Journal of Chemical Sciences[Formerly: Proceedings (Chemical Sciences)] Vol. 126, No. 2, March 2014

CONTENTSSpecial issue on Catalysis for Sustainable DevelopmentForeword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309

Concept and progress in coupling of dehydrogenationand hydrogenation reactions through catalysts

C V Pramod, C Raghavendra, K Hari Prasad Reddy,G V Ramesh Babu, K S Rama Raoand B David Raju . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311–317

Coupling of dehydrogenation and hydrogenation reactions are advantageousnot only in eliminating the use of external hydrogen but also helps inmaintaining good thermal balance between the two reactions apart from savingtime and catalyst material.

Pd(OAc)2/DPPF-catalysed microwave-assisted cyanide-freesynthesis of aryl nitriles

Dinesh N Sawant and Bhalchandra M Bhanage . . . . . . . . . 319–324

This study reports microwave-assisted, cyanide-free synthesis of aryl nitriles fromaryl halides using palladium acetate/1,1-bis(diphenylphosphino)ferrocene, a newcatalyst system. Reported protocol is rapid, cyanide-free, solvent-free singlestep-reaction, wherein formamide acts as a solvent as well as a source of cyanide.

DIFLUORPHOS and SYNPHOS in asymmetric catalysis:Synthetic applications

Sebastien Prevost, Tahar Ayad, Jean-Pierre Genet,Phannarath Phansavath andVirginie Ratovelomanana-Vidal . . . . . . . . . . . . . . . . . . . . 325–340

Enantiomerically pure diphosphines play an important role in varioushomogeneous metal-catalysed asymmetric reactions. This study shows the highcatalytic performances of atropisomeric ligands DIFLUORPHOS, SYNPHOS andSYNPHOS analogues for some C-H and C-C bond-forming processes as well asfor the synthesis of bio-relevant targets.

Engineering reactors for catalytic reactions

Vivek V Ranade. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341–351

Catalytic reactions are ubiquitous in chemical and allied industries. Someaspects of engineering of catalytic reactors (which include evolving bestpossible hardware and operating protocol for transformation of raw materialsinto value added products) are discussed here along with some real lifeexamples of performance enhancement.

Development of new deactivation method for simulation of fluidcatalytic cracking equilibrium catalyst

T Chiranjeevi, D T Gokak, V Ravikumarand P S Viswanathan . . . . . . . . . . . . . . . . . . . . . . . . . . . 353–360

New deactivation method is developed for the simulation of fluid catalytic crackingequilibrium catalyst in laboratory. New deactivation method significantly reducescatalyst evaluation and selection time and is more cost-effective.

303

SEM image of Plant E-Cat SEM image of simulated E-Cat

Novel nanostructured CeO2 as efficient catalyst for energyand environmental applications

Sumanta Kumar Meher and G Ranga Rao . . . . . . . . . . . . . 361–372

CeO2 with engineered microstructure promotes CO oxidation, soot oxidationand alcohol electro-oxidation for energy and environmental applications.

Value addition to lignocellulosics and biomass-derived sugars:An insight into solid acid-based catalytic methods

Prasenjit Bhaumik, A K Deepa, Tanushree Kaneand Paresh Laxmikant Dhepe. . . . . . . . . . . . . . . . . . . . . . 373–385

Efficient methods for the synthesis of xylose+arabinose, furfural, HMF andaromatic monomers from hemicellulose, fructose and lignin, respectively, usingsolid catalysts were described. Catalysts were characterized with variousphysico-chemical techniques.

Effective utilization of glycerol for the synthesis of 2-methylpyrazineover ZnO-ZnCr2O4 catalyst

AVenugopal, R Sarkari, S Naveen Kumar, M Kotesh Kumar,S Syed John, J Krishna Reddy and A Hari Padmasri . . . . . 387–393

Dehydrocyclization of glycerol and ethylenediamine proceeded through a cyclictransition of 2-pyrazinylmethanol to produce 2-methylpyrazine.

Enhancement of reaction rates for catalytic benzaldehydehydrogenation and sorbitol dehydration in water solventby addition of carbon dioxide

Masayuki Shirai, Osamu Sato, Norihito Hiyoshiand Aritomo Yamaguchi . . . . . . . . . . . . . . . . . . . . . . . . . 395–401

Addition of carbon dioxide enhanced the reaction rates of heterogeneousbenzaldehyde hydrogenation over Pd/C and homogeneous sorbitol dehydrationin aqueous phase.

