruthe-nium-based metathesis catalysts (for example

Grubbs’ catalyst) and the application of rutheni-um in silane production are other emergingtechnology areas.

The Non-Patent LiteratureWhile patents are an extremely important

source of technical and commercial intelligence,there is also a huge amount of non-patent litera-ture covering the pgms. This is illustrated in Figure9, which compares the size of the patent literatureon ruthenium with that of the non-patent scientif-ic literature on the uses of this metal inchemistry-related areas. The top ten uses forruthenium in the non-patent literature, based oncontrolled index terms used in the ChemicalAbstracts database, are shown in Table V.Specialised software tools such as STN®

AnaVistTM (7) are now available to assist with theanalysis of non-patent (as well as patent) literature,similar to that described above for the patent data.


Fig. 5 PGM patent map timeslice 2003–2007, showing occurrences of platinum patents (red dots), palladium patents(green dots), and patents covering both platinum and palladium (white dots)

ConclusionsThe patent literature is an extensive and

detailed source of information on existing andpotential new applications for the pgms. At the

time of writing, there are in the region of 13,540inventions, covering the period from January1983, in which the use of one or more pgms is akey part of the inventive step. There are many oth-ers in which pgms may be used, for example aspart of a complex organic synthesis route. Growthof this literature is expected to continue toincrease at a rate slightly higher than that of cer-tain base metals.

Patent mapping tools can be used to identifykey areas of development and ‘hot spots’ ofactivity which may lead to future volume applica-tions. ‘Hot spot’ areas for the minor metalsruthenium and iridium currently include iridiumin organic light emitting diodes (OLEDs), ruthe-nium-based interconnects and electrodes,iridium-based capacitor materials, new magneticmaterials containing iridium and/or ruthenium,and the application of ruthenium in silane production.


Fig. 6 PGM patent map timeslice 2003–2007, showing occurrences of rhodium patents (yellow dots), iridium patents(dark blue dots), ruthenium patents (light blue dots), osmium patents (purple dots), and patents covering two or moreminor metals (white dots)

Table V

Top Ten Uses for Ruthenium from the Non-PatentChemical Literature, 2003–2007

Publication index term Proportion of total,2003–2007, %

Fuel cells 11.2Oxidation catalysts 10.7Hydrogenation catalysts 9.4Nanoparticles 5.2Oxidation, electrochemical 4.4Carbon black, uses 4.1Fluoropolymers, uses 3.7Magnetisation 3.7Spin valves 3.7Vapour deposition process 3.4


Fig. 7 PGM patent map timeslice 1993–1997, showing occurrences of rhodium patents (yellow dots), iridium patents(dark blue dots), ruthenium patents (light blue dots), osmium patents (purple dots), and patents covering two or moreminor metals (white dots)

IridiumOLED

Electroluminescent

Fig. 8 Magnified view ofcentre-right box shown inFigure 6 for timeslice2003–2007, showingoccurrences of iridiumpatents (dark blue dots),ruthenium patents (lightblue dots), and patentscovering two or moreminor metals (white dots)


350030002500200015001000

5000

Num

ber o

f pub

licat

ions

1983–1987

2003–2007

1998–2002

1993–1997


Patents

Non-patents(uses)

Fig. 9 Trends in thenon-patent literature –number of publicationsin patent and non-patentliterature for ruthenium

The AuthorRichard Seymour is the Head of TechnologyForecasting and Information at the JohnsonMatthey Technology Centre, U.K. He isinterested in the use of information in theareas of competitive intelligence andcommercial development.

1 I. Wishart, Platinum Metals Rev., 2005, 49, (2), 982 R. Seymour, Platinum Metals Rev., 2006, 50, (1), 273 Thomson Reuters, Scientific: Products: Aureka®:

http://scientific.thomsonreuters.com/products/aureka/4 World Intellectual Property Organization, IP

Services, WIPO International Classifications:

http://www.wipo.int/classifications/5 J. A. G. Williams, Platinum Metals Rev., 2007, 51, (2),

856 R. J. Potter, Platinum Metals Rev., 2008, 52, (3), 155 7 CAS, STN® AnaVistTM:

http://www.cas.org/products/anavist/

References

From 4th to 9th May 2008, 149 participants metin Bad Berneck, a small village close to Bayreuth,Germany, for the 11th International Conferenceon Creep and Fracture of Engineering Materialsand Structures, in short, Creep 2008 (1, 2). Theattendees came from twenty-two different nationsall over the world to participate in Creep 2008,organised by Uwe Glatzel (Metals and Alloys,University Bayreuth, Germany) and by GuntherEggeler (Research Group for Materials Scienceand Engineering, Ruhr-University Bochum,Germany). During five days 111 oral presentationswere given. The programme was divided intotwenty sessions: General I–III, Steel I–VI, NickelI–III, Refractory I–II, Ti & TiAl, Magnesium, Cu& MMC (Metal Matrix Composites), SteelWelding, Light Metals and Testing Techniques.

Creep deformation is a time-dependent defor-mation of materials at high temperatures. Hence,the topics of the conference included modellingand simulation of creep deformation, high resolu-tion microanalysis and the development of newhigh-temperature materials. During the meetingengineers and scientists shared their experienceand knowledge in order to explore new materialsand applications. A short overview of the talksrelated to platinum group metals (pgms) is givenhere.

L. A. Cornish (University of the Witwatersrand,Johannesburg, South Africa) gave an overview ofthe ‘Derivation of the Creep Properties of Two-phase Pt-Al-Cr-Ru Alloys by Modelling’. Shepresented the development of two-phase Pt-basedalloys, which have a similar structure to the well-known and very successful nickel-based

superalloys. Progress in developing a thermody-namic database for phase diagram predictions wasalso presented (see also References (3–5)). The aimof this work is to use these predictions to calculatethe volume fraction of the Pt3Al precipitates, thencombine microstructural data derived from a seriesof different alloy compositions to develop a relationship for the stability of the precipitates. Asshe pointed out, this allows the size and precipitatedistribution against temperature to be modelled fora given alloy composition in the (Pt) and (Pt3Al)phase field in the Pt-Al-Cr-Ru quaternary system.

K. Maruyama (Tanaka Kikinzoku Kogyo K.K.,Japan) reviewed ‘High Temperature Creep ofGTH (Gottsu-Tsuyoi Hakkin)’. In his talk, high-temperature creep properties of GTH and GTHR,which are trade names of oxide dispersionstrengthened platinum alloys developed by theTanaka Kikinzoku Group, are explained and com-pared with commercial platinum andplatinum-rhodium alloys. It was presented that,comparing the same rupture time; GTHR is sever-al times stronger than the normal Pt-10% Rh alloy,which may be of interest for the glass meltingindustry for the production of liquid crystal dis-plays and optical glass and the spinning of glassfibres.

The presentation of J. Preußner (Metals andAlloys, University Bayreuth, Germany) addressedthe ‘Determination of Phases in the System Pt-Al-Cr-Ni and Thermodynamic Calculations’. Pt basealloys have been developed at the Metals andAlloys group to receive creep, oxidation and corro-sion resistant alloys for high-temperatureapplications with room temperature ductility.

241Platinum Metals Rev., 2008, 52, (4), 241–242

Creep 2008: 11th International Conferenceon Creep and Fracture of EngineeringMaterials and StructuresHIGH-TEMPERATURE BEHAVIOUR OF PLATINUM GROUP METALS

Reviewed by J. Preußner, R. Völkl and U. Glatzel*Metals and Alloys, University Bayreuth, Ludwig-Thoma-Straße 36b, D-95447 Bayreuth, Germany;

*E-mail: [email protected]

DOI: 10.1595/147106708X363888

Thermodynamic modelling has been used to sup-port the alloy development. The Cr-Pt system hasbeen reassessed with the CALPHAD methodbased on experimental data and first-principlescalculations. He presented a calculated Cr-Ni-Ptternary phase diagram and an outlook on the cal-culation of the quaternary Pt-Al-Cr-Ni system.

R. Völkl (Metals and Alloys, UniversityBayreuth, Germany) summarised the‘Development of a Precipitation Strengthened PtBase Superalloy’. He reviewed the process ofdesigning an alloy with good mechanical proper-ties and excellent oxidation resistance up to veryhigh temperatures. Similarly to the approach ofCornish (described above), Pt-Al-Cr has been usedas a starting point for alloy development. A varietyof ternary additions to the Pt-Al base have beeninvestigated to secure the L12 structure of thehardening Pt3Al phase. He explained that Ni hasbeen added for solid solution strengthening. Acomparison to the common alloy developmentroute in the industry has been shown.

P. Panfilov (Urals State University,Ekaterinburg, Russia) gave a presentation ‘OnSpecific Feature of Plastic Deformation inIridium’. He stated that the refractory f.c.c.-metalIr, with a melting point of 2443ºC, exhibits excel-lent mechanical properties at high temperatures.According to experiments he presented, the defor-mation behaviour of Ir is well in accordance withempirical knowledge on f.c.c.-metals, while somefeatures of Ir seem to be puzzling. He compared

the deformation behaviour of single crystals topolycrystalline material at different temperatures.One feature of the deformation behaviour of Ir,he pointed out, is that single crystals show aremarkable total elongation, but no necking,whereas polycrystals only reach a small deforma-tion, but considerable necking. With the help oftransmission electron micrographs, Panfilovexplained the dislocation structures in deformed Irsamples.

A collection of the conference contributionswill be published in a special issue of the journalMaterials Science and Engineering A (6). The 12thInternational Conference on Creep and Fractureof Engineering Materials and Structures, Creep2011, will be held in Japan, and will be chaired byKouichi Maruyama (Tohoku University) andHideharu Nakashima (Kyushu University).

References 1 Creep 2008: 11th International Conference on

Creep and Fracture of Engineering Materials andStructures:http://www.metalle.uni-bayreuth.de/creep2008

2 Abstract Book for Creep 2008:http://www.metalle.uni-bayreuth.de/creep2008/abstractbook_Creep2008.pdf

3 L. A. Cornish, R. Süss, A. Watson and S. N. Prins,Platinum Metals Rev., 2007, 51, (3), 104

4 A. Watson, R. Süss and L. A. Cornish, PlatinumMetals Rev., 2007, 51, (4), 189

5 J. Preußner, S. N. Prins, M. Wenderoth, R. Völkland U. Glatzel, Platinum Metals Rev., 2008, 52, (1), 48

6 Mater. Sci. Eng. A, in press (publication date will beearly 2009)

Johannes Preußner is a scientific researcherand Ph.D. student at the Chair of Metals andAlloys at the University Bayreuth, Germany.His main interests include modelling andsimulation in materials science and newhigh-temperature materials.

Professor Dr.-Ing. Uwe Glatzel is head of theChair of Metals and Alloys at the UniversityBayreuth, Germany. His work has had a bigimpact on the development of modern high-temperature alloys, mainly nickel basesuperalloys. He advises several researchgroups, including those working onplatinum-based superalloys and other alloys

for high-temperature applications, laser metallurgy, materialanalysis and artificial knee joints.

Dr.-Ing. Rainer Völkl is senior researcher atthe Chair of Metals and Alloys, UniversityBayreuth, Germany. His main fields ofresearch include alloys of platinum groupmetals as well as nickel base alloys, testingof mechanical properties at hightemperatures and electron microscopy.

The Reviewers

242Platinum Metals Rev., 2008, 52, (4)

Global Release Liner Industry Conference 2008was organised by AWA Alexander WatsonAssociates BV and took place from 6th to 8thFebruary 2008, at the Hilton Amsterdam Hotel,The Netherlands (1). It was attended by all themajor players in the silicones industry, major labeland paper manufacturers and representatives ofthe precious metals industry. The conferencefocused much attention on the development ofnext-generation low platinum catalyst solutionsand the potential for complete removal of plat-inum from silicone curing systems. This reviewdescribes the technical developments, their relatedbenefits and shortcomings, and summarises thetrends expected to prevail in the release linerindustry during the next few years. The releaseliner industry is an important sector of the overallmarket for silicones.

BackgroundSilicones, or polyorganosiloxanes, are used in a

variety of applications, particularly in pressure-sen-sitive adhesives and release coatings. A key marketin this sector is that of release liner coatings forlabels and tapes, where the good adhesion andclean release properties of silicone release coatingsare highly desirable.

Platinum is widely used as a catalyst for the cur-ing of these silicones by promoting ahydrosilylation reaction, Reaction (i), (2):

Ptcatalyst

R3SiH + H2C=CHR' R3SiCH2CH2R' (i)

Karstedt’s catalyst (chloroplatinic acid-sym-divinyltetramethyldisiloxane complex) is a Pt(0)complex containing vinyl-siloxane ligands, and itinitiates the addition of a silicon–hydrogen bondacross a carbon–carbon double bond, known ascuring, which hardens the silicone by crosslink-ing siloxane chains, Figure 1. The reaction, attemperatures in the region of 80 to 120ºC, is car-ried out in a platinum-containing Karstedt’scatalyst bath in which the silicone is cured rapid-ly as the paper label, or ‘labelstock’, is applied toits backing, forming a release coating betweenthe two layers on a sub-second timescale. Freeradical-based alternatives to platinum catalysis,initiated either by ultraviolet (UV) light or anelectron beam, can be used to generate the radi-cal initiator, but require labile groups such asepoxides or acrylates and thus the properties ofthe cured silicone vary from conventional silicones.


Global Release Liner Industry Conference 2008 OPTIMISED TECHNOLOGIES ARE EMERGING WHICH REDUCE PLATINUM USAGEIN SILICONE CURING

Reviewed by Andrew J. HolwellJohnson Matthey, Precious Metals Marketing, Orchard Road, Royston, Hertfordshire SG8 5HE, U.K.;


DOI: 10.1595/147106708X366975

(a) (b)

O

CH3

CH3

OSi

x

(CH3)3Si

H

CH3

OSi

y

Si(CH3)3 O

CH3

CH3

OSi

x

CH3

OSi

yCH3

CH3

Si

CH3

CH3

Si

Fig. 1 (a) Silicone monomer typically used in solventless platinum-catalysed hydrosilylation reactions; (b) Conventional crosslinker for platinum-catalysed hydrosilylation reactions

Platinum in the Release LinerIndustry

Presentations were given by silicones suppli-ers Dow Corning, Bluestar Silicones and WackerSilicones, and perhaps the hottest topic of theconference was that of platinum, its price andways to reduce its usage. Platinum-catalysedthermal curing remains the industry standardapproach and because the catalyst is irretrievablylost in the product, the cost of platinum is oneof the biggest challenges facing the industrytoday.

Highlights related to platinum included a jointpresentation by Norm Kanar (Dow Corning,U.S.A.) and Wolfgang Wrzesniok-Rossbach (W. C.Heraeus, Germany) entitled ‘Platinum Challenges:Trends and Developments’, showcasing the costbenefits of Dow Corning’s low platinum productseries. There was also a paper by KarstenSchlichter (Bluestar Silicones, France), entitled‘Radiation Curing Silicone Release Systems, the PtAlternative?’, appraising a range of curingchemistries. According to this presentation, themarket split between platinum and radiation curedsystems is expected to stand at around 80:20 by2015 compared to 85:15 at present. A small anddiminishing share of the market uses solvent-basedtin-catalysed emulsions, but this is expected to fallto zero within the next few years, according tothese projections. Taking a slightly different angle,Hans Lautenschlager (Wacker Silicones, Germany)described smarter ways of monitoring and usingsilicone in his presentation ‘More or LessSilicone?’.

