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解析钴催化剂驱动析氢反应的机理途径

Unravelling the Mechanistic Pathway of the Hydrogen Evolution Reaction Driven by a Cobalt Catalyst.

作者信息

Jiang Bing, Gil-Sepulcre Marcos, Garrido-Barros Pablo, Gimbert-Suriñach Carolina, Wang Jia-Wei, Garcia-Anton Jordi, Nolis Pau, Benet-Buchholz Jordi, Romero Nuria, Sala Xavier, Llobet Antoni

机构信息

Departament de Química, Universitat Autònoma de Barcelona Cerdanyola del Valles, 08193, Barcelona, Spain.

Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, 43007, Tarragona, Spain.

出版信息

Angew Chem Int Ed Engl. 2022 Oct 4;61(40):e202209075. doi: 10.1002/anie.202209075. Epub 2022 Aug 24.

DOI:10.1002/anie.202209075
PMID:35922381
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9804897/
Abstract

A cobalt complex bearing a κ-N P ligand is presented (1 or Co (L), where L is (1E,1'E)-1,1'-(pyridine-2,6-diyl)bis(N-(3-(diphenylphosphanyl)propyl)ethan-1-imine). Complex 1 is stable under air at oxidation state Co thanks to the π-acceptor character of the phosphine groups. Electrochemical behavior of 1 reveals a two-electron Co /Co oxidation process and an additional one-electron reduction, which leads to an enhancement in the current due to hydrogen evolution reaction (HER) at E =-1.6 V vs Fc/Fc . In the presence of 1 equiv of bis(trifluoromethane)sulfonimide, 1 forms the cobalt hydride derivative Co (L)-H (2 ), which has been fully characterized. Further addition of 1 equiv of CoCp* (Cp* is pentamethylcyclopentadienyl) affords the reduced Co (L)-H (2 ) species, which rapidly forms hydrogen and regenerates the initial Co (L) (1 ). The spectroscopic characterization of catalytic intermediates together with DFT calculations support an unusual bimolecular homolytic mechanism in the catalytic HER with 1 .

摘要

本文报道了一种带有κ-N P配体的钴配合物（1或Co (L)，其中L为(1E,1'E)-1,1'-(吡啶-2,6-二基)双(N-(3-(二苯基膦基)丙基)乙-1-亚胺）。由于膦基团的π-受体特性，配合物1在空气中处于Co氧化态时是稳定的。1的电化学行为揭示了一个双电子Co /Co氧化过程和一个额外的单电子还原过程，这导致在E = -1.6 V vs Fc/Fc时由于析氢反应（HER）而使电流增强。在存在1当量双(三氟甲烷)磺酰亚胺的情况下，1形成了钴氢化物衍生物Co (L)-H（2），该衍生物已得到充分表征。进一步加入1当量的CoCp*（Cp*为五甲基环戊二烯基）得到还原态的Co (L)-H（2）物种，其迅速生成氢气并再生初始的Co (L)（1）。催化中间体的光谱表征以及密度泛函理论计算支持了1催化HER过程中一种不寻常的双分子均裂机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d642/9804897/2bea2b999f17/ANIE-61-0-g006.jpg
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