Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

Special issue on Catalysis for Efficient Production of Chemicals

 

 

VOLUME 53A

NUMBER 4-5

APRIL-MAY 2014

CONTENTS

 

459

 

Characterization and reactivity of Pd supported on ZnAl2O4 catalysts for direct coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yengaldas Harikrishna, Vanama Pavan Kumar, Komandur V R Chary & Vattikonda Venkat Rao*

 

 

 

Direct coupling of dehydrogenation of ethylbenzene with hydrogenation of nitrobenzene over ZnAl2O4 supported palladium catalysts is slightly exothermic and also surpasses thermodynamic constraints. The ZnAl2O4 supported Pd catalyst with palladium loading of 0.5 wt% exhibits good coupling performance to give high ethylbenzene conversion (52.3%) and styrene selectivity (88.3%) at 823 K.

 

 

 

 

467

 

Partial oxidation of methane to synthesis gas over
Ni-supported ceria catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rajib Kumar Singha, Astha Shukla, Shubhadeep Adak, Chandrashekar Pendem, Sandeep Saran & Rajaram Bal*

 

 

 

 

 

 

472

 

In2O3/TiO2 nano photocatalysts for solar hydrogen production from methanol:water mixtures

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

K Lalitha, V Durga Kumari* & M Subrahmanyam

 

 

 

 

478

 

Methane reforming with carbon dioxide over
La-Nix-Ce1-x mixed oxide catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

T V Sagar, N Sreelatha, G Hanmant, K Upendar,
N Lingaiah, Kamaraju Seetha Rama Rao,
C V V Satyanarayana, I A K Reddy & P S Sai Prasad
*

 

 

 

 

 

 

 

484

 

Catalytic oxidation of CO in presence of ozone over supported palladium catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Keshav Soni*, S Chandra Shekar, Beer Singh & Anidha Agrawal

 

 

 

 

 

 

493

 

Molybdenum oxide supported on COK-12: A novel catalyst for oxidative dehydrogenation of ethylbenzene using CO2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ramudu Pochamoni, Anand Narani,
Venkata Ramesh Babu Gurram,
Murali Dhar Gudimella, P S Sai Prasad,
David Raju Burri & Kamaraju Seetha Rama Rao
*

 

 

 

Oxidative dehydrogenation of ethylbenzene to styrene using CO2 as a soft oxidant has been studied over molybdenum oxide supported on COK-12. The reaction is highly selective for
styrene as a product and shows maximum activity over
14wt% MoO3/COK-12.

 

 

 

 

499

 

Mineralization of aqueous organic pollutants using a catalytic plasma reactor

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Manoj Kumar Reddy, Sk Mahammadunnisa &
Ch Subrahmanyam
*

 

 

 

Plasma reactor has been utilized for the degradation and mineralization of a model aqueous organic pollutant, viz.,
methyl orange. Both degradation efficiency and mineralization of the dye increase as a function of time.

 

 

 

 

 

 

504

 

Effective oxidative decolourization of azo dyes over Indian Ocean manganese nodules

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A K Sahoo, K M Parida* & P K Satapathy

 

 

 

Manganese nodules show promising results for dye decolourization (100%) within a short time period. The decolourization is enhanced in the presence of NO3 and SO4.

 

 

 

511

 

Selective CO oxidation over Fe5(PO4)3(OH)5 supported Pt catalyst: Kinetic and mechanistic studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A Hari Padmasri*, P Anil Kumar, S Naveen Kumar, A Venugopal & Sooboo Singh

 

 

 

Pt supported on Fe5(PO4)3(OH)5 sample is found active for water gas shift at low reaction temperatures and is suitable for reverse water gas shift at high reaction temperatures.

 

 

 

516

 

Characterization and reactivity of TiO2 supported nano ruthenium catalysts for vapour phase hydrogenolysis of glycerol

 

 

 

 

 

 

 

 

 

 

 

 

 

Vanama Pavan Kumar, Yengaldas Harikrishna, Nekkala Nagaraju & Komandur V R Chary*

 

 

 

Ruthenium on titania catalysts prepared by deposition-precipitation method shows better conversion/selectivities during vapour phase hydrogenolysis of glycerol at moderate temperature and atmospheric pressure. The higher activity of Ru/TiO2 catalyst is attributed to the presence of well-dispersed nanosized Ru particles on anatase titania.

 

 

 

524

 

Selective etherification of glycerol with tert-butanol over 12-tungstophosphoric acid catalysts supported on Y-zeolite

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Srinivas, Rekha Sree, G Raveendra,
Ch Ramesh Kumar, P S Sai Prasad & N Lingaiah
*

 

 

 

 

 

530

 

Catalytic tri-reforming of glycerol for hydrogen generation

 

 

 

 

 

 

 

 

 

 

 

M Ashwani Kumar, Ch Venumadhav, T V Sagar,
M Surendar, N Lingaiah, G Nageswara Rao &
P S Sai Prasad
*

 

 

 

 

 

535

 

Preparation and structural investigations of new hexadentate Schiff base ligands and their bivalent metal complexes, and, catalytic applications of the complexes in allylic and benzylic CH bond activation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Jyothi, G Raghava Rao, K Shashank, K Sridhar, Anjali Reddy, P Someshwar & S Jagannatha Swamy*

 

 

 

Co(II), Ni(II) and Cu(II) complexes of two new Schiff base ligands have been prepared and characterized. These complexes catalyze the allylic and benzylic group oxidation reactions with (CH) bond activation.

