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51.
Chockalingam Karunakaran Premkumar Anilkumar 《Central European Journal of Chemistry》2009,7(3):519-523
Oxidation of iodide ion from an air-saturated solution under natural sunlight (900±50 W m−2) on the surfaces of TiO2, ZnO, Fe2O3, MoO3 and CeO2 enhances by 6 to 12-fold on application of a cathodic bias of −0.2 to −0.3 V (vs NHE) to the semiconductors; light, the semiconductor and dissolved oxygen are essential for iodine generation. The semiconductors
under an anodic bias of +0.2 to +0.3 V (vs NHE) fail to oxidize iodide ion from air-saturated solution under sunlight. Under cathodic bias, semiconductor mixtures like
TiO2-ZnO, TiO2-Fe2O3 and ZnO-Fe2O3 show enhanced photocatalytic activity, indicating improved charge separation in oxide mixtures. The mechanism of photocatalysis
under cathodic bias is discussed.
相似文献
52.
Selectivity in photocatalysis by particulate semiconductors 总被引:1,自引:0,他引:1
Chockalingam Karunakaran Ramamoorthy Dhanalakshmi 《Central European Journal of Chemistry》2009,7(1):134-137
TiO2, Fe2O3, CuO, ZnO, ZnS, Nb2O5, MoO3, CdO, CdS, Sb2O3, CeO2, HgO, Pb2O3, PbO2 and Bi2O3 microparticles exhibit band gap excitation with UV-A light but they are selective to photodegrade phenols. While TiO2 anatase and ZnO photocatalyze the degradation of phenol, o-aminophenol, m-aminophenol, p-aminophenol, o-chlorophenol, m-chlorophenol,
p-chlorophenol, o-nitrophenol, p-nitrophenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and quinol, MoO3 does not photodegrade any of the fifteen phenols. Fe2O3, CuO, ZnS, Nb2O5, CdO, CdS, Sb2O3, CeO2, HgO, Pb2O3, PbO2 and Bi2O3 are selective in photodegrading the fifteen phenols; however, the phenols get adsorbed over all sixteen particulate semiconductors.
相似文献
53.
Chockalingam Karunakaran Premkumar Anilkumar Paramasivan Gomathisankar 《Monatshefte für Chemie / Chemical Monthly》2010,7(3):529-537
Abstract
Ag-doped TiO2 (anatase) samples (mass fraction w Ag = 0.01 and w Ag = 0.02) of 15.9 and 14.5 nm mean particle size and 11.46 and 10.14 m2 g−1 BET surface area were prepared by photodeposition. Doping results in surface plasmon resonance of the metallic silver nanoclusters at around 500 nm, but the absorption edge remains unaltered at 365 nm. Ag-doping remarkably enhances the photooxidation of iodide ion under UV light; iodine formation with Ag/TiO2 with w Ag = 0.01 is 16 times greater than with bare TiO2. The reaction conforms to Langmuir–Hinshelwood kinetics with regard to both I− and O2. Increase of pH slows down iodine formation and sacrificial electron donors arrest the reaction. Pre-sonication of the catalyst slurry hinders the photocatalysis. Generation of iodine is much greater in acetonitrile than in water. Under the experimental conditions, Ag/TiO2 with w Ag = 0.01 is more efficient than Ag/TiO2 with w Ag = 0.02, and the enhanced photocatalysis is likely to be because of suppression of electron–hole pair recombination. Kinetic analysis reveals that increasing the Ag mass fraction from 0.01 to 0.02 enhances the surface pseudo-first-order rate constant but inhibits the adsorption of iodide ion and the oxygen molecule on the illuminated oxide surface. 相似文献54.
