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Application

catalysis today

Catalysis Today 20 ( 1994) 199-2 18

of Zr02 as a catalyst and a catalyst support

Tsutomu Yamaguchi* Department of Chemrstry, Faculty of Scrence. Ho!&ardo L~mretxty. Sapporo 060, Japan

Abstract

Examples of the application of ZrO, for catalysts and catalyst supports are reviewed. The specificity of the structure and the surface properties including the behavior of surface OH groups are introduced. The catalytic properties of dispersed and promoted ZrO, are presented. The novel application to the photocatalytic total decomposition of water is also presented.

1. Introduction

Zirconium dioxide is an oxide with a high melting point (about 27OO”C), a low thermal conductivity, and a high resistance for corrosion which has been used for refractories, pigments, piezoelectric devices, ceramic condensers, and oxygen sensors. The development of a partially stabilized zirconia with high mechanical strength and high tenacity has opened up a new application field of zirconia in line ceramics.

Attempts have been made to use zirconium dioxide as a catalyst for various reactions both in the form of a single oxide and combined oxides, and important and interesting results have been reported (see ref. [ 1 ] and the other chapters in this issue). Applications as catalyst supports are promising since zirconia has a high thermal stability and both acid and base properties. Although TiOz, which is a second generation as a catalyst support after SiO, and A1203, is reducible under the reduced pressure or the reducing atmosphere, zirconia is stable under those conditions and even under the photo irradiation.

*Correspondmg author. Present address: Department of Applied Chemistry, Faculty of Engineering, Ehime University, Matsuyama 790, Japan.

0920-586 l/94/$07.00 0 1994 Elsevler Science B.V. All rights reserved SSDI 0920-586 1(94)00025-W

200 T Yamaguchl / Catai.vso Today 20 (1994) 199-218

2. Preparation of zirconium compounds

Zirconium compounds are prepared from natural ores, Zircon (ZrSiO,) or Baddeleyite, by an alkali fusion method, a plasma fusion method, or a carbon reduction method. For instance the process of the industrial preparation of zir- conium dioxide by the alkali fusion method is as follows. 1. Fusion of zircon and sodium hydroxide or sodium carbonate; formation of

NazZrSi05

ZrSiO, + 2NaOH (or Na, CO3 ) -Na, ZrSiO, + H2 0 (or CO, )

2. Washing of Na,ZrSi05 and reaction with mineral acid

NazZrSiO, + 4HCl-ZrOClz + 2NaCl+ SiO, + 2H? 0

3. Neutralization of Zr salt with alkali

ZrOCl, + 2NH4 OH- ZrO (OH ) 2 + 2NH4 Cl

4. Calcination

ZrO(OH),-ZrO,

Natural ores usually contain 1 to 3% of Hf. Because of the similarities of the physical and chemical properties of Zr and Hf, the complete separation is diffi- cult. Thus Hf contained in ores is always found in the final Zr products. The main impurities which may be contained in Zr compounds are Si, Na, and Cl. Other impurities may be Al, Fe, Ti, and S. Since the existence of even a small amount of such impurities may strongly modify surface properties, careful examination of the purity levels should be made when necessary.

Contamination of inorganic impurities may be avoided by using zirconium al- koxide as a starting material to prepare the hydroxide or hydrated zirconia, how- ever, an appreciable amount of hydrocarbons can be found in the hydroxide, so attention should be paid to the calcination process.

Partially stabilized zirconia containing Ca or Y is manufactured by: 1. A wet method which consists of coprecipitation of the solutions of a mixture

of zirconium salt and yttrium (or calcium) salt. 2. A thermal method which consists of the calcination of a mixture of ZrO, and

Y203 (or CaO). 3. An electric fusion of ores with Y203 (or CaO).