 

 

 

545

 

Triflamide anchored SBA-15 catalyst for nitration of alkyl aromatics in microwave

 

 

 

 

 

 

 

 

 

 

 

Venkata Siva Prasad Ganjala, Suresh Mutyala, Chinna Krishna Prasad Neeli, Mukkanti Khagga*, Kamaraju Seetha Rama Rao & David Raju Burri*

 

 

 

 

 

550

 

Vapour phase hydrogenation of nitrobenzene over metal (Ru, Ni, Pt, Pd) supported on Ca5(PO4)3(OH) catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Sudhakar, M Lakshmi Kantam*, R Kishore,
S Naveen Kumar & A Venugopal
*

 

 

 

Hydroxyapatite is identified as a good support for palladium in the hydrogenation of nitrobenzene to aniline.

 

 

 

553

 

Gas phase dehydrogenation of n-butanol to butyraldehyde on magnesia supported copper catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

Yadagiri Jyothi, Venkateswarlu Vakati,
Tirumalasetty Satyanarayana &
Puppala Veerasomaiah
*

 

 

 

Gas phase hydrogenation of n-butanol to butyraldehyde has been carried out at atmospheric pressure on magnesia supported copper catalysts. Amongst the Cu/MgO catalysts with varying Cu loadings, the 10%Cu/MgO catalyst exhibits superior activity with 89% conversion of n-butanol and 98% selectivity for butyraldehyde.

 

 

557

 

Vapor phase chemoselective conjugate hydrogenation of isophorone over Pd/SBA-15 catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

Venkateswarlu Vakati, Saidulu Ganji,
Ravi Kumar Marella, Kamaraju Seetha Rama Rao & David Raju Burri
*

 

 

 

Pd/SBA-15 catalysts with 1, 2, 3, 4 wt% Pd loading prepared by a conventional impregnation method exhibit 100% conversion and 100% selectivity in gas phase at atmospheric pressure for chemoselective hydrogenation of isophorone to dihydroisophorone.

 

 

 

 

 

561

 

Synthesis, characterization and studies on optical properties of indium doped ZnO nanoparticles

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Manu Sharma & P Jeevanandam*

 

 

 

Indium doped ZnO nanoparticles have been synthesized by a simple aqueous solution based method. Doping leads to change in morphology of ZnO and the band gap of doped zinc oxide nanoparticles depends on the concentration of indium.

 

 

 

566

 

Synthesis and characterization of Pt supported on Fe5(PO4)3(OH)5 catalysts

 

 

 

 

 

 

P Anil Kumar, A Hari Padmasri*, S Naveen Kumar,
A Venugopal* & Sooboo Singh

 

 

 

Iron hydroxyphosphate has been identified as a non-reducible material when subjected to high temperature in H2.

 

 

 

572

 

Catalytic dehydration of 1-phenylethanol over chromia-carbon composite derived from metal organic framework, CrMIL-101

 

 

 

 

 

 

 

 

 

 

 

 

 

Suresh Mutyala, Raveendranath Reddy Kanchamreddy, Madhavi Jonnalagadda,
David Raju Burri, Kamaraju Seetha Rama Rao,
M Lakshmi Kantam & Pavuluri Srinivasu
*

 

 

 

Chromia-carbon composite material is synthesized by direct thermal treatment of metal organic framework, Cr-MIL-101, at 498 K. The nanoparticles of chromia on carbon facilitate the catalytic activity of the composite material for dehydration of
1-phenylethanol to selectively produce styrene.

 

 

 

576

 

Unusual catalytic activity of iron containing mesoporous materials for synthesis of diphenylmethane

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Raveendranath Reddy Kanchamreddy,
Suresh Mutyala, M Lakshmi Kantam &
Pavuluri Srinivasu
*

 

 

 

Synthesis of diphenylmethane through Friedel-Crafts alkylation reaction of alkyl halide and aromatic compound over ordered mesoporous ferrosilicates is reported. PS-1(46) demonstrates 100% conversion and selectivity in a short reaction time (15 min) under solvent-free conditions. The catalyst is stable and reusable for several cycles.