Growth in the silicones industry is stronglylinked to growth in consumer spending, aslabelstock is primarily a consumer-driven indus-try. Annual global growth of around 5 per centis expected for the next few years. In terms of platinum uptake, industry growth will be at leastoffset by the increased use of low platinumsolutions, particularly when platinum prices arehigh. During this conference, platinum succes-sively set then-record high prices, fixing inLondon at U.S.$1852 per troy ounce on 7thFebruary and U.S.$1860 per troy ounce on 8thFebruary (3).

Low Platinum TechnologiesJohnson Matthey estimates that the silicones

industry worldwide used around 180,000 troyounces (5.6 tonnes) of platinum in 2007 (4), whichat average Johnson Matthey base prices for theyear of U.S.$1307 per troy ounce, is worth aroundU.S.$235 million; in the eighteen months from thestart of 2007 to July 2008, the price of platinumalmost doubled (3). This accelerated the develop-ment of low platinum technologies, which have theadvantage of being largely drop-in replacementsystems for existing coating units, unlike free radi-cal initiated systems. Through advancedengineering of the silicone polymers and crosslink-ers, Dow Corning has developed a system whichallows the use of a catalyst bath containing only25–35 ppm platinum, compared to the standard100 ppm typically in use around the industry. DowCorning claims that its “branched polymers [and] anew crosslinker structure… [which] enables cureof the release coating at platinum catalyst levels aslow as 25 ppm” (5) can overcome operational andperformance issues typically seen with the modi-fied components in the radiation-cured field.Bluestar Silicones and other companies marketsimilar solutions, which are commercially available.The feeling in the industry is that platinum reduc-tion, rather than widespread uptake of UVsolutions, is likely to be the key trend in the nextdecade. The technical barriers to reduced platinumusage are less significant, less costly and appearcloser to being resolved.

The market share of platinum-based solventlessemulsions remains at around 85% according toBluestar Silicones, who themselves offer a plat-inum-free option to paper manufacturers. Thislevel of market share is unlikely to decline signifi-cantly in the near future, although as explainedbelow, platinum-free UV cured systems will con-tinue to take some market share, most likely inlower performance applications.

Non-Platinum TechnologiesFree radical-initiated curing was pioneered by

Goldschmidt GmbH, latterly Degussa and nowEvonik, in the early 1980s and has gradually takenlimited market share since that time. The technol-


ogy uses unconventional side chains such asepoxy and acrylate groups to generate free radicalsat ambient temperature, usually by UV activation,as shown in Figure 2, (6). Occasionally cationiccuring can be used, although only under certainprocess and substrate conditions. Evonik statethat ‘post-curing’ in both UV-initiated and in par-ticular cationic systems can be a problem (7), inother words the rate of curing is not comparableto the platinum-catalysed reaction. The UVprocess itself displays operational and productperformance limitations, in terms of clean releaseand rate of curing, which has a direct impact onthe throughput of the coating equipment. It isgenerally thought that both coat weights and cur-ing times are higher for radiation-cured silicones,although a number of companies claim to haveachieved similar curing times and thereforethroughput to the conventional process. Thiswould represent a significant technical advance,and may promote the transition to non-platinumtechnologies in the future.

In a paper entitled ‘The Influence of theRelease Liner on Label Properties’, Hervé Vigny(Label Experts, France) described a phenomenonknown as the ‘zippy effect’, observed in UV-initi-ated systems. After curing, the adhesion of thelabel to the release liner takes some time to sta-bilise, compromising the clean releaseperformance of the product. Although the effect isnot fully understood at this time, the cause is wide-ly thought to be the modified side chains whichare essential for UV-initiated processes.

Perhaps the greatest barrier to a move to UV

technologies is the significant capital and opera-tional expenditure needed to install the UV lightsource and its related equipment. There are alsoprocess control issues associated with the require-ment to carry out the reaction in an inertatmosphere of nitrogen. Opinion varies onwhether the transition is financially viable at all,even at the platinum prices that were current at thetime of the conference. In an industry relativelyaverse to change, conventional methodology is notexpected to be displaced quickly.

ConclusionsGlobal Release Liner Industry Conference

2008 focused on the key topic of platinum usagein silicone curing applications and potential oppor-tunities for reducing the amount of platinum used.These include the use of advanced siliconemonomers and crosslinkers to reduce the amountof platinum catalyst required, or the use of alterna-tive curing technologies, specifically UV-initiatedfree radical curing. Low platinum solutions arebecoming available to the release liner industryfrom silicones manufacturers and are expected toachieve significant market share within a few years,as high platinum prices (at the time of this confer-ence) stimulate efforts to use less of the preciousmetal. Doubts over the financial viability ofinstalling and using radiation curing technologyremain, as do technical limitations of the productand process, meaning that this production methodwill only be used for around twenty per cent ofrelease liner curing applications in the next decade,with the balance still to use platinum catalysts.


O

CH3

CH3

OSi

x

(CH3)3Si

R

CH3

OSi

y

Si(CH3)3O

CH3

CH3

OSi

x

(CH3)3Si

R

CH3

OSi

y

Si(CH3)3

O

O O

(a) (b)

R = (CH2)n

Fig. 2 (a) Acrylate-based crosslinked silicone, as produced by UV-cured process; (b) Epoxy-based crosslinked silicone,as produced by UV-cured process (6)

AcknowledgementsPublically available literature from Dow

Corning (8), Bluestar Silicones (9), WackerSilicones (10) and Evonik (11) was used as back-ground information for this review. Global ReleaseLiner Industry Conference 2008 was organised byAWA Alexander Watson Associates BV.

References1 Global Release Liner Industry Conference 2008:

http://www.awa-bv.com/?c=event&t=brochure&id=352 L. N. Lewis, J. Stein, Y. Gao, R. E. Colborn and G.

Hutchins, Platinum Metals Rev., 1997, 41, (2), 663 Johnson Matthey, Platinum Today, Price Charts:

http://www.platinum.matthey.com/prices/price_charts.html

4 Johnson Matthey Precious Metals Marketing, U.K.

5 ‘Release System Information Guide, Syl-Off ®

Advantage Series Solventless Release Coatings fromDow Corning’, Dow Corning Corporation, U.S.A.,2006

6 ‘Free Radical Curing TEGO® RC Silicones, APractical Guide’, Goldschmidt GmbH, Essen,Germany, 06/2007

7 ‘Goldschmidt Radiation Curable Silicones, AnOverview’, Goldschmidt GmbH, Essen, Germany,08/2007

8 Dow Corning Silicones: http://www.dowcorning.com/

9 Bluestar Silicones: http://www.bluestarsilicones.com/

10 Wacker Silicones: http://www.wacker.com/cms/en/wacker_group/divisions/silicones/silicones.jsp

11 Evonik Industries: http://corporate.evonik.com/


The ReviewerAndy Holwell is a Market Analyst forJohnson Matthey PLC. He received anMChem in Chemistry from the University ofYork, U.K., in 2004. He joined JohnsonMatthey in September 2005, initially as aProcess Development Chemist specialisingin autocatalyst development, and has heldhis current position since January 2007.

Mr Holwell specialises in pgm market research in the chemical,petroleum and energy sectors and is a member of the RoyalSociety of Chemistry.

The author, Eric Scerri, teaches chemistry andthe history and philosophy of science at theUniversity of California, Los Angeles, U.S.A. Hehas published widely about the development andstructure of the Periodic Table, and is the Editor-in-Chief of the journal Foundations of Chemistry (1).He was an invited speaker at the 2003 confer-ence, “The Periodic Table: Into the 21stCentury” (see also (2)). This book is timely – it isover thirty years since books about the periodicsystem by Mazurs (3) and van Spronsen (4) werepublished.

It is not simply a plodding, step by step history nor a collection of all known tabulararrangements of the elements. The authordescribes developments, explains what led tothem, comments on them and discusses theirimplications. He carefully describes the philo-sophical thinking of Dimitri Mendeleev and howhe differentiated between “the element” and“simple substance”, a difference that was criticalin helping Mendeleev deduce the periodic lawand system.

One must ask: for whom is this book written?It is for all chemists. What is there for thechemist involved with the platinum group metals(pgms)? Mendeleev in 1869 (5, 6) specificallyquotes the similar atomic weights of platinum,iridium and osmium as being an important foun-dation of his periodic system. Now jump forwardfifty years to quantum mechanics and the deduc-tion of electron configurations of the elements.The commonly held doctrine says that the chem-ical properties of an element are determined bythe configuration of the valence electrons. Thisimplies that elements in the same group, having

similar chemical properties, will have the sameelectron configurations. Unfortunately, this isnot true. An example is the group: nickel, palladium, platinum: Ni 4s 2 3d 8 ; Pd 5s 0 4d 10;Pt 6s1 4f 14 5d 9 . It is evident to any pgm chemistthat these electron configurations do not fit thechemistry of refining. Conversely, we have thegroup copper, silver, gold: Cu 4s1 3d 10; Ag 5s1 4d 10;Au 6s1 4f 14 5d 10, whose common oxidation statesare Cu2+, Ag1+, Au3+. The author discusses theseproblems.

The brightly coloured cover is attractive andcalls out: “Read me”. There are many black-and-white portraits of chemists. Unfortunately, thoseof de Chancourtois, Newlands and Odling aremissing although their contributions are dis-cussed at length. There is one surprisingomission. There is no current form PeriodicTable. Similarly it would have been valuable tohave had the 1950 short form “W. M. WelchScientific Company” table for comparison,known as the Periodic Chart of the Atoms.

There is a very complete set of references andnotes at the back of the book which are keyed tothe relevant pages in the text. These are a mine ofinformation for those who want to further pur-sue this interesting subject.

There is one surprising and disappointingshortcoming. There seem to be a larger-than-normal number of printing errors. Some exam-ples are: p. 129, it is stated that “Based on itsformation of tetravalent compounds, Mendeleevrealized that uranium had a predominant valenceof 4, as do such elements as chromium.” (sic); p. 217, iutetium (for lutetium); p. 239, 4s 2 3dshould be 4s 2 3d 9 for copper. There are others,

247Platinum Metals Rev., 2008, 52, (4), 247–248

“The Periodic Table: Its Story and Its Significance”BY ERIC R. SCERRI (University of California, Los Angeles, U.S.A.), Oxford University Press, Inc, New York, U.S.A., 2007,

368 pages, ISBN 978-0-19-530573-9, £19.99, U.S.$35.00

Reviewed by Michael LaingProfessor Emeritus, University of KwaZulu-Natal;

61 Baines Road, Durban 4001, South Africa; E-mail: [email protected]

DOI: 10.1595/147106708X364481

which will (I hope) be corrected in the nextprinting. This book deserves better editing andproofreading.

This is a book for the thinking chemist. Itreflects the personal interests of the author.Scerri advocates a different layout: the left-steptable of Janet, in which the long periods followthe Madelung rule and begin with Group 3 ele-ments: boron, aluminium; scandium, yttrium;lanthanum, actinium; and helium is above berylli-um. His discussion of this topic is valuable. Thereis no requirement that we agree with all of hisconclusions, but Eric Scerri makes us think, andthat, after all, is what good science is all about.This is a book that is well worth reading.

The ReviewerMichael Laing was born in Durban, South Africa, and obtained his B.Sc.(Hons) and M.Sc. degrees from the University of Natal in 1960. He earnedhis doctorate from the University of California, Los Angeles, U.S.A., in1964, and taught Inorganic Chemistry at the University of Natal, Durban,from 1965 until he retired in 1997. He was twice Visiting Professor atCalifornia State University, Northridge. His main field of interest was thedetermination of molecular structure and bonding by single crystal X-raydiffraction. He has also applied the X-ray powder diffraction method to theanalysis of materials such as urinary calculi, fossil-bearing breccia, failedconstruction materials and intractables from a pgm refinery. He also

generated specialist academic courses, including metal extraction for chemical engineers, materialfailures for architects and explosives for graduate chemists. He has over 200 publications in suchdiverse fields as crystallography, bonding, coordination compounds, the Periodic Table, chemicaleducation and military history.

References1 Foundations of Chemistry, Philosophical, Historical,

Educational and Interdisciplinary Studies ofChemistry, Editor-in-Chief Eric R. Scerri, Springer,The Netherlands:http://www.springer.com/philosophy/philosophy+of+sciences/journal/10698

2 “The Periodic Table: Into the 21st Century”, eds. D.H. Rouvray and R. B. King, Research Studies Press,Baldock, Hertfordshire, U.K., 2004

3 E. G. Mazurs, “Graphic Representations of thePeriodic System During One Hundred Years”, 2ndEdn., University of Alabama Press, Alabama, U.S.A.,1974

4 J. W. van Spronsen, “The Periodic System ofChemical Elements: A History of the First HundredYears”, Elsevier, Amsterdam, The Netherlands,1969

5 D. Mendeleev, Zhur. Russ. Khim. Obshch., 1869, 1, 606 D. Mendelejeff, Z. Chem., 1869, 12, 405

248Platinum Metals Rev., 2008, 52, (4)

“The most exciting expression uttered by a scientist, the one that heralds new discoveries andinventions, is not ‘Eureka!’ …… but ‘That’sfunny’.” Isaac Asimov could have been thinking ofJohn Jenkins when he made this comment. Johnwas an instinctive lateral thinker, who could take asimple laboratory test and turn it into one of themost widely used techniques for characterisingcomplex solid materials, or could see the potentialfor a new hydrogen-generating technology in aspontaneous catalytic reaction that was takingplace in a small glass tube in a fume cupboard.

John was born on 23rd March 1932 in theU.S.A., but grew up in England’s Lake District,which instilled in him his love of nature and thecountryside. After studying Natural Sciences atCambridge University, U.K., he returned to theU.S.A. to complete his education, with a Master’sin Chemical Engineering at Princeton University.His scientific career fell into two almost equalhalves. He worked for Shell in their HydrocarbonCracking group at their MTM Process R & D

Laboratory in Texas for twenty years, before heand his family finally settled in the U.K. when heaccepted a research post at the Johnson MattheyTechnology Centre in 1976. After a similar lengthof time at the Technology Centre, he retired fromscience in 1995, and he and his wife moved to afarm in West Sussex.

While at Shell, John perfected the technique ofmonitoring the controlled reduction of catalyticmaterials (1), which many of us now recognise astemperature-programmed reduction (TPR). Hisrole is often overlooked because TPR is one ofthose inventions that was never patented.However, as a non-proprietary technique, it couldbe quickly adopted in laboratories around theworld, as news of it spread through the scientificliterature (see, for example, Reference (2)). Johnwas also particularly proud of the fact that its use-fulness relies on the skill with which the resultsare interpreted and not on the cost of the equip-ment! John’s personal TPR rig, which hardly even registered as a capital asset, followed


John Ward Jenkins A TRIBUTE

DOI: 10.1595/147106708X366704

John Ward Jenkins

him from lab to lab throughout his career, andcould be stripped down and reassembled in thespace of a couple of hours.

