炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究

doi:10.15541/jim20240487

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1293-1299.DOI: 10.15541/jim20240487

炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究

任先培¹(), 李超¹, 凌芳¹, 胡启威¹, 于俊玲¹, 向晖¹(), 彭跃红²()

1.四川轻化工大学物理与电子工程学院, 自贡 643000
2.楚雄师范学院物理与电子科学学院, 楚雄 675000

收稿日期:2024-11-18 修回日期:2025-02-18 出版日期:2025-03-19 网络出版日期:2025-03-19
通讯作者: 向晖, 副教授. E-mail: hxiang0717@163.com;
彭跃红, 副教授. E-mail: pyh@cxtc.edu.cn
作者简介:任先培(1982-), 男, 副教授. E-mail: renxianpei@163.com

CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electrocatalytic H₂ Evolution

REN Xianpei¹(), LI Chao¹, LING Fang¹, HU Qiwei¹, YU Junling¹, XIANG Hui¹(), PENG Yuehong²()

1. School of Physics and Electronic Engineering, Sichuan University of Science and Engineering, Zigong 643000, China
2. School of Physics and Electronical Science, Chuxiong Normal University, Chuxiong 675000, China

Received:2024-11-18 Revised:2025-02-18 Published:2025-03-19 Online:2025-03-19
Contact: XIANG Hui, associate professor. E-mail: hxiang0717@163.com;
PENG Yuehong, associate professor. E-mail: pyh@cxtc.edu.cn
About author:REN Xianpei (1982-), male, associate professor. E-mail: renxianpei@163.com
Supported by:
Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652B004);Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(2024RC13);Special Basic Cooperative Research Programs of Yunnan Provincial Undergraduate Universities Association(202101BA070001-085)

摘要/Abstract

摘要：

过渡金属二硫属化物(TMDs)在电催化分解水制氢方面具有较好的应用前景, 引起了人们的广泛关注, 然而, 它们的电催化制氢性能与金属铂还有较大差距。构建异质结合金被认为是提高析氢活性的有效方法。本研究采用简单的溶胶-凝胶工艺在炭黑(CB)颗粒表面合成了一种新型的四元CoMoSSe复合材料(CoMoSSe@CB)。与CoSe@CB以及MoS₂@CB相比, CoMoSSe@CB表现出更加优异的析氢活性, 在-10 mA·cm^-2阴极电流密度下的过电位仅为190 mV, Tafel斜率为62 mV·dec^-1。这主要归因于复合材料的异质结构以及Co、Mo、S和Se原子之间的合金效应, 调节了电子结构和氢原子吸附的自由能, 从而增加了催化剂的活性位点数量、增强了催化剂电荷转移能力。这项工作可为设计新型高效TMDs电催化剂提供指导。

关键词: 过渡金属硫族化合物, 合金, 异质结构, 析氢反应

Abstract:

Transition metal dichalcogenides (TMDs) recently attracted widespread attention due to their potential application to the electrocatalysis of the hydrogen evolution reaction (HER). However, their HER performance is far inferior to that of platinum (Pt) metal. Preparation of multi-elemental alloy and construction of heterostructure are considered as highly effective methods to enhance hydrogen production activity. Herein, a novel quaternary CoMoSSe alloy with heterostructure was synthesized on the surface of carbon black (CB) particles (CoMoSSe@CB) by a simple Sol-Gel process and thereafter served as HER catalyst. Compared to CoSe@CB and MoS₂@CB electrocatalysts, CoMoSSe@CB exhibits superior HER activity with a low overpotential of 190 mV at -10 mA·cm^-2 and a Tafel slope of 62 mV·dec^-1. This improvement is attributed to the alloying effects among Co, Mo, S and Se, as well as the heterogeneous structure in the composite material, which regulate the electronic structure and intermediate free energy, thereby increasing the number of active sites and enhancing charge-transfer ability. This work can provide new ideas and concepts for designing novel and efficient TMD electrocatalysts.

Key words: transition metal dichalcogenide, alloy, heterostructure, hydrogen evolution reaction

中图分类号:

任先培, 李超, 凌芳, 胡启威, 于俊玲, 向晖, 彭跃红. 炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究[J]. 无机材料学报, 2025, 40(11): 1293-1299.

REN Xianpei, LI Chao, LING Fang, HU Qiwei, YU Junling, XIANG Hui, PENG Yuehong. CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electrocatalytic H₂ Evolution[J]. Journal of Inorganic Materials, 2025, 40(11): 1293-1299.

图/表 13

Scheme 1 Schematic diagram of CoMoSSe@CB synthesis

Fig. 1 (a, d) TEM and (b, c, e, f) HRTEM images of (a-c) CoSe@CB and (d-f) MoS2@CB

Fig. 2 (a) TEM image, (b, c) HRTEM images, and (d) HAADF STEM image and its corresponding EDS mappings of CoMoSSe@CB

Fig. 3 XRD patterns of CoSe@CB, MoS2@CB and CoMoSSe@CB Among them, the diffraction intensity of CoSe@CB has been divided by 6

Fig. 4 High-resolution (a) Mo3d, (b) Co2p, (c) S2p, and (d) Se3d XPS spectra of samples

Fig. 5 HER performances of different catalysts (a) LSV curves and (b) corresponding Tafel plots obtained from CoSe@CB, MoS2@CB, CoMoSSe@CB, and Pt/C catalysts in 0.5 mol·L-1 H2SO4 at a scan rate of 5 mV·s-1; (c) EIS spectra at 0.4 V (vs. RHE) for CoSe@CB, MoS2@CB and CoMoSSe@CB electrodes with inset showing equivalent circuit; (d) Cdl of the electrocatalysts obtained by CV in non-Faradic potential window

Fig. S1 HAADF STEM image and its corresponding EDS mappings of CoSe@CB

Fig. S2 HAADF STEM image and its corresponding EDS mappings of MoS2@CB

Fig. S3 HRTEM image of CoMoSSe@CB

Fig. S4 XPS survey spectra of CoSe@CB, MoS2@CB and CoMoSSe@CB

Fig. S5 CV curves of (a) CoSe@CB, (b) MoS2@CB and (c) CoMoSSe@CB at 20, 40, 60, 80, and 100 mV·s-1 within 0.10-0.20 V (vs. RHE)

Fig. S6 Polarization curves of CoMoSSe@CB electrocatalyst before and after 1000 CV cycles in 0.5 mol·L-1 H2SO4

Fig. S7 (a) TEM and (b) HRTEM images of CoMoSSe@CB after HER stability test in 0.5 mol·L-1 H2SO4

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炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究

CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electrocatalytic H₂ Evolution

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炭黑表面CoMoSSe异质结构合金的制备及其高效析氢研究

CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electrocatalytic H2 Evolution

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CoMoSSe Alloy with Heterostructure on Carbon Black for Enhanced Electrocatalytic H₂ Evolution