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nxl5096224(½ð±Ò+2):3Q! 2010-07-31 15:27:59
Science 16 April 2010
DOI: 10.1126/science.1185372

A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals
Qiushi Yin, Jeffrey Miles Tan, Claire Besson, Yurii V. Geletii, Djamaladdin G. Musaev, Aleksey E. Kuznetsov, Zhen Luo, Ken I. Hardcastle, Craig L. Hill

Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co4(H2O)2(PW9O34)2]10¨C, comprising a Co4O4 core stabilized by oxidatively resistant polytungstate ligands, is a hydrolytically and oxidatively stable homogeneous water oxidation catalyst that self-assembles in water from salts of earth-abundant elements (Co, W, and P). With [Ru(bpy)3]3+ (bpy is 2,2'-bipyridine) as the oxidant, we observe catalytic turnover frequencies for O2 production 5 s¨C1 at pH = 8. The rate¡¯s pH sensitivity reflects the pH dependence of the four-electron O2-H2O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co4(H2O)2(PW9O34)2]10¨C is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.
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