A Dinuclear Cobalt Cryptate as a Homogeneous Photocatalyst for Highly Selective and Efficient Visible-Light Driven CO₂ Reduction to CO in CH₃CN/H₂O Solution

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• 作者：Ting Ouyang ; Hai-Hua Huang ; Jia-Wei Wang ; Dr. Di-Chang Zhong and Prof. Tong-Bu Lu
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：January 16, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：738-743
• 全文大小：1442K
• ISSN：1521-3773

文摘

A dinuclear cobalt complex [Co₂(OH)L¹](ClO₄)₃ (1, L¹=N[(CH₂)₂NHCH₂(m-C₆H₄)CH₂NH(CH₂)₂]₃N) displays high selectivity and efficiency for the photocatalytic reduction of CO₂ to CO in CH₃CN/H₂O (v/v=4:1) under a 450 nm LED light irradiation, with a light intensity of 100 mW cm⁻². The selectivity reaches as high as 98 %, and the turnover numbers (TON) and turnover frequencies (TOF) reach as high as 16896 and 0.47 s⁻¹, respectively, with the calculated quantum yield of 0.04 %. Such high activity can be attributed to the synergistic catalysis effect between two Co^II ions within 1, which is strongly supported by the results of control experiments and DFT calculations.