Indian Journal of Chemistry

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

 

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VOLUME 48A

NUMBER 10

October 2009

CONTENTS

 

1345

 

Synthesis of carbon nanotube supported Pt-Sn nanoparticles by replacement reaction and their electrocatalytic properties for ethanol oxidation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

B Zhang, Y J Kuang, H L Pang, B Liu, J H Chen* & X H Zhang*

 

 

 

 

Carbon nanotube supported Pt-Sn nanoparticles have been prepared by replacement reaction method. The obtained Pt-Sn/CNT nanoparticles exhibit higher electrocatalytic activity and better long-term stability for ethanol oxidation as compared to the PtSn/CNT nanoparticles prepared by the conventional coreduction method.

 

 

 

1352

 

High surface area Ce0.9Cu0.1O2-δ and Ce0.9Mn0.1O2-δ solid solutions for CO and HCHO oxidation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xue-Song Liu, Ji-Qing Lu, Ling-Yun Jin,
Xiao-Yan Xiao & Meng-Fei Luo*

 

 

 

 

Ce0.9Cu0.1O2-δ and Ce0.9Mn0.1O2-δ solid solutions with high surface area (> 100 m2 g-1) have been prepared by a modified citrate
sol-gel method. For CO oxidation, Ce0.9Cu0.1O2-δ
shows higher activity, while for HCHO oxidation, Ce0.9Mn0.1O2-d shows slightly higher activity than Ce0.9Cu0.1O2-δ.

 

 

1358

 

Liquid phase hydrogenation of chloronitrobenzene to chloroaniline with PtM/CNTs (M=La, Ce, Pr, Nd and Sm) catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Juhong Yang, Chunhua Xiong, Xiaoxiang Han*
& Lingxiao Zhou

 

 

 

 

Hydrogenation properties of chloronitrobenzene with Pt/CNT and PtM/CNTs catalysts (M = La, Ce, Pr, Nd and Sm) have been studied in ethanol at 303 K and normal pressure. The conversion of chloronitrobenzene is above 99% and chloroaniline is the main product in hydrogenation with PtM/CNTs catalysts. PtCe/CNTs catalyst exhibits the best catalytic activity
(TOF = 0.47 s-1) and the highest yield of p-CAN (97.5 mol%). PtSm/CNTs catalyst shows the best yields for
m-CAN (98.0 mol%) and o-CAN (96.9 mol%). PtCe/CNTs
(1.0 wt%) catalyst exhibits good stability for hydrogenation of
p chloronitrobenzene.

 

 

 

1364

 

Artificial light assisted photocatalytic degradation of lissamine fast yellow dye in ZnO suspension in a slurry batch reactor

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Brijesh Pare*, Pardeep Singh & S B Jonnalgadda

 

 

 

 

The photocatalytic degradation of lissamine fast yellow has been carried out in the aqueous suspension of ZnO under artificial light. ZnO degrades the dye effectively in the presence of both artificial and solar light respectively. H2O2/Fe3+/ZnO/AR is more efficient than Fe3+/ZnO/AR for the decolorisation of the selected dye. Increased COD-removal percentage, significant release of NO3- and SO42- ions and
UV-vis spectral analysis confirm mineralization of the selected dye in aqueous phase.

 

 

 

 

 

1370

 

Synthesis, characterization and superoxide dismutase activity of some four coordinated copper(II) complexes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

R N Patel

 

 

 

 

Mixed ligand copper(II) complexes, viz., [Cu(Br-SAA)(ImH)], [Cu(Br-SAA)(MeImH)], [Cu(Br-SAA)(EtImH)], [Cu(Br-SAA)-(BenzImH)] and [Cu(Br-SAA)(MebenzImH)], where Br-SAA =
5-bromosalicylideneanthranilic acid, ImH = imidazole, MeImH = 2-methyl imidazole, EtImH = 2-ethyl imidazole, BenzImH = benzimidazole, MebenzImH = 2-methyl benzimidazole, are synthesized and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements. FAB mass, IR, electronic, EPR spectral and cyclic voltammetric studies. The complex, [Cu(Br-SAA)(ImH)], crystallizes in the triclinic space group P-1 with unit cell parameters: a = 3.7875(15), b = 10.6246(19), c = 19.977(3), α = 96.565(14), β = 94.45(2), γ = 92.32 (2) and Z = 2.