At Johnson Matthey, John worked on a seriesof innovative projects. These mostly addressedenvironmental challenges, such as the replace-ment of base metal paint pigments by non-toxic

alternatives, but also included fundamental studies of platinum group metal (pgm) catalystbehaviour (3). Latterly, though, his name wasinvariably associated with the HotSpotTM reactor(Figure 1), which he had invented in the late1980s (4–6). The reformer can be used to gener-ate H2 from hydrocarbon fuels and oxygenates in the presence of a pgm-containingcatalyst, and may yet prove to be a key technolo-gy in a future hydrogen economy.

John Jenkins died on the 28th May 2008. He isfondly remembered as a caring and influential colleague and as an impressive scientist. Quite afew of us working in catalysis have benefitedfrom his encouragement and wisdom, and manymore of us have benefited – perhaps unknowingly– from the products of his inventive mind.

S. E. GOLUNSKI

From John’s former colleagues at the Johnson MattheyTechnology Centre, Blount’s Court, Sonning Common,Reading RG4 9NH, U.K.

References 1 S. D. Robertson, B. D. McNicol, J. H. de Baas, S.

C. Kloet and J. W. Jenkins, J. Catal., 1975, 37, (3),424

2 A. Jones and B. D. McNicol, “Temperature-Programmed Reduction for Solid MaterialsCharacterization”, CRC Press, Boca Raton,Florida, 1986

3 J. W. Jenkins, Platinum Metals Rev., 1984, 28, (3), 984 J. W. Jenkins and E. Shutt, Platinum Metals Rev.,

1989, 33, (3), 1185 J. W. Jenkins, Johnson Matthey PLC, European

Patent Appl. 0,217,532; 19876 J. W. Jenkins, Johnson Matthey PLC, European

Patent Appl. 0,262,947; 1988


Fig. 1 A prototype of the HotSpotTM reactor forhydrogen generation (4)

CATALYSIS – APPLIED AND PHYSICAL ASPECTSComparative Study of Aromatization SelectivityDuring n-Heptane Reforming on Sintered Pt/Al2O3

and Pt-Re/Al2O3 CatalystsA. A. SUSU, J. Chem. Technol. Biotechnol., 2008, 83, (6), 928–942

The main products of n-heptane reforming on fresh Ptwere CH4, toluene and benzene, while on fresh Pt-Re,only CH4 was obtained. For Pt/Al2O3, the productsranged from only toluene at a sintering temperature (ST)of 500ºC to CH4 at a ST of 650ºC, with no reaction at800ºC. On Pt-Re/Al2O3, CH4 was the sole product at aST of 500ºC while only toluene was produced at a ST of800ºC. Pt-Re/Al2O3 exhibited superior selectivity.

Carbon-Carbon Cross-Coupling Reactions underContinuous Flow Conditions Using Poly(vinylpyridine) Doped with PalladiumK. MENNECKE, W. SOLODENKO and A. KIRSCHNING, Synthesis,2008, (10), 1589–1599

The coordinative immobilisation of an oxime-basedpalladacycle to PVP/glass composites shaped asRaschig rings or placed within a PASSflowTM microre-actor affords devices that can be used for Pd-catalysedC–C cross-coupling in the flow-through mode.Reusability of the immobilised precatalyst as well asreactions in the microwave field were investigated.

CATALYSIS – INDUSTRIAL PROCESSDevelopment of a Mild and Robust Method forLarge-Scale Palladium-Catalysed Cyanation ofAryl Bromides: Importance of the Order of AdditionP. RYBERG, Org. Process Res. Dev., 2008, 12, (3), 540–543

The title reaction is sensitive to cyanide poisoningof the catalyst. For Pd(dba)2 + P(tBu)3 the order ofadding the reagents affected the performance of thereaction. Addition of the cyanide source (Zn(CN)2) toa preheated mixture of the aryl bromide, catalyst andZn dust was found to be critical. This reaction couldbe run to full conversion within 3 h at 50ºC on a 6.7kg scale. New efficient catalysts were identified.

CATALYSIS – REACTIONSEnhancing H2 and CO Production from GlycerolUsing Bimetallic SurfacesO. SKOPLYAK, M. A. BARTEAU and J. G. CHEN, ChemSusChem,2008, 1, (6), 524–526

TPD experiments revealed an increased productionof H2 from glycerol on the Ni surface monolayer onPt(111) (designated Ni-Pt-Pt(111)) as compared tothat on Pt(111), Ni(111) and Pt-Ni-Pt(111). Glycerolreforming activity trends were similar to previousresults for ethylene glycol and EtOH. Smaller oxy-genates can therefore be used as good models forreforming of larger, biomass-derived oxygenates.

Efficient and Recyclable Catalyst of PalladiumNanoparticles Stabilized by Polymer MicellesSoluble in Water for Suzuki-Miyaura Reaction,Ostwald Ripening Process with PalladiumNanoparticlesI. P. BELETSKAYA, A. N. KASHIN, I. A. KHOTINA and A. R.KHOKHLOV, Synlett, 2008, (10), 1547–1552

The Suzuki-Miyaura cross-coupling of ArX (X = I,Br) with Ar'B(OH)2, catalysed by a Pd-containingH2O-soluble micelle formed by PS-PEO and N-cetylpyridinium chloride, was investigated in H2O andMeOH. The reaction was performed at ≤ 50ºC. Thecatalyst can be recycled (5 runs) by ultrafiltration.

Direct Coupling of Arenes and IodoarenesCatalyzed by a Rhodium Complex with a Stronglyπ-Accepting Phosphite LigandS. YANAGISAWA, T. SUDO, R. NOYORI and K. ITAMI, Tetrahedron,2008, 64, (26), 6073–6081

A solution of [RhCl(CO)2]2 and P[OCH(CF3)2]3 indry toluene was stirred at 50ºC for 2 h under Ar tosynthesise RhCl(CO){P[OCH(CF3)2]3}2 (1). Underthe catalytic influence of (1) and Ag2CO3, the directC–H arylation of heteroarenes and arenes withiodoarenes was achieved. The product biaryls wereobtained in good to excellent yields with high regios-electivity. This method can be used for thiophenes,furans, pyrroles, indoles and alkoxybenzenes.

Vinyl and Ring-Opening MetathesisPolymerization of Norbornene with Novel Half-Sandwich Iridium(III) Complexes BearingHydroxyindanimine LigandsX. MENG, G.-R. TANG and G.-X. JIN, Chem. Commun., 2008,(27), 3178–3180

Half-sandwich Ir(III) complexes bearing hydroxy-indanimine ligands were synthesised. The complexeswere used as catalysts for the ROMP and vinyl-typepolymerisation of norbornene in the presence ofmethylaluminoxane (MAO). Pure ROMP polymerand vinyl-type polymer were obtained depending onthe amount of MAO employed (0–30 equiv. forROMP and > 30 equiv. for vinyl-type polymerisation).

EMISSIONS CONTROLImpact of Redox Conditions on ThermalDeactivation of NOx traps for DieselK. M. ADAMS and G. W. GRAHAM, Appl. Catal. B: Environ.,2008, 80, (3–4), 343–352

Lean and rich agings were investigated for a modelNOx trap, Pt-Ba/Al2O3. These were carried out at 950ºCfor 3 h, in air and in 1% H2/N2, respectively.Pretreatments were examined for a commercially feasi-ble NOx trap and two model NOx traps, Pt-Ba/Al2O3

and Pt-Ba-Ce/Al2O3, at 600ºC for 10 min, using feed gasthat simulated diesel exhaust under various conditions.


ABSTRACTS

DOI: 10.1595/147106708X366858


Enhanced Degradation of Tetrachloroethylene byGreen Rusts with PlatinumJ. CHOI and W. LEE, Environ. Sci. Technol., 2008, 42, (9),3356–3362

The reductive dechlorination of tetrachloroethylene(PCE) by green rusts (GRs) (layered Fe(II)–Fe(III)hydroxide solids with anions such as Cl–, SO4

2–,CO3

2–, F–) in the presence of Pt was carried out usinga batch reactor system. The rate of PCE reductionwas greatly enhanced with the addition of Pt(IV)(95% of PCE was removed in 30 h). PCE was mostlytransformed to acetylene. The estimated kinetic rateconstants of GR-Cl(Pt) increased significantly with anincremental addition of Pt from 0.5 to 2 mM.

FUEL CELLSApplication of Atomic Layer Deposition ofPlatinum to Solid Oxide Fuel CellsX. JIANG, H. HUANG, F. B. PRINZ and S. F. BENT, Chem. Mater.,2008, 20, (12), 3897–3905

Atomic layer deposition (ALD) was used to depositPt thin films as an electrode/catalyst layer for SOFCs.The measured fuel cell performance showed thatcomparable peak power densities were achieved forALD-deposited Pt anodes with only one-fifth of thePt loading relative to dc-sputtered Pt anodes. Amicropatterned Pt structure was fabricated via area-selective ALD and used as a current collectorgrid/patterned catalyst for the fuel cells.

Platinum Black Polymer Electrolyte MembraneBased Electrodes RevisitedL. KRISHNAN, S. E. MORRIS and G. A. EISMAN, J. Electrochem.Soc., 2008, 155, (9), B869–B876

Pt black-coated diffusion media of varying anodeand cathode catalyst loadings with H2/air demon-strated successful performance and stability for anodecatalyst loadings down to 0.25 mg cm–2 while operat-ing on pure H2 and with a cathode loading of 0.62 mgcm–2, without significant voltage losses. The voltagelosses from reducing the Pt black cathode loadings(from 2.6 to 0.62 mg cm–2) are consistent with kinet-ic losses associated with the O2 reduction reactionand lower electrocatalyst utilisation. Optimisation ofthe three-phase interface – electrode, electrolyte andreactant gas – was shown to be dependent on the effi-cacy of the membrane–catalyst layer interface.

The Improved Methanol Tolerance Using Pt/C inCathode of Direct Methanol Fuel CellY.-H. CHO, H.-S. PARK, Y.-H. CHO, I.-S. PARK and Y.-E. SUNG,Electrochim. Acta, 2008, 53, (20), 5909–5912

MEAs were prepared using PtRu black and 60 wt.%Pt/C as their anode and cathode catalysts, respective-ly. The cathode catalyst layers were fabricated using0.5, 1.0, 2.0 and 3.0 mg cm–2 of Pt. The performanceof the single cell that used Pt/C as the cathode cata-lyst was higher than a single cell that used Pt black;this result was pronounced when highly concentratedMeOH (> 2.0 M) was used as the fuel.

Graphite Nanofibers as Catalyst Support forProton Exchange Membrane Fuel CellsH. XU, L. LU and S. ZHU, Chin. J. Catal., 2008, 29, (6), 542–546

Graphite nanofibres (GNFs) were prepared fromused C paper by a ball-milling method. 20% Pt wasloaded on the GNFs and Vulcan XC-72 to fabricatePt/GNFs and Pt/XC-72, respectively. CV showedthat Pt/GNFs had the same electrochemical surfacearea (ESA) as Pt/XC-72. The electrochemical stabili-ty was measured for XC-72, GNFs, Pt/XC-72 andPt/GNFs electrodes by the constant potential oxida-tion. The peak current increased by 2% for GNFsand 60% for XC-72. The corrosion current forPt/XC-72 was 1.4 times of that for Pt/GNFs. 84.7%ESA was lost for Pt/XC-72 after oxidation for 60 h,while only 37.2% ESA was lost for Pt/GNFs.

METALLURGY AND MATERIALSPurification of Iridium by Electron Beam MeltingE. K. OHRINER, J. Alloys Compd., 2008, 461, (1–2), 633–640

The purification of Ir metal by electron beam melt-ing has been characterised for 48 impurity elements.The average levels of individual elemental impuritiesin the starting Ir powder varied from 37 μg g–1 to 0.02μg g–1. Li, Na, Mg, P, S, Cl, K, Ca, Mn, Co, Ni, Cu,Zn, As, Pd, Ag, Cd, Sn, Sb, Te, Ba, Ce, Tl, Pb and Biwere not detectable following the purification. Nosignificant change in the concentration of Ti, V, Zr,Nb, Mo and Re was found. B, C, Al, Si, Cr, Fe, Ru,Rh and Pt were partially removed by vaporisation.

Effects of Alloying Elements on DendriticSegregation in Iridium AlloysY. LIU, C. T. LIU, L. HEATHERLY and E. P. GEORGE, J. AlloysCompd., 2008, 459, (1–2), 130–134

The effects of alloying elements on dendritic segre-gation in ‘Ir-Nb’ (Ir-10Nb-0.5Zr-0.3W-0.3C-0.006Th,at.%) and ‘Ir-Zr’ (Ir-4.5Zr-0.3W-0.3C-0.006Th, at.%)alloys were investigated by Auger electron spec-troscopy. The Nb addition induces significantsegregation of C and Th to dendritic interfaces. TheZr addition leads to the formation of an Ir3Zr inter-metallic phase, which results in less dendriticsegregation of C and Th. This dendritic segregationmay cause the severe cracking observed in the ‘Ir-Nb’alloy after casting and heat treatment.

Synthesis of Ruthenium Particles byPhotoreduction in Polymer SolutionsM. HARADA and S. TAKAHASHI, J. Colloid Interface Sci., 2008,325, (1), 1–6

Colloidal dispersions of poly(N-vinyl-2-pyrroli-done)-protected Ru particles were conveniently andefficiently synthesised by the photoreduction ofRu(III) ionic solutions (using RuCl3·nH2O) in thepresence of a photoactivator. Metallic Ru particles(1.3 nm average diameter) were obtained in the pres-ence of benzophenone, although mixtures of partlyoxidised Ru particles and metallic Ru particles wereproduced in the presence of benzoin.

Platinum Metals Rev., 2008, 52, (4)

APPARATUS AND TECHNIQUEDetermination of Alcohols Using a Ni–Pt AlloyAmperometric SensorJ.-J. HUANG, W.-S. HWANG, Y.-C. WENG and T.-C. CHOU, ThinSolid Films, 2008, 516, (16), 5210–5216

Ni-Pt films were electrodeposited on Au/Al2O3.Electrodes with Ni:Pt atomic proportions of 100:0,25:75, 70:30, 82:18 and 0:100 all have a linear relation-ship between response current and EtOHconcentration for 50–300 ppm EtOH in alkaline solu-tions. With increasing Pt content, the response timewas reduced and the sensitivity was decreased. Thesensor with 70 at.% Pt was most stable (9 weeks).

A Multi-Walled Carbon Nanotube/PalladiumNanocomposite Prepared by a Facile Method forthe Detection of Methane at Room TemperatureY. LI, H. WANG, Y. CHEN and M. YANG, Sens. Actuators B: Chem.,2008, 132, (1), 155–158

A composite (1) of Pd and C MWNTs was preparedby reducing their aqueous mixtures with NaBH4.TEM and AFM were used to investigate the mor-phology of (1). The electrical responses of (1) to CH4

were measured at room temperature. (1) exhibited aresponse magnitude of ~ 4.5% towards 2% CH4.

