Pugliesi Matteo, Volpato Giulia Alice, Ritacco Ida, Tuci Giulia, Cattelan Mattia, Rossin Andrea, Liu Yuefeng, Caporaso Lucia, Camellone Matteo Farnesi, Santoriello Giuseppe, Colusso Elena, Agnoli Stefano, Giambastiani Giuliano
Institute of Chemistry of OrganoMetallic Compounds, ICCOM-CNR and INSTM unit, Via Madonna del Piano 10, Sesto Fiorentino, Florence 50019, Italy.
Department of Chemical Science, University of Padua and INSTM unit, Via Marzolo 1, Padova 35131, Italy.
ACS Catal. 2025 Jul 18;15(15):13278-13287. doi: 10.1021/acscatal.5c02610. eCollection 2025 Aug 1.
The surface functionalization of chemically exfoliated MoS (-MoS) nanoflakes with Brønsted-acid end-capped aryl fragments adds an additional level of complexity to the comprehension of the correlation between the electron-donating strength of covalently grafted organic groups (Hammett parameter) and the HER performance of these hybrids. MoS nanoflakes decorated with aryl-sulfonic acids promote proton transfer via tunneling of H-species, where weaker benzoic acid groups fail. Thus, surface-engineered -MoS bearing sulfonic-acid end-capped dangling arms acts as an electrocatalyst that boosts HER kinetics even under an alkaline environment, where water dissociation represents the bottleneck of the process. Density functional theory (DFT) calculations have been used to corroborate experimental evidence and speculate on the role of acidic moieties with respect to water molecule and dissociation at the surface of the functionalized chalcogenide. The study represents a significant advance in the development of pH-insensitive electrocatalysts for HER.
用布朗斯特酸封端的芳基片段对化学剥离的MoS₂（-MoS₂）纳米片进行表面功能化，为理解共价接枝有机基团的给电子强度（哈米特参数）与这些杂化物的析氢反应（HER）性能之间的相关性增添了额外的复杂性。用芳基磺酸修饰的MoS₂纳米片通过H物种的隧穿促进质子转移，而较弱的苯甲酸基团则无法做到这一点。因此，带有磺酸封端悬空臂的表面工程化-MoS₂即使在碱性环境中也能作为一种电催化剂来加速HER动力学，在碱性环境中，水的离解是该过程的瓶颈。密度泛函理论（DFT）计算已被用于证实实验证据，并推测酸性部分在功能化硫族化物表面对水分子离解的作用。该研究代表了用于HER的pH不敏感电催化剂开发方面的一项重大进展。
