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

Rui-Juan Xiang; Hong-Yan Wang; Zhi-Juan Xin; Cheng-Bo Li; Ya-Xing Lu; Xue-Wang Gao; Hua-Ming Sun; Rui Cao

doi:10.1002/chem.201504066

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

Chemistry. 2016 Jan 26;22(5):1602-7. doi: 10.1002/chem.201504066. Epub 2016 Jan 7.

Authors

Rui-Juan Xiang^{1

2}, Hong-Yan Wang^{3

4}, Zhi-Juan Xin^{1

2}, Cheng-Bo Li⁵, Ya-Xing Lu², Xue-Wang Gao⁶, Hua-Ming Sun², Rui Cao^{7

8}

Affiliations

¹ Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119 (P. R. China).
² School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China.
³ Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119 (P. R. China). hongyan-wang@snnu.edu.cn.
⁴ School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China. hongyan-wang@snnu.edu.cn.
⁵ College of Chemistry & Materials Science, Northwest University, Xi'an, 710127, P. R. China.
⁶ Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
⁷ School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China. ruicao@ruc.edu.cn.
⁸ Department of Chemistry, Renmin University of China, Beijing, 100872, P. R. China. ruicao@ruc.edu.cn.

PMID: 26640173
DOI: 10.1002/chem.201504066

Abstract

The water-soluble polypyridine copper complex [Cu(F3TPA)(ClO4)2] [1; F3TPA=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 O2 evolution with a maximum turnover frequency (TOF) of (1.58 ± 0.03) × 10(-1) s(-1) and a maximum turnover number (TON) of 11.61 ± 0.23. In comparison, the reference [Cu(TPA)(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.

Keywords: copper; electrocatalysis; homogeneous catalysis; photochemistry; water oxidation.

Publication types

Research Support, Non-U.S. Gov't