BIOMEDICAL AND DENTALInfluence of the Spacer Length on the in VitroAnticancer Activity of Dinuclear Ruthenium–AreneCompoundsM.-G. MENDOZA-FERRI, C. G. HARTINGER, R. E. EICHINGER, N.STOLYAROVA, K. SEVERIN, M. A. JAKUPEC, A. A. NAZAROV andB. K. KEPPLER, Organometallics, 2008, 27, (11), 2405–2407

The title complexes exhibited promising cytotoxiceffects in human cancer cells, which could be increasedto an IC50 of 0.29 μM by increasing the spacer lengthbetween the metal centres. Cytotoxicity could be cor-related with lipophilicity and H2O solubility.1,12-Bis{chlorido[3-(oxo-κO)-2-methyl-4-pyridinonato-κO4](η6-p-isopropyltoluene)ruthenium}dodecane ismore active than chlorido[3-(oxo-κO)-2-methyl-4-pyronato-κO4](η6-p-isopropyltoluene)ruthenium.

Novel Ru(II) Oximato Complexes with Silent OxygenAtom: Synthesis, Chemistry and Biological ActivitiesN. CHITRAPRIYA, V. MAHALINGAM, L. C. CHANNELS, M. ZELLER,F. R. FRONCZEK and K. NATARAJAN, Inorg. Chim. Acta, 2008,361, (9–10), 2841–2850

[Ru(CO)(EPh3)2(bhmh)] (E = P or As; H2bhmh =benzoic acid (2-hydroxyimino-1-methyl-propylidene)-hydrazide), [Ru(CO)(EPh3)2(ihmh)] (H2ihmh =isonicotinic acid (2-hydroxyimino-1-methyl-propyli-dene)-hydrazide) and [Ru(CO)(EPh3)2(hhmh)] (H2hhmh= 2-hydroxy-benzoic acid (2-hydroxyimino-1-methyl-propylidene)-hydrazide) were prepared. The hydrazoneligand coordinates through the N atoms of the imine andoxime and the O atom of the amide. The N–OH moietyof the oxime is deprotonated. Antibacterial activity andDNA-binding ability of the complexes were investigated.

CHEMISTRYRuO2–TiO2 Mixed Oxides Prepared From theHydrolysis of the Metal AlkoxidesJ. R. OSMAN, J. A. CRAYSTON, A. PRATT and D. T. RICHENS, Mater.Chem. Phys., 2008, 110, (2–3), 256–262

Ru alkoxide/Ti tetraethoxide mixtures were hydrolysedto give gels and powders containing 30–40 mol% Ru.Basic or neutral conditions gave powders consistingof crystalline RuO2 nanoparticles (2–10 nm diameter)embedded in a matrix of crystalline (anatase) andamorphous TiO2. Acid hydrolysis conditions led togels containing smaller, amorphous RuO2 nanoparti-cles (1–3 nm). Acid or neutral hydrolysis of Ruethoxide gave samples with lower surface Ru:Ti ratioscompared to the bulk, which also contained morelow-valent Ru.

ELECTRICAL AND ELECTRONICSSynthesis of Ru/Multiwalled Carbon Nanotubes byMicroemulsion for Electrochemical SupercapacitorS. YAN, P. QU, H. WANG, T. TIAN and Z. XIAO, Mater. Res. Bull.,2008, 43, (10), 2818–2824

Ru nanoparticles were prepared by H2O-in-oilreverse microemulsion, and then anchored on CMWNTs. EDX spectra confirmed the presence of Ruoxide in the as-prepared composites after electro-chemical oxidation. CV demonstrated that the specificcapacitance of deposited Ru oxide electrode was sig-nificantly greater than that of a C MWNTs electrode.

PHOTOCONVERSIONPhosphorescent Iridium(III) Complexes withNonconjugated Cyclometalated LigandsY.-H. SONG, Y.-C. CHIU, Y. CHI, Y.-M. CHENG, C.-H. LAI, P.-T.CHOU, K.-T. WONG, M.-H. TSAI and C.-C. WU, Chem. Eur. J.,2008, 14, (18), 5423–5434

Ir(III) complexes (1–4) with nonconjugated N-ben-zylpyrazole ligands exhibit blue phosphorescencewith yields of 5–45 % in degassed CH2Cl2. (1) showedemission that was nearly true blue at 460 nm with alack of vibronic progression. (1) was used as the hostfor the green-emitting Ir(ppy)3 dopant in an OLED.

REFINING AND RECOVERYSynthesis of Highly Porous Chitosan MicrospheresAnchored with 1,2-Ethylenedisulfide Moiety forthe Recovery of Precious Metal IonsY. KANAI, T. OSHIMA and Y. BABA, Ind. Eng. Chem. Res., 2008,47, (9), 3114–3120

Highly porous chitosan microspheres (EDSC) withlarge pores anchoring 1,2-ethylenedisulfide as a ligandwere synthesised for perfusion chromatography bymeans of an oil-in-H2O-in-oil emulsion method.EDSC was found to be a selective adsorbent forPd(II), Au(III) and Pt(IV) over base metals in HCl.The adsorbed Pd(II) was completely desorbed usingaqueous thiourea solution.

253


CATALYSIS – APPLIED AND PHYSICAL ASPECTSCationic Rhodium Complexes JOHNSON MATTHEY PLC World Appl. 2008/084,258

A cationic Rh complex can be synthesised by mix-ing a Rh-diolefin-1,3-diketonate compound and a Pligand in a ketone solvent; mixing with an acid toform a solution of the Rh complex; evaporating atleast part of the solvent; optionally treating with anether; and treating the resulting complex with an alco-hol. The Rh complex may be recovered and used as acatalyst, for example in hydrogenation reactions.

Palladium-Germanium Transalkylation CatalystsUOP LLC U.S. Patent 7,378,364

Alkylaromatic transalkylation catalysts containingacidic molecular sieve, Pd and Ge are claimed to havegood activities and attenuate aromatic ring saturationand lights co-production, provided that sufficient Pd ispresent. Pd is 0.2–1 wt.% and the atomic ratio of Ge:Pdis at least 0.9:1. The molecular seive has pore size ≥ 6 Å.

CATALYSIS – INDUSTRIAL PROCESSAdhesive Silicone CompositionBLUESTAR SILICONES FRANCE World Appl. 2008/080,791

A crosslinkable adhesive silicone composition withshort crosslinking time giving suitable mechanicalproperties for use as an adhesive joint and for water-proofing a seam is claimed. The compositionincludes: (a) a polyorganosiloxane with at least twoalkenyl groups, preferably C2–C6, linked to Si; (b) apolyorganosiloxane crosslinking agent with at leasttwo H atoms linked to Si; (c) a metal catalyst, prefer-ably Pt; and (d) a reinforcing mineral filler. There isalso a polyorganosiloxane gum containing 0.001–0.2wt.% alkenyl group(s), preferably vinyl groups.

Silicone-Based Pressure-Sensitive AdhesiveDOW CORNING TORAY CO LTD World Appl. 2008/081,913

The title composition contains: (a) the condensationreaction product of a diorganopolysiloxane havingsilanol groups on both molecular terminals and twoor more Si-bonded alkenyl groups in side molecularchains, with an organopolysiloxane resin having oneor more hydrolysable groups, in the presence of a cat-alyst; (b) an organohydrogenpolysiloxane; (c) adiorganopolysiloxane having Si-bonded alkenylgroups on both molecular terminals; (d) anorganopolysiloxane resin; and (e) a platinum catalyst.

Thermoneutral Oil Reforming Catalyst T. INUI et al. U.S. Appl. 2008/0,152,572

A catalyst containing Ni, Ce2O3, La2O3, Pt, ZrO2,Rh and Re can be used for the thermoneutral reform-ing of liquid hydrocarbon fuels to give synthesis gas(H2, CO, CO2 and CH4). The catalyst contains (inwt.%): 0.5–15 Ni, 0.5–10 Ce2O3, 0.5–5 La2O3, 0.1–2Pt, 0.5–3 ZrO2, 0.1–2 Rh and 0.1–2 Re.

CATALYSIS – REACTIONS5-Fluoro-N-hydroxy-pyridine-2-carboxamidineASTRAZENECA AB World Appl. 2008/054,284

The title compound (1) is synthesised by reacting 2-bromo-5-fluoropyridine with a Pd source in thepresence of 1-1'-bis(diphenylphosphino)ferrocene(DPPF) and acetate ions, then with a cyanide sourceto give 5-fluoro-pyridine-2-carbonitrile (2). The Pdsource may be tris(dibenzylideneacetone)dipalladi-um(0) or Pd acetate. (2) is then reacted with ethanoland hydroxylamine to produce (1).

Optically Active 2-Amino-1-phenylethanolsLONZA AG World Appl. 2008/077,560

The title compounds or salts thereof are prepared byasymmetric hydrogenation of the corresponding 2-aminoacetophenones in the presence of a Ru complexcatalyst with a chiral phosphine ligand. The chiralphosphine ligand may be a diphosphine, and the Rucomplex catalyst may also have a chiral diamine ligand.

EMISSIONS CONTROLCatalyst for Purification of Exhaust Gas EAST CHINA UNIV. SCI. TECHNOL.

World Appl. 2008/086,662A close coupled three-way catalyst includes a sup-

port selected from cordierite honeycomb ceramicmaterials having a pore volume of 0.25–0.35 ml g–1.The coating layer contains a mixture of hexaalumi-nates, perovskite type composite oxides, CeO2-ZrO2

solid solutions, rare earth oxides, alumina, alkali earthmetals and zeolites having a high Si:Al ratio. Theactive components are Pd-Rh, rare earth oxides andtransition metals in the hexaaluminates and perovskitetype composite oxides. The catalyst works for lowtemperature oxidation of HC and reduction of NOx.

Engine Exhaust Catalysts Containing Palladium-GoldNANOSTELLAR INC European Appl. 1,925,362

A catalyst for cleaning engine exhaust is claimed tohave improved CO oxidation characteristics. The cat-alyst includes a first supported catalyst containing Pt,Pt-Pd or Pt plus a promoter such as Bi. A second sup-ported catalyst contains Pd and Au in the weight ratioPd:Au of ~ 0.5:1.0–1.0:0.5, preferably ~ 0.84:1.0. Toimprove aged catalyst performance, the first and sec-ond supported catalysts are coated onto differentlayers, zones or monoliths of the substrate.

Exhaust Emission Control DeviceMAZDA MOTOR CORP Japanese Appl. 2008-075,638

A catalyst system for exhaust gas purificationremoves HC and CO from exhaust gas at engine startwhen the exhaust gas temperature is low, particulateswhich are collected by a filter, and NOx. An active O2

generating device, an oxidation catalyst, a particulatefilter and a Pt-Rh catalyst are arranged in this orderfrom the upstream side of the exhaust passage.

DOI: 10.1595/147106708X370880

NEW PATENTS

FUEL CELLSNanowire Supported CatalystsGM GLOBAL TECHNOL. OPERATIONS INC

World Appl. 2008/070,482A fuel cell electrode is formed from C fibres with

metal oxide or C-coated metal nanowires directlygrown on them, which carry deposited nanoparticlesof Pt, Pd, Rh or Ru catalyst material. The metaloxide may be SnO2, TiO2 or WO3, alternatively theC-coated metal may be Sn, Ti or W. The supportedcatalysts can be used for an electrode in a PEM for aH2/O2 fuel cell.

Fuel Electrode CatalystSANYO ELECTRIC CO LTD Japanese Appl. 2008-091,102

An electrode catalyst is claimed to have improved COpoisoning resistance. An electrode for an MEA isformed by arranging an alloy catalyst layer containingPt, Ru and one or more of Co, Ni, Mo, Pb, Fe, W orCr; an alloy catalyst layer containing Pt-Ru; and a Rucatalyst layer, in this order from the polyelectrolytemembrane to the gas diffusion layer. The fuel for thefuel cell system may be reformed gas or organic matter.

APPARATUS AND TECHNIQUEPalladium Alloy Composite MembraneJ.-S. PARK et al. U.S. Appl. 2008/0,116,078

The title composite for H2 separation includes anoptional first metal coating layer selected from Ag,Ni, Cu, Ru or Mo, applied by an electroplatingprocess onto a porous support which is preferablyporous Ni; a Pd coating layer applied using a sput-tering process; and a second metal coating layer,preferably Cu. The second metal coating layer isheat treated to form an alloy layer of Pd and the sec-ond metal.

Nonlinear Optical Organic Single Crystal FormationFURUKAWA CO LTD Japanese Appl. 2008-001,529

A single crystal of an organic substance such as 4-dimethylamino-N-methyl-4-stilbazolium tosylate canbe formed on a Pt wire in a supersaturated solutionof the organic substance by cooling the supersaturat-ed solution. The crystal nucleus is preferentiallygenerated on the surface of the Pt wire. Generationof multiple nucleation points is suppressed and crys-tals can be grown at a low degree of supersaturation.

BIOMEDICAL AND DENTALOrganometallic Compounds for Cancer TreatmentUNIV. NEUCHÂTEL European Appl. 1,950,217

Novel organometallic compounds for photody-namic therapy against cancer include a centralporphyrin or phthalocyanine backbone with ligandlinkers coordinated to at least one transition metalselected from Ru, Rh, Os, Ir or Fe, preferably Ru. Apreferred compound is a tetranuclear Ru(II) complexsuch as [Ru4(η6-arene)4(TPP)Cl8] (TPP = 5,10,15,20-tetra(4-pyridyl)porphyrin).

ELECTRICAL AND ELECTRONICSSealed Penetration for Lithium BatteryCOMMISSARIAT À L’ÉNERGIE ATOMIQUE

U.S. Appl. 2008/0,118,831A glass-to-metal penetration for the electrical insula-

tion between two poles of a Li battery includes glasssuch as TA23 or Cabal 12 glass, a Pt-Ir pin containingPt:Ir in the weight ratio 90:10, and a body made fromSS304L stainless steel. The coefficient of thermalexpansion (CTE) of the pin is 8.7 × 10–6 ºC–1. Theglass has good resistance in organic electrolyte medi-um combined with Li salt and a CTE < 8.7 × 10–6 ºC–1.

Organic Memory DeviceSAMSUNG ELECTRONICS CO LTD

U.S. Appl. 2008/0,146,802An organic memory device includes a first elec-

trode, an organic active layer which contains an Irorganometallic compound and an electrically conduc-tive polymer, and a second electrode. Advantagesclaimed are rapid switching time, decreased operatingvoltage, decreased fabrication costs, increased relia-bility and improved non-volatility. The Ir organo-metallic compound has a maximum emission wave-length of 450–550 nm.