3. Structure and surface properties

3.1. Structure

Basically three crystalline modifications of zirconium dioxide are known; the monoclinic which is stable up to 12OO”C, the tetragonal which is stable up to 19OO”C, and the cubic which is stable above 1900°C. In addition, above three

T Yamaguchr / Catalysrs Today 20 (1994) 199-218 201

modifications, a metastable tetragonal form is known and is stable up to 650°C. Two interpretations why this tetragonal form can exist even at low temperature have been proposed; an impurity effect [ 2-5 ] and a crystallite size effect [ 6-8 1.

Temperature ranges where the above-mentioned crystal forms are stabilized are varied upon the presence of impurities or additives. Transformation of the metastable tetragonal form to the monoclinic form is sensitive to the existence of impurities or additives and they usually stabilize the metastable tetragonal form to higher temperatures.

Transformation of the metastable form of pure ZrO, is complete at around 650-700°C. Phase transformation between the monoclinic and the tetragonal takes place above 1000°C and since this transformation is accompanied with a volume change, mechanical and thermal stability is not satisfactory for the use of ceramics. The addition of yttria or calcia stabilizes the cubic form and the tetra- gonal form (partially stabilized zirconia; PSZ).

Zirconium dioxides used as catalysts are the metastable tetragonal, the mono- clinic, and the tetragonal. Recently, the use of hydrated zirconium dioxide (zir- conium hydroxide ) for organic syntheses has been reported [ 91.

The surface area is not large compared with SiO, or A1203 which have fre- quently been used as catalyst supports. A typical change in the surface area caused by a change in the calcination temperatures is shown in Fig. 1 as well as a change in the crystal form.

The surface area depends on the calcination temperature, as typically shown in Fig. 1, and starting hydroxides, and is in the range of 40- 100 m’/g when calcined at 600°C. A higher surface area may be obtained by adding a second component or by dispersing it on the high surface area supports. However, these method may modify the surface properties of resultant ZrO? itself.

DTA-TG analysis shows a sharp, exothermic peak at around 420°C without weight change. This has been attributed to the phase change from the amorphous

200 300 600 800 lOi0

Calcination Temp. I “C

Fig. 1. Changes in the surface area and crystal form of Zr02 by calcination temperature.

202 T. Yamaguchr / Catalysu Today 20 (1994) 199-218

0 0.5 I 1.5 2 2.5 3 3.5

G)nc. of 112SOj I mol I- *

-iOO

r’: 0 0.s 1.0 I.5 2.0

Cr content I mm01 g l

Fig. 2. Effect of additives on the temperature of the exothermic peak m DTA. (a) SO:-. (b) Cr Ion.

“()\ /()” “‘Z /()” ‘T /()” ttti/‘~r“‘ot~ i

,Zr %r

\ HO ‘to, //Ott HO,\ ,()I’

/ \

‘,()/ \ 0” ll(/j.j()‘, Zr,

“(y&It (\//o” ‘I’\ / ‘(\ /OH

HO’ ’ ‘y/;; \OH

1 ‘\

\ / tto~~y/r 0”

“0 ’ Zr/

OH

tttf ‘OH ’ ’ ‘otr HO / ’ ‘OH HO

a -type p -type

Fig. 3. Model structures of zirconium polycation.

y -type

phase to the crystallized phase, though an apparent crystallographic change could not be observed by the XRD analysis. The peak position shifts usually to higher temperatures due to the presence of contaminants or additives regardless of an- ions or cations. Examples are shown in Fig. 2 where SO,“- ions and Cr ions were added to the hydroxide.

Zirconium dioxide can be obtained by the calcination of its hydroxide which is prepared by hydrolysis of zirconium salts. The crystal forms of ZrO, depend on how the hydroxide is prepared and treated. Aging for a long period (e.g. 100’ C, 120 h) results in a preferred formation of the monoclinic form after calcination while the tetragonal is dominant when aging is omitted [ lo]. Steaming of the hydroxide results in the formation of the monoclinic form, while a vacuum treat- ment results in the tetragonal form [ 111. The influence of the precipitation con- ditions and the heating program of the hydroxide on the final crystal form of ZrO, is interpreted in terms of the change of the unit structure of the hydroxide,

T. Yamaguchi / Catalym Today 20 (1994) 199-218 203

which was proposed by Murase et al. by taking the original model of Zaitsev [ 12 ] into consideration, and a proposed model is shown in Fig. 3. An a-type of the hydroxide is the major product just after the precipitate is formed by the hydrol- ysis. However, the aging brings about a modification of the structure from an a- type hydroxide to a P-type, and finally a y-type by the loss of OH groups. The CY- type hydroxide is the precursor of the tetragonal ZrOz and the y-type is the monoclinic.