 

 

 

 

Authors for correspondence are indicated by (*)

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 459-466

 

 

Characterization and reactivity of Pd supported on ZnAl2O4 catalysts for direct coupling of ethylbenzene dehydrogenation with
nitrobenzene hydrogenation

Yengaldas Harikrishna, Vanama Pavan Kumar, Komandur V R Chary & Vattikonda Venkat Rao*

Catalysis Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: vattikondav@yahoo.com

Received 18 December 2013; revised and accepted 26 February 2014

The ZnAl2O4 supported palladium catalysts have been described for the first time in the direct coupling of dehydrogenation of ethylbenzene with hydrogenation of nitrobenzene, in a fixed bed catalytic reactor at atmospheric pressure in the temperature range of 673−823 K. The former reaction is reversible, endothermic, thermodynamically limited and also supplies hydrogen to produce styrene. However, the latter is irreversible, exothermic and consumes in situ hydrogen to produce aniline, thereby making the coupling reaction slightly exothermic and additionally overcoming thermodynamic constraints. A series of palladium (0.25−4.0 wt%) catalysts supported on crystalline ZnAl2O4 have been prepared and their catalytic activities studied in the coupling reaction. The catalyst samples are characterized by X-ray diffraction, H2-temperature programmed reduction, CO chemisorption and BET surface area data. The metal dispersion and particle size are obtained by CO chemisorption method. The reaction profile shows that 0.5 wt% palladium is an optimum loading to obtain maximum conversions of ethylbenzene (52.3%) and nitrobenzene (43.9%) to give 88.3% and 100% selectivity of styrene and aniline products respectively.

Keywords: Catalysts, Palladium catalysts, Coupling reactions, Supported catalysts, Dehydrogenation, Hydrogenation, Spinel oxides, Zinc aluminate, Ethylbenzene, Nitrobenzene

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014 pp. 467-471

 

 

Partial oxidation of methane to synthesis gas over Ni-supported
ceria catalyst

Rajib Kumar Singha, Astha Shukla, Shubhadeep Adak, Chandrashekar Pendem,
Sandeep Saran & Rajaram Bal*

Catalytic Conversion & Processes Division, CSIR-Indian Institute of Petroleum,
Dehradun 248 005, India

Email: raja@iip.res.in

Received 21 December 2013; revised and accepted 29 March 2014

Partial oxidation of methane to synthesis gas (a mixture of H2 and CO) over 5 wt.% Ni/CeO2 catalysts has been studied in a fixed bed down flow reactor. The catalyst has been characterized by XRD, N2-sorption, SEM, TEM, ICP-AES and XPS data. It is found that the Ni-CeO2 catalyst can activate methane at 500 C, and with increase in temperature the conversion increases up to 86.1% at 800 C. The H2/CO mole ratio is almost constant at 1.9 in the temperature range from 500800 C. The activity of the catalyst remains constant till 30 h, which is the main advantage of the present catalyst. Various reaction parameters like temperature, time-on-stream and GHSV are studied in detail.

Keywords: Catalysts, Supported catalysts, Oxidation, Partial oxidation, Methane, Synthesis gas, Nickel, Ceria,
Carbon monoxide, Hydrogen

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 472-477

 

 

In2O3/TiO2 nano photocatalysts for solar hydrogen production from methanol:water mixtures

K Lalitha, V Durga Kumari* & M Subrahmanyam

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500 607, India

Email: durgakumari@iict.res.in

Received 30 January 2014; revised and accepted 11 February 2014

In2O3/nano TiO2 and In2O3/TiO2 (P-25) photocatalysts with different In2O3 loadings have been prepared by solid state dispersion method. These catalysts are characterized by XRD, surface area, TEM, UV-vis DRS and XPS techniques. XRD analysis shows the fine dispersion of In2O3 on the surface of TiO2. The photocombinates of In2O3 prepared using the lab-made TiO2 are nano sized with an average size of 810 nm compared to the particle size of In2O3/TiO2 (P-25) combinates. The In2O3/nano TiO2 photocatalysts show higher surface area as compared to In2O3/TiO2 (P-25) photocatalysts due to nanosize of the particles. UV-vis DRS results show the visible light absorption of the catalysts in both the series. XPS analysis shows the interaction between In2O3 and TiO2, although the extent of interaction is low. Photocatalytic hydrogen evolution studies have been conducted over these catalysts from water and methanol:water mixtures under solar light irradiation. The 2 wt% In2O3 loaded nano TiO2 and P-25 catalysts show maximum hydrogen production activity from pure water splitting. A very good improvement in the activity is seen when the reaction is carried out in methanol:water mixtures. Maximum hydrogen production of 4080 moles/hour is observed on 5 wt% In2O3/nano TiO2 catalyst, which is almost double the activity observed on In2O3/ TiO2 (P-25) catalyst.

