Modulating the electrocatalytic activity of mononuclear nickel complexes toward water oxidation by tertiary amine...

Water oxidation is the bottleneck of water splitting, which is a promising strategy for hydrogen production. Therefore, it is significant to develop efficient water oxidation catalysts. Herein, electrochemical water oxidation catalyzed by three nickel complexes, namely [Ni(bptn)(H₂O)](ClO₄)₂ (1), [Ni(mbptn)(CH₃CN)](ClO₄)₂ (2), and [Ni(tmbptn)(H₂O)](ClO₄)₂ (3) (bptn = 1,9-bis(2-pyridyl)-2,5,8-triazanonane, mbptn = 5-methyl-1,9-bis(2-pyridyl)-2,5,8-triazanonane, and tmbptn = 1,9-bis(2-pyridyl)-2,5,8-triazanonane), is studied under near-neutral condition (pH 9.0). Meanwhile, the homogeneous catalytic behaviors of the three mononuclear nickel complexes were investigated and confirmed by scanning electron microscopy, energy dispersive spectrometry, X-ray photoelectron spectroscopy and electrochemical method. Complex 1 stabilized by a pentadentate ligand with three N-H fragments homogeneously catalyzes water oxidation to oxygen with the lowest onset overpotential. Complex 2 stabilized by a similar ligand with two N-H groups and one N-CH₃ group exhibits relatively higher onset overpotential but higher catalytic current and turnover frequency. However, complex 3 with three N-CH₃ coordination environment shows the highest onset overpotential and the highest catalytic current at higher potential. Comparison of catalytic behaviors and ligand structure of the three complexes reveals that the methyl group on the polypyridine amine ligand affects the water oxidation activity of the complexes obviously. The electronic effect of N-CH₃ coordination environment leads to higher redox potential of the metal center and potential demand for water oxidation, while it leads to higher reaction activity of high-valent intermediates, which account for higher catalytic current and efficiency of water oxidation. This work reveals that electrocatalytic water oxidation performance of nickel complexes can be finely modulated by constructing suitable N-CH₃ coordination.