大连理工大学李福胜团队报道了基于Mn（2,2 '' -联吡啶-6,6 '' -二羧酸盐）的氢键有机框架对酸性水氧化的机理研究。相关研究成果发表在2025年1月23日出版的《结构化学》。

基于地球丰富材料的酸性稳定析氧反应（OER）催化剂对于基于质子交换膜的水电解很重要，但很少见。

该文中，锰与2,2′-联吡啶-6,6′-二羧酸配体Mn（bda）配位的含金属氢键有机框架（HOF）通过氢键和π-π堆积相互连接，被用作酸性水氧化的非均相OER催化剂（Mn（bda-HOF）），并表现出相当好的OER性能。电化学结果表明，在870 mV的过电位下，Mn（bda）-HOF的频率为1 s^-1。

同时，这种Mn（bda-HOF表现出不同寻常的pH值对性能的依赖性，其中反应速率随着pH值的降低而增加。全面的机理研究表明，电荷转移触发的两种金属氧物种Mn⁵⁺（O）的偶联是速率决定步骤，这导致了这种不同寻常的pH对OER性能的依赖。

附：英文原文

Title: Mechanistic insights into acidic water oxidation by Mn(2,2′-bipyridine-6,6′-dicarboxylate)-based hydrogen-bonded organic frameworks

Author: Shuai Liu, Wen Wu, Peili Zhang, Yunxuan Ding, Chang Liu, Yu Shan, Ke Fan, Fusheng Li

Issue&Volume: 2025-01-23

Abstract: Acidic-stable oxygen evolution reaction (OER) catalysts based on earth-abundant materials are important but rare for the proton exchange membrane-based water electrolysis. In this study, a metal-containing hydrogen-bonded organic framework (HOF) of manganese coordinated with 2,2′-bipyridine-6,6′-dicarboxylate ligands, Mn(bda), interconnected through hydrogen bonding and π-π stacking was used as a heterogeneous OER catalyst (Mn(bda)-HOF) for acidic water oxidation and exhibited a considerable OER performance. Electrochemical results showed that Mn(bda)-HOF displayed a turn of frequency of 1 s1 at an overpotential of 870 mV. Meanwhile, this Mn(bda)-HOF showed an unusual pH dependence on performance, where the reaction rate increased with the decrease in pH. A comprehensive mechanistic study reveals that the charge transfer triggered coupling of two metal-oxo species Mn5+(O) is the rate-determining step, which leads to this unusual pH dependence on the OER performance.

DOI: 10.1016/j.cjsc.2025.100535

Source: http://cjsc.ac.cn/cms/issues/761