近日，哈尔滨工业大学宋波团队实现了同位素依赖的塔菲尔分析探测电催化水分裂过程中的质子转移动力学。该研究于2025年9月9日发表在《自然-化学》杂志上。

在电催化水裂解生成绿色氢的过程中，质子转移在析氢和析氧反应中都起着重要作用。然而，直接采用传统的质子/氘动力学同位素效应来研究多相电催化过程中的质子转移颇具挑战性。

研究组提出将质子和氘电解质之间的Tafel斜率的变化或Tafel斜率同位素效应作为质子转移特性的有效探测。他们比较了不同pH环境下不同析氢析氧反应电催化剂的Tafel斜率同位素效应，发现质子转移既依赖于pH，也依赖于结构。以氧化钌为例，研究表明，局部结构修饰可使其由质子-电子协同转移的电化学速率决定步骤转变为化学速率决定步骤，提高其在酸中的析氧活性。同位素依赖的Tafel分析将有助于更好地理解电催化过程中的质子转移行为，并为设计高效的电催化剂提供指导。

附：英文原文

Title: Isotope-dependent Tafel analysis probes proton transfer kinetics during electrocatalytic water splitting

Author: Huang, Jinzhen, Wang, Ran, Sheng, Hongyuan, Zhu, Xiaorong, Dominic Ross, R., Hua, Daxing, Lin, Lei, Li, Yafei, Zhang, Qinghua, Gu, Lin, Wang, Xianjie, Xu, Ping, Lu, Jun, Jiang, Sida, Han, Jiecai, Song, Bo, Jin, Song

Issue&Volume: 2025-09-09

Abstract: Proton transfer plays an important role in both hydrogen and oxygen evolution reactions during electrocatalytic water splitting to produce green hydrogen. However, directly adapting the conventional proton/deuterium kinetic isotope effect to study proton transfer in heterogeneous electrocatalytic processes is challenging. Here we propose using the shift in the Tafel slope between protic and deuteric electrolytes, or the Tafel slope isotope effect, as an effective probe of proton transfer characteristics. Comparison of the Tafel slope isotope effect for diverse hydrogen and oxygen evolution reaction electrocatalysts in different pH environments reveals that proton transfer is both pH and structure dependent. Using ruthenium oxide as an example, we show that local structure modification can change the rate-determining step from an electrochemical, concerted proton–electron transfer step to a chemical step and improve the oxygen evolution activity in acid. The isotope-dependent Tafel analysis will facilitate a better understanding of the proton transfer behaviours during electrocatalytic processes and provide guidance for designing efficient electrocatalysts.

DOI: 10.1038/s41557-025-01934-5

Source: https://www.nature.com/articles/s41557-025-01934-5