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)

 

 

 

 

 

VOLUME 54A

NUMBER 10

OCTOBER 2015

 

CONTENTS

 

 

1175

 

Alumina-supported Mn(III) and Fe(III) complexes of tridentate Schiff base ligand having ONO-donor sites: Syntheses, characterization and olefin epoxidation study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jaydeep Adhikary, Priyabrata Banerjee &
Tanmay Chattopadhyay
*

 

 

Alumina supported ONO donor Schiff-base complexes of Mn(III)I and Fe(III) have been explored in alkene epoxidation study using PhIO and TBHP as terminal oxidant.

 

 

 

 

 

1183

 

Nanoparticle mediated copper(II) catalyzed oxidation of mercaptosuccinic acid by methylene blue in aqueous acetone medium: Non-Arrhenius behaviour

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mahender Pal*, Maya Shukla, Ranjana Sharma &
K K Mishra
*

 

 

Cu(II) catalyzed oxidation of mercaptosuccinic acid by methylene blue in acidic medium shows non-Arrhenius behaviour between
20 and 30 C. TEM, SEM, XRD and FTIR analyses indicate temperature and time dependent changes in size and morphology of nanoparticles and a variation in the Fermi band gap energy.

 

 

 

 

1192

 

Synthesis of 2,3,3,3-tetrafluoropropene by catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane over Ni-Cr2O3 Catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Fang Wang, Yan Liang, Wen-Xia Zhang,
Yue-Juan Wang, Ji-Qing Lu & Meng-Fei Luo
*

 

 

2,3,3,3-Tetrafluoropropene (HFO-1234yf) has been synthesized from 1,1,1,3,3-pentafluoropropane (HFC-245fa) by dehydrofluorination over a series of Ni-Cr2O3 catalysts with >99% conversion of
HFC-245fa. On increasing the Ni doping in the Ni-Cr2O3 catalysts, the initial selectivity to HFO-1234yf gradually increases due to the increase of
Lewis acid sites. When Ni doping is 210%, the catalysts have the appropriate surface acid density, which makes the selectivity to HFO-1234yf relatively stable during 310 h reaction time.

 

图片1-1

 

 

 

1198

 

Effect of phase transformation on the stability of
Ni-Mg-Al catalyst for dry reforming of methane

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Na Li, Chaofeng Shen, Pengjia Tan, Zhijun Zuo* & Wei Huang*

 

 

A series of Ni/Mg(Al)O hydrotalcite-derived catalysts has been prepared by carbonate co-precipitation method at different calcination temperatures. The decrease in activity of the catalysts calcined at 600, 700, and 800 C is due to the MgO film surrounding the Ni0 particles in the initial reaction stage. The activity is renewed and maintained when the MgO film surrounding Ni0 is destroyed on reaction with Al2O3 to form the MgAl2O4 spinel-like phase. The conversion of CH4 and CO2 is stable at over 95% after reaction for 2000 h.

 

IJCA-187_GA.tif

 

 

 

1206

 

Interaction of thiolated amino acids and peptide onto the gold nanoparticle surface: Radical scavenging activity

 

 

 

 

 

 

 

 

 

 

Manmohan L Satnami *, Kumudini Chandraker, Sandeep K Vaishanav & Rekha Nagwanshi

 

 

 

 

Notes

 

1215

 

Liquid-free alkaline gel filled reference electrode based on Cr2O3 spheres

 

 

 

 

 

 

 

 

 

 

 

 

 

V Maruthapandian*, S Muralidharan & V Saraswathy

 

 

 

Ball yarn-like Cr2O3 non-agglomerated spheres, synthesized through electrochemical route, have been fabricated into liquid-free alkaline gel filled Cr2O3 based reference electrode. The electrode exhibits stable potential, comparable to conventional reference electrodes like SCE. It is independent of pH and has an extended shelf-life.

