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《Acta Chimica Sinica》 2008-08
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Electrocatalytic Oxidation of 4-Methylpyridine by Cr(Ⅲ)-Substituted Phosphorus Heteropolytungstate

WANG,Chong-Tai,a,b HUA,Ying-Jieb LI,Gao-Rena TONG,Ye-Xianga LI,Yu-Guang,a(a Institute of Optoelectronic and Functional Composite Materials,School of Chemistry and Chemical Engineering,Zhongshan University,Guangzhou 510275)(b Department of Chemistry,Hainan Normal University,Haikou 571158)  
On the basis of the characters that PW11O39CrⅢ(H2O)4-is oxidized or reduced in the in-ner-sphere electron transfer manner and that the sixth coordinate water bound to Cr(Ⅲ) center is readily re-placed by other ligand,the electrocatalytic oxidation of 4-methylpyridine by PW11O39CrⅢ(H2O)4-was in-vestigated.Vis spectrum confirmed the existence of PW11O39CrⅢ(NC6H7)4-due to a ligand exchange reac-tion between 4-methylpyridine and H2O in PW11O39CrⅢ(H2O)4-.Cyclic voltammetric and poten-tial-controlled electrolyte experiments indicated that the molecule of 4-methylpyridine modified onto the Cr(Ⅲ) active center was oxidized via a two electron transfer to form pyridine-4-methanol,pyri-dine-4-carboxaldehyde and 4-picolinic acid in turn.A novel electrocatalytic mechanism involving in in-tramolecular electron transfer was proposed,and thus a possible application to the electrocatalytic oxidation of substrate by transition metal-substituted heteropolyanions was provided according to this model.
【Fund】: 海南省教育厅高等学校科研(No.Hjkj200617)资助项目
【CateGory Index】: O641.4
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