PdNi bimetallic nanoparticles coated onto manganite (MN) nanocatalyst was used for ethylene glycol (EG) and glycerol (Gly) electrooxidation in alkaline media. The MN nanorods were prepared by hydrothermal method, and the PdNi was coated on the rods by an in situ reduction method. The prepared nanocomposite was characterized by scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM), Energy dispersive X-ray spectroscopy (EDS), and electrochemical methods. The SEM and TEM images exhibit the formation of nanorods of 10?nm and also show the formation of nanocrystalline PdNi on the walls of the MN nanorods. This study shows that the MN nanorods can be excellent support material and they supply oxygen to the catalyst, by which the catalytic activity is enhanced. The electrooxidation reactions in strong alkaline condition containing various concentrations of EG have been studied. Among the different concentrations, 9?M KOH/6?M EG exhibits the highest activity. PdNi/MN nanocatalyst exhibits better activity even in higher electrolytic concentrations of EG and alkali. 相似文献
55.
R.T. Karunakaran K. Marimuthu S. Surendra Babu S. Arumugam 《Journal of luminescence》2010,130(6):1067-7433
Thermal, structural and optical properties of Dy3+-doped alkali fluoroborate glasses with composition (in mol%), 49B2O3+25XO+25NaF+1Dy2O3 (where X=Li2, Na2, K2, Mg and Ca), have been investigated. Thermal analysis revealed the homogeneous formation of the glasses. The FTIR spectra reveal that the glasses contain BO3, BO4 non-bridging oxygen atoms and strong OH− bonds. From the optical absorption spectra, Judd-Ofelt intensity parameters (Ωλ, λ=2, 4 and 6) have been evaluated and are in turn used to predict radiative properties such as radiative transition probability (A), stimulated emission cross-section () and branching ratios (βR) for the excited levels of Dy3+ ions in alkali fluoroborate glasses. The dependence of the spectral characteristics of Dy3+ ions due to compositional changes has been examined and reported. 相似文献
56.
Chandra Sekhar Prasanth Suneesh C. Karunakaran Albish K. Paul Vesselin Kussovski Vanya Mantareva Danaboyina Ramaiah Leslie Selvaraj Ivan Angelov Latchezar Avramov Krishnankutty Nandakumar Narayanan Subhash 《Photochemistry and photobiology》2014,90(3):628-640
The Gram‐negative Aggregatibacter actinomycetemcomitans and Fusobacterium nucleatum are major causative agents of aggressive periodontal disease. Due to increase in the number of antibiotic‐resistant bacteria, antimicrobial Photodynamic therapy (aPDT) seems to be a plausible alternative. In this work, photosensitization was performed on Gram‐positive and Gram‐negative bacteria in pure culture using new‐age cationic porphyrins, namely mesoimidazolium‐substituted porphyrin derivative ( ImP ) and pyridinium‐substituted porphyrin derivative ( PyP ). The photophysical properties of both the sensitizers including absorption, fluorescence emission, quantum yields of the triplet excited states and singlet oxygen generation efficiencies were evaluated in the context of aPDT application. The studied porphyrins exhibited high ability to accumulate into bacterial cells with complete penetration into early stage biofilms. As compared with ImP, PyP was found to be more effective for photoinactivation of bacterial strains associated with periodontitis, without any signs of dark toxicity, owing to its high photocytotoxicity. 相似文献
57.
M. Karunakaran C.T. Vijayakumar D. Muthamil Selvan C. Magesh 《Journal of Saudi Chemical Society》2013,17(1):1-8
o-Cresol–thiourea–formaldehyde terpolymer resin was synthesized through the condensation of o-cresol and thiourea with formaldehyde in the mole ratio 1:3:5 in the presence of 2 M hydrochloric acid as a catalyst. The resulting copolymer was characterized with IR and 1H NMR spectral data. The average molecular weight of the resin was determined by Gel permeation chromatography. Thermal study of the resin was carried out to calculate the activation energy (Ea), enthalpy of activation (H3), entropy of activation (S3), free energy of activation (G3), and pre-exponential factor (A) of various steps of thermal decomposition of the terpolymer. The Dharwadkar and Kharkhanavala method has been used to calculate thermal activation energy and thermal stability. The chelation ion-exchange properties were also studied with the batch equilibrium method. The chelation ion-exchange properties of the copolymer was studied for Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+ and Cd2+ ions. The resin was proved to be selective chelating ion-exchange copolymer for certain metals. The study was carried out over a wide pH range and in media of various ionic strengths. 相似文献
58.