 

 

 

 

1221

 

Electrocatalytic properties of cobalt ferrites obtained by glycine sol-gel route for oxygen evolution in alkaline medium

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ritu Yadav & Narendra Kumar Singh*

 

 

 

Partial substitution of Co for Fe in the base oxide greatly enhances its apparent electrocatalytic activity towards oxygen evolution reaction. Based on the apparent electrocatalytic scale, CoFe2O4 is found to be the best electrocatalyst among the investigated cobalt ferrites. The catalytic activity of the most active electrode is found to be 34 times higher than that of the base oxide.

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1175-1182

 

 

Alumina-supported Mn(III) and Fe(III) complexes of tridentate Schiff
base ligand having ONO-donor sites: Syntheses, characterization and
olefin epoxidation study

Jaydeep Adhikarya, Priyabrata Banerjeeb & Tanmay Chattopadhyay c, *

aDepartment of Chemistry, University of Calcutta, 92, APC Road, Kolkata 700 009, India

bDepartment of Surface Engineering and Tribology, CSIR-CMERI, Durgapur 713 209, India

cDepartment of Chemistry, Panchakot Mahavidyalaya, Purulia 723 121, India

Email: tanmayc2003@gmail.com

Received 17 March 2015; revised and accepted 21 September 2015

Two new mononuclear Schiff base complexes, [MLCl(H2O)2] [M = Mn(III) or Fe(III); H2L =
2-phenoliminomethylphenol],
have been prepared and characterized by elemental analysis, thermogravimetric analysis, UV-vis and FT-IR spectroscopy, cyclic voltammetry and ESI-MS analyses. Both complexes show excellent alkenes epoxidation activity and thus these complexes have been infused over neutral active alumina to prepare the heterogeneous catalysts. These catalysts are characterized by solid UV-vis and FT-IR spectroscopy, thermogravimetric and powder XRD and FE-SEM studies. Finally, the catalysts have been studied for the epoxidation of different types of olefins in presence of terminal oxidants (PhIO and t-BHP) and are easily recyclable.

Keywords: Catalysts, Supported catalysts, Alumina, Epoxidation, Schiff bases, Manganese, Iron

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1183-1191

 

 

Nanoparticle mediated copper(II) catalyzed oxidation of mercaptosuccinic acid by methylene blue in aqueous acetone medium:
Non-Arrhenius behaviour

Mahender Pal*, Maya Shukla, Ranjana Sharma & K K Mishra*

Department of Post Graduate Studies and Research in Chemistry, Rani Durgavati University,
Jabalpur 482 001, India

Email: kkmishra.chem@gmail.com (KKM)/palmahendra100@gmail.com (MP)

Received 10 March 2015; revised and accepted 14 September 2015

The oxidation of mercaptosuccinic acid by methylene blue catalyzed by Cu(II) (ca. 2.010-5 M) in acidic medium leads to the formation of the corresponding disulphide and leuco dye. A half order kinetics is followed in methylene blue while the order in the substrate varies between half and unity. The rate constant increases linearly on increasing [Cu(II)] while remaining unaffected on varying [H+]. At lower concentrations of hydrogen ion, however, the reaction exhibits zero order kinetics in methylene blue. The reaction shows a
non-Arrhenius behaviour between 20
C and 30 C but subsequently the rate constant increases at 35 C and attains a limiting value. The rate of reaction increases on increasing the time of incubation of the catalyst. TEM, SEM, XRD and FTIR data indicate the participation of copper nanoparticles and XRD analysis suggests the population of (100), (111), (210) and (211) planes at 35 C. A new active facet, (200), is created in the face centered cubic lattice of Cu on increasing the time of incubation. The non-Arrhenius behaviour is attributed to the temperature dependent changes in size and morphology of the nanoparticles and to a variation in the Fermi band gap energy.

Keywords: Kinetics, Nanocatalysis, Nanoparticles, Oxidation, Non-Arrhenius behaviour, Copper, Mercaptosuccinic acid, Methylene blue

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1192-1197

 

 

Synthesis of 2,3,3,3-tetrafluoropropene by catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane over Ni-Cr2O3 catalyst

Fang Wang, Yan Liang, Wen-Xia Zhang, Yue-Juan Wang, Ji-Qing Lu & Meng-Fei Luo*

Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry,
Zhejiang Normal University, Jinhua 321004, PR China
Email:
mengfeiluo@zjnu.cn

Received 20 May 2015; revised and accepted 17 September 2015

2,3,3,3-Tetrafluoropropene (HFO-1234yf) has been synthesized from 1,1,1,3,3-pentafluoropropane (HFC-245fa) by dehydrofluorination over a series of Ni-Cr2O3 catalysts. HFC-245fa could be readily dehydrofluorinated to HFO-1234yf and 1,3,3,3-tetrafluoropropene (HFO-1234ze) over these catalysts. Characterization results reveal that the Ni species in the catalysts is mainly metallic. Ammonia temperature-programmed desorption results indicate that the surface acidity is enhanced with increasing Ni contents in the catalysts, which is responsible for the increased selectivity towards HFO-1234yf. The formation of carbon during the reaction led to the coverage of surface acidic sites, which accounted for the decrease of the selectivity to HFO-1234yf.

Keywords: Catalysts, Nickel catalysts, Dehydrofluorination, Nickel, Nickel acetate, Chromium, Pentafluoropropane, Tetrafluoropropene

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1198-1205

 

 

Effect of phase transformation on the stability of Ni-Mg-Al catalyst for
dry reforming of methane

Na Li, Chaofeng Shen, Pengjia Tan, Zhijun Zuo* & Wei Huang*

Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province,
Taiyuan University of Technology, Taiyuan 030024, China

Email: huangwei@tyut.edu.cn (WH)/ zuozhijun5134@gmail.com (ZZ)

Received 16 April 2015; accepted 25 September 2015

A series of Ni/Mg(Al)O hydrotalcite-derived catalysts are prepared via the carbonate co-precipitation method at different calcination temperatures. The performance and stability of the catalysts are studied through carbon dioxide reforming of CH4 to synthesis gas at 800 C, atmospheric pressure, and gas hourly space velocity of 8000 mL/gcat h. The decrease in activity of catalysts calcined at 600, 700, and 800 C results from the MgO film surrounding the Ni0 particles in the initial reaction stage. The activity is renewed and maintained when the MgO film is destroyed on reaction with Al2O3 to form the MgAl2O4 spinel-like phase. Formation of the MgAl2O4 spinel-like phase during the reaction is considered beneficial to the catalytic activity because of removal of the MgO film surrounding Ni0. The conversion of CH4 and CO2 is stable at over 95% after reaction for 2000 h. The catalysts have small Ni-metal particles, strong metal-support interaction and excellent
anti-carbon deposition.

Keywords: Catalysts, Hydrotalcite catalysts, Dry reforming, Carbon dioxide reforming, Syngas,
Methane, Nickel, Magnesium oxide films,
Aluminium12

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1206-1214

 

 

Interaction of thiolated amino acids and peptide onto the gold nanoparticle surface: Radical scavenging activity

Manmohan L Satnamia, *, Kumudini Chandrakera, Sandeep K Vaishanava & Rekha Nagwanshib

aSchool of Studies in Chemistry, Pt Ravishankar Shukla University, Raipur (CG) 492 010, India