 

 

Notes

 

1378

 

Effect of surface area, pore volume and particle size of P25 titania on the phase transformation of anatase to rutile

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

K Joseph Antony Raj & B Viswanathan*

 

 

 

 

The effect of calcination on P25 titania at different temperatures has been studied by XRD, nitrogen adsorption-desorption isotherm, BET-surface area, pore volume, pore size, particle size and crystallite size. Although the crystallinity remains the same, the sample calcined at 900oC for 4 hours shows complete conversion of anatase into rutile. Nitrogen adsoption by the samples decreases appreciably with crystallinity. The isotherms show the non-porous characteristics of the P25 samples. The particle size, crystallite size, and pore size show an increase, while the surface area and pore volume decrease, with increase in temperature.

 

 

1383

 

Effect of polar dopants on structure of emission spectrum of crystalline anthracene powders

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M N Gharge, S L Bhattar, G B Kolekar & S R Patil*

 

 

 

 

The effect of polar dopant, fluorescent 9-vinylanthracene, on the spectral properties of crystalline anthracene is studied as a function of concentration by steady state fluorescence spectroscopy. Higher dopant concentration induces significant enhancement in the intensity of low energy (01) vibronic band at the expense of high energy (00) band with wavelength of maximum emission shifted from 427 to 446 nm.

 

 

 

 

1388

 

Synthesis, characterization and X-ray single crystal studies of mono-n-butyltin(IV) dichloride complex of pyruvic acid-2-pyridylhydrazone [n-BuSnCl2(PAP)]

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M A Affan*, I P P Foo, B A Fasihuddin,
M A Hapipah & M Shamsuddin

 

 

 

 

Mono-n-butyltin(IV) dichloride complex with the general formula [n-BuSnCl2(PAP)] has been synthesized by direct reaction of
n-BuSnCl3 with pyruvic acid-2-pyridylhydrazone in the presence of KOH in equimolar ratio in absolute methanol under nitrogen atmosphere. [n-BuSnCl2(PAP)] is nonelectrolytic in nature. Single crystal X-ray diffraction studies indicate that
[n-BuSnCl2(PAP)] is six-coordinated and adopts a distorted octahedral configuration with the coordination via carboxylic-O, imine-N and pyridyl-N atoms from the ligand. The crystal system of [n-BuSnCl2(PAP)] is tetragonal with space group I41/a and the unit cell dimensions: a = 16.602(3), b = 16.602(3),
c = 23.922(8),
α = β = γ = 90.

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1345-1351

 

Synthesis of carbon nanotube supported Pt-Sn nanoparticles by replacement reaction and their electrocatalytic properties
for ethanol oxidation

B Zhang, Y J Kuang, H L Pang, B Liu, J H Chen* & X H Zhang*

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering
Hunan University, Changsha, 410082, PR China

Email: chenjinhua@hnu.cn/guoxin512@tom.com

Received 5 June 2009; revised and accepted 1 September 2009

Carbon nanotube supported Pt-Sn nanoparticles have been prepared by using a replacement reaction method. The micrography, elemental composition and structure analysis of Pt-Sn catalysts have been studied by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffractograms, respectively. The electrocatalytic activity of Pt-Sn/CNTs for ethanol electrooxidation has been investigated by cyclic voltammetry in 1.0 M CH3CH2OH + 0.5 M H2SO4 solution. The results show that the obtained Pt-Sn/CNT nanoparticles exhibit higher electrocatalytic activity and better long-term stability for ethanol oxidation as compared to the PtSn/CNT nanoparticles prepared by the conventional coreduction method.