Iridium Oxide Film for a Semiconductor DeviceOKI ELECTRIC IND. CO LTD Japanese Appl. 2008-075,134

An electrode includes an Ir oxide film with a metalmembrane formed on its surface. High adhesion isclaimed at the boundary between the films. The electrode can be used in a dielectric capacitor for asemiconductor device. The Ir film is formed by areactive sputtering method using an O2-containinggas and an Ir target with film deposition temperatureof 275–400ºC and sputtering pressure of 0.69–1.09 Pa.

SURFACE COATINGSSprayable Water-Base PGM-Containing PaintGENERAL ELECTRIC CO European Appl. 1,936,010

A Pt group metal containing layer can be depositedon a substrate by spraying a H2O-based paint con-taining metallic Pt group metal powder, H2O and amethyl cellulose binder. Heat can be applied to inter-diffuse the Pt group metal containing layer.Optionally an additional layer of NiAl may be appliedas an underlayer. The Pt group metal is ≥ 96 wt.% ofthe paint composition exclusive of H2O and binder.

Methods of Depositing a Ruthenium Film ASM GENITECH KOREA LTD U.S. Appl. 2008/0,171,436

A Ru film can be deposited on a substrate byapplying deposition cycles of a Ru organometalliccompound gas; purging the reactor; supplyingRuO4 gas; and purging the reactor. Alternatively,each cycle includes simultaneously supplying RuO4

and a reducing agent gas; purging; and supplying areducing agent gas. A high deposition rate isclaimed, with good step coverage over structureswhich have a high aspect ratio.



NAME INDEX TO VOLUME 52Page Page Page Page

Abd-El-Aziz,A. S. 46

Abu-Reziq, R. 56Acerbi, N. 222Acres, G. 19Adams, K. M. 251Adamson, K.-A. 123Adcock, P. 15Aiello, I. 58Aiyer, R. C. 201Aladjem, A. 121Aldrich-Wright,

J. R. 98Alivisatos, A. P. 57Allaert, B. 124Alper, H. 56Andersson, S. 125Antunes, O. A. 124Arends, I. 83Arndt, A. 58Ash, P. 205Atanasoski, R. 201

Baba, Y. 253Baidina, I. A. 126Balcom, J. 18Ballauff, M. 124Balme, G. 174Baranowski, B. 120Barnard, C. 38, 110Barteau, M. A. 251Batcha Seneclauze,

J. 58Baudoin, O. 175Baylet, A. 226Bedford, R. 111Beletskaya, I. P. 56, 251Bellusci, A. 58Bent, S. F. 252Beretta, A. 56Bhushan, B. 202Bion, N. 224Birss, V. I. 126Birtill, J. 229Blomen, L. 14Blume, R. 224Bode, M. 13Bond, G. C. 107Borg, A. 126

Bredesen, R. 126Bucur, R. 120Burch, R. 226

Cai, F. 56Calvo, F. 107Cameron, D. S. 12Campagna, S. 58Campbell, C. T. 57Campesi, R. 201Cao, C.-N. 202Cao, F. 125Carraher, Jr., C. E. 46Carrettin, S. 226Carson, N. A. P. 132Carty, A. J. 58Castellano, C. 134Cate, D. M. 57Cavallaro, S. 58Cele, L. M. 124Centi, G. 229Cermák, J. 120Chan, W. K. 47Chang, F. Y. 200Chang, S.-Y. 58Chang, Z. 126Channels, L. C. 253Che, C.-M. 96Chen, J. C. 200Chen, J. G. 251Chen, M. 126Chen, P. 200Chen, S. 57Chen, W. 57Chen, X.-Z. 163Chen, Y. 57, 200, 253Chen, Z. 200Cheng, K. W. 47Cheng, Y.-M. 58, 253Chi, Y. 58, 253Chiarello, G. L. 225Chitrapriya, N. 253Chiu, Y.-C. 253Cho, Y.-H. 252Choi, J. 252Chou, P.-T. 58, 253Chou, T.-C. 253Clark, Jr., W. M. 200Coelho, A. V. 124

Colacot, T. J.124, 172, 175

Connick, W. B. 202Copping, B. W. 132Corbos, E. C. 226Corcoran, C. 200Cornish, L. A. 241Corti, C. 52Coville, N. J. 124Crayston, J. A. 253Crispini, A. 58Cuevas, F. 201

Dai, Q. 200De Lima, P. G. 124de Lucas-Consuegra,

A. 227De Souza, A. L. F. 124de Vries, J. 110Debe, M. K. 201Di Noto, V. 125Dixneuf, P. 174Doppelt, P. 126Dragutan, I. 71, 157Dragutan, V. 71, 157Dunn, P. 110Dyson, P. J. 98

Egerton, T. A. 202Eggeler, G. 241Eichinger, R. E. 253Eisman, G. A. 252El-Shall, M. S. 107Elzanowska, H. 126Enick, R. 58Es-Souni, M. 125

Fan, H. 126Fang, Y. 126Faravelli, T. 56Farmer, D. B. 58Farrauto, R. 134Farrell, N. P. 97Filatov, E. Yu. 126Flanagan, T. B. 120Fricker, S. P. 97Fronczek, F. R. 253

Fu, G. 174Fu, X. 200Fujitani, T. 200

Gac, W. 124Gadiou, R. 201Gancs, L. 201Garje, A. D. 201Gauffier, A. 57Gélin, P. 226George, E. P. 252Ghedini, M. 58Ghiotti, G. 124Glatzel, U. 48, 241Godbert, N. 58Goltsov, V. A. 121Golunski, S. E. 249Goodman, S. N. 200Gordon, R. G. 58Graham, G. W. 251Granite, E. J. 144Grasa, G. A. 124Griffith, W. P. 114Grönbeck, H. 226Groppi, G. 56Gross, S. 125Grove, L. J. 202Grubbs, R. H. 222Grünert, W. 56Grunwaldt, J.-D. 225Gulari, E. 56Guryev, Yu. V. 56Gushchin, A. V. 124Gustafsson, K. 125

Habouti, S. 125Habtemariam, A. 97Haghighat, F. 125Hamada, H. 200Hambley, T. W. 97Haneda, M. 200Hanefeld, U. 83Harada, M. 125, 252Haridoss, P. 125Hartinger, C. G.

96, 253He, L.-N. 56He, P. 126


He, Y. 200Heatherly, L. 252Hedley, G. J. 126Heinzel, J. 16Henry, C. R. 108Hii, M. 112Hirscher, M. 201Hiyama, T. 174Holwell, A. J. 243Hou, P. Y. 57Hou, S.-Q. 163Hou, X. 125Hou, Y.-Y. 202Hu, F. P. 201Hu, J.-M. 202Huang, C. 126Huang, H. 57, 200, 252Huang, J.-J. 253Hung, J.-Y. 58Hutchings, G. J.

108, 226Hwang, S.-H. 47Hwang, W.-S. 253Hyakutake, T. 201Hyde, T. 129

Ikushima, Y. 124Ilinich, O. 134Inukai, J. 201Ioannides, T. 124Ishigami, Y. 201Itami, K. 251Ivanova, I. I. 56Iyoha, O. 58

Jakupec, M. A. 253Jang, J. H. 18Janiak, T. 200Jenkins, J. W. 249Jennings, Z. 14Jiang, X. 252Jin, G.-X. 251Johansson, M. 224Johnson, T. 23Jones, C. J. 21Jones, S. 100

Kanai, Y. 253Kanar, N. 244

Kandasamy, K. 120Karlberg, G. S. 125Kartopu, G. 125Kasem, K. K. 100Kashin, A. N. 251Kato, K. 201Kavitha, J. 58Kawanami, H. 124Kawi, S. 200Kayama, T. 56Keane, M. A. 56Kempe, R. 124Keppler, B. K. 253Khodadadi, A. 125Khokhlov, A. R.

56, 251Khotina, I. A. 251Kiely, C. J. 108Killimeyer, R. 58Kim, I. J. 202Kim, J. 57Kim, S. 57Kim, Y. K. 202Kim, Y. S. 202Kimura, Y. 125Kirschning, A. 251Kitagawa, H. 201Kizaki, Y. 56Klette, H. 126Kobayashi, H. 201Kobayashi, T. 201Koermer, G. 134Korenev, S. V. 126Kraft, A. 177Krause, J. A. 202Krishnan, L. 252Kubota, Y. 201Kudo, A. 227Kumar, K. S. 125

Laffont-Dantras, L. 84Lai, C.-H. 253Laing, M. 247Lanza, S. 58Lapeña Rey, N. 16Latroche, M. 201Lautenschlager, H. 244Lavina, S. 125Ledoux, N. 124Lee, E. P. 57Lee, G.-H. 58

Lee, W. 252Leiva, E. P. M. 107Leroy, E. 201Leung, S.-K. 202Lewis, F. A. 120Li, C. 201Li, D. 200Li, E. Y. 58Li, F. 126Li, H. 58Li, L. 126Li, P. 200Li, W. 200Li, Y. 201, 253Lin, X. 58Lin, Y. 58Liu, C. T. 252Liu, M. 201Liu, W.-P. 163Liu, Y. 134, 252Liu, Z. 126Livi, M. 124Lo, K. K.-W. 202Lou, L.-G. 163Lu, L. 252Lu, Y. 124Luan, W. 57Lucas, M. F. A. 126Lunin, V. V. 56

Machocki, A. 124MacLachlan, M. J. 46Macquarrie, D. 83Maerz, J. J. 52Maestri, M. 56Mahalingam, V. 253Mallick, K. 46Malysheva, Y. B. 124Manners, I. 46Maruyama, K. 241Mathiyarasu, J. 57Mattinson, J. A. 202Mazzolai, F. 120McLean, G. 17McPherson, J. 226Meek, G. 111Meggers, E. 97Mei, Y. 124Mejdell, A. L. 126Mendoza-Ferri,

M.-G. 253

Meng, X. 251Mennecke, K. 251Merki, D. 200Miasek, E. 126Middelman, E. 14Milhano, C. 202Miller, A. 16Mimura, N. 227Miyatake, K. 201Moini, A. 134Mondal, K. C. 124Morandi, S. 124Morreale, B. 58Morris, S. E. 252Mortazavi, Y. 125Motohiro, T. 56Mottet, C. 108

Nagumo, Y. 201Narayanan, S. R. 201Nastasi, F. 58Natarajan, K. 253Nazarov, A. A. 253Negishi, E. 172Negro, E. 125Newkome, G. R. 47Nishide, H. 201Nogami, M. 57Nørskov, J. K. 223Noyori, R. 251

Ohriner, E. K. 186, 252Okumura, K. 56Oliver, A. G. 202Orvig, C. 96Oshima, T. 253Osman, J. R. 253Owston, N. 113Ozkaya, D. 61

Pacchioni, G. 223Pace, G. 125Palacio, M. 202Palmeri, N. 58Panfilov, P. 242Park, H.-S. 252Park, I.-S. 252Pashkova, A. 227Pastor, G. M. 108

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Paul, M. 225Pavelka, M. 126Peng, Z. 57Pérez-Tijerina, E. 108Perutz, R. 96Phani, K. L. N. 57Pittman, Jr., C. U. 46Pitts, M. R. 64Pizzaro, D. 14Pletcher, D. 202Poizot, P. 84Pollock, T. M. 125Post, M. 56Potter, R. J. 155Pratt, A. 253Presto, A. A. 144Preußner, J. 48, 241Prinetto, F. 124Prins, S. N. 48Prinz, F. B. 252Proch, S. 124Pugliese, T. 58Puntoriero, F. 58

Qazi, A. 112Qi, Y. 57Qu, P. 253

Ramachandran, A. 126Reedijk, J. 2Reinecke, H. 18Retailleau, P. 58Revere, A. 52Richens, D. T. 253Rider, D. A. 46Rostrup-Nielsen, J. 12Ruseckas, A. 126Russo, N. 126Ryberg, P. 251

Sadler, P. J. 21, 97Saiz, E. 57Sakamoto, Y. 56, 120Samuel, I. D. W. 126Scerri, E. R. 247Schauermann, S. 224Schlichter, K. 244Schofield, E. 222Seo, J. H. 202

Sermon, P. A. 108Seshadri, S. K. 125Setsune, J. 202Severin, K. 253Seymour, R. 231Sheldon, R. A. 83Shen, P. K. 201Shen, W. 224Shinjoh, H. 56Shipman, P. O. 46Shubin, Yu. V. 126Simonet, J. 84Skea, J. 13Skoplyak, O. 251Smith, M. B. 215Solodenko, W. 251Somorjai, G. A. 57Song, Y.-H. 253Spadoni, C. 222Stasinska, B. 124Stockdale, G. W. 200Stolyarova, N. 253Su, Q. 163Sudo, T. 251Sultana, A. 200Sun, S. 57Sun, X.-J. 202Sung, Y.-E. 252Susu, A. A. 251Suzuki, A. 172

Tada, M. 227Tai, Y.-C. 201Takahashi, S. 252Takahashi, T. 172Takata, M. 201Tamao, K. 173Tanaka, A. 201Tang, G.-R. 251Tang, M.-C. 202Tarasenko, E. A. 56Terada, Y. 208Theis, J. R. 56Thomas, Sir J. M. 108Thompsett, D. 108Thornback, J. R. 21Thurier, C. 126Tian, T. 253Toda, M. 202Tompos, A. 225Tomsia, A. P. 57

Tong, X.-Q. 120Topsøe, H. 12Torker, S. 200Tromp, M. 108Tronconi, E. 56Tsai, M.-H. 253Tsiouvaras, N. 227Tu, S.-T. 57Turner, G. 112Tysoe, W. T. 224Tyurin, V. S. 56

Ubbelohde, A. R. 120Ueji, M. 125Ueno, F. 17Uma, T. 57

Vaccari, A. 124Valdez, T. I. 201van Bokhoven, J. A. 223van den Berg,

M. W. E. 56van Dokkum, J. 13van Santen, R. A. 229Venkataramanan,

N. S. 124Verpoort, F. 124Vigny, H. 245Visart de Bocarmé,

T. 223Vix-Guterl, C. 201Vlassak, J. 58Völkl, R. 48, 241, 242

Wang, D. 56Wang, E. 56Wang, H. 200, 253Wang, J.-Q. 56Wang, X. 124Wang, Y. 57Wang, Y.-M. 163Wang, Z. 201Wardell, J. L. 124Watanabe, M. 201Wells, P. 108Wenderoth, M. 48Weng, Y.-C. 253Weston, M. 14Wey, M. Y. 200

Whitacre, J. F. 201Whiting, A. 112Wicke, E. 121Wickleder, M. S. 58Wicks, M. 12Wieckowski, A. 201Wilkie, J. 14Witcomb, M. J. 124Wong, K.-T. 253Wrzesniok-Rossbach,

W. 244Wu, C.-C. 253Wu, X. 113, 200

Xia, Y. 57Xiao, J. 200Xiao, Z. 253Xiong, G. 57Xu, H. 57, 125, 252

Yamauchi, M. 201Yan, S. 253Yanagisawa, S. 251Yang, H. 57Yang, M. 253Yang, S. 200Yang, Y.-P. 163Yates, J. T. 57Ye, Q.-S. 163Yersin, H. 155Yi, T. 126Yin, Y. 57Yoshida, T. 202Yu, M. 126Yu, Y. 163Yusenko, K. V. 126