Keywords: Catalysts, Photocatalysts, Nanoparticles, Photocatalytic hydrogen evolution, Hydrogen production,
Indium oxide, Titania

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 478-483

 

 

Methane reforming with carbon dioxide over La-Nix-Ce1-x
mixed oxide catalysts

T V Sagara, N Sreelathaa, G Hanmantb, K Upendara, N Lingaiaha, Kamaraju Seetha Rama Raoa,
C V V Satyanarayanab, I A K Reddyc & P S Sai Prasada, *

aCSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: saiprasad@iict.res.in

bCSIR-National Chemical Laboratory, Pune 411 008, India

cNational Institute of Technology, Warangal 506 004, India

Received on 31 January 2014; revised and accepted on 20 February 2014

La-Nix-Ce1-x mixed oxide (0≤x≤1) catalysts have been hydrothermally prepared, characterized by physico-chemical techniques and evaluated for CO2 reforming of methane. High conversions are achieved for both methane and carbon dioxide over the LaNi0.6Ce0.4O3 catalyst tested under the conditions of CO2/CH4/N2 ratio of 80/80/80 (total flow rate = 240 mL/min), space velocity of 28,800 h-1 and at a temperature of 800 C. The H2/CO ratio in the syngas is stable at 0.930.02. Exchanging Ni with Ce, rather than with La as reported in the literature, appears to be a better option for the improved performance of the catalysts.

Keywords: Catalysts, Carbon dioxide reforming, Dry reforming, Hydrothermal synthesis, Methane reforming,
Mixed oxides, Nickel, Lanthanum, Cerium

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 484-492

 

 

Catalytic oxidation of CO in presence of ozone over
supported palladium catalysts

Keshav Soni*, S Chandra Shekar, Beer Singh & Anidha Agrawal

Protective Devices Divisions, Defence R&D Establishment, Gwalior 474 002, India

Email: keshavsoni2k@gmail.com

Received 30 January 2014; revised and accepted 18 March 2014

Palladium supported Al2O3 and SiO2 catalysts have been synthesized and evaluated for carbon monoxide oxidation in the presence of ozone. The factors affecting the CO oxidation such as Pd loading (wt%), contact time, reaction temperature and O3/CO molar ratio have been studied. The extent of ozone decomposition on Pd catalysts is proportional to the CO oxidation activity. High reaction temperature or high Pd loading results in the high catalytic activity for CO oxidation. CO chemisorption study shows maximum CO uptake at higher Pd loading. XRD, CO chemisorption and TEM results show that Pd disperses better on alumina than on silica support. The physicochemical properties are well correlated with catalytic activity data. The ozone decomposition on palladium is responsible for the low temperature the CO oxidation. The CO oxidation follows Langmuir Hinshelwood (surface) and Eley-Rideal (surface CO and gas phase ozone) type mixed mechanisms in presence of ozone. The catalytic activity and stability have been tested for 60 hours.

Keywords: Catalysts, Supported catalysts, Oxidation, Carbon monoxide oxidation, Ozone decomposition, Chemisorption, Palladium, Alumina, Silica

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 493-498

 

 

Molybdenum oxide supported on COK-12: A novel catalyst for
oxidative dehydrogenation of ethylbenzene using CO2

Ramudu Pochamonia, Anand Narania, Venkata Ramesh Babu Gurrama, Murali Dhar Gudimellab,
P. S Sai Prasad Potharajua, David Raju Burria & Kamaraju Seetha Rama Raoa, *

aCatalysis Laboratory, CSIR-Indian institute of Chemical Technology, Hyderabad 500 607, India

Email: ksramarao@iict.res.in

bChemical Engineering Department, Gayatri Vidya Parishad College of Engineering, Visakhapatnam, India

Received 6 December 2013; revised and accepted 13 February 2014

P6m-type mesoporous silica (COK-12) prepared at quasi-neutral pH in a buffered medium using sodium silicate as a silica source has been used as a support to prepare a series of MoO3/COK-12 catalysts with variable MoO3 loadings by wet impregnation technique. Among these catalysts, 14 wt% MoO3/COK-12 with small particle size of MoO3 shows superior activity for the oxidative dehydrogenation of ethylbenzene to styrene in the presence CO2.

Keywords: Catalysts, Supported Catalysts, Dehydrogenation, Oxidative dehydrogenation, Ethylbenzene, Styrene, Molybdenum oxide, Mesoporous silica, Silica

 

 

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014 pp. 499-503

 

 

Mineralization of aqueous organic pollutants using a catalytic
plasma reactor

P Manoj Kumar Reddy, Sk Mahammadunnisa & Ch Subrahmanyam*

Energy and Environmental Research Laboratory, Department of Chemistry,
Indian Institute of Technology Hyderabad, Hyderabad 502 205, Andhra Pradesh, India

Email: csubbu@iith.ac.in

Received 6 December 2013, revised and accepted 18 February 2014

Electrical discharges generated at water-gas interface in a dielectric barrier discharge reactor has been utilized for the degradation and mineralization of a model aqueous organic pollutant, viz., methyl orange. Mineralization of the dye is identified by an online infrared gas analyzer and confirmed by a total organic carbon analyzer. It has been observed that both degradation efficiency and mineralization of the dye increases on addition of modified alumina catalyst to the plasma reactor. On addition of FeOx/Al2O3 catalyst, the mineralization efficiency increases from 31% with plasma reactor alone to 38%. It has been observed that dye degradation followes first-order kinetics and degree of mineralization increases as a function of time with decreasing energy yield.

