The high-valence NiOOH active phase generated by in-situ reconstruction of nickel-based catalysts plays an important role in the nucleophilic electrooxidation of small organic molecules. This paper systematically reviews the mechanism of high-valence metal regulation of the electrochemical reconstruction process of nickel-based catalysts and its application progress in the nucleophilic oxidation of small organic molecules. First, it outlines the characteristics of some nucleophilic electrooxidation reactions of small organic molecules and the evolution of nickel-based structures. Then, it discusses the regulatory mechanism of high-valence metals promoting the evolution of nickel-based structures from the perspectives of the introduction of high-valence metals, the promoting effect of high-valence metals on the formation kinetics of NiOOH, the regulation of the electronic structure of Ni by high-valence metals, and the synergistic reconstruction of interfacial charges between high-valence metals and nickel. Regarding the regulation mechanism of high-valence metals in nucleophilic electrooxidation reactions, it discusses the adsorption and activation behavior of nucleophiles, the stability and energy barrier changes of reaction intermediates, the inhibition of competitive oxygen evolution reactions, and the commonalities and differences in different nucleophilic reaction systems. After summarizing the progress in these mechanism studies, it looks forward to some current research problems and challenges, such as the stabilization mechanism of high-valence Ni sites under complex environments, and points out the direction for future solutions through multi-scale characterization, theoretical guidance, and engineering design. This review is of great help in understanding the structural evolution and research progress of high-valence metal-driven nickel-based nucleophilic electrooxidation catalysts.

Contents

1 Introduction

2 Overview of nucleophile electrooxidation reactions and structural evolution of nickel-based catalysts

2.1 Nucleophile electrooxidation reactions

2.2 NiOOH active phase formation and catalytic mechanism

3 Mechanisms of structural evolution in nickel-based catalysts induced by high-valence metals

3.1 Strategies for introducing high-valence metals

3.2 Promotional effect of high-valence metals on the formation kinetics of NiOOH

3.3 Regulation of Ni electronic structure and valence-state distribution by high-valence metals

3.4 Synergistic structure and interfacial charge reconstruction between high-valence metals and nickel

4 Mechanisms by which high-valence metals regulate nucleophile electrooxidation reactions

4.1 Regulation of nucleophile adsorption and activation behavior

4.2 Stability and energy barrier variation of key reaction intermediates

4.3 Suppression of the competitive oxygen evolution reaction

4.4 Common features and differences among various nucleophile electrooxidation systems

5 Conclusion and outlook