Zadesenets, A. V. 126Zeller, M. 253Zhang, J. 57Zhang, J.-Q. 202Zhang, K. Y. 202Zhang, X. 201Zhao, K. 126Zhao, Q. 126Zheng, S. 201Zhu, S. 252Zhu, X. 58Ziessel, R. 58

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SUBJECT INDEX TO VOLUME 52Page Page

a = abstract

AFM Probes, Pt, Pt-Ir, Pt-Ni, coated, a 202Alcohols, EtOH, sensors, a 253

MeOH, decomposition 222fuel 12, 134oxidation 125, 222

steam reforming 134, 222for synthesis of amides 110

Aldehydes, by hydroformylation 110hydrogenation 110reduction, a 200unsaturated, hydrogenation, selective, a 56

Alkanes, conversions 107Alkenes, C–C coupling 38Alkyl Halides, one-electron cleavage of C–Br, C–I 84Alkynes, C–C coupling 38

carbonylation 215hydrogenation, selective, a 56

Amides, synthesis 110Amines, secondary, tertiary, by hydroaminomethylation 110

for synthesis of amides 110Aminocarbonylation, aryl halides 110Apparatus and Technique, a 57–58, 125–126, 201, 253Arenes, + iodoarenes, coupling reactions, a 251Aryl Halides, reactions 38, 56, 110, 124, 172, 200, 215, 251Arylation 110, 124Arylboronic Acids, reactions 110, 251

Biaryls, synthesis 110Biological Activity, Ru(II) oximato complexes, a 253Biological Probes, luminescent, Ir(III)-polypyridines, a 202Biomedical and Dental, a 126, 253Biosensors, DNA, a 126Book Reviews, “Adventures at the Bench” 52

“Catalysis for Renewables” 229“Frontiers in Transition Metal-Containing Polymers” 46“Green Chemistry and Catalysis” 83“Highly Efficient OLEDs with Phosphorescent

Materials” 155“Medicinal Applications of Coordination Chemistry” 21“The Periodic Table: Its Story and Its Significance” 247

Boranes, C–C coupling 38Boronates, C–C coupling 38Boronic Acids, C–C coupling 38Boronic Esters, C–C coupling 38

CALPHAD, Cr-Pt 241Cancer, anti-, agents, aminoalcohol-Pt complexes 96

azido-Pt(IV) complexes 2azolato-bridged dinuclear Pt compounds 2BBR3464 21bis(azpy)Ru(II) 2di-Pt complexes 21dinuclear cationic species containing Ru(II) and Pt(II) 2dinuclear Ru-arenes, a 253KP1019 96NAMI-A 2, 96Pd complexes 21Pt chxn 96Pt(II), Pt(IV) complexes 96Rh complexes 21Ru complexes 21Ru organometallics 96Ru quinonediimines 96Ru(II), Ru(III), Ru(IV) complexes 96[Ru(sandwich)(diamine)Cl] 2tri-Pt complexes 21

drugs, carboplatin 2, 96, 126, 163cisplatin 2, 21, 96, 163

Cancer, (cont.)eptaplatin 163iproplatin 96lobaplatin 163nedaplatin 163oxaliplatin 2, 163picoplatin 96, 163satraplatin 2, 96, 163

Carbenes 38, 71, 200Carbon, catalyst support, Pt/C, TEM 61Carbon Oxides, CO, addition, H–D exchange reaction 222

combustion, a 56from glycerol, a 251+ NO 107oxidation 56, 222for reduction, of NO, a 200sensors 201, 215transport, through Pt@CoO nanoparticles, a 57

CO2, supercritical, hydrogenation, + HN(CH3)2 215solvent, a 56

Carbonylation, alkynes 215Carboxylic Acids, for synthesis of amides 110Catalysis, Applied and

Physical Aspects, a 56, 124, 200, 251asymmetric 110book reviews 83, 229conferences 110, 172, 222, 229in green chemistry 83, 110Industrial Process, a 56, 200, 251microwave heating 64Reactions, a 56, 124, 200, 251for renewables 229

Catalysts, analysis, Pt 205encapsulated 64nanoalloys 107pgm, fundamental studies 249pgm/support, 2D mapping 222recycling 56, 64, 71, 157, 215, 251supported, analysis, crystallite size, by XRD 129

particle size, by TEM 61temperature-programmed reduction 249

Catalysts, Iridium, H–D exchange reaction; + CO 222hydrogenation 229Ir/CeO2, steam reforming of EtOH 222

Catalysts, Iridium Complexes, amides, from alcohols 110half-sandwich Ir(III) hydroxyindanimines, ROMP of

norbornene, a 251vinyl polymerisation of norbornene, a 251

intermolecular enantioselective hydroamination 110Ir-N-tosyldiamines, aldehyde reduction, in H2O, a 200monotosylated ethylenediamine Ir(III), hydrogenation 110

Catalysts, Osmium Complexes, Os EnCat 40 64Catalysts, Palladium, aqueous reforming 229

dehydrogenation 229electrocatalysts, CuPd, a 202

Ni-Pd, anodes, for DMFCs, a 125Pd/hollow C spheres, for DAFCs, a 201Pd/Vulcan XC-72 C, for DAFCs, a 201Pd-Co-Ag/C, -Au/C, -Pt/C, cathodes, for DMFCs, a 57Pd-Co-CN, for PEFCs, a 125

H–D exchange reaction; + CO 222hydrogenation 229hydrogenolysis 229oxidation 229Pd(111), ethene + acetic acid 222Pd(0) EnCat, microwave heating, hydrogenations 64Pd(0) EnCat NP30, microwave, nitro reduction 64

transfer hydrogenation 64Pd nanoparticles, Heck reactions 38Pd tip of field ion microscope, H2 + NO 222Pd/Al2O3 , + Co, Cu, Na, Ni, NO reduction/CO, a 200

combustion of natural gas 222

Catalysts, Palladium, (cont.)dechlorination of PVC, a 56MeOH steam reforming 134oxidation of CH4, a 124preparation, by flame-spray pyrolysis 222total oxidation of CH4 222

Pd/(Al2O3 + MOx), oxidation of CH4, a 124Pd/alumina beads, Hg oxidation 144Pd/BaSO4, Stille cross-couplings, a 124Pd/C, o-chlorotoluene hydrogenolysis, a 200

Heck reactions 38Pd/C microspheres, hydrogenation of ethylene, a 124Pd/LaCoO3(flame-spray pyrolysis), NO reduction/H2 222Pd/LaCoO3(impregnation), NO reduction/H2 222Pd/(La0.2Sr0.3Ba0.5)(MnAl11)O19, natural gas combustion 222Pd/membrane, synthesis of H2O2 222Pd/YSZ, natural gas combustion 222Pd nanoparticles/Celite®, Heck reactions 38Pd nanoparticles/spherical polyelectrolyte brushes, a 124PdO/support, natural gas combustion 222Pd particles/Fe2O3 film/Pt(111), MeOH decomposition 222PdAu, ethene + acetic acid 222Pd-Ag/membrane, synthesis of H2O2 222Pd-Au/Al2O3, selective oxidation of styrene, a 124PdAu/Al2O3, /C, /TiO2, H2O2 synthesis 107PdRh/γ-Al2O3, NO-CO reaction 107‘Pd-Zn/oxide support’, mechanical strength 134

MeOH steam reforming 134‘Pd-ZnO/Al2O3’, MeOH steam reforming 134

Catalysts, Palladium Complexes, aminocarbonylationof aryl halides, synthesis of amides 110

biaryl synthesis 110+ bidentate phosphines, dippb, dppe, Heck reactions 38+ Buchwald ligands, Suzuki couplings 172+ Buchwald ligands, Suzuki-Miyaura reactions 38C–C bond forming 83C–C coupling 38C–H activation 110, 172C-5 arylation of thiazoles 110carbene complexes, Heck reactions 38Csp3–Csp3 coupling 172cyclisation of 2-substituted halogenoarenes 110‘cyclo-functionalising’ unactivated C–C multiple

bonds 1721,6-diene Pd(0) monophosphine, Suzuki-Miyaura

reactions 38DPEphosPdCl2, organozinc-based transformations 172dppfPdCl2, organozinc-based transformations 172

Suzuki couplings 172dtbpfPdCl2, coupling reactions 172(DtBPF)PdX2, α-arylation of ketones, a 124enantioselective –OH addition, in cyclisation 110Hiyama couplings 172homogeneous telomerisation 229intermolecular enantioselective hydroamination 110Kumada couplings 172+ N-heterocyclic carbenes, Kumada reactions 38

Stille reactions 38Suzuki-Miyaura reactions 38

oxime-based palladacycle/composite, C–C coupling, a 251palladacycle complexes, Heck reactions 38

Suzuki-Miyaura reactions 38+ PCy3, Stille reactions 38

Suzuki-Miyaura reactions 38Pd(II) acetate, vinylic substitution reactions, aryl

halides 38[PdBr(P(tBu)3)]2, Suzuki-Miyaura reactions 38Pd(tBu3P)2, organozinc-based transformations 172

Suzuki couplings 172[PdCl(η3-C3H5)]2, Hiyama reactions 38PdCl(CH2Ph)(PPh3)2, Stille reactions 38PdCl2/CuCl, scCO2/PEG, aerobic oxidation, styrene, a 56PdCl2(dppf), Kumada reactions 38PdCl2(PhCN)2, Sonogashira reactions 38PdCl2(P(iPr)3)2, Hiyama reactions 38

Catalysts, Palladium Complexes, (cont.)PdCl2(PPh3)2, Negishi reactions 38

Sonogashira reactions 38Pd2dba3 + IMes·HCl, Suzuki-Miyaura reactions 38Pd2(dba)3 + IPr·HCl, Kumada reactions 38Pd2dba3 + IPr·HCl, Suzuki-Miyaura reactions 38Pd(dba)2 + P(tBu)3, cyanation of aryl bromides, a 251Pd diphosphine dendrimer/SiO2, intramolecular

cyclocarbonylation of iodinated aryl amines 215Pd/dppf-based, Negishi reactions 38Pd EnCat, microwave, cross-coupling reactions 64Pd EnCat 30, microwave, cross-coupling reactions 64Pd EnCat polyTPP30, microwave, cross-couplings 64Pd(II) + ethylphosphatrioxaadamantane/SiO2, Suzuki

coupling 110Pd nanoparticles, stabilised by polymer micelles,

Suzuki-Miyaura cross-coupling, a 251Pd(OAc)2, olefins + aryl halides 38Pd(OAc)2 + IPr·HCl, Stille reactions 38Pd(OAc)2/Cy3P, Suzuki coupling 172Pd(OAc)2/PPh3, Heck reactions 38Pd P–C–N–C–P diphosphine/SiO2, carbonylative

cross-couplings 215Pd(P(tBu)3)2, Negishi reactions 38

Stille reactions 38Pd(Ph3P)4, Suzuki couplings 172

synthesis of tetradecane 172Pd(PPh3)4, Kumada reactions 38


Pd(II) phosphine, Suzuki couplings 215Pd4 phosphine metallodendrimer, Suzuki couplings 215Pd(II) salts + diphenyl-2-pyridylphosphine, alkyne

carbonylation 215Pd(II) with S donors/SiO2, Suzuki coupling 110Pd/poly(N-vinylimidazole), Mizoroki-Heck reaction, a 56Pd/poly(N-vinylimidazole-co-N-vinylcaprolactam),

Mizoroki-Heck reaction, a 56phosphine-ArgoGel-Pd, Suzuki-Miyaura couplings 215pincer complexes, Heck reactions 38+ P(tBu)3, Heck reactions 38


Q-Phos based FibreCat, coupling reactions 172Suzuki coupling, in synthesis of palytoxin 172Suzuki-Miyaura reactions 110

Catalysts, Platinum, aqueous reforming 229BaO(100)/Pt(100), absorption of NO2 222electrocatalysis 229electrocatalysts, FePt, formic acid electrooxidation, a 57

Pd-Co-Pt nanoparticles/C, cathodes, for DMFCs, a 57platinised C, cathodes, for fuel cells, microchips 12Pt, nanostructured thin film, a 201

for PAFCs 12for PEMFCs 12, 201for SOFCs, a 252

Pt black, cathodes, for DMFCs, a 252electrodes, for PEMs, a 252

Pt/C, aged, SAXS, TEM, XRD 129cathodes, for DMFCs, a 252

O2 reduction reaction, mechanism 222electrodes, in H2/O2 fuel cells, a 57modified by CeO2, cathodes, for PEMFCs, a 125

Pt/GNFs, for PEMFCs, a 252Pt/XC-72, for PEMFCs, a 252Pt3Cr nanoalloy, for fuel cells 107PtNiFe, Pt59Ni39Fe2, nanostructured thin film, a 201PtNiZr, for PEMFCs, a 201PtRu, see Catalysts, Ruthenium

green rusts(Pt), dechlorination, tetrachloroethylene, a 252H–D exchange reaction; + CO 222hydrogenation 229Ni-Pt-Pt(111), glycerol reforming, a 251oxidation 229Pt, diesel oxidation catalyst 23


Page Page

Catalysts, Platinum, (cont.)diesel particulate filter 23selective catalytic reduction, NOx control 23

Pt(111), glycerol reforming, a 251Pt(0) EnCat, microwave, hydrogenations, reductions 64Pt(0) EnCat 40, microwave, hydrogenations 64Pt nanoparticles, encapsulated in hollow metal oxide

spheres, CO oxidation 222Pt tip of field ion microscope, H2 + NO 222Pt/activated C fibre cloth, H2 sensor, a 57Pt/Al2O3, preparation, by flame-spray pyrolysis 222

sintered, n-heptane reforming, a 251total oxidation of CH4 222

Pt/β-Al2O3 + K+, combustion of propane 222Pt/alumina beads, Hg oxidation 144Pt–Al2O3/Si, NO + H2, a 56Pt-Ba/Al2O3, Pt-Ba-Ce/Al2O3, NOx trap, a 251Pt/Ba/γ-alumina, NOx storage 222Pt/K/Al2O3, lean NOx trap, CO oxidation, a 56Pt/C, particle size analysis, by TEM 61Pt/ceria-containing supports, > 800ºC, redispersion 222Pt/Cu–Mg(Al)O, NOx storage, a 124Pt–Mg(Al)O, NOx storage, a 124Pt/SiO2 filter, for TiO2-based O2 sensor, a 125Pt/TiO2, degradation of dichloroacetate anion, UV, a 202

visible light, a 202Pt/TiO2–xNx, degradation of VOCs, visible light, a 200Pt/zeolites, NO reduction, with diesel, a 200Pt nanoparticles/magnetite nanoparticles, selective

hydrogenation, a 56PtAu, PtSn, nanoparticles, alkane conversions 107Pt-Ni-Pt(111), glycerol reforming, a 251Pt-Pd-Au/CeO2, total oxidation of CH4 222Pt-Re/Al2O3, metal segregation, a 56

sintered, n-heptane reforming, a 251Pt-Rh/Al2O3, preparation, by flame-spray pyrolysis 222

total oxidation of CH4 222Pt-Ru/Al2O3, preparation, by flame-spray pyrolysis 222

total oxidation of CH4 222steam reforming 229

Catalysts, Platinum Complexes, Karstedt’s catalyst,hydrosilylation, curing of silicones 243