Zirconium hydroxide (or hydrated zirconia) adsorbs both cations and anions in an aqueous solution. In an acidic solution, it adsorbs anions such as SO:- ions, while in a basic solution, cations are preferentially absorbed.

3.2. Surface properties

The surface of the metal oxides exhibit acidic, basic, oxidizing, and/or reduc- ing properties. Most metal oxides show one of the properties stronger than the others at the surface. A characteristic property of ZrO, is that both acidic and basic properties are found on the surface though their strength is rather weak; oxidizing and reducing properties are also found. In solutions, acid and base are neutralized immediately, however, they may exist independently at the surface. Thus acidic and basic sites on the surface of oxides work both independently and cooperatively. In this sense, ZrO, is an acid-base bifunctional oxide. One exam- ple indicating the existence of both properties is evidenced by the adsorption of CO, and NH3 (Fig. 4) [ 13 1. SiO?-AllO adsorbs ammonia, which is a basic mol- ecule, but not COz, which is an acidic one. Thus Si02-A&O3 is a typical solid acid. MgO adsorbs CO2 but not ammonia. Thus MgO behaves as a typical solid base. On the other hand, ZrO, adsorbs both CO* and ammonia and thus pos- sesses both acidic and basic properties. ZrO, is an typical acid-base bifunctional

100 10 )r

SA 4 M60

. co2

b)

.

l * . . .

Temperature I “C

Fig. 4. TPD profiles of NH3 and CO2 on Si02-A1203, MgO and Zr02.

204 T. Yamaguchl / Catalps Today 20 (1994) 199-218

oxide. Part of the ammonia and the CO2 interact with each other via through- bond interaction [ 13 1.

The numbers of acid sites and basic sites have been measured as the amount of irreversibly adsorbed ammonia and COz, respectively. ZrO? calcined at 600°C exhibits 0.6 pmol/m’ of acidic sites and 4 pmol/m’ of basic sites. Infrared spec- troscopic studies of adsorbed pyridine revealed the presence of Lewis type acid sites, but not protonic (Bronsted acid) sites [ 141.

3.3. Surface OH groups

SOO”C-evacuated ZrO, exhibits two types of OH groups. They appear at 3780 and 3680 cm-’ [ 15-l 71. The latter appears after the low temperature evacuation and the former is observed by increasing the evacuation temperature. 3780 and 3680 cm-’ bands have been assigned to the terminal and bridged OH groups, respectively [ 171.

A detailed IR study on the adsorption of H2 on ZrO, is investigated by Domen et al. [ 18-201. They found four types of adsorbed species: 1. Molecularly adsorbed hydrogen appeared at 4029 cm-’ which is observed be-

low 173 K and disappears during the evacuation. 2. Zr < E species ( 1540 cm-’ ) produced by homolytic dissociative adsorption

which is observed below 373 K and is stable below 178 K. 3. ZrH ( 1560 cm-’ ) and ZrOH (3668 cm- ’ ) which are produced by heterolytic

dissociative adsorption and are observed at 223-373 K. 4. Two OH groups (3772 and 3668 cm-‘) which are stable above room

temperature. ZrOz catalyzes the CO hydrogenation [ 2 l-27 ] and the hydrogenation of ok-

fins [ 28,291 and dienes [ 30-33 1. He and Eckerdt investigated IR spectroscopi- cally the adsorptions and the interactions of OH groups with CO, CO,, H7. HCOOH and CH30H [ 221 and found the formation of carbonate, bicarbonate. formate, and methoxide species. They pointed out that surface OH groups were involved in the formation of formate and methoxide species. The carbonates or the bicarbonate species were formed by the interaction of CO- with terminal OH groups and the formate was produced with bridged OH groups. The details of the mechanism of the hydrogenation of ethylene is also discussed by Domen et al. ~291.