Novel catalysts for valorization of biomass to value-addedchemicals and fuels

Nishita Lucas, Narasimha Rao Kanna, Atul S Nagpure,Ganesh Kokate and Satyanarayana Chilukuri . . . . . . . . . . . 403–413

Biomass valorization to get platform chemicals and fuels such as HMF, FDCAand DMF is discussed. Solid acids were explored to get HMF from fructosewhile oxidation and hydrogenolysis of HMF were explored on a novel catalyst2wt%Ru-K-OMS-2.

Role of catalysis in sustainable production of synthetic elastomers

Vivek K Srivastava, Madhuchhanda Maiti, Ganesh C Basakand Raksh V Jasra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415–427

Development fromTitanium- to latest Neodymium-based Z–N commercial catalystis a strong evidence of promising future of catalysis in synthetic elastomer business.The research is mainly focused on development of novel single-site metalloceneand allyl-derivatives based catalysts to obtain high molecular weight polymers withprecise control upon chemo- and stereo-selectivity.

304 Contents

Facile synthesis of catalytically active CeO2–Gd2O3 solid solutionsfor soot oxidation

D Naga Durgasri, T Vinodkumarand Benjaram M Reddy . . . . . . . . . . . . . . . . . . . . . . . . . 429–435

Incorporation of gadolinium cations into the ceria matrix favoured the creationof more structural defects, which accelerated the oxidation rate of soot.

Effect of method of preparation on hydrodesulphurization activityof Co- or Ni-promoted MoS2/SBA-15 catalysts

Shelu Garg, Kapil Soni, V V D N Prasad, Manoj Kumar,Thallada Bhaskar, J K Gupta, G Murali Dharand C S Gopinath. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437–444

The ordered mesoporous material SBA-15 prepared using triblock polymer isused to prepare Mo, CoMo, and NiMo catalysts by PFHS technique. Acomparison with γ-Al2O3-supported catalysts indicated that this support andpreparation method combination increases the activities by about three times.

Characterization and reactivity of 11-molybdo-1-vanadophosphoricacid catalyst supported on zirconia for dehydration of glycerolto acrolein

Balaga Viswanadham, Amirineni Srikanthand Komandur V R Chary. . . . . . . . . . . . . . . . . . . . . . . . 445–454

Zirconia-supported H4PMo11VO40 catalysts have been investigated in thevapour dehydration of glycerol to acrolein. The catalysts are highly active andselective during dehydration of glycerol under mild reaction conditions. Thehigh selectivity of acrolein is attributed to the presence of Brønsted acidic sitesin the catalysts.

Cs salt of tungstophosphoric acid-promoted zirconium titaniumphosphate solid acid catalyst: An active catalyst for the synthesisof bisphenols

Niranjan Biswal, Dipti Prakasini Dasand Kulamani Parida . . . . . . . . . . . . . . . . . . . . . . . . . . . 455–465

60CsTPA-ZTP is an efficient catalyst for the condensation of 8 mmol phenoland 1 mmol acetone/formaldehyde at relatively low temperature (70-C) in 7 hto give the highest conversion of 61.73% and 71.20% with selectivity of 85%and 88.35% towards Bisphenol A/Bisphenol F, respectively.

Role of vanadium in Keggin heteropoly molybdate supportedon titania catalysts for oxidation reactions

A Srivani, K T Venkateswara Rao, P S Sai Prasadand N Lingaiah . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467–472

An efficient synthesis of phthalide was achieved over vanadium incorporatedmolybdophosporic acid supported on titania catalysts. The oxidation ability ofthe catalyst depends on the number of V atoms in the Kegginmolybdophosporic acid.

Contents 305

600 700 800 900 1000

0

20

40

60

80

100

87474

5

n (

%)

oisrevnoctoo sdezila

m roN

Temperature (K)

CG 773 CG 1073 C 773 Uncatalysed

OH

2 +

CH3

CH3

OHHOH3C

O

CH3

p, p' - Bisphenol A

Or

CH3

CH3

OH

OH

o, p' - Bisphenol A

CsTPA-ZTP

70 oC,7 h

OH

2 + H

O

HHO OH

+ H2O

Bisphenol F

Anomalous hydrocracking of triglycerides overCoMo-catalyst–influence of reaction intermediates

M Anand, M G Sibi, D Vermaand A K Sinha. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473–480

Undesired C-C coupling reactions such as aldol condensation, and ketonizationtaking place over CoMo/Al2O3 lead to competitive reactions which decreaseselectivity of desired product and reduce catalyst life.

