甲醇
化学
催化作用
钴
活动站点
酞菁
吸收光谱法
光化学
电子转移
无机化学
反应性(心理学)
加合物
电催化剂
X射线吸收光谱法
有机化学
物理化学
电化学
电极
医学
物理
替代医学
病理
量子力学
作者
Conor L. Rooney,Mason Lyons,Yueshen Wu,Gongfang Hu,Maoyu Wang,Chungseok Choi,Yuanzuo Gao,Chun‐Wai Chang,Gary W. Brudvig,Zhenxing Feng,Hailiang Wang
标识
DOI:10.1002/anie.202310623
摘要
Abstract Many metal coordination compounds catalyze CO 2 electroreduction to CO, but cobalt phthalocyanine hybridized with conductive carbon such as carbon nanotubes is currently the only one that can generate methanol. The underlying structure–reactivity correlation and reaction mechanism desperately demand elucidation. Here we report the first in situ X‐ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc‐catalyzed CO 2 reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi‐electron CO 2 reduction. CO, the key intermediate in the CO 2 ‐to‐methanol pathway, is found to be labile on the active site, which necessitates a high local concentration in the microenvironment to compete with CO 2 for active sites and promote methanol production. A comparison of the electrocatalytic performance of structurally related porphyrins indicates that the bridging aza‐N atoms of the Pc macrocycle are critical components of the CoPc active site that produces methanol. In situ X‐ray absorption spectroscopy identifies the active site as Co(I) and supports an increasingly non‐centrosymmetric Co coordination environment at negative applied potential, likely due to the formation of a Co−CO adduct during the catalysis.
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