4. Application to catalyst and catalyst support

4.1. Single oxide

Table 1 summarizes examples of ZrO, being used as catalysts as a single com- ponent. Typical reactions such as the synthesis of cu-olefins from alcohols, for- mation of 1 -butene from 2-butanamine, acetonitrile from triethylamine, allyl-al- cohol from epoxide, ketone synthesis, reductions of aldehydes, carboxylic acids,

Table 1

T Yarnaguchr / Catal.vsls Today 20 (1994) 199-218 205

Application of ZrOz for catalytic reactions as a single component

Reaction Reactant Ref. No.

Orrglnal paper Alkylation Amination Ammoxidation Cracking Cyclization Deamination Dehydration Dehydrogenation HC synthesis Hydrocrackmg hydrogenation Hydrolysis Isomerizatron Oxidation Polymerization

Patent Alkylation .Amination Ammoxidation Condensation Cracking Cyclization Deacetylation Dehydration Dehydrogenation Esterification Etherilication Hydration Hydrogenation Isomerization Oxidation

o-Cresol Phenol Methylamsole Ethylbenzene Hydrazones Butanamine Alcohols Alcohols co Coal CO, benzene, butadiene Et, Me acetate Alkene. epoxy CO, NH, Lactams

Aromatic compounds [491 Aliph. aldehydes [501 Alkenes 1511 Aldehydes, carboxyhc acids 1521 Gas 011 [531 Ethanol amme [541 Acetylcaprolactum [551 Hydroxy(methyl)propanamide [561 Ale.. alk., ethylbenzene 1571 Dibasic acids [581 Phenol derivatives 1591 Alkenes 1601 Caprolactum. adiponitrile Lb11 Alkenes [621 Alkane. alkene 1631

341 351 361 371 381 391 401 411 421

431 [441 1451 1461 1471 (481

and esters with alcohols, esteritication and ester exchange, amination and acetal- ization, hydrogenation of olefins and dienes by HI! and cyclohexadiene, hydro- genation of carbon dioxide, and hydrogenation of aromatic carboxylic acids to the corresponding aldehydes have been introduced [ 11.

Only one example is presented here. One characteristic catalytic property of ZrOz is selective dehydration. This properties is successfully applied to the selec- tive dehydration of I-amino-2-propanol to form allylamine by Koei Chemicals

[641.

Hz N-CH2 -CH2-CH3 -+ H2 N-CH? -CH=CH? + H7 0

OH

206 T. Yatnaguchr / Catalws Today 20 (1994) 199-215

Table 2 Reaction of 1-ammo-2-propanol over various catalystsa

Catalyst Reaction condltlon Conv. (%) Select. (% )

Reactlon temp. (‘C)

Space velocity hk’

ZrOz 400 2000 98 64 Y*O, 430 1900 67 52 La203 400 1800 80 54 CeO, 400 3200 21 59 TiOz 400 600 48 15 41203 410 1800 58 12 ZrOz+LizO 400 2000 91 75 ZrOz + NazO 400 1800 92 74 ZrOz + KS0 400 1800 98 82 ZrOz + RbzO 400 1800 95 79 ZrOz+ MgO 400 1800 94 79 ZrOz+CaO 400 1800 99 74 ZrOz+TI,O 400 1800 95 72

Allylamine can be synthesized from allylchloride, acrylonitrile, or allylalcohol, but the above process is more attractive. The result is shown in Table 2.

4.2. Dispersed and promoted oxide and support

Table 3 also summarizes the use of ZrOz as mixed oxides including promoted ZrOz, and as a support for various reactions.

4.2. I. Dispersed ZrOz Since the surface area of ZrO, is not large, attempts have been carried out to

obtain large surface area ZrO, by utilizing various preparation methods or by adding second components.

