A Nickel(II) Complex as a Homogeneous Electrocatalyst for Water Oxidation at Neutral pH: Dual Role of HPO42- in Catalysis

作者：Wang, Jia-Wei; Zhang, Xiang-Qiong; Huang, Hai-Hua; Lu, Tong-Bu^*

来源：ChemCatChem, 2016, 8(20): 3287-3293.

DOI：10.1002/cctc.201600796

• electrocatalysis
• homogeneous catalyst
• molecular catalysis
• nickel
• water oxidation

A new mononuclear nickel complex, featuring two cis-relative labile sites, is reported as a homogeneous electrocatalyst for water oxidation in a neutral phosphate buffer. The water oxidation catalysis can be initiated at a moderate overpotential of approximately 0.48V. Mechanistic studies reveal that the oxidation of water by a two-electron oxidized species of the nickel catalyst is feasible, with formation of a peroxide intermediate through intramolecular O-O coupling. Interestingly, it has been found that the buffer base (HPO42-) plays a dual role in the catalytic system: it acts as a proton acceptor to expedite proton-coupled electron transfer (PCET) during catalysis, but it also suppresses the electrocatalysis through an anation process.

• 出版日期2016-10-20
• 单位中山大学