Keywords: Catalyst, Dye degradation, Degradation, Dielectric barrier discharge reactor, Catalytic plasma reactor,
Plasma reactor, Energy yield, Mineralization, Nonthermal plasma, Total organic carbon, Methyl orange,
Iron oxide, Alumina

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 504-510

 

 

Effective oxidative decolourization of azo dyes over Indian Ocean manganese nodules

A K Sahooa, K M Paridab, * & P K Satapathyc

aF M Junior College, Balasore 756 001, Odisha, India

bColloids and Materials Chemistry Department, CSIR-Institute of Minerals and Materials Technology,
Bhubaneswar 751 013, Odisha, India

cPG Department of Chemistry, North Orissa University, Baripada 757 003, Odisha, India

Email: paridakulamani@yahoo.com

Received 17 December 2013, revised and accepted 19 March 2014

The degradation of cationic dyes such as methylene blue is studied using Indian Ocean manganese nodules. Effect of various parameters, such as catalyst loading, dye concentration, initial pH of the solution, effect of various electrolytes and effect of heat treatment of manganese nodules on the decolourization of methylene blue is investigated. The extent of decolourization decreases with increase in pH and increases in the presence of NaCl. Anions like CO32-, PO43-, Cl- inhibit decolourization, whereas SO42- and NO3- accelerate the decolourization rate of methylene blue to a remarkable extent. The rate of dye degradation is dramatically reduced with increase in calcination temperature.

Keywords: Manganese nodules, Degradation, Dye degradation, Decolourization, Methylene blue

 

 

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 511-515

 

 

Selective CO oxidation over Fe5(PO4)3(OH)5 supported Pt catalyst:
Kinetic and mechanistic studies

 

A Hari Padmasria, *, P Anil Kumarb, S Naveen Kumarb, A Venugopalb & Sooboo Singhc

aDepartment of Chemistry, University College for Women, Osmania University, Koti, Hyderabad 500 095, AP, India

bInorganic and Physical Chemistry, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, AP, India

cSchool of Chemistry, University of KwaZulu-Natal, Private Bag X54001, Durban 4000, South Africa

Email: ahpadmasri@gmail.com

Received 16 January 2014; revised and accepted 13 February 2014

Iron hydroxyphosphate as support for Pt catalysts is explored for preferential oxidation of CO using simulated reformate gas mixture in the temperature range 40-240 C. The CO oxidation activity and selectivity at low reaction temperatures are enhanced on addition of H2O but decrease at high temperatures due to the reverse water gas shift reaction. X-ray diffraction patterns of the supported and unsupported catalysts show very weak diffraction lines due to the Fe5(PO4)3(OH)5 phase. The chemical composition of this phase on the catalyst surface has been confirmed by X-ray photoelectron spectroscopy results.

Keywords: Catalysts, Supported catalysts, Platinum catalysts, Oxidation, Carbon monoxide oxidation,
Iron hydroxyphosphate

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 516-523

 

 

Characterization and reactivity of TiO2 supported nano ruthenium catalysts
for vapour phase hydrogenolysis of glycerol

Vanama Pavan Kumar, Yengaldas Harikrishna, Nekkala Nagaraju & Komandur V R Chary*

Catalysis Division, CSIR- Indian Institute of Chemical Technology, Hyderabad 500 007, India.

Email: kvrchary@iict.res.in

Recieved 21 December 2013; revised and accepted 27 Febraury 2014

A series of catalysts with varying Ru content supported on anatase titania have been prepared by deposition-precipitation method. These catalysts have been characterized by X-ray diffraction, H2-temperature programmed reduction, TEM, BET-surface area, and H2-chemisorption measurements. The catalytic properties of nano Ru/TiO2 catalysts have been evaluated during vapour phase selective hydrogenolysis of glycerol at moderate temperature and atmospheric pressure. The glycerol conversion and the selectivity of various products depend on the catalyst preparation method and also on the Ru loading. The higher activity of Ru/TiO2 catalysts is attributed to the presence of well-dispersed nanosized Ru particles on titania.

Keywords: Catalysts, Ruthenium catalysts, Hydrogenolysis, Vapour phase hydrogenolysis, Nanoparticles, Glycerol, Titania

 

 

 

 

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 524-529

 

 

Selective etherification of glycerol with tert-butanol over 12-tungstophosphoric acid catalysts supported on Y-zeolite

 

M Srinivas, Rekha Sree, G Raveendra, Ch Ramesh Kumar, P S Sai Prasad & N Lingaiah*

Catalysis Laboratory, I&PC Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: nakkalingaiah@iict.res.in

Received 13 February 2014; revised and accepted 13 march 2014

Selective etherification of glycerol with t-butyl alcohol has been investigated over tungstophosphoric acid (TPA) supported on Y-zeolite. The catalysts have been characterized by FT-IR spectroscopy, X-ray diffraction, scanning electron microscopy and temperature-programmed desorption of NH3. The catalytic activity varies with the content of TPA on the support and the catalyst with 20 wt.% TPA shows the high activity. The catalytic activity is found to depend on the acidity which varies with the dispersion of TPA over zeolite. The etherification activity of catalysts has been correlated with the structural aspects and the acidity. Various parameters such as reaction temperature, reaction time, catalyst concentration and molar ratio of tert-butanol-to-glycerol have been studied to optimize the reaction conditions.

