过渡金属多核配合物Cu₄的合成与电催化水氧化性能

Synthesis and Electrocatalytic Water Oxidation Properties of Transition Metal Polynuclear Complex Cu₄

摘要

利用2-羟基-3-甲氧基苯甲醛和2-氨基-3-苯基丙醇为原料制备了一种具有立方烷构型的四核金属配合物Cu₄, 并对该配合物在均相条件下的电催化水氧化性能进行了系统研究. 结果表明, Cu₄具有较高的催化水氧化活性, 在1.75 V时催化水氧化的周转频率(TOF)达到119 s⁻¹, 法拉第效率为88.2%. 出色的电催化性能可归因于Cu₄中易于暴露的多金属协同催化活性位点, 在显著提高催化效率的同时又避免了高价金属中间体的形成. 本研究不仅为深入理解水氧化的多电子多质子催化过程提供了重要线索, 同时也证明了多金属协同催化策略在调控O—O键形成方式上的有效性, 为设计新一代高效水氧化催化剂提供了新的视角和策略.

Abstract

A cubane-like tetranuclear copper（II） complex Cu ₄（CCDC： 2501687） was synthesized using 2-hydroxy-3-methoxybenzaldehyde and 2-amino-3-phenylpropanol as ligands. Its performance as a homogeneous electrocatalyst for the water oxidation reaction was systematically evaluated. Cu ₄ exhibited high catalytic activity， achieving a remarkable turnover frequency（TOF） of 119 s⁻¹ at an applied potential of 1.75 V（vs. NHE） with a Faradaic efficiency of 88.2%. This high performance is attributed to the readily accessible bimetallic synergistic catalytic sites within theCu ₄ core. These sites facilitate efficient catalysis while circumventing the formation of high-valent metal intermediates. This study provides insights into the multi-electron/multi-proton processes of water oxidation and demonstrates the effectiveness of a polymetallic cooperative strategy in modulating O—O bond formation， offering new perspectives for designing next-generation efficient water oxidation catalysts.

关键词

过渡金属多核配合物 / 分子催化剂 / 电催化 / 协同催化效应 / 水氧化

Key words

Transition metal polynuclear complex / Molecular catalyst / Electrocatalysis / Synergistic-catalysis effect / Water oxidation

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基金资助

福建高校产学合作项目(2023H6021)

中央引导地方科技发展资金(2023L3016)

福建省自然科学基金(2024J01313)

福建省自然科学基金(2025J011045)

福建省区域发展项目(2025Y3004)

三明市重大科技创新平台科研专项(2024-G-004)