Catalysts, Rhodium, H–D exchange reaction; + CO 222hydrogenation 229PdRh/γ-Al2O3, NO-CO reaction 107Pt-Rh/Al2O3, preparation, by flame-spray pyrolysis 222

total oxidation of CH4 222Rh/Al2O3, CO combustion, H2 combustion, a 56

preparation, by flame-spray pyrolysis 222total oxidation of CH4 222

Rh/MgAl2O4/Al2O3, steam reforming of bioethanol 222 Ru/SiTiO3:Rh, solar H2 production 222

Catalysts, Rhodium Complexes, BINAPHOS,enantioselective hydroformylation 110

BIPHEPHOS, hydroformylation 110bisphosphine, asymmetric hydrogenation 110diazaphospholane, enantioselective hydroformylation 110Hiyama couplings 172homogeneous hydrogenation 229hydroaminomethylation of olefins 110hydroformylation of olefins, LP OxoSM Process 110monophosphoramidite, asymmetric hydrogenation 110phosphite, enantioselective hydroformylation 110RhCl(CO){P[OCH(CF3)2]3}2, arenes + iodoarenes, a 251RhCl(PPh3)3/dendritic SBA-15, hydroformylation, a 200Wilkinson’s catalyst/dendritic SBA-15, a 200

Catalysts, Ruthenium, aqueous reforming 229electrocatalysts, PtRu, nanostructured thin film, a 201

PtRu black, anodes, for DMFCs, a 252PtRu/C, + Mo, for DMFCs 222

H–D exchange reaction; + CO 222hydrogenation 229oxidic Ru surfaces, oxidation of MeOH 222Pt-Ru/Al2O3, preparation, by flame-spray pyrolysis 222

total oxidation of CH4 222

Catalysts, Ruthenium, (cont.)Ru nanoparticles/MgAl spinel, NH3 synthesis 222Ru/SiTiO3:Rh, solar H2 production 222RuSn/SiO2, cyclododecatriene selective hydrogenation 107

Catalysts, Ruthenium Complexes, amide preparation 110C–C bond forming 83Cp*Ru(COD)Cl, oxidation, regio-, stereoselective 172F-containing polymer-bound Ru alkylidene, RCM 71fluoro-tagged, first-generation Grubbs-Hoveyda 157

second-generation Grubbs-Hoveyda 157Grubbs’ catalyst, conversion of seed oils 222

olefin metathesis 222polymer-based phosphine resin scavengers 215

Hoveyda’s second-generation, RCM, to SB-462795, a 200immobilised NHC Ru complex, CM, RCM 71immobilised Ru benzylidene complex, RCM, dienes 157

self-metathesis, internal olefins 157ionic liquid-tagged, NHC-Ru, PCy3-Ru 157NHC Ru complex immobilised on monolithic support 71oxidation 83phosphine-ArgoGel-Ru(II), hydrogenation, of scCO2 215polymer-bound NHC Ru complex, soluble, RCM 71polystyrene-Ru-allenylidene, cyclisation of olefins 157

hydrogenation of olefins 157RCM of olefins 157

Ru alkylidenes, immobilisation, via alkylidene ligands 71via anionic ligands 157via the arene ligand 157via N-heterocyclic carbene ligands 71via phosphane ligands 71via the Schiff base ligand 157

tagged, fluoro, ionic liquid 157Ru-based, H2O-soluble, metathesis, RCM, ROMP 71Ru carbenes, metathesis, gas-phase, a 200Ru O-hydroxyaryl-substituted NHCs, ROMP, a 124Ru-pincer, synthesis of amides 110supported NHC Ru complexes, RCM, ROM/CM 71zeolite-supported, RCM 71

Chemistry, a 58, 126, 202, 253Cisplatin 2, 21, 96, 163Coatings, Ir, by CVD, EBVD, PVD 186

on Rh nozzles 186IrO2, on DSA®, on Ti electrodes 177IrO2/RuO2, on DSA®, on Ti electrodes 177mixed Ir/Ru oxide, on Ti electrodes 177Pt, on Ti electrodes 177RuO2, on Ti electrodes 177

Coefficient of Thermal Expansion, Ir3X 208Colloids, PVP-coated, Pd particles, Pt particles, a 125Combustion, CO, H2, a 56

natural gas 222propane 222

Composites, Ir-Y2O3 electrode 186Pd nanoparticle/C template, a 201

Conferences, Catalysis for Renewables,The Netherlands, 2006 229

Challenges in Catalysis for Pharmaceuticals andFine Chemicals, U.K., 2007 110

Creep 2008, Germany, 2008 241Creep 2011, Japan, 2011 241Cross Coupling and Organometallics, France, 2007 172Dalton Discussion 10: Applications of Metals in

Medicine and Healthcare, U.K., 2007 96EuropaCat VIII: “From Theory to Industrial

Practice”, Finland, 2007 222EuropaCat IX: “Catalysis for a Sustainable World”,

Spain, 2009 222Faraday Discussion 138: Nanoalloys – From

Theory to Applications, U.K., 2007 10710th Grove Fuel Cell Symp., London, 2007 12

Copper, palladised 84Coupling Reactions, arenes + iodoarenes, a 251

C–C 38, 124, 251carbonylative 215conference 172


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Creep, conference 241GTH, GTHR, oxide dispersion strengthened Pt alloys 241Pt alloys 241Pt-Al-Cr-Ru, by modelling 241Pt-Rh 241Ru-Ni-Al, ternary B2 alloys, a 125

Cross Metathesis, using immobilised Ru alkylidenes 71Crucibles, Ir 186CVD, Ir coatings 186

pulsed, Ru thin films, a 58Cyanation, aryl bromides, a 251Cyclisation, 2-substituted halogenoarenes 110

by enantioselective –OH addition 110olefins 157

Cyclocarbonylation, intramolecular, iodinated arylamines 215

Dechlorination, PVC, a 56tetrachloroethylene, a 252

Decomposition, MeOH 222Deformation, plastic, Ir 241Deposition, atomic layer deposition, Ru thin films, a 58

CVD, EBVD, PVD, Ir 186Pd, on Cu substrate 84pulsed CVD, Ru thin films, a 58

Deuterium, H–D exchange reaction 222Diesel, emission control 23

heavy-duty engines, regulations; developments 23light-duty engines, regulations; developments 23NOx control 23NOx traps, a 251particulate matter control 23for reduction, of NO, a 200

Diesel Oxidation Catalysts 23Diesel Particulate Filters 23Dihydroxylation, encapsulated catalyst, microwave 64Disinfection, electrochemical, H2O 177

Electrical and Electronics, a 202, 253Electrochemistry, a 202

formation, IrOx/polyaniline composite films, a 126H2O disinfection 177measurements, Pt reference electrode 100

Electrodeposition, CuPd, a 202Ir 186Ni-Pt films, on Au/Al2O3, a 253Pd nanowire arrays, a 125

Electrodes, Cu-Pd, disordered, cleavage, C–Br, C–I 84modified, reduction, alkyl bromides, iodides 84

in fuel cells, see Fuel CellsIr-Y2O3 composite 186IrO2-coated DSA®, free Cl2 production 177IrO2-coated Ti, hypochlorite generation 177

lifetime 177IrO2-type DSA®, degradation, a 202IrO2/RuO2-coated DSA®, free Cl2 production 177IrO2/RuO2-coated Ti, hypochlorite generation 177

lifetime 177micro-, Pt 100mixed Ir/Ru oxide-coated Ti, in disinfection devices 177Pd nanoparticles/MWCNTs/Nafion/GCE, a 126platinised Ti electrodes, in disinfection device 177Pt, electrochemical reference 100Pt black, electroplated, human blood cell sensing, a 201Pt-coated Ti electrodes, lifetime 177Pt wire, electrochemical reference 100reference, electrochemical, Pt wire 100RuO2-coated Ti electrodes, lifetime 177

Emissions Control, a 56, 200, 251–252catalysts, analysis by ICPES 205diesel engines, heavy-duty, light-duty 23

Engines, heavy-duty diesel, light-duty diesel 23Ethylene, hydrogenation, a 124

Films, Ir oxide/polyaniline composite, a 126Ni-Pt, electrodeposition, on Au/Al2O3, a 253

Filters, Ir 186‘Final Analysis’ 61, 129, 205Fine Chemicals, by catalysis 110, 172Flue Gas, Hg oxidation 144Formic Acid, electrooxidation, a 57Fuel Cells, a 57, 125, 201, 252

catalysts, analysis by ICPES 205Pt/C, O2 reduction reaction, mechanism 222

conference 12DAFC, electrocatalysts, Pd/hollow C spheres, a 201DMFC, catalysts 222

anodes, cathodes, a 252conference 12electrocatalysts, anodes, a 125MeOH, fuel 134nanocatalysts, cathodes, a 57O distribution, visualisation, using a Pt porphyrin, a 201

electrocatalysts, nanostructured thin films, a 201Pt/C, aged, XRD 129Pt3Cr, O reduction activity 107

electrodes, conference 12Pt/C, a 57

fuel, H2 12, 57, 134, 229MeOH 12

“Fuel Cell Today Industry Review 2008” 123membrane electrode assemblies, conference 12PAFC, conference 12PEFC, electrocatalysts, a 125PEMFC, catalysts, high throughput study, a 201

conference 12electrocatalysts, cathodes, a 125graphite nanofibres as catalyst support, a 252miniature, power source 134portable applications 134

power, consumer electronics, large stationary 12reformed MeOH, H2, fuel 134SOFC, conference 12

current collector grid/patterned catalyst, by ALD, a 252electrode/catalyst layer, by ALD, a 252

transport: airplane, locomotives, marine, road vehicles 12Fuels, H2 12, 57, 134, 229, 249

hydrocarbons, a 57MeOH 12, 134

Gauze, Pt, Pt nanowire coating, a 57Glycerol, reforming, a 251Green Chemistry, catalysis 83, 110

Heck Reactions, Pd-catalysed 38n-Heptane, reforming, a 251Heterocycles, synthesis 110High Temperature, ultra-, Ir3X, thermophysical prop. 208High Throughput Screening Techniques 134, 201History, Periodic Table 114, 247HIV, anti-, Pt(II), Ru(II), Ru(III), Ru(IV) complexes 96Hiyama Couplings 38, 172HotSpotTM Reactor, H2 generation 249Human Blood Cells, sensor, a 201Hydrides, Pd 120Hydroamination, intermolecular, enantioselective 110Hydroaminomethylation, olefins 110Hydrocarbons, reforming 57, 249Hydroformylation, enantioselective 110

olefins 110styrene, a 200

Hydrogen, absorption 120, 201combustion, a 56diffusion coefficients, in Pd0.77Ag0.23 120from bioethanol 222from glycerol, a 251from H2O 222


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Hydrogen, (cont.)from hydrocarbons, oxygenates 249fuel 12, 57, 134, 229, 249H–D exchange reaction 222membranes 120, 126+ NO 56, 222sensors, a 57, 201storage, Pd nanoparticle/C template composites, a 201for synthesis of H2O2 222uphill diffusion, ‘Lewis Effect’, Pd 120

Hydrogen Peroxide, synthesis 107, 222Hydrogen Sulfide, + Pd, + Pd-Cu membranes, a 58

sensors 215Hydrogenation, aldehydes 110, 200

asymmetric 110encapsulated catalyst, microwave heating 64ethylene, a 124olefins 157scCO2, + HN(CH3)2 215selective, alkynes, a 56

cyclododecatriene 107unsaturated aldehydes, a 56

transfer, aldehydes 110encapsulated catalyst, microwave heating 64

Hydrogenolysis, o-chlorotoluene, a 200Hydrolysis, Ru alkoxide/Ti tetraethoxide, a 253Hydrosilylation, curing of silicones, Pt-catalysed 243Hypochlorite, generation 177

ICPES, determination of Pt in solution 205Ionic Liquids 38, 83Iridium, coatings, by CVD, EBVD, PVD 186

on Rh nozzles 186crucibles 186deformation processing 186deposition, electrodeposition 186filters 186Ir-Y2O3 composite electrode 186joining 186melting 186, 252nanoparticles, a 126Periodic Table 114, 247plastic deformation 241plating 186powder metallurgy 186processing 186purification 186, 252single crystals, deformation 241sponge 186welding 186wire 186

Iridium Alloys, deformation processing 186DOP-26 186Ir-Pt, powder metallurgy 186‘Ir-Nb’, dendritic segregation, a 252‘Ir-Zr’, dendritic segregation, a 252joining 186melting 186processing 186Pt-Ir, coating, AFM probes, a 202welding 186

Iridium Complexes, cyclometalated Ir(III)-polypyridinesin biological probes, luminescence, a 202

encapsulated Ir porphyrins, O2 sensors 46Ir acetylacetonate, for CVD 186Ir-allyl, for CVD 186Ir(III) N-benzylpyrazoles, phosphorescence, a 253Ir(btp)2(acac), in OLEDs 155Ir-carbonyl, for CVD 186Ir(COD)(MeCp), for CVD 186Ir-cyclooctadienyl, for CVD 186Ir(dfppy)2(pq), in OLEDs, a 202Ir(ppy)2(DBM), Ir(ppy)2(SB), phosphorescence, a 126Ir(ppy)3, luminescence, a 126

Iridium Complexes, (cont.)in OLEDs 155, 253

Ir(III) pyridylphosphines 215Ir(III)/Au(I) phosphines 215OLEDs 155, 202, 231, 253

Iridium Compounds, electrodes, see Electrodesintermetallic, thermal conductivity, thermal expansion 208Ir chloride solutions, for plating of Ir 186Ir hexafluoride, for CVD 186Ir oxide, in chemical refining of Ir 186Ir oxide/polyaniline composite films, a 126sodium hexabromoiridate(II) solutions, plating of Ir 186

Jewellery, Pt, manufacture 52Johnson Matthey, “Platinum 2007 Interim Review” 54

“Platinum 2008” 198sustainability 132

Joining, Ir, Ir alloys 186

Kumada Couplings 38, 172

Lasers, Pt jewellery, manufacture 52welding, Ir alloy 186

Lewis Effect, uphill diffusion of H, in Pd 120Lipoid, with Pt(II) containing salicylate derivative 163Lipophilicity, Pt(II) containing salicylate derivative 163LPG, sensors, a 201Luminescence, cyclometalated Ir(III)-polypyridines, a 202

dendritic tetranuclear Ru(II) complex 46Ir(ppy)3, a 126Pt(II) isoquinolinyl indazolates, a 58Pt porphyrin, a 201switching, Pt(II) dithiooxamides, a 58