Keywords: Catalysts, supported catalysts, Etherification, Glycerol, Butanol, Tungstophosphoric acid, Zeolite

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 530-534

 

 

Catalytic tri-reforming of glycerol for hydrogen generation

M Ashwani Kumara, Ch Venumadhava, T V Sagara, M Surendara, N Lingaiaha,
G Nageswara Raob & P S Sai Prasada, *

aCSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

bDepartment of Chemistry, Andhra University, Visakhapatnam 530 003, India.

Email: saiprasad@iict.res.in

Received 30 January 2014; revised and accepted 18 February 2014

Tri-reforming of glycerol has been carried out, for the first time, on CeO2, ZrO2 and CeO2-ZrO2 supported 10 wt.% Ni catalysts. The catalysts have been characterized by nitrogen adsorption, X-ray diffraction, temperature programmed reduction, scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy and tested for glycerol tri-reforming at atmospheric pressure and 673-1073 K. Ni/CeO2-ZrO2 has shown 95% of thermodynamic limit for hydrogen production, at 873 K. Also, the catalyst shows good stability.

Keywords: Catalysts, Supported catalysts, Nickel catalysts, Ceria, Zirconia, Glycerol, Tri-reforming, Synthesis gas, Hydrogen production

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 535-544

 

 

Preparation and structural investigations of new hexadentate Schiff base ligands and their bivalent metal complexes, and, catalytic applications
of the complexes in allylic and benzylic CH bond activation

S Jyothi, G Raghava Rao, K Shashank, K Sridhar, Anjali Reddy, P Someshwar & S Jagannatha Swamy*

Department of Chemistry, Kakatiya University, Warangal 506 009, Andhra Pradesh, India

Email: sj_swamy@yahoo.com

Received 2 January 2014; revised and accepted 18 March 2014

The reaction between 2-hydroxybenzaldehyde and piperazine-1,4-diylbis((2-aminophenyl)methanone) or N,N'-(ethane-1,2-diyl)bis(2-amino-N-methyl-benzamide) yields new hexadentate Schiff base ligands, (Z)-piperazine-1,4-diylbis((2-((Z)-(2-hydroxy-benzylidene)amino)phenyl)methanone) (PHMAPM) and 2-((2-hydroxybenzylidene)amino)-N-(2-(2-((E)-(2-hydroxybenzylidene)-amino)-N-methyl-benzimido)ethyl)-N-methylbenzamide (EHBAMB) respectively. PHMAPM crystallizes in the monoclinic space group P21/C. The Co(II), Ni(II) and Cu(II) complexes of these ligands have been prepared and characterized by elemental analyses, conductance, magnetic susceptibility and spectral investigations. The complexes are found to have the formula [M(PHMAPM)] and [M(EHBAMB)] respectively. The catalytic activity of these complexes in allylic and benzylic (CH) activation has been investigated. The Cu(II) complexes are found to exhibit better activity in acetonitrile as compared to in other solvents.

Keywords: Coordination chemistry, Schiff bases, Catalytic activity, Oxidation, Benzylic oxidation, Copper, Nickel, Cobalt, Allylic oxidation

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 545-549

 

 

Triflamide anchored SBA-15 catalyst for nitration of alkyl
aromatics in microwave

Venkata Siva Prasad Ganjalaa, b, Suresh Mutyalaa, Chinna Krishna Prasad Neelia, Mukkanti Khaggab, *,
Kamaraju Seetha Rama Raoa & David Raju Burria, *

aCatalysis Laboratory, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 607, India

Email: david@iict.res.in

bCentre for Chemical Sciences & Technology, Institute of Science and Technology, Jawaharlal Nehru Technological University, Kukatpally, Hyderabad, 500 085, India

Email: kmukkanti@jntuh.ac.in

Received 20 January 2014; revised and accepted 29 January 2014

A series of triflamide anchored SBA-15 (SBA-NH-TA) catalysts with 5-20 wt% triflic acid (TA) loadings have been synthesized through the functionalization of propylamine on the surface of SBA-15 (SBA-NH2), followed by covalent attachment of triflic acid with NH2 group of SBA-NH2. With SBA-NH-TA as catalyst and 69% HNO3 as nitrating agent, highly accelerated and safe nitration of aromatic compounds in microwave under solvent-free conditions has been achieved. The structural and textural characteristics of SBA-NH-TA catalysts have been determined from N2 sorption and low-angle XRD techniques. As the loading of TA increases, the conversion of alkylaromatics to their nitrated products increases significantly. Reaction parameters like amount of catalyst, amount of triflic acid loading, substrate to nitric acid ratio, reaction temperature and reaction time have been investigated.

