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高价金属促进镍基亲核电氧化催化剂结构演变的研究进展

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Research Progress on the Structural Evolution of Nickel-Based Nucleophilic Electrooxidation Catalysts Promoted by High-Valence Metals

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摘要

镍基催化剂的原位重构生成的高价NiOOH活性相在有机小分子亲核电氧化反应中具有重要的作用。本文系统综述了高价金属调控镍基催化剂电化学重构过程的作用机制及其在有机小分子亲核氧化反应中的应用进展。首先概述了一些有机小分子亲核电氧化反应及镍基结构演变的特点;接着,从高价金属的引入方式、高价金属对NiOOH形成动力学的促进作用、高价金属对Ni电子结构的调控和高价金属与镍的界面电荷协同重构讨论了高价金属促进镍基结构演变的调控机制。在高价金属对亲核电氧化反应的作用机制调控方面,讨论了亲核分子的吸附与活化行为、反应中间体的稳定性与能垒变化、对竞争性析氧反应的抑制和不同亲核反应体系中的共性与差异等研究焦点。在总结这些机制研究的进展后,我们展望了目前研究的一些问题与挑战,比如高价Ni位点在复杂环境下的稳定机制,指出将来通过多尺度表征、理论指导和工程化设计的协同解决问题的方向。该综述对理解高价金属促进镍基亲核电氧化催化剂结构演变与研究进展具有很大的帮助。

Abstract

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

关键词

高价金属 / 结构演变 / 镍基催化剂 / 亲核电氧化

Key words

High-valence metals / structural evolution / nickel-based catalysts / nucleophilic electrooxidation

引用本文

引用格式 ▾
尹春, 冯立纲. 高价金属促进镍基亲核电氧化催化剂结构演变的研究进展[J]. 化学进展, , (): 20260503-20260503 DOI:10.7536/PC20260503
Chun Yin, Ligang Feng. Research Progress on the Structural Evolution of Nickel-Based Nucleophilic Electrooxidation Catalysts Promoted by High-Valence Metals[J]. Progress in Chemistry 20260503-20260503 DOI:10.7536/PC20260503

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