Magnetism, nanoalloys, CoPt, CoRh, PdAu, PdFe,PdNi, PtAu, PtFe, PtNi 107

Mannich Condensation, P-based, for aminophosphines 215MEAs, conference 12Medical Uses, pgm complexes, anti-HIV 96

anticancer 2, 21, 96, 126, 163Melting, Ir, a 252

Ir alloys 186Membranes, Pd, sulfidisation, a 58

Pd/modified α-Al2O3, in reactor, H2 production, a 57Pd/Ag23%, heat treatment, a 126Pd0.77Ag0.23, H2 diffusion coefficients, uphill effects 120Pd-Cu, sulfidisation, a 58

Mercury, oxidation 144Metal-Ligand Exchange Kinetics, Pt, Ru complexes 2Metallodendrimers, encapsulated, Ir, Pd, Pt porphyrins 46Metallurgy and Materials, a 57, 125, 201, 252Metathesis, olefins 71, 157, 222Methane, oxidation, a 124

sensors, a 253total oxidation 222

Microwaves, in organic synthesis 38, 64syntheses of cycloplatinated complexes, a 58

Mizoroki-Heck Reactions, a 56Molten Salts, electrodeposition of Ir 186

Nanoalloys, CoPt, CoRh, PdAu, PdFe, PdNi, PdRh,PtAu, Pt3Cr, PtFe, PtNi, PtSn 107

Nanocomposites, C MWNT/Pd, for detection of CH4, a 253Pd nanoparticles-polyphenosafranine, nitrate sensing, a 58Ru nanoparticles/C MWNT, for supercapacitor, a 253

Nanoparticles, FePt, a 57Ir, a 126Pd 38, 58, 124, 126, 201, 251PdAu 107Pd-Co-Ag, Pd-Co-Au, Pd-Co-Pt, a 57


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Nanoparticles, (cont.)Pd/Pt, a 201Pt 56, 61, 222Pt@CoO, a 57PtAu 107PtSn 107Ru 222, 253RuO2, a 253

Nanostructures, yolk–shell, Pt@CoO nanoparticles, a 57Nanowires, arrays, Pd, a 125

Pt, on metal gauze, a 57Natural Gas, combustion 222Natural Products, synthesis, by cross-coupling 172Negishi Couplings 38, 172Nitrite, sensors, a 58Nitrogen, adsorption, on Pt(111), a 125

on Pt(111)(1×1)H, a 125Nitrogen Oxides, NO, + CO 107

+ H2 56, 222reduction, with CO, a 200

with diesel, a 200NO2, adsorption 222NOx, control 23lean, trap 23, 56selective catalytic reduction 23storage, by catalysts 124, 222traps, for diesel, a 251

Norbornene, ROMP, a 251vinyl polymerisation, a 251

Oils, seed, conversion 222OLEDs 155, 202, 231, 253Olefins, C–C couplings, a 124

cyclisation 157Heck reactions 38hydroformylation 110hydrogenation 157internal, self-metathesis 157metathesis 71, 157, 222RCM 157

OMCVD, Pt, precursor chemistry, processes, a 126Organometallics, Pd 172Organosilanes, cross-coupling 172Osmium, Periodic Table 114 , 247Osmium Complexes, OLEDs 155

organometallic polymers 46Oxidation, aerobic, styrene, a 56

CH4, a 124CO 222electro-, formic acid, a 57Hg 144MeOH 125, 222regio-, stereoselective, using Cp*Ru(COD)Cl 172Ru catalysts 83selective, styrene, a 124total, CH4 222

Oxygen, sensors 46, 125for synthesis of H2O2 222

Oxygenates, reforming 249

Palladium, absorption, H2 120C MWNT/Pd nanocomposite, for detection of CH4, a 253colloidal particles, PVP-coated, a 125deposition, on Cu substrate 84H2 storage 12hydrides 120membranes, a 57nanoparticles 38, 58, 124, 126, 201nanowire arrays, a 125Pd nanoparticle/C template composites, a 201Pd nanoparticles-polyphenosafranine, nitrate sensing, a 58PdAu particles/Al2O3 film, by sequential condensation 107Periodic Table 114, 247

Palladium, (cont.)uphill diffusion, ‘Lewis Effect’, H2 120

Palladium Alloys, absorption, H2 120Cu-Pd, disordered, electrodes 84

modified, electrodes 84CuPd, crystal structure information 84

electrocatalytic properties, a 202electrodeposition, a 202

hydrides 120membranes 58, 120, 126nano-, PdAu, PdFe, PdNi, PdRh 107PdAu nanoparticles, synthesis, in a sputter reactor 107PdNi, PdZn, nanosized powders, a 126

Palladium Complexes, anticancer agents 21dichloropalladium(II) ditertiary phosphines 215dichloropalladium(II) pyridylphosphines 215encapsulated Pd porphyrins, O2 sensors 46OLEDs 155organometallic polymers 46[Pd]10[MTD]163, [Pd]50[MTD]113, complex-block 46Pd(acac)2, decomposition, reduction, a 125[Pd(NH3)4][Ni(Ox)2(H2O)2]·2H2O, thermal decomp., a 126[Pd(NH3)4][Zn(Ox)2(H2O)2]·2H2O, thermal decomp., a 126Pd oxoselenates, preparation, a 58Pd(Se2O5), Pd(SeO3), Pd(SeO4), preparation, a 58Ru2Pd phosphaadamantane 215

Palladium Compounds, K2PdCl4 in H2SO4 electrolyte, a125Pd(II), recovery, with chitosan microspheres, a 253PdCl2, in HCl, for Pd deposition 84Pd(NO3)2, in HNO3, for Pd deposition 84PdSO4·2H2O, in H2SO4, for Pd deposition 84

Particle Size Analysis, Pt/C catalysts, by TEM 61Particulate Matter, control 23Patents 59–60, 127–128, 203–204, 254–255

analysis 231mapping 231

Periodic Table 114, 247Pharmaceuticals, by catalysis 110, 172Phase Diagrams, Cr-Ni-Pt 241

Cr-Pt 48Pt-Al-Cr-Ni 48

Phases, Pt-Al-Cr-Ni 241Phosphines, pgm complexes, applications, properties 215Phosphorescence, electro-, Ir(dfppy)2(pq), in OLEDs, a 202

Ir(III) N-benzylpyrazoles, a 253Ir(ppy)2(DBM), Ir(ppy)2(SB), a 126Pt(II)–acetylides, a 58

Photocatalysis, degradation, of dichloroacetate anion, a 202of VOCs, a 200

H2O, to H2 222Photoconversion, a 58, 126, 202, 253Photoreduction, Ru(III) ionic solutions, a 252Plating, Ir 186Platinum, additions, NiAl, wetting, of alumina, a 57

coating, AFM probes, a 202colloidal particles, PVP-coated, a 125Cr-Ni-Pt, phase diagram 241Cr-Pt, CALPHAD 241determination, in solution 205doped, TiO2, O2 sensor, a 125electrodes, see Electrodesgauze, Pt nanowire coating, a 57jewellery, manufacture 52nanoparticles 56, 61, 201nanowires, a 57particles, particle size analysis, by TEM 61Periodic Table 114, 247phase diagrams 48Pt(111), Pt(111)(1×1)H, adsorption of N2, a 125Pt-Al-Cr 241Pt-Al-Cr-Ni, phases 241

thermodynamic database 48PtAl12Cr6, PtAl12Cr6Ni5, PtAl12Ni6 48thin films, by OMCVD, a 126

Platinum Alloys, creep 241


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Platinum Alloys, (cont.)Ir-Pt, powder metallurgy 186jewellery, manufacture 52nano-, CoPt, PtAu, Pt3Cr, PtFe, PtNi, PtSn 107Ni-Pt amperometric sensor, for alcohols, a 253NiPtAl, wetting, of alumina, a 57oxide dispersion strengthened, GTH, GTHR, creep 241Pt-Al-Cr-Ru, creep properties, by modelling 241Pt-Ir, Pt-Ni, coating, AFM probes, a 202PtNi, PtZn, nanosized powders, a 126Pt-Rh, creep 241superalloys, Pt base 241thermodynamic database 48

Platinum Complexes, anticancer agents, see Canceranticancer drugs, see Cancercarbazole-based Pt(II)–acetylides, preparation, a 58(cod)Pt(Me)2, for OMCVD, a 126cycloplatinated complexes, synthesis, a 58encapsulated Pt porphyrins, O2 sensors 46EtCpPtMe3, MeCpPtMe3, for OMCVD, a 126fluorene-based Pt(II)–acetylides, preparation, a 58OLEDs 155organometallic polymers 46[Pt]50[MTD]113 complex-block 46Pt(acac)2, decomposition, reduction, a 125Pt(II) dithiooxamides, luminescence, switching, a 58Pt(II) isoquinolinyl indazolates, luminescence, a 58[Pt(Me2bzimpy)Cl](PF6)·DMF, vapochromic, a 202[Pt(NH3)4][Ni(Ox)2(H2O)2]·2H2O, thermal decomp., a 126[Pt(NH3)4][Zn(Ox)2(H2O)2]·2H2O, thermal decomp., a 126Pt porphyrin, luminescence, a 201Pt(II) pyridylphosphines 215[Pt(R2-dto)2], + HCl, photoluminescence; + NH3, a 58Ru2Pt phosphaadamantane 215

Platinum Compounds, anticancer agents, see CancerPtCl2 solution, dip coating, nano SnO2 thick films, a 201Pt(II) salicylate derivatives, biological evaluation,

characterisation, design, lipophilicity,liposomal formulation, synthesis 163

Pt(IV), recovery with chitosan microspheres, a 253Platinum Group Metals, patents 231

Periodic Table 114, 247Polymerisation, by metathesis 71, 124

vinyl-type, norbornene, a 251Polymers, Ir oxide/polyaniline composite films, a 126

organometallic 46PVC, dechlorination, a 56PVP-coated, Pd, Pt, colloidal particles, a 125PVP-protected, Ru particles, a 252transition metal-containing 46

Powder Metallurgy, Ir, Ir alloys 186Propane, combustion 222PVD, Ir 186

RCM, olefins 157Ru carbene catalysts, a 200synthesis, dicyclic compounds 71

macrocyclic compounds 71SB-462795, a 200

using immobilised Ru alkylidenes 71Reactors, membrane, H2 production, a 57

packed bed, Hg oxidation 144Redox Systems, Pt reference electrode 100Reduction, aldehydes, a 200

electrochemical, alkyl bromide, chlorides, iodides 84NO, with CO, a 200

with diesel, a 200with H2 222

temperature-programmed, catalytic materials 249Refining, chemical, Ir 186Refining and Recovery, a 253Reformer, micro-, H2 production 134Reforming, catalysts, metal segregation, a 56

ethylene glycol, EtOH, a 251

Reforming, (cont.)glycerol, a 251n-heptane, a 251hydrocarbons, a 57steam, bioethanol, EtOH 222

MeOH 134using HotSpotTM reactor, hydrocarbons, oxygenates 249

Release Liners, silicone 243Renewables, catalysis 229Rhodium, Periodic Table 114Rhodium Alloys, nano-, CoRh, PdRh 107

Pt-Rh, creep 241Rhodium Complexes, anticancer agents 21

OLEDs 155Rh porphyrinoids, synthesis, dynamic structure, a 202Rh(III) pyridylphosphines 215

ROMP, norbornene, a 251Ru-based NHC-arene systems, a 124using immobilised Ru alkylidenes 71

Ruthenium, Periodic Table 114PVP-protected Ru particles, by photoreduction, a 252Ru nanoparticles/C MWNTs, for supercapacitor, a 253thin films, a 58

Ruthenium Alloys, Pt-Al-Cr-Ru, creep, modelling 241Ru-Ni-Al, ternary B2, a 125

Ruthenium Complexes, anticancer agents, see Cancerdendritic tetranuclear Ru(II) complex, luminescence 46OLEDs 155organometallic polymers 46phosphine-ArgoGel-[Ru5C(CO)15], gas sensors 215phosphine-ArgoGel-[Ru6C(CO)17] 215Ru(II) oximato, preparation, biological activity, a 253Ru(II) pyridylphosphines 215Ru(II)/Au(I) phosphines 215Ru2Pd phosphaadamantane, Ru2Pt phosphaadamantane 215

Ruthenium Compounds, bis(N,N'-di-tert-butyl-acetamidinato)Ru(II) dicarbonyl, deposition, a 58

electrodes, see ElectrodesRuCl3·nH2O, for photoreduction, a 252RuO2 nanoparticles, a 253RuO2-TiO2 mixed oxides, preparation, a 253

Scavengers, polymer-based phosphine resins 215Selective Catalytic Reduction, NOx control 23Self-Metathesis, internal olefins 157Sensors, CH4, a 253

CO 201, 215EtOH, a 253H2, a 57, 201H2S 215human blood cells, a 201LPG, a 201nitrite, a 58O2 46, 125SO2 215

Silicones, Pt-catalysed hydrosilylation; release liners 243Single Crystals, Ir, deformation 241Soldering, Pt jewellery, manufacture 52Solvent Extraction, Ir 186Solvents, in catalysis 83, 110Sonogashira Couplings 38, 64Sponge, Ir 186Sputtering, PdAu nanoparticles 107Stille Couplings 38, 124Styrene, hydroformylation, a 200

oxidation, aerobic, a 56selective, a 124

Sulfidisation, Pd membranes, Pd-Cu membranes, a 58Sulfur Oxides, SO2, sensors 215Superalloys, Pt base 241

Pt-based, thermodynamic database 48Supercapacitors, Ru nanoparticles/C MWNTs, a 253Supercritical Fluids 38, 56Surface Coatings, a 58, 126, 202


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Sustainability, Editorial 132Suzuki Couplings 110, 172, 215Suzuki-Miyaura Couplings 38, 110, 215, 251

TEM, Pt/C catalysts, particle size analysis 61Temperature-Programmed Reduction, catalysts 249Tetrachloroethylene, dechlorination, a 252Thermal Conductivity, Ir3X (X = Hf, Nb, Ta, Ti, V, Zr) 208Thermal Expansion, Ir3X (X = Hf, Nb, Ta, Ti, V, Zr) 208Thermodynamic Database, Pt-based superalloys 48Thermophysical Properties, Ir3X 208Thiazoles, C-5 arylation 110Thin Films, nanostructured, Pt, PtNiFe, PtRu, a 201

Ru, deposition, by atomic layer deposition, by CVD, a 58

Ultrasound, in C–C couplings 38

Vapochromism, [Pt(Me2bzimpy)Cl](PF6)·DMF, a 202VOCs, degradation, a 200

Water, electrochemical disinfection 177solvent 110, 200, 251

Welding, Ir 186Ir alloys 186

Wire, Ir 186

XRD, Pt/C catalysts, crystallite size analysis 129


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Platinum Metals ReviewJohnson Matthey Plc, Precious Metals Marketing, Orchard Road, Royston, Hertfordshire SG8 5HE, U.K.

E-mail: [email protected]://www.platinummetalsreview.com/

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Platinum Metals Review - Johnson Matthey …E-mail: [email protected] Platinum Metals Rev., 2008, 52, (4), 208–214 208 The L1 2 intermetallic compounds based on irid-ium (Ir 3 X)