CO2 hydrogenation to hydrocarbons over iron nanoparticlessupported on oxygen-functionalized carbon nanotubes

Ly May Chew, Holger Ruland, Hendrik J Schulte, Wei Xiaand Martin Muhler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481–486

CO2 hydrogenation to short chain hydrocarbons was achieved using ironnanoparticles supported on oxygen-functionalized carbon nanotubes. Theconversion of CO2 was found to be limited by the reverse water gas shiftequilibrium in the temperature range from 320° to 420°C.

Ammoxidation of 2-methyl pyrazine on supported ammoniumsalt of 12-molybdophosphoric acid catalysts: The influenceof nature of support

Katabathini Narasimharao, B Hari Babu, N Lingaiah, P S Sai Prasad,and Shaeel A Al-Thabaiti . . . . . . . . . . . . . . . . . . . . . . . . 487–498

Ammonium salt of 12-molybdophosphoric acid (AMPA) supported on niobia,silica and alumina was studied for the ammoxidation of 2-methylpyrazine to2-cyanopyrazine. The Keggin ion existed as five different species on thesupports. The interacted and/or the lacunary species were proposed to be theactive sites for the ammoxidation.

Solid, double-metal cyanide catalysts for synthesisof hyperbranched polyesters and aliphatic polycarbonates

Joby Sebastian and Srinivas Darbha . . . . . . . . . . . . . . . . . 499–509

Influence of method of preparation on physicochemical and catalytic propertiesof Fe-Zn and Co-Zn DMC complexes in the preparation of hyperbranchedpolyesters and polycarbonates using renewable feedstock is investigated.

Determination of conduction and valence band electronic structureof anatase and rutile TiO2

Jakub Szlachetko, Katarzyna Michalow-Mauke, Maarten Nachtegaaland Jacinto Sá . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511–515

The resonant X-ray emission spectroscopy around Ti k-edge was applied toprobe local electronic structure of TiO2 rutile and anatase. By measuring1s→3d excitation and 3p→1s decay channel, differences between localized anddelocalized orbitals were determined. The 3d pre-edge structures werecompared with ab initio multiple scattering simulations.

A. ALDOL Condensation

Aldol Condensation

B. Ketonization Reaction

CO2 H2O++

C. Cracking Reactions

Cracking

306 Contents

Synthesis and visible light photocatalytic activity of nanocrystallinePrFeO3 perovskite for hydrogen generation in ethanol–watersystem

S N Tijare, S Bakardjieva, J Subrt, M V Joshi, S S Rayalu,S Hishita and Nitin Labhsetwar . . . . . . . . . . . . . . . . . . . . 517–525

PrFeO3–type perovskite was synthesized by sol–gel, template and combustionmethods. PrFeO3 synthesized by sol–gel method consists of crystallite size ofabout 20 nm with absorption maxima at 595 nm wavelength in visible light range.This photocatalyst shows hydrogen generation of about 2847 µmol.g-1.h-1, undervisible light irradiation in ethanol-water system, and follows semiconductor typemechanism with alcohol acting as sacrificial donor.

Metal organic framework MIL-101(Cr) for dehydration reactions

M Suresh, B David Raju, K S Rama Rao, K Raveendranath Reddy,M Lakshmi Kantam and Pavuluri Srinivasu . . . . . . . . . . . . 527–532

Dehydration of 1-phenyl ethanol and 1,4-butanediol has been carried out overCr-MIL-101 catalyst in vapour phase in the temperature range of 498–533K atatmospheric pressure, which shows highest conversion and selectivity ofstyrene and tetrahydrofuran respectively, due to availability of co-ordinatedunsatured sites and uniform distribution of pores of the catalyst.

Contents 307

Indexed in CURRENT CONTENTS ISSN 0974-3626

Edited and published by R Ramaswamy for the Indian Academy of Sciences, Bangalore 560 080.Printed at Printek Printers, Bangalore 560 079.

Cover picture: Coupling of catalytic reactions. For details, see the paper by C VPramod et al. (pp. 311–317).

HOOH

1,4 - Butane diol O

Tetrahydrofuran

OH

1-Phenyl ethanolStyrene

Cr–MIL-101

513 –533 K

498 –523 K