Keywords: Fuel cells, Catalysts, Carbon nanotubes, Nanomaterials, Electrocatalysis, Pt-Sn nanoparticles,
Replacement reactions, Oxidations, Ethanol oxidation, Electrooxidations


IPC Code:
Int. Cl.9 B01J21/18C; C25B3/02; H01M4/00

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1352-1357

 

High surface area Ce0.9Cu0.1O2-δ and Ce0.9Mn0.1O2-δ solid solutions for
CO and HCHO oxidation

Xue-Song Liu, Ji-Qing Lu, Ling-Yun Jin, Xiao-Yan Xiao & 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 24 June 2009; revised and accepted 22 September 2009

Ce0.9Cu0.1O2-δ and Ce0.9Mn0.1O2-δ solid solutions with high surface area (> 100 m2 g-1) have been prepared by a modified citrate sol-gel method. XRD results confirm the formation of Ce0.9X0.1O2-δ (where X = Cu or Mn) solid solution. Raman results indicate that a higher concentration of oxygen vacancies is obtained on the Ce0.9Cu0.1O2-δ catalyst compared to that of Ce0.9Mn0.1O2-d. In situ DRIFTS results show the chemisorption of CO on the Ce0.9Cu0.1O2-δ catalyst, but there is no chemisorption of CO on the Ce0.9Mn0.1O2-d catalyst. For CO oxidation, Ce0.9Cu0.1O2-δ shows higher activity than Ce0.9Mn0.1O2-d, due to the higher concentration of oxygen vacancies and the strong chemisorption of CO on the catalyst. For HCHO oxidation, Ce0.9Mn0.1O2-d shows slightly higher activity than Ce0.9Cu0.1O2-δ, due to the fact that the lattice oxygen is more easily reducible in Ce0.9Mn0.1O2-d than in Ce0.9Cu0.1O2-δ.

Keywords: Catalysts, Solid solutions, Oxidations, Sol-gel process, Oxides, Cerium, Copper, Manganese, Formaldehyde, Carbon monoxide

 

IPC Code: Int. Cl.9 C07B33/00; C01J21/00; C01J37/00

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1358-1363

 

Liquid phase hydrogenation of chloronitrobenzene to chloroaniline with PtM/CNTs (M=La, Ce, Pr, Nd and Sm) catalysts

Juhong Yang a, b, Chunhua Xionga, Xiaoxiang Hana, * & Lingxiao Zhoua

aDepartment of Applied Chemistry, College of Food Science & Biotechnology Engineering,
Zhejiang Gongshang University, Hangzhou 310035, PR China

Email: han-xx74@163.com

bZhejiang Medical College, Hangzhou 310053, PR China

Received 11 May 2009; revised and accepted 16 September 2009

Hydrogenation properties of chloronitrobenzene with Pt/CNT and PtM/CNT catalysts (M = La, Ce, Pr, Nd and Sm) have been studied in ethanol at 303 K and normal pressure. The results show that the hydrogenation of chloronitrobenzene can be carried out with PtM/CNT catalysts. The conversion of chloronitrobenzene is above 99% and chloroaniline is the main product in hydrogenation with PtM/CNT catalysts. Electron deficient species of the second element promote the specific rate constant turnover frequency expressed as per surface Pt atom by activating the nitrogen-oxygen bond. PtCe/CNT catalyst exhibits the best catalytic activity (TOF = 0.47 s-1) and the highest yield of p-CAN (97.5 mol%). PtSm/CNT catalyst shows the best yields for m-CAN (98.0 mol%) and o-CAN (96.9 mol%). PtCe/CNT (1.0 wt%) catalyst exhibits good stability for hydrogenation of p chloronitrobenzene.

