Self-activated oxophilic surface of porous molybdenum carbide nanosheets promotes hydrogen evolution activity in alkaline environment

IF 9.4 1区化学 Q1 CHEMISTRY, PHYSICAL

Journal of Colloid and Interface Science Pub Date : 2025-03-23 DOI:10.1016/j.jcis.2025.137423

Yong Li , Weining Song , Teng Gai , Lipeng Wang , Zhen Li , Peng He , Qi Liu , Lawrence Yoon Suk Lee

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Abstract

Molybdenum carbides are promising alternatives to Pt-based catalysts for the hydrogen evolution reaction (HER) due to their similar d-band electronic configuration. Notably, Mo_xC exhibits superior HER kinetics in alkaline media compared to acidic conditions, contrasting with Pt-based catalysts. Herein, we present 3D porous β-Mo₂C nanosheets, achieving an overpotential of 111 mV at 10 mA cm⁻² in 1 M KOH, significantly lower than in acidic environments. Simulations on pristine Mo₂C surface reveal that water dissociation poses a higher energy barrier in alkaline media, suggesting that crystal structure alone does not dictate kinetics. Operando attenuated total reflection surface-enhanced infrared absorption spectroscopy shows that Mo₂C activates interfacial water, generating liquid-like and free water, and facilitates hydroxyl species adsorption, reducing activation energy to below 38.43 ± 0.19 kJ/mol. Our findings on the self-activation effect offer insights into the HER mechanism of Mo-based electrocatalysts and guide the design of highly active HER catalysts.

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碳化钼由于其相似的 d 波段电子构型，在氢进化反应（HER）中有望成为铂基催化剂的替代品。值得注意的是，与铂基催化剂相比，碳化钼在碱性介质中表现出更优越的氢进化反应动力学。在此，我们提出了三维多孔β-Mo2C纳米片，在1 M KOH中，10 mA cm-2的过电位为111 mV，明显低于酸性环境中的过电位。对原始 Mo2C 表面的模拟显示，水解离在碱性介质中构成了更高的能量障碍，这表明晶体结构本身并不决定动力学。运算衰减全反射表面增强红外吸收光谱显示，Mo2C 能激活界面水，生成液态水和自由水，并促进羟基物种的吸附，从而将活化能降低到 38.43 ± 0.19 kJ/mol 以下。我们关于自活化效应的研究结果有助于深入了解 Mo 基电催化剂的 HER 机理，并为设计高活性 HER 催化剂提供指导。

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来源期刊

Journal of Colloid and Interface Science 化学-物理化学

CiteScore

16.10

自引率

7.10%

发文量

2568

审稿时长

2 months

期刊介绍： The Journal of Colloid and Interface Science publishes original research findings on the fundamental principles of colloid and interface science, as well as innovative applications in various fields. The criteria for publication include impact, quality, novelty, and originality. Emphasis: The journal emphasizes fundamental scientific innovation within the following categories: A.Colloidal Materials and Nanomaterials B.Soft Colloidal and Self-Assembly Systems C.Adsorption, Catalysis, and Electrochemistry D.Interfacial Processes, Capillarity, and Wetting E.Biomaterials and Nanomedicine F.Energy Conversion and Storage, and Environmental Technologies