Molecules, Vol. 29, Pages 1694: Electrocatalytic Reduction of CO2 to CO by Molecular Cobalt & ndash;Polypyridine Diamine Complexes

Molecules, Vol. 29, Pages 1694: Electrocatalytic Reduction of CO2 to CO by Molecular Cobalt–Polypyridine Diamine Complexes
Molecules doi: 10.3390/molecules29081694
Authors:
Yong Yang
Fang Xie
Jiahui Chen
Si Qiu
Na Qiang
Ming Lu
Zhongli Peng
Jing Yang
Guocong Liu

Cobalt complexes have previously been reported to exhibit high faradaic efficiency in reducing CO2 to CO. Herein, we synthesized capsule-like cobalt–polypyridine diamine complexes [Co(L1)](BF4)2 (1) and [Co(L2) (CH3CN)](BF4)2 (2) as catalysts for the electrocatalytic reduction of CO2. Under catalytic conditions, complexes 1 and 2 demonstrated the electrocatalytic reduction of CO2 to CO in the presence or absence of CH3OH as a proton source. Experimental and computational studies revealed that complexes 1 and 2 undergo two consecutive reversible one-electron reductions on the cobalt core, followed by the addition of CO2 to form a metallocarboxylate intermediate [CoII(L)–CO22−]0. This crucial reaction intermediate, which governs the catalytic cycle, was successfully detected using high resolution mass spectrometry (HRMS). In situ Fourier-transform infrared spectrometer (FTIR) analysis showed that methanol can enhance the rate of carbon–oxygen bond cleavage of the metallocarboxylate intermediate. DFT studies on [CoII(L)–CO22−]0 have suggested that the doubly reduced species attacks CO2 on the C atom throu...

Source: Molecules - April 9, 2024 Category: Chemistry Authors: Yong Yang Fang Xie Jiahui Chen Si Qiu Na Qiang Ming Lu Zhongli Peng Jing Yang Guocong Liu Tags: Article Source Type: research