Nickel Complexes with Non-innocent Ligands as Highly Active Electrocatalysts for Hydrogen Evolution

作者：Chen, Zhixin; Wang, Tao; Sun, Tingting; Chen, Zhiyong; Sheng, Tian; Hong, Yu-Hao; Nan, Zi-Ang; Zhu, Jun^*; Zhou, Zhi-You^*; Xia, Haiping^*; Sun, Shi-Gang

来源：Chinese Journal of Chemistry, 2018, 36(12): 1161-1164.

DOI：10.1002/cjoc.201800359

• hydrogen evolution
• molecular electrocatalysis
• non-innocent ligand
• electrochemistry
• homogeneous catalysis
• N ligands

Rational design of a molecular catalyst for a hydrogen evolution reaction (HER) with both high rates and low overpotential remains a challenge. Here we report a series of Ni-based catalysts incorporating non-innocent ligands and aimed at reduction of the overpotential by reserving electrons in the ligand, which could decouple the correlation between metal center reduction and metal hydride formation. The third-order rate constant of our catalysts can be increased by 2 orders of magnitude without increase of overpotential by altering the substituents in the imide since the electronic effect of substituents can change the kinetics of metal hydride formation dramatically. Furthermore, constructing a proton shuttle in the ligand further improves the activity. The catalyst with both of these features can catalyze HER at a turnover frequency of 2572 s(-1) with low concentrations of acid and an extremely high third-order rate constant of 2.7x10(6) M-2 center dot s(-1) at a low overpotential.

• 出版日期2018-12
• 单位厦门大学