Homogeneous Electrocatalytic Water Oxidation at Neutral pH by a Robust Macrocyclic Nickel(II) Complex

ニッケルオキシルラジカルをていしょうしています。

Angewandte Chemie International Edition by Mei Zhang, Ming-Tian Zhang, Cheng Hou, Zhuo-Feng Ke, Tong-Bu Lu  /  14d  //  keep unread  //  hide  //  preview Abstract The development of an earth-abundant, first-row water oxidation catalyst that operates at neutral pH and low overpotential remains a fundamental chemical challenge. Herein, we report the first nickel-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at neutral pH and low overpotential in phosphate buffer. The results of DFT calculations verify that the OO bond formation in catalytic water oxidation prefers a HOOH coupling mechanism from a cis-isomer of the catalyst. The first nickel-based homogeneous water oxidation catalyst has been reported, which can efficiently electrocatalyze water oxidation at neutral pH in phosphate buffer. The cis-conformation of the catalyst is the key active intermediate (see scheme; PCET=proton-coupled electron transfer).