A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals
A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals
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DOI：
10.1126/science.1185372
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发表时间：
2010-04-16
期刊：
影响因子：
56.9
通讯作者：
Hill, Craig L.
中科院分区：
文献类型：
--
作者：
Yin, Qiushi;Tan, Jeffrey Miles;Hill, Craig L.
传统的均相水氧化催化剂存在反应条件不稳定的问题。我们报道了配合物[Co-4（H2O）（2）（PW 9 O34）（2）]（10-），由抗氧化的多钨酸盐配体稳定的Co 4 O 4核组成，是一种水解和氧化稳定的均相水氧化催化剂，可在水中由地球上丰富的元素（Co，W和P）的盐自组装。以[Ru（bpy）（3）]（3+）（bpy是2，2 '-bipyridine）为氧化剂，在pH = 8时，我们观察到O-2产生的催化转换频率>= 5 s（-1）。速率的pH敏感性反映了四电子O-2-H2O对的pH依赖性。广泛的光谱、电化学和抑制研究明确表明，[Co-4（H2O）（2）（PW 9 O34）（2）]（10-）在催化转化条件下是稳定的：既不会原位形成水合钴离子，也不会原位形成氢氧化钴/氧化钴颗粒。
Traditional homogeneous water oxidation catalysts are plagued by instability under the reaction conditions. We report that the complex [Co-4(H2O)(2)(PW9O34)(2)](10-), 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 O-2 production >= 5 s(-1) at pH = 8. The rate's pH sensitivity reflects the pH dependence of the four-electron O-2-H2O couple. Extensive spectroscopic, electrochemical, and inhibition studies firmly indicate that [Co-4(H2O)(2)(PW9O34)(2)](10-) is stable under catalytic turnover conditions: Neither hydrated cobalt ions nor cobalt hydroxide/oxide particles form in situ.