The difference Se makes : a bio-inspired dppf-supported nickel selenolate complex boosts dihydrogen evolution with high oxygen tolerance

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 H2 evolution turnover frequency (TOF) of 7838 ...

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Main Authors: Pan, Zhong-Hua, Tao, Yun-Wen, He, Quan-Feng, Wu, Qiao-Yu, Cheng, Li-Ping, Wei, Zhan-Hua, Wu, Ji-Huai, Lin, Jin-Qing, Sun, Di, Zhang, Qi-Chun, Tian, Dan, Luo, Geng-Geng
Other Authors: School of Materials Science & Engineering
Format: Article
Language:English
Published: 2020
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Online Access:https://hdl.handle.net/10356/139416
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Institution: Nanyang Technological University
Language: English
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Summary: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 H2 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 H2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O2 and H2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts.