Premium
The Difference Se Makes: A Bio‐Inspired Dppf‐Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance
Author(s) -
Pan ZhongHua,
Tao YunWen,
He QuanFeng,
Wu QiaoYu,
Cheng LiPing,
Wei ZhanHua,
Wu JiHuai,
Lin JinQing,
Sun Di,
Zhang QiChun,
Tian Dan,
Luo GengGeng
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801893
Subject(s) - catalysis , nickel , electrocatalyst , ferrocene , electrochemistry , chemistry , selenium , oxygen evolution , metal , oxygen , combinatorial chemistry , inorganic chemistry , electrode , organic chemistry
Inspired by the metal active sites of [NiFeSe]‐hydrogenases, a dppf‐supported nickel(II) selenolate complex (dppf=1,1′‐bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme‐like H 2 evolution turnover frequency (TOF) of 7838 s −1 under an Ar atmosphere, which markedly surpasses the activity of a dppf‐supported nickel(II) thiolate analogue with a low TOF of 600 s −1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio‐inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H 2 production. For the first time, this type of Ni selenolate‐containing electrocatalyst displays a high degree of O 2 and H 2 tolerance. Our results should encourage the development of the design of highly efficient oxygen‐tolerant Ni selenolate molecular catalysts.