Keywords: Catalysts, Hydrogenation, Liquid phase hydrogenation, Haloamines, Platinum, Carbon nanotubes


IPC Code: Int. Cl.9: B01J21/18C; B01J23/42; C07B35/02, C07C5/02, C07C17/354

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1364-1369

 

Artificial light assisted photocatalytic degradation of lissamine fast yellow dye in ZnO suspension in a slurry batch reactor

Brijesh Parea, *, Pardeep Singha & S B Jonnalgaddab

aLaboratory of Photocatalysis, Department of Chemistry, Govt Madhav Science Post Graduate College
Vikram University, Ujjain (MP) 456 010, India

bUniversity of KwaZulu-Natal, Westville, Durban, South Africa

Email: brijeshpare2009@hotmail.com/ pardeepchem@gmail.com

Received 10 February 2009; re-revised and accepted 7 September 2009

The photocatalytic degradation of lissamine fast yellow has been carried out in the aqueous suspension of ZnO under artificial light. The effects of process parameters such as catalyst loading, H2O2, FeCl3, etc., on the extent of degradation have been studied. The influence of pH, bubbling of N2 and O2 and temperature on degradation of the dye has also been studied. ZnO degrades the dye effectively in the presence of both artificial and solar light. The pH has a significant effect on reaction rate. H2O2, O2, and FeCl3 have a synergetic effect on degradation of the dye. The rate constant has an optimal value at 35C. N2 has a detrimental effect on dye degradation. Both Fe3+/ZnO/AR and H2O2/Fe3+/ZnO/AR processes have been found to be effective for the decolorisation of dye. However, the H2O2/Fe3+/ZnO/AR process is more efficient for the decolorisation of the selected dye. Increased COD-removal percentage, significant release of NO3- and SO42- ions and UV-vis spectral analysis confirm mineralization of the selected dye in aqueous phase. Power law has been applied to find the net rate of degradation.

Keywords: Photocatalysis, Degradations, Dyes, Azo dyes, Zinc oxide

 

IPC Code: Int. Cl.9 B01J23/06; C09B27/00

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1370-1377

 

Synthesis, characterization and superoxide dismutase activity of some four coordinated copper(II) complexes

R N Patel

Department of Chemistry, APS University, Rewa (MP) 486 003, India

Email: rnp64@yahoo.co.uk

Received 16 April 2009; revised and accepted 7 September 2009

Mixed ligand copper(II) complexes, viz., [Cu(Br-SAA)(ImH)], [Cu(Br-SAA)(MeImH)], [Cu(Br-SAA)(EtImH)], [Cu(Br-SAA)(BenzImH)] and [Cu(Br-SAA)(MebenzImH)], where Br-SAA = 5-bromosalicylideneanthranilic acid, ImH = imidazole, MeImH = 2-methyl imidazole, EtImH = 2-ethyl imidazole, BenzImH = benzimidazole, MebenzImH = 2-methyl benzimidazole are synthesized and characterized by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, FAB mass, IR, electronic, EPR spectral and cyclic voltammetric studies. The complex [Cu(Br-SAA)(ImH)] structurally characterized by single crystal X-ray crystallography, crystallizes in the triclinic space group P-1 with unit cell parameters: a = 3.7875(15), b = 10.6246(19), c = 19.977(3), α = 96.565(14), β = 94.45(2), γ = 92.32 (2) and Z = 2. The one electron paramagnetic complexes show a d-d band near 700 nm in DMSO and a cyclic voltammetric response due to Cu(II)/Cu(I) couple. The complexes show the presence of a distorted square planar CuN2O2 coordination geometry. Superoxide dismutase activity of these complexes have also been examined.

Keywords: Coordination chemistry, Copper, Imidazole, Schiff bases, X- ray crystallography

 

IPC Code: Int. Cl.9 C07C251/02; C07F1/08

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1378-1382

 

Effect of surface area, pore volume and particle size of P25 titania on the phase transformation of anatase to rutile

K Joseph Antony Raj & B Viswanathan*

National Centre for Catalysis Research, Indian Institute of Technology Madras, Chennai 600 036, India

Email: bvnathan@iitm.ac.in

Received 9 June 2009; revised and accepted 11 September 2009

The effect of calcination on P25 titania at different temperatures has been studied by XRD, nitrogen adsorption-desorption isotherm, BET-surface area, pore volume, pore size, particle size and crystallite size in order to understand the conversion of anatase phase to rutile phase. The fraction of anatase and rutile has been determined using XRD. Although the crystallinity remains the same, the phase change of anatase to rutile is inevitable with temperature. The isotherms show the non-porous characteristics of the P25 samples. In addition, nitrogen adsoption by the samples decreased appreciably with crystallinity. The pore volume and BET surface area show a large decrease at 900oC. The particle size, crystallite size, and pore size show an increasing trend with increase in temperature. Analysis of the physical characteristics indicates that P25 titania samples can be used for catalytic applications at less than 500oC.

Keywords: Catalysts, Phase transformations, Titania, Pore volume, Crystallinity, Particle size, Surface area

 

IPC Code: Int. Cl.9 B01J21/00

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1383-1387

 

Effect of polar dopants on structure of emission spectrum of crystalline anthracene powders

M N Gharge, S L Bhattar, G B Kolekar & S R Patil*

Fluorescence Spectroscopy Laboratory, Department of Chemistry Shivaji University, Kolhapur 416 004, India

Email: srp_fsl@rediffmail.com

Received 30 April 2009; revised and accepted 14 September 2009

The effect of polar dopants on the spectral properties of crystalline anthracene is studied as a function of concentration by steady state fluorescence spectroscopy. The dopant is a fluorescent 9-vinylanthracene. The incorporation of the dopant not only quenches the fluorescence but also changes the structure of emission of anthracene. The higher dopant concentration induces significant enhancement in the intensity of low energy (01) vibronic band at the expense of high energy (00) band and wavelength of maximum emissions is shifted from 427 nm to 446 nm. The characteristic monomer and excimer emission of dopant are not observed even at higher concentration in the fluorescence spectra of doped anthracene. This observation rules out the possibility of excitation energy transfer from anthracene to dopant molecule. The shift in structure of emission of anthracene has been attributed to the local electric field generated by the polar dopant which is acting across the anthracene molecule and induces the changes both in the molecular vibrational levels and in transition dipoles. This effect is similar to solid state solvation effect and favors transition to the higher vibrational level of the ground state.

Keywords: Fluorescence, Emission spectra, Anthracene, Polar dopants, Spectral shifts, Oscillatory transitions

 

IPC Code: Int. Cl.9 G01N21/64

 

Indian Journal of Chemistry

Vol. 48A, October 2009, pp. 1388-1393

 

Synthesis, characterization and X-ray single crystal studies of mono-n-butyltin(IV) dichloride complex of pyruvic acid- 2-pyridylhydrazone [n-BuSnCl2(PAP)]

M A Affana, *, I P P Fooa, B A Fasihuddina, M A Hapipahb & M Shamsuddinb

aDepartment of Chemistry, Faculty of Resource Science and Technology, Universiti Malaysia Sarawak,
94300 Kota Samarahan, Sarawak, Malaysia

Email: maaffan@frst.unimas.my

bDepartment of Chemistry, Faculty of Science, University Teknologi Malaysia, 81310 UTM, Skudai, Johor, Malaysia

Received 26 March 2009; revised and accepted 18 September 2009

Mono-n-butyltin(IV) dichloride complex with the general formula [n-BuSnCl2(PAP)] has been synthesized by direct reaction of n-BuSnCl3 with pyruvic acid-2-pyridylhydrazone in the presence of KOH in equimolar ratio in absolute methanol under nitrogen atmosphere. Both, the ligand as well as the complex, have been characterized by elemental analyses, UV-visible, IR, 1H NMR spectral and X-ray diffraction studies. [n-BuSnCl2(PAP)] is nonelectrolytic in nature. Single crystal X-ray diffraction studies indicate that [n-BuSnCl2(PAP)], is six-coordinated and adopts a distorted octahedral configuration with the coordination via carboxylic-O, imine-N and pyridyl-N atoms from the ligand. The crystal system of [n-BuSnCl2(PAP)] is tetragonal with space group I41/a and the unit cell dimensions:
a = 16.602(3), b = 16.602(3), c = 23.922(8), α = β = γ = 90˚.

Keywords: Coordination chemistry, Crystal structure, Tin, Hydrazones

 

IPC Code: Int. Cl.9 CO7F7/22