A PEGylated Tin Porphyrin Complex for Electrocatalytic Proton Reduction: Mechanistic Insights into Main‐Group‐Element Catalysis
A PEGylated Tin Porphyrin Complex for Electrocatalytic Proton Reduction: Mechanistic Insights into Main‐Group‐Element Catalysis
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用于电催化质子还原的聚乙二醇化锡卟啉配合物：对主族元素催化的机理见解
DOI：
10.1002/anie.202206325
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Jiang, Jianbing
中科院分区：
文献类型：
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作者：
Chaturvedi, Ashwin;McCarver, Gavin A.;Sinha, Soumalya;Hix, Elijah G.;Vogiatzis, Konstantinos D.;Jiang, Jianbing
电催化质子还原生成氢气（H2）是一种以化学键形式储存能量的有效方法。在这项研究中，我们验证了基于主族元素的锡卟啉配合物作为质子还原的有效分子电催化剂的适用性。聚乙二醇化的锡卟啉复合物（SnPEGP）在乙腈（MeCN）中以三氟乙酸（TFA）作为质子源显示出高活性（在-1.7 V vs. Fc/Fc+时为-4.6 mA cm-2）和高选择性（在-1.7 V vs. Fc/Fc+时为94%的H2法拉第效率）。 H2生产的最大周转频率（TOFmax）为1099 s-1。 光谱电化学分析结合量子化学计算表明，质子还原通过电子-化学-电子-化学（ECEC）途径发生。这项研究表明，锡卟啉催化剂作为一个新的平台，研究分子电催化反应，并提供了新的机制的见解质子还原。
Electrocatalytic proton reduction to form dihydrogen (H2) is an effective way to store energy in the form of chemical bonds. In this study, we validate the applicability of a main‐group‐element‐based tin porphyrin complex as an effective molecular electrocatalyst for proton reduction. A PEGylated Sn porphyrin complex (SnPEGP) displayed high activity (−4.6 mA cm−2at −1.7 V vs. Fc/Fc+) and high selectivity (H2Faradaic efficiency of 94 % at −1.7 V vs. Fc/Fc+) in acetonitrile (MeCN) with trifluoroacetic acid (TFA) as the proton source. The maximum turnover frequency (TOFmax) for H2production was obtained as 1099 s−1. Spectroelectrochemical analysis, in conjunction with quantum chemical calculations, suggest that proton reduction occurs via an electron‐chemical‐electron‐chemical (ECEC) pathway. This study reveals that the tin porphyrin catalyst serves as a novel platform for investigating molecular electrocatalytic reactions and provides new mechanistic insights into proton reduction.