Keywords: Catalysts, Nitration, Metal-free nitration, Triflamide anchored SBA-15, Alkyl aromatics, Xylene

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 550-552

 

 

Vapour phase hydrogenation of nitrobenzene over metal (Ru, Ni, Pt, Pd) supported on Ca5(PO4)3(OH) catalysts

M Sudhakar, M Lakshmi Kantam*, R Kishore, S Naveen Kumar & A Venugopal*

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: mlakshmi@iict.res.in (MLK)/ akula@iict.res.in (AV)

Received 28 January 2014; revised and accepted 13 February 2014

Vapour phase hydrogenation of nitrobenzene is carried out over metal (Pt, Pd, Ru, Ni) supported on hydroxyapatite (HAP) catalysts at atmospheric pressure and low temperatures ranging from 225350 C. The time-on-stream analysis reveals that 2 wt.%Pd/HAP is quite stable up to 6 h of continuous operation and is found to be an efficient catalyst. The other metal catalysts suffer deactivation, which is probably due to either carbon deposition or the in situ generation of water.

Keywords: Catalysts, Supported catalysts, Hydrogenation, Vapour phase hydrogenation, Hydroxyapatite, Nitrobenzene, Platinum, Palladium, Ruthenium, Nickel

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 553-556

 

 

Gas phase dehydrogenation of n-butanol to butyraldehyde on
magnesia supported copper catalysts

Yadagiri Jyothia, Venkateswarlu Vakatib, Tirumalasetty Satyanarayanac & Puppala Veerasomaiaha, *

aDepartment of Chemistry, University college of Science, Osmania University, Hyderabad 500 007, Andhra Pradesh, India

Email: vs_puppala@rediffmail.com

bCatalysis Laboratory, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500 007, Andhra Pradesh, India

cDepartment of Chemistry, PG College, Osmania University, Mirzapur, Medak District 502 249, Andhra Pradesh, India

Received 10 January 2014; revised and accepted 11 March 2014

Gas phase dehydrogenation of n-butanol to butyraldehyde has been carried out at atmospheric pressure using magnesia supported copper catalysts, which are prepared by a conventional impregnation method by varying the loading of Cu with 5, 10 and 15% by weight. These catalysts have been characterized by X-ray diffraction and temperature programmed reduction techniques. Among the series of Cu/MgO catalysts, 10%Cu/MgO catalyst exhibits superior activity with 89% conversion of n-butanol and 98% selectivity for butyraldehyde.

Keywords: Catalysts, Supported catalysts, Dehydrogenation, Gas phase dehydrogenation, Butanol, Butyraldehyde, Magnesia, Copper

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 557-560

 

 

Vapor phase chemoselective conjugate hydrogenation of isophorone
over Pd/SBA-15 catalysts

Venkateswarlu Vakati, Saidulu Ganji , Ravi Kumar Marella, Kamaraju Seetha Rama Rao &
David Raju Burri*

Catalysis Laboratory, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 607, India

Email: david@iict.res.in

Received 10 January 2014; revised and accepted 12 March 2014

A series of Pd/SBA-15 catalysts with 1, 2, 3, 4% (by weight) Pd loading has been prepared by a conventional impregnation method and characterized by N2-sorption, low-angle and wide-angle XRD, XPS and TEM techniques. These catalysts exhibit excellent activities for chemoselective hydrogenation of isophorone to dihydroisophorone showing 100% conversion and 100% selectivity in gas phase at atmospheric pressure. The structural and textural characteristics of the catalysts play a crucial role in exhibiting high conversion and selectivity.

Keywords: Catalysts, Supported catalysts, Palladium catalysts, Hydrogenation, Isophorone, Carbonyl compounds

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 561-565

 

 

Synthesis, characterization and studies on optical properties of
indium doped ZnO nanoparticles

Manu Sharma & P Jeevanandam*

Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India

Email: jeevafcy@iitr.ac.in

Received 26 December 2013; revised and accepted 17 February 2014

Indium doped zinc oxide hierarchical nanostructures have been synthesized using a simple aqueous solution based method. A change in morphology from hierarchical nanostructures in ZnO to nanorods after doping with indium has been observed. The optical properties of nanostructures have been investigated using diffuse reflectance and photoluminescence spectroscopy. The band gap of zinc oxide nanoparticles changes after the incorporation of indium and a blue shift of band gap is observed.

Keywords: Nanostructures, Nanorods, Doping, Optical properties, Photoluminescence,
Diffuse reflectance spectroscopy, Zinc oxide, Indium

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 566-571

 

 

Synthesis and characterization of Pt supported on Fe5(PO4)3(OH)5 catalysts

P Anil Kumara, A Hari Padmasrib, *, S Naveen Kumara, A Venugopala, * & Sooboo Singhc

aInorganic and Physical Chemistry, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500 007, AP, India

Email: akula@iict.res.in

bDepartment of Chemistry, University College for Women, Osmania University, Koti, Hyderabad 500 095, AP, India

Email: ahpadmasri@gmail.com

cSchool of Chemistry, University of KwaZulu-Natal, Private Bag X54001, Durban 4000, South Africa

Email: singhso@ukzn.ac.za

Received 16 January 2014, revised and accepted 31 January 2014

Pt supported on iron hydroxyphosphate catalysts has been synthesized and characterized by various adsorption and spectroscopic methods. X-ray diffraction patterns of the supported and unsupported catalysts indicate a very weak diffraction line due to the Fe5(PO4)3(OH)5 phase. The X-ray photoelectron spectroscopic studies reveal a surface composition attributed to Fe5(PO4)3(OH)5 species. The temperature programmed sequential reduction-oxidation-reduction of 1wt.% Pt/Fe5(PO4)3(OH)5 indicates the absence of H2 spillover due to Pt on the Fe5(PO4)3(OH)5 support. The temperature programmed reduction studies also show the non-reducible behavior of Fe5(PO4)3(OH)5 phase.

