Thiosulfate oxidation: Catalysis of synthetic sphalerite doped with transition metals

Abstract The rate of thiosulfate oxidation to tetrathionate by dissolved molecular oxygen was measured in aqueous suspensions of synthetic sphalerites doped with first row transition metals (Mn, Fe, Co, Ni, Cu). Pure sphalerite and Mn-doped sphalerite show no catalytic activity for this reaction. Catalytic activity increases from Fe to Ni, which has maximum activity, with a slight decrease moving to Cu. The catalytic activity of the doped sphalerites is proportional to the concentration of dopant. This trend in catalytic activity from pure sphalerite to Cu-doped sphalerite can be explained using the band structures of these solids.

[1]  A. Zunger,et al.  Many-electron multiplet effects in the spectra of 3 d impurities in heteropolar semiconductors , 1984 .

[2]  Arun S. Mujumdar,et al.  Introduction to Surface Chemistry and Catalysis , 1994 .

[3]  D. P. Kelly,et al.  Cyanolysis and spectrophotometric estimation of trithionate in mixture with thiosulfate and tetrathionate , 1969 .

[4]  S. Yanagida,et al.  Semiconductor photocatalysis. 13. Effective photoreduction of carbon dioxide catalyzed by zinc sulfide quantum crystallites with low density of surface defects , 1992 .

[5]  D. Nordstrom,et al.  Sampling and analysing mixtures of sulphate, sulphite, thiosulphate and polythionate. , 1984, Talanta.

[6]  A. Bard,et al.  Semiconductor Electrodes LI . Efficient Electroluminescence at Electrode in Aqueous Electrolytes , 1983 .

[7]  M. Pourbaix,et al.  Potential-pH equilibrium diagrams for the system S-H2O from 25 to 150°C: Influence of access of oxygen in sulphide solutions , 1992 .

[8]  P. Kohl,et al.  Semiconductor electrodes. 13. Characterization and behavior of n-type zinc oxide, cadmium sulfide, and gallium phosphide electrodes in acetonitrile solutions , 1977 .

[9]  T. Freund.  Electron injection into zinc oxide. , 1969 .

[10]  A. Fujishima,et al.  Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders , 1979, Nature.

[11]  Isolated iron and chromium as recombination centers in ZnS , 1990 .

[12]  J. Drever,et al.  Aquatic Chemical Kinetics , 1991 .

[13]  R. Heitz,et al.  The copper centre: a transient shallow acceptor in ZnS and CdS , 1992 .

[14]  J. Tossell,et al.  Electronic structure and the chemical reactivity of the surface of galena , 1987 .

[15]  G. Nickless.  Inorganic sulphur chemistry , 1968 .

[16]  A. Zunger,et al.  A universal trend in the binding energies of deep impurities in semiconductors , 1984 .

[17]  M. Schoonen,et al.  Removal of dissolved oxygen from water: A comparison of four common techniques. , 1994, Talanta.

[18]  Yong Xu,et al.  The stability of thiosulfate in the presence of pyrite in low-temperature aqueous solutions , 1995 .

[19]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[20]  J. Tossell,et al.  The bonding of ferrous iron to sulfur and oxygen in tetrahedral coordination: A comparative study using SCF Xα scattered wave molecular orbital calculations , 1974 .

[21]  H. Fujita,et al.  Semiconductor photocatalysis. I. Quantitative photoreduction of aliphatic ketones to alcohols using defect-free zinc sulfide quantum crystallites , 1990 .

[22]  John O’M. Bockris,et al.  Surface Electrochemistry: A Molecular Level Approach , 1993 .

[23]  W. Harrison.  Surface reconstruction on semiconductors , 1976 .

[24]  Johnson,et al.  Synchrotron radiation study of Cd1-xMnxTe (0 <= x <= 0.65). , 1986, Physical Review B (Condensed Matter).

[25]  Krueger,et al.  First-principles calculation of the electronic structure of the wurtzite semiconductors ZnO and ZnS. , 1993, Physical review. B, Condensed matter.

[26]  Jean François Dr. Reber,et al.  Photochemical production of hydrogen with zinc sulfide suspensions , 1984 .

[27]  Leena‐Sisko Johansson,et al.  XPS studies of the Zn1-xCoxS electronic structure , 1994 .

[28]  Wei,et al.  Total-energy and band-structure calculations for the semimagnetic Cd1-xMnxTe semiconductor alloy and its binary constituents. , 1987, Physical review. B, Condensed matter.

[29]  R. Shuey.  Semiconducting ore minerals , 2012 .

[30]  S. R. Morrison,et al.  The Chemical Physics of Surfaces , 1977 .

[31]  J. Craig,et al.  Mineral chemistry of metal sulfides , 1978 .