Details

Autor(en) / Beteiligte

• 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

Titel

The Difference Se Makes: A Bio‐Inspired Dppf‐Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance

Ist Teil von

• Chemistry : a European journal, 2018-06, Vol.24 (33), p.8275-8280

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. Breaking new ground with Se: A dppf‐supported NiII diselenolate complex was synthesized and used as an efficient and robust oxygen‐tolerant dihydrogen‐production electrocatalyst. More importantly, the selenium‐based complex represents a 13‐fold enhancement in catalytic activity vs. the sulfur‐containing analogue. As indicated by DFT studies, the Se atom as a bio‐inspired proton relay plays a key role in facilitating protonation of a Ni‐hydride species and H2 evolution.