Chockalingam Karunakaran Arumugam Vijayabalan Govindasamy Manikandan 《Research on Chemical Intermediates》2013,39(3):1437-1446
Cd-doped TiO2 nanoparticles have been obtained by polyethylene glycol-assisted sol–gel synthesis and characterized by powder X-ray diffraction, energy dispersive X-ray analysis, high-resolution scanning electron microscopy and UV–visible diffuse reflectance, photoluminescence and impedance spectroscopies. Use of polyethylene glycol as templating agent provides club-shaped particles. Doping TiO2 with Cd decreases the average crystallite size and charge transfer resistance, increases the capacitance, and leads to blue emission. Cd-doping enhances the visible light photocatalytic disinfection of bacteria but not dye degradation. 相似文献
59.
Prakash S Rajesh S Singh SK Bhargava K Ilavazhagan G Vasu V Karunakaran C 《Talanta》2011,85(2):964-969
A highly sensitive NOx sensor was designed and developed by electrochemical incorporation of copper nanoparticles (CuNP) on single-walled carbon nanotubes (SWCNT)-polypyrrole (PPy) nanocomposite modified Pt electrode. The modified electrodes were characterized by scanning electron microscopy and energy dispersive X-ray analysis. Further, the electrochemical behavior of the CuNP-SWCNT-PPy-Pt electrode was investigated by cyclic voltammetry. It exhibited the characteristic CuNP reversible redox peaks at −0.15 V and −0.3 V vs. Ag/AgCl respectively. The electrocatalytic activity of the CuNP-SWCNT-PPy-Pt electrode towards NOx is four-fold than the CuNP-PPy-Pt electrode. These results clearly revealed that the SWCNT-PPy nanocomposite facilitated the electron transfer from CuNP to Pt electrode and provided an electrochemical approach for the determination of NOx. A linear dependence (r2 = 0.9946) on the NOx concentrations ranging from 0.7 to 2000 μM, with a sensitivity of 0.22 ± 0.002 μA μM−1 cm−2 and detection limit of 0.7 μM was observed for the CuNP-SWCNT-PPy-Pt electrode. In addition, the sensor exhibited good reproducibility and retained stability over a period of one month. 相似文献
60.
Chockalingam Karunakaran Jayaraman Jayabharathi Marimuthu Venkatesh Perumal Venugopal Thanikachalam Prasoon Kumar Thakur 《Journal of Physical Organic Chemistry》2013,26(5):386-406
Phenanthrimidazoles as hole transport materials have been synthesized, characterized, and applied as nondoping emitters in organic light emitting devices. The synthesized molecules possess high fluorescent quantum yield and thermal properties and display film forming abilities. The highest occupied molecular orbital (HOMO) energies of these materials are shallower than the reported tris(8‐hydroxyquinoline)aluminum (Alq3), which enables the hole transport ability of these phenanthrimidazoles. Taking advantage of the thermal stability and hole transporting ability, these compounds can be used as a functional layer between NPB [4,4‐bis(N‐(1‐naphthyl)‐N‐phenylamino)biphenyl] and Alq3 layers and show that these phenanthrimidazoles can be alternatively used as novel hole transport materials and to improve the device performances. Geometrical, optical, electrical, and electroluminescent properties of these molecules have been probed. Further, natural bond orbital, nonlinear optical materials (NLO), molecular electrostatic potential, and HOMO–lowest unoccupied molecular orbital (LMO) energy analysis have been made by density functional theory (DFT) method to support the experimental results. Hyperpolarizability analysis reveals that the synthesized phenanthrimidazoles possess NLO behavior. The chemical potential, hardness, and electrophilicity index of phenanthrimidazoles have also been computed by DFT method. Photoinduced electron transfer explains the enhancement of fluorescence by nanoparticulate ZnO, and the apparent binding constant has been obtained. Adsorption of the fluorophore on ZnO nanoparticle lowers the HOMO and LUMO energy levels of the fluorophore. The strong adsorption of the phenanthrimidazoles on the surface of ZnO nanocrystals is likely due to the chemical affinity of the nitrogen atom of the organic molecule to Zn(II) on the surface of nanocrystal. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献