A Bio-inspired Cu4 O4 Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Xin Jiang; Jian Li; Bing Yang; Xiang-Zhu Wei; Bo-Wei Dong; Yi Kao; Mao-Yong Huang; Chen-Ho Tung; Li-Zhu Wu

doi:10.1002/anie.201803944

A Bio-inspired Cu₄ O₄ Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Angew Chem Int Ed Engl. 2018 Jun 25;57(26):7850-7854. doi: 10.1002/anie.201803944. Epub 2018 May 25.

Authors

Xin Jiang^{1

2}, Jian Li^{1

2}, Bing Yang^{1

2}, Xiang-Zhu Wei^{1

2}, Bo-Wei Dong³, Yi Kao³, Mao-Yong Huang^{1

2}, Chen-Ho Tung^{1

2}, Li-Zhu Wu^{1

2}

Affiliations

¹ Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing, 100190, P. R. China.
² School of Future Technologies, University of Chinese Academy of Sciences, Beijing, 100190, P. R. China.
³ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.

PMID: 29701323
DOI: 10.1002/anie.201803944

Abstract

Inspired by the cubic Mn₄ CaO₅ cluster of natural oxygen-evolving complex in Photosystem II, tetrametallic molecular water oxidation catalysts, especially M₄ O₄ cubane-like clusters (M=transition metals), have aroused great interest in developing highly active and robust catalysts for water oxidation. Among these M₄ O₄ clusters, however, copper-based molecular catalysts are poorly understood. Now, bio-inspired Cu₄ O₄ cubanes are presented as effective molecular catalysts for electrocatalytic water oxidation in aqueous solution (pH 12). The exceptional catalytic activity is manifested with a turnover frequency (TOF) of 267 s^-1 for [(L_Gly -Cu)₄ ] at 1.70 V and 105 s^-1 for [(L_Glu -Cu)₄ ] at 1.56 V. Electrochemical and spectroscopic study revealed a successive two-electron transfer process in the Cu₄ O₄ cubanes to form high-valent Cu^III and Cu^III O^. intermediates during the catalysis.

Keywords: copper complexes; cubane-like cores; molecular catalysis; oxygen-evolution reactions; water oxidation.

Publication types

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