Attempts were also performed by dispersing the oxide to large surface area sup- ports as in the case of dispersing metals. The dispersion of metal oxides may have two objectives. One is to obtain a large exposed surface area of active components and the other is to control the orientation of exposed surfaces such as ( 1 1 1 ), (110) andsoon.

Niemantsverdriet and co-workers [ 891 prepared SiO?-supported ZrO? by the reaction of zirconium ethoxide with a SiOz surface using CH,OOH/EtOH as a solvent, followed by calcination. The good dispersion of thus obtained ZrO, was confirmed by SIMS, IR, TPO, and XPS. When a traditional impregnation method was applied by using zirconyl nitrate as a starting material, poorly dispersed ZrO, was obtained.

Dispersed ZrO, on SiO? was also prepared by using zirconyl nitrate or zirco- nium isopropoxide as a starting material where water, methanol, or toluene was used as a solvent and the acid and base properties of the resultant Zr0,/Si02 were evaluated by temperature-programmed desorption (TPD) of CO, and NH3

Table 3

T Yamaguchr / Catalysis Today 20 (I 994) 199-218 201

Application of ZrO, for catalytic reactions as mixed oxide and support

Reaction Reactant Ref. No.

As axed oxide Acylation Alkylation Ammation Ammoxidation Cracking Dehydration FT synthesis HC conversion qy synthesis Hydropolymerization Isomerization MeOH synthesis Oxtdation Reforming

As support Dehydrogenation Homologation Hydrocracking Hydrogenation Metathesis Methanation Oxidation Polymerization Reduction Reformmg (steam)

( Friedel-Crafts ) Benzene with propene Pyridine Toluene Gas oils Alcohols

CO, syn gas Alkene Alkane, alkene, xylenes

Isobutyric acid Alkene Diphenylmethane CO, COz, alkene Alkene co Alcohol, alkene, toluene Ethylene NO, with Hz, NH3

Lb51 1661 Lb71 1681 [691 1701 [711 1721 [731 [741 [751 1761 [771 [781

[791 [gOI [811 [=I [831 [841 [851 [861 1871 [881

[ 901. ZrO? possesses both acidic and basic properties. However, when this was dispersed on SiOz, the basic properties were selectively lost though the acidic properties were conserved.

The surface electronic structure of ZrOJSiOz was studied by means of XPS and the decrete variational (DV) X, cluster model calculation [ 9 11. The results showed that when ZrO, was dispersed on the SiOz surface, the Si-0 bond of Si04, neighboring ZrO,, became stronger and that the Bronsted acid site H which was located on the SiOj unit exhibited stronger acidity.

Below 10 wt.-% loading, the structure of dispersed ZrO, was found to be amor- phous. However, the tetragonal form of ZrO? was developed by the increase in ZrO, loaded [ 92 1. This means that the transformation of the metastable tetra- gonal form to the monoclinic form was retarded by the dispersion. Although a strong anisotropic crystal growth was found when a thin film of ZrOz was pre- pared by the CVD method from Zr (acac) on the surfaces of Si and a glass plate [ 93 1, no such anisotropy was observed in ZrO,/SiOz [ 921. XAFS analysis re- vealed the existence of a precursor of tetragonal form, with an imperfect struc-

208 T. Yamaguchl / Catalws Today 20 (I 994) 199-218

ture, at low loading, growing to a perfect tetragonal structure when the amount of loading was increased [ 92 1.

Zr02 was deposited on an oxidized surface of Si ( 100) from Zr ethoxide [ 941. Since a charge-up phenomena can be avoided in these type of samples, an excel- lent, well-resolved XPS spectrum was obtained.

4.2.2. Promotes ZrUz Acid and base properties of ZrC& can be modified by the addition of cationic

or anionic substances. Acidic properties may be suppressed by the addition of alkali cations whereas they may be promoted by the addition of anions such as halogen ions. The suppression of acidic properties improves the selectivity in the dehydration of alcohols and propanolamine.

