复旦大学材料科学系吴仁兵研究组的一项最新研究研制了电子离域调节羟基结合增强析氢反应活性。相关论文于2025年2月17日发表在《科学通报》杂志上。

在此，该课题组研究人员提出了一种碱土金属阳离子驱动的电子离域策略，以精心定制羟基与活性位点的结合。以fenimg -层状双氢氧化物（FeNiMg-LDH）为原型，联合操作光谱分析和理论计算表明，在固溶相中引入Mg阳离子可以产生局部电子场，使Fe与吸附羟基之间的电子离域，从而优化羟基的结合强度。因此，fenmg - ldh降低过电位，提供10 mA cm^-2与FeNi-LDH和Ni-LDH催化剂相比，在碱性电解液中分别降低了39和64mV。本研究为合理设计碱性水电解用高级HER电催化剂提供了理论依据。

研究人员表示，引入亲氧性较高的外来金属是促进水解离和碱性析氢反应（HER）动力学的一种有前途的策略。然而，HER活性的进一步提高受到水解离产生的羟基与活性位点不利相互作用的限制。

附：英文原文

Title: Electron delocalization-modulated hydroxyl binding for enhanced hydrogen evolution reaction activity

Author: Renbing Wu

Issue&Volume: 2025/02/17

Abstract: The introduction of foreign metals with a higher oxophilicity represents a promising strategy to promote water dissociation and in turn kinetics of alkaline hydrogen evolution reaction (HER). However, the further improvement of HER activity is limited by the unfavorable interaction of hydroxyl generated by the dissociation of water with active sites. Herein, we propose a strategy of alkaline earth metal cations-driven electron delocalization to elaborately tailor the binding of hydroxyl with the active sites. Taking FeNiMg-layered double hydroxides (FeNiMg-LDH) as a prototypical example, the combined operando spectroscopy analysis and theoretical calculations show that the introduction of Mg cations in solid- solution phase can create a local electronic field and delocalize the electron between Fe and adsorbed hydroxyl, resulting in an optimization of hydroxyl binding strength. Accordingly, FeNiMg-LDH lowers the overpotentials to deliver 10 mA cm^-2 in alkaline electrolyte by 39 and 64 mV, compared to FeNi-LDH and Ni-LDH catalysts, respectively. This work sheds light on the rational design of advanced HER electrocatalyst for alkaline water electrolysis.

DOI: 10.1016/j.scib.2025.02.024

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927325001860