Hydrogen will be an important energy vector of the future, and improved efficiency in electrohydrolysis will accelerate this transition. In a fundamental study, we have prepared Co(II) and Ni(II) complexes of a new PNN type ligand N-((diphenylphosphanyl)methyl)-2-amino-1,10-phenanthroline (dppmaphen) incorporating the photoactive 1,10-phenanthroline group and the strongly coordinating diphenylphosphine to obtain photoelectrochemical (PEC) catalysts [Co(dppmaphen)2(NO3)2] (1) and [Ni(dppmaphen)2Cl]Cl (2) which catalyzed the hydrogen evolution reaction (HER) in alkaline media (1 M KOH). Overpotentials (η10) of 430 (1) and 364 mV (2) could be reduced to 345 (1) and 284 mV (2) under Xe light irradiation. This irradiation generated photocurrent responses of 528 (1) and 357 uA/cm2 (2). Density function theory (DFT) calculation on the frontier orbitals of 1 and 2 were useful in understanding these differences in catalytic performance.

中文翻译：

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PNN型配体的钴（II）和镍（II）配合物作为光增强电催化剂用于氢释放反应。

氢将成为未来的重要能源载体，提高电水解效率将加速这一转变。在一项基础研究中，我们制备了一种新的PNN型配体N-（（（二苯基膦基）甲基）-2-氨基-1,10-菲咯啉（dppmaphen）并结合了光敏性1， 10-菲咯啉基团和强配位的二苯膦获得光电化学（PEC）催化剂[Co（dppmaphen）2（NO3）2]（1）和[Ni（dppmaphen）2Cl] Cl（2），该催化剂催化制氢反应（HER） ）在碱性介质（1 M KOH）中。430（1）和364 mV（2）的过电势（η10）在Xe光照射下可以降低到345（1）和284 mV（2）。这种照射产生的光电流响应为528（1）和357 uA / cm2（2）。