A typical and drastic improvement of acidic properties [ 951 can be seen by the addition of sulfate ions to produce the solid superacid. This type of solid super- acid was employed to catalyze the skeletal isomerization of alkanes, the Friedel- Crafts acylation and alkylation, and many other reactions. One disadvantage of the catalyst is its relatively quick deactivation which is typically seen in the skel- etal isomerization. The deactivation may originate from the removal of sulfur, reduction of sulfur and the formation of carbonaceous polymers. This may be overcome by the addition of platinum and by using hydrogen as an atmosphere [ 96,971. More investigations are necessary to improve catalytic stabilities.

Details on the use of sulfated ZrO, as a superacid may be found in the literature [98-1001.

4.2.3. sup,nort Although the surface area of ZrO, is not large, it is stable under oxidizing and

reducing atmospheres and possesses both acid and base properties. Thus the use of ZrO, as a support may be promising. An addition of a second component brings about the formation of new compounds or solid solutions as in the case of Al,03. However, ZrOz does not form such compounds, as is typically seen in CrO,fZrO? and Cr203-Zr02 which has been pointed by Wu et al. [ 1011. The reaction of alkoxysilane with the surface of TiOz resulted in the formation of a surface sub- layer of mixed oxide, whereas a Si02 thin film about 1 nm thick forms on ZrO? without the formation of a mixed oxide [ 102 1.

Hence unique catalytic activities and/or selectivities can be obtained by using proper combination of metals or metal oxides with Zr02. One example is the supported perovskite (La-Sr-Co-O ) catalyst for the propane oxidation [ 103 1. AllO and SiOz, both of which are known as high surface area supports, were not effective, while the dispersion of perovskite on ZrO, was found to be quite effec- tive, catalytic activity being enhanced 10 times higher than that of the original perovskite. ZrOz was also found to be an superior support for Re and Rh in the hydrogenation of CO? [ 104- 106 1.

As can be seen in a following example, ZrO, can be used as the additive for supported metal catalysts. When ZrO, was dispersed on a SiO? support and the

T Yamaguchl / Catalym Today 20 (1994) 199-218 209

Table 4 CO/H2 and C02/HZ reaction over ZrO,-supported catalysts

Component Reactant Reaction Ref. No.

CU Cu (ammine complex) CU Rh Rh Rh (Rh4(C0),20rRhCl,) Rh Rh (Rh cluster) Re Nl Ni NI. Co-N1 Cu/La2Zr,0, Cu,Zr, Cu-Zr alloy 4uz5Zr7, alloy Rhzs-, Pdz5-, Ok-, Ir,,-, Ptz5-ZrTS Ni6,ZrX3 alloy Pdj5Zr,, alloy

CO/Hz, CWHz MeOH +H20

COJH2 CO/Hz. COz/Hz CO/Hz. CO/HI CO/H? CO/H2 CO/Hz COJHZ CO/Hz CO/H,

CO/H2 COJHZ COJHz CO/H2 CO/HZ

CO/HZ CO/H2

MeOH synthesis Steam reforming MeOH synthesis Hydrocarbon Hydrocarbon

MeOH synthesis Methanatton Methanation

MeOH synthesis

Methanation Methanatton

Methanation Methanation

[ 108,109]

[1101 [1111 [112]

11131 11141 [1151 11161 11171 [1181 [I191 [ 1201 11211 [ 122.1231 11241 11251

[I261 ~1271

resultant combined support was used to anchor a Rh carbonyl cluster, selectivity for the formation of alcohol in the CO/H, reaction was markedly enhanced [ 107 1.

ZrO,-supported metals and/or metal catalysts with better dispersion can be obtained by the oxidative decomposition of amorphous alloys such as Cu,Zr,.

Examples of ZrO?-supported catalysts for CO/H2 and COJH2 reactions are summarized in Table 4.

