钴钼共掺杂构筑CoMoNiSx/NF用于高效硫氧化反应

doi:10.15541/jim20260090

无机材料学报

• 研究论文 •

钴钼共掺杂构筑CoMoNiS_x/NF用于高效硫氧化反应

王浩^1,2, 李光兰³, 张雅静¹, 肖永厚^2,4

1.沈阳化工大学化学工程学院,沈阳 110142;
2.大连理工大学盘锦产业技术研究院,盘锦 124221;
3.大连理工大学化工海洋生物学院,盘锦 124221;
4.上海第二工业大学能源与材料学院,上海 201208

收稿日期:2026-03-03 修回日期:2026-05-11
作者简介:王浩(2000-), 男, 硕士研究生. E-mail: 15041522293@163.com
基金资助:
石油化工环境污染防治技术国家地方联合工程研究中心及工业废水资源化与无害化国家工程研究中心2025年度开放课题(34880000-25-ZC0607-0123); 辽宁省自然科学基金联合基金(2024-MSLH-379); 2025年度高校基本科研项目(LJ212510149002)

Construction of CoMoNiS_x/NF via Co-Mo Co-Doping for Efficient Sulfur Oxidation Reaction

WANG Hao^1,2, LI Guanglan³, ZHANG Yajing¹, XIAO Yonghou^2,4

1. College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China;
2. Panjin Institute of Industrial Technology, Dalian University of Technology, Panjin 124221, China;
3. School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin 124221, China;
4. School of Energy and Materials, Shanghai Polytechnic University, Shanghai 201209, China

Received:2026-03-03 Revised:2026-05-11
About author:WANG Hao (2000-), male, Master candidate. E-mail: 15041522293@163.com
Supported by:
National & Local Joint Engineering Research Center for Petrochemical Environmental Pollution Prevention and Control Technology, and National Engineering Research Center for Industrial Wastewater Resource Recovery and Harmless Treatment — 2025 Open Research Projects(34880000-25-ZC0607-0123) Liaoning Provincial Natural Science Foundation Joint Fund (2024-MSLH-379); 2025 University Basic Scientific Research Project (LJ212510149002)

摘要/Abstract

摘要： 将高能耗的析氧反应替换为热力学更有利的硫氧化反应(Sulfide Oxidation Reaction, SOR),是实现节能制氢并协同回收高附加值硫产品的有效策略。但阳极表面不可控的固态硫沉积易钝化活性位点和阻滞反应动力学,严重影响催化剂稳定性。本研究采用两步水热法在泡沫镍(NF)上制备了具有独特“无定形-微晶”异质结构的钴钼共掺杂镍基硫化物电催化剂(CoMoNiS_x/NF)。得益于原位构建的CoMoO₄/硫化物亲水界面与丰富的S₂^2-缺陷位点,该催化剂展现出优异的SOR性能,仅需0.28 V(vs. RHE)的超低过电位即可驱动100 mA·cm^-2的电流密度,并稳定运行超过300 h。在碱性环境下的SOR过程中原位生成的多硫化物可溶解于电解液体系,显著抑制了固态硫在电极表面沉积,避免了电极钝化。此外,组装的SOR||HER双电极电解槽仅需约1.0 V的槽压即可达到100 mA·cm^-2,制氢法拉第效率高达98.6%。

关键词: 硫氧化反应, 析氢反应, 无定形-微晶异质结构, 二硫键缺陷, 节能制氢硫资源回收

Abstract: Replacing the energy-intensive oxygen evolution reaction with the thermodynamically more favorable sulfide oxidation reaction (SOR) is an effective strategy for achieving energy-saving hydrogen production while simultaneously recovering high-value sulfur products. However, uncontrollable solid sulfur deposition on the anode surface tends to cause active site passivation and sluggish reaction kinetics, severely impacting catalyst stability. Here, a cobalt‑molybdenum co‑doped nickel sulfide electrocatalyst with a unique "amorphous‑microcrystalline" heterostructure (CoMoNiS_x/NF) is fabricated on nickel foam via a two‑step hydrothermal method. Benefiting from an in‑situ constructed CoMoO₄/sulfide hydrophilic interface and abundant S₂^2- defect sites, the catalyst exhibits excellent SOR performance, delivering a current density of 100 mA·cm^-2 at an ultralow overpotential of just 0.28 V (vs. RHE) and operating stably for over 300 h. The in-situ generated polysulfides during the SOR process under alkaline conditions are soluble in the electrolyte system, which significantly suppresses the deposition of solid sulfur on the electrode surface and thus prevents electrode passivation. Furthermore, the assembled SOR||HER two‑electrode electrolyzer requires a cell voltage of only 1.0 V to reach 100 mA·cm^-2, achieving a Faradaic efficiency of 98.6% for hydrogen production.

Key words: sulfide oxidation reaction, hydrogen evolution reaction, amorphous-nanocrystalline heterostructure, disulfide defects, energy-saving hydrogen production and sulfur recovery

中图分类号:

O614

王浩, 李光兰, 张雅静, 肖永厚. 钴钼共掺杂构筑CoMoNiS_x/NF用于高效硫氧化反应[J]. 无机材料学报, DOI: 10.15541/jim20260090.

WANG Hao, LI Guanglan, ZHANG Yajing, XIAO Yonghou. Construction of CoMoNiS_x/NF via Co-Mo Co-Doping for Efficient Sulfur Oxidation Reaction[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260090.

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钴钼共掺杂构筑CoMoNiS_x/NF用于高效硫氧化反应

Construction of CoMoNiS_x/NF via Co-Mo Co-Doping for Efficient Sulfur Oxidation Reaction

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钴钼共掺杂构筑CoMoNiSx/NF用于高效硫氧化反应

Construction of CoMoNiSx/NF via Co-Mo Co-Doping for Efficient Sulfur Oxidation Reaction

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钴钼共掺杂构筑CoMoNiS_x/NF用于高效硫