A Water-Soluble Copper-Polypyridine Complex as a Homogeneous Catalyst for both Photo-Induced and Electrocatalytic O2 Evolution

被引：78

作者：

Xiang, Rui-Juan ^{[1
,2
]}

Wang, Hong-Yan ^{[1
,2
]}

Xin, Zhi-Juan ^{[1
,2
]}

Li, Cheng-Bo ^{[3
]}

Lu, Ya-Xing ^{[2
]}

Gao, Xue-Wang ^{[4
]}

Sun, Hua-Ming ^{[2
]}

Cao, Rui ^{[2
,5
]}

机构：

[1] Shaanxi Normal Univ, Sch Chem & Chem Engn, Key Lab Macromol Sci Shaanxi Prov, Xian 710119, Peoples R China

[2] Shaanxi Normal Univ, Sch Chem & Chem Engn, Xian 710119, Peoples R China

[3] NW Univ Xian, Coll Chem & Mat Sci, Xian 710127, Peoples R China

[4] Chinese Acad Sci, Key Lab Photochem Convers & Optoelect Mat, Tech Inst Phys & Chem, Beijing 100190, Peoples R China

[5] Renmin Univ China, Dept Chem, Beijing, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 05期

基金：

中国国家自然科学基金;

关键词：

copper; electrocatalysis; homogeneous catalysis; photochemistry; water oxidation; NEUTRAL AQUEOUS-SOLUTION; OXIDATION CATALYSTS; DIOXYGEN; COBALT; REDUCTION; LIGAND; IRON; PROTEINS; PH;

D O I：

10.1002/chem.201504066

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The water-soluble polypyridine copper complex [Cu(F(3)TPA)(ClO4)(2)] [1; F(3)TPA=tris(2-fluoro-6-pyridylmethyl)amine] catalyzes water oxidation in a pH 8.5 borate buffer at a relatively low overpotential of 610 mV. Assisted by photosensitizer and an electron acceptor, 1 also exhibits activity as a homogeneous catalyst for photo-induced O-2 evolution with a maximum turnover frequency (TOF) of (1.58 +/- 0.03) x 10(-1) s(-1) and a maximum turnover number (TON) of 11.61 +/- 0.23. In comparison, the reference [Cu(T-PA)(ClO4)(2)] [TPA=tris(2-pyridylmethyl)amine] displayed almost no activity under either set of conditions, implying the crucial role of the ligand in determining the behavior of the catalyst. Experimental evidence indicate the molecular catalytic nature of 1, leading to a potentially practical strategy to apply the copper complex in a photoelectrochemical device for water oxidation.

引用

页码：1602 / 1607

页数：6

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