Two examples are shown below:

4.2.3.1. Supported chromium oxide. Tan-no and co-workers have investigated [ 128,129 ] the structure and morphology of supported chromium oxide by using XRD and EPR and concluded that a two dimensional octahedral or square py- ramidal chromium oxide species was developed over ZrOz and this grew to -Cr203 by increasing the amount of chromium oxide loaded, while a three di- mensional tetrahedral species was obtained as crystallites even at low loading on SiO,. Surface properties of CrO,/SiO1, CrO,/ZrOz, and CrO,/Al,O~ were ex- amined by IR and TPD of adsorbed NO, CO, NzO, and 02, and by catalytic reactions of CO-O?, CO-NO, and CO-N,0 [ 130 1. The catalytic activity of CrO,/ ZrO, (0.5 mmol Cr/g ZrO,) was the highest of the three catalysts for all the reactions as shown in Fig. 5.

Extensive work on supported chromium oxide have also been reported by Cim- ino et al. [ 13 1 1, Indovina et al. [ 132 1, and Ghiotti et al. [ 133 1.

210 T. Yamaguchl / Catalps Today 20 (I 994) 199-218

Fig. 5. Catalytic activities of chromium oxide supported on !30z, ZrOz, and A1203 for CO oxldatlon.

Since ZrO, is transparent to an IR beam down to 800 cm-l, the structure and the reactivity of oxo-species can be examined. Cr=O species which show absorp- tions around 1000 cm-’ can be removed by 200°C reduction and are recovered by contact with 02, NO, and NzO below 200°C [ 1341.

4.2.3.2. Supported copper oxide. The methanol synthesis from CO2 and H, was examined under 50 atm using binary or ternary copper catalysts and the highest yield was obtained over a Cu/ZrOl catalyst [ 135 1.

Methanol synthesis from CO, or CO with H2 was investigated under I, 10, and 26 atm by using supported copper catalysts [ 136,137]. A high methanol yield from CO/H, was obtained over MgO-, La203-, and Sm,O,-supported catalysts, though the C02/H2 reaction did not take place over these catalysts. The reactiv- ity of the two reactions was reversed over A1103- and ZnO-supported catalysts. Cu/ZrO* catalyzed both reactions and gave a high methanol yield.

Takezawa et al. have reported that Cu/ZrO, which was prepared from a copper ammine complex exhibited a high activity and selectivity for the steam reforming of methanol [ 138 1. Highly dispersed precursor species of copper compounds are readily reduced on ZrO, to form Cu crystallite. On a ZrO, support calcined at 700’ C, bulky CuO was obtained above 3OO”C, whereas on ZrOz calcined at 300 o C it was obtained above 700 ’ C [ 139 1.

4.2.4. Photocatalytic decomposition of water Photocatalytic decomposition of water consists for the most part in photosyn-

thesis and the artificial reconstruction of the photosynthesis is being explored in both fundamental and applied research. The production of hydrogen from water may become very important in the near future when considering the expected shortage of petroleum which is now an important source of hydrogen. The pho- tocatalytic total decomposition of water ( 2H,0+2H2+02) should be a quite interesting target.

The photocatalytic total decomposition of Hz0 was discovered by Sato and White using Pt/TiO? in a liquid phase [ 1401 and by Kawai and Sakata using

T Yamagucht /Catalysts Today 20 (1994) 199-1718 211

RuOJTiOz in a gas phase [ 14 11, both in 1980. Since then numerous attempts have been made. Recently, high activities of a series of A4Nb6017 (A=K, Rb) compounds and a layered perovskite family doped with Pt or Ni [ 142-1441 as well as Wadsley-Anderson type and pentagonal prism type metal oxides with a tunnel structure combined with RuO, have been reported [ 145 147 1. Very re- cently, Sayama et al. found a pronounced activity of ZrOz for the photocatalytic total decomposition of water under UV irradiation [ 148- 150 1. This is an inter- esting finding, since a combination with metals is necessary to improve the pho- tocatalytic activity of metal oxide semiconductors to constitute photochemical diodes. However, in the case of ZrO, the assistance of such metals is not neces- sary to promote the reaction. The addition of metals tends to retard the reaction. Thus a novel type of reaction mechanism may be operating on ZrOz and this will encourage us to develop a new type of photocatalyst.

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