Keywords: Catalysts, Supported catalysts, Reduction, Oxidation, Iron hydroxyphosphate,
Photoelectron spectroscopy

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 572-575

 

 

Catalytic dehydration of 1-phenylethanol over chromia-carbon composite
derived from metal organic framework, CrMIL-101

Suresh Mutyala, Raveendranath Reddy Kanchamreddy, Madhavi Jonnalagadda, David Raju Burri,
Kamaraju Seetha Rama Rao, M Lakshmi Kantam & Pavuluri Srinivasu*

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: pavuluri.srini@iict.res.in

Received 9 February 2014; revised and accepted 27 March 2014

The synthesis and characterization of a new composite material containing chromia and carbon using metal organic framework (Cr-MIL-101) is presented. The dispersion of chromia particles on carbon material by direct thermal treatment of Cr-MIL-101 containing terephthalate is also described. The investigation of removal of guest molecules in Cr-MIL-101 leading to the formation of chromia in the temperature range of 373-473 K has been studied. The catalytic activity of the composite material for dehydration of 1-phenylethanol is tested as a possible application. The composite catalytic system can be used up to 10 h without significant loss of activity.

Keywords: Catalysis, Dehydration, Metal organic frameworks, Composites, Chromia-carbon composite, Phenylethanol

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 576-579

 

 

Unusual catalytic activity of iron containing mesoporous materials for
synthesis of diphenylmethane

Raveendranath Reddy Kanchamreddy, Suresh Mutyala, M Lakshmi Kantam & Pavuluri Srinivasu*

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: pavuluri.srini@iict.res.in

Received 11 February 2014; revised and accepted 20 March 2014

Mesoporous ferrosilicates with various Si/Fe mole ratios have been prepared for the Friedel-Crafts alkylation reaction to synthesize diphenylmethane selectively under solvent-free reaction conditions. Mesoporous ferrosilicates (PS-1) have high BET specific surface area (ca. 1050 m2 g-1) and ordered pore structure. The incorporation of iron into the framework of mesoporous silica is characterized and confirmed by various techniques such as XRD, N2-sorption and FTIR. The nitrogen sorption results show that the sample with Si/Fe mole ratio of 46 possesses improved textural properties as compared with 91 and 125 mole ratios. The catalytic activity of PS-1 catalysts has been tested in the Friedel-Crafts alkylation of aromatic compound for the selective synthesis of diphenylmethane. The results of the alkylation reaction indicate that the PS-1(46) catalyst shows higher activity as compare to other mesoporous ferrosilicates prepared under similar experimental conditions.

Keywords: Catalysts, Mesoporous catalysts, Alkylation, Friedel-Crafts alkylation, Benzylation, Aromatics, Ferrosilicates, Diphenylmethane

 

 

Indian Journal of Chemistry

Vol. 53A, April-May 2014, pp. 576-579

 

 

Unusual catalytic activity of iron containing mesoporous materials for
synthesis of diphenylmethane

Raveendranath Reddy Kanchamreddy, Suresh Mutyala, M Lakshmi Kantam & Pavuluri Srinivasu*

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Hyderabad 500 007, India

Email: pavuluri.srini@iict.res.in

Received 11 February 2014; revised and accepted 20 March 2014

Mesoporous ferrosilicates with various Si/Fe mole ratios have been prepared for the Friedel-Crafts alkylation reaction to synthesize diphenylmethane selectively under solvent-free reaction conditions. Mesoporous ferrosilicates (PS-1) have high BET specific surface area (ca. 1050 m2 g-1) and ordered pore structure. The incorporation of iron into the framework of mesoporous silica is characterized and confirmed by various techniques such as XRD, N2-sorption and FTIR. The nitrogen sorption results show that the sample with Si/Fe mole ratio of 46 possesses improved textural properties as compared with 91 and 125 mole ratios. The catalytic activity of PS-1 catalysts has been tested in the Friedel-Crafts alkylation of aromatic compound for the selective synthesis of diphenylmethane. The results of the alkylation reaction indicate that the PS-1(46) catalyst shows higher activity as compare to other mesoporous ferrosilicates prepared under similar experimental conditions.

Keywords: Catalysts, Mesoporous catalysts, Alkylation, Friedel-Crafts alkylation, Benzylation, Aromatics, Ferrosilicates, Diphenylmethane