Bioinspired Trinuclear Copper Catalyst for Water Oxidation with a Turnover Frequency up to 20000 s-1
Bioinspired Trinuclear Copper Catalyst for Water Oxidation with a Turnover Frequency up to 20000 s-1
复制标题
DOI：
10.1021/jacs.1c08078
复制
发表时间：
2021-12-01
影响因子：
15
通讯作者：
Zhang, Ming-Tian
中科院分区：
文献类型：
--
作者：
Chen, Qi-Fa;Cheng, Ze-Yu;Zhang, Ming-Tian
太阳能水分解是构建用于生产太阳能燃料的人工光合作用系统的理想反应。自然光系统 II 是通过将水氧化成分子氧并为燃料生产提供四个电子来研究人工太阳能转换的原型模板。尽管已经开发了一系列合成分子水氧化催化剂，但对这种多电子和多质子催化过程中O-O键形成的理解有限，因此水氧化仍然是一个巨大的挑战。在此，我们报道了一种三核铜簇，受多铜氧化酶（MCO）的启发，它对催化水氧化表现出出色的反应活性，它可以有效地将 O-2 催化四电子还原为水。该合成模拟物在碳酸氢钠溶液中的周转频率为20000 s(-1)，分别比单核Cu催化剂(F-N2O2Cu，131.6 s(-1))和双核Cu-2配合物(HappCu(2)，1375 s(-1))高约150和15倍。这项工作表明，多种金属之间的合作是调节水氧化催化中O-O键形成的有效策略。
Solar-powered water splitting is a dream reaction for constructing an artificial photosynthetic system for producing solar fuels. Natural photosystem II is a prototype template for research on artificial solar energy conversion by oxidizing water into molecular oxygen and supplying four electrons for fuel production. Although a range of synthetic molecular water oxidation catalysts have been developed, the understanding of O-O bond formation in this multielectron and multiproton catalytic process is limited, and thus water oxidation is still a big challenge. Herein, we report a trinuclear copper cluster that displays outstanding reactivity toward catalytic water oxidation inspired by multicopper oxidases (MCOs), which provides efficient catalytic four-electron reduction of O-2 to water. This synthetic mimic exhibits a turnover frequency of 20000 s(-1) in sodium bicarbonate solution, which is about 150 and 15 times higher than that of the mononuclear Cu catalyst (F-N2O2Cu, 131.6 s(-1)) and binuclear Cu-2 complex (HappCu(2), 1375 s(-1)), respectively. This work shows that the cooperation between multiple metals is an effective strategy to regulate the formation of O-O bond in water oxidation catalysis.