Theoretical Study on the Electro-Reduction of Carbon Dioxide to Methanol Catalyzed by Cobalt Phthalocyanine

化学 质子化 催化作用 甲醇 配体(生物化学) 酞菁 光化学 一氧化碳 氧化还原 密度泛函理论 药物化学 无机化学 计算化学 有机化学 离子 生物化学 受体
作者
Le‐Le Shi,Man Li,Bo You,Rong‐Zhen Liao
出处
期刊:Inorganic Chemistry [American Chemical Society]
卷期号:61 (42): 16549-16564 被引量:31
标识
DOI:10.1021/acs.inorgchem.2c00739
摘要

Density functional theory (DFT) calculations have been conducted to investigate the mechanism of cobalt(II) tetraamino phthalocyanine (CoPc-NH2) catalyzed electro-reduction of CO2. Computational results show that the catalytically active species 1 (4[CoII(H4L)]0) is formed by a four-electron-four-proton reduction of the initial catalyst CoPc-NH2. Complex 1 can attack CO2 after a one-electron reduction to give a [CoIII-CO22-]- intermediate, followed by a protonation and a one-electron reduction to give intermediate [CoII-COOH]- (4). Complex 4 is then protonated on its hydroxyl group by a carbonic acid to generate the critical species 6 (CoIII-L•--CO), which can release the carbon monoxide as an intermediate (and also as a product). In parallel, complex 6 can go through a successive four-electron-four-proton reduction to produce the targeted product methanol without forming formaldehyde as an intermediate product. The high-lying π orbital and the low-lying π* orbital of the phthalocyanine endow the redox noninnocent nature of the ligand, which could be a dianion, a radical monoanion, or a radical trianion during the catalysis. The calculated results for the hydrogen evolution reaction indicate a higher energy barrier than the carbon dioxide reduction. This is consistent with the product distribution in the experiments. Additionally, the amino group on the phthalocyanine ligand was found to have a minor effect on the barriers of critical steps, and this accounts for the experimentally observed similar activity for these two catalysts, namely, CoPc-NH2 and CoPc.
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