Email: manmohanchem@gmail.com

bDepartment of Chemistry, Govt. Madhav Science PG College, Ujjain 456 010, India

Received 6 April 2015; revised and accepted 22 September 2015

The interaction of gold nanoparticles (AuNPs) with thiolated amino acid, L-cysteine, and peptide, glutathione, is reported. Additionally, thioglycolic acid has also been employed to study the effect of other functional groups such as amine on interparticle interaction mechanism. The functionalized AuNPs have been characterized through UV-visible spectroscopy, FTIR analysis and transmission electron microscopy. The plasmon-plasmon interactions amongst the functionalized AuNPs are found to be dependent on ligand concentration, pH and salt environment. The assembly of AuNPs mediated by L-Cys and GSH has been monitored by the evolution of the surface plasmon resonance absorption. The optical spectra of AuNPs is shifted to the red region, indicating dipole-dipole interactions in the AuNPs assembly. The self-assembly is more pronounced in the case of amino acid and tripeptide, due to the zwitterion-type electrostatic interactions between amino acid groups of L-Cys/GSH bound to different NPs. Furthermore, the scavenging behavior of the studied thiolated ligands and the corresponding AuNPs has been studied by using 1,1-diphenyl 2-picryl hydrazil radical. AuNPs significantly reduces the radical scavenging ability of thiolated antioxidants.

Keywords: Interparticle interactions, Plasmon-plasmon interactions, Zwitterion-type electrostatic interactions,
Self-assembly, Nanoparticles, Gold nanoparticles, Amino acids, Thiolated amino acids, Peptides,
Radical scavenging, Scavenging

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1215-1220

 

 

Liquid-free alkaline gel filled reference electrode based on
Cr2O3 spheres

V Maruthapandian*, S Muralidharan & V Saraswathy

Corrosion and Materials Protection Division, CSIR-Central Electrochemical Research Institute,
Karaikudi 630 006, Tamilnadu, India

Email: maruthuori.tn@gmail.com

Received 8 July 2015; revised and accepted 25 September 2015

Ball yarn-like Cr2O3 non-agglomerated spheres have been synthesized through electrochemical route and fabricated into a new kind of polymer gel filled reference electrode. The potential stability and reproducibility in varying pH have been evaluated. Results demonstrate stable potential, independent of pH and extended
self-life for the intensive usage for the fabricated electrode. Electrochemical studies show excellent potential over a wide range of pH in aqueous medium. This fabricated liquid-free reference electrode/sensor opens up new possibilities for multi-orientation usage.

Keywords: Electrochemistry, Electrodes, Reference electrodes, Gel electrolytes, Electroanalysis,
Chromium oxide

 

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, October 2015, pp. 1221-1225

 

 

Electrocatalytic properties of cobalt ferrites obtained by glycine sol-gel route for oxygen evolution in alkaline medium

Ritu Yadav & Narendra Kumar Singh*

Department of Chemistry, Faculty of Science, University of Lucknow, Lucknow 226 007, India

Email: nksbhu@yahoo.com/ singh_narendra@lkouniv.ac.in

Received 26 June 2015; revised and accepted 29 September 2015

Nano-sized cobalt ferrites have been synthesised by novel sol-gel auto combustion route using a mixture of glycine and ammonium nitrate as fuel with stoichiometric ratio of metal nitrates. The materials so obtained, are characterized by X-ray diffraction, scanning electron micrographs and IR data. Preliminary study shows the formation of spinel phase of the material along with some impurity. Cyclic voltammetry and anodic polarization of each oxide have been carried out in the form of electrode on Ni-substrate. The CV curve of each oxide electrode exhibits redox peaks (EPa = 48012 mV and EPc = 3626) prior to the oxygen evolution reaction. The anodic polarization curve of each oxide electrode has been recorded in 1 M KOH at 25 C for the determination of electrocatalytic activity. Among the prepared oxides, the activity is highest with 1.0 mol
Co-substitution in Fe3O4 matrix. The most active oxide electrode shows overpotential 503 mV at 100 mA cm-2 current density. Tafel slope values range from 47-59 mV decade-1. The activation energy has also been estimated by recording the anodic polarization curve at different temperatures.

Keywords: Electrocatalysis, Nanoparticles, Spinel ferrites, Ferrites, Cobalt ferrites, Sol-gel method,
Oxygen evolution