Chaturvedi Ashwin, McCarver Gavin A, Sinha Soumalya, Hix Elijah G, Vogiatzis Konstantinos D, Jiang Jianbing
Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, USA.
Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA.
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202206325. doi: 10.1002/anie.202206325. Epub 2022 Jul 11.
Electrocatalytic proton reduction to form dihydrogen (H ) 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 at -1.7 V vs. Fc/Fc ) and high selectivity (H Faradaic 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 (TOF ) for H production was obtained as 1099 s . 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.
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式。在本研究中，我们验证了一种基于主族元素的锡卟啉配合物作为质子还原有效分子电催化剂的适用性。一种聚乙二醇化锡卟啉配合物（SnPEGP）在以三氟乙酸（TFA）为质子源的乙腈（MeCN）中显示出高活性（相对于Fc/Fc⁺，在-1.7 V时为-4.6 mA cm⁻²）和高选择性（相对于Fc/Fc⁺，在-1.7 V时H₂法拉第效率为94%）。产生H₂的最大周转频率（TOF）为1099 s⁻¹。光谱电化学分析与量子化学计算相结合表明，质子还原通过电子-化学-电子-化学（ECEC）途径发生。本研究表明，锡卟啉催化剂是研究分子电催化反应的新型平台，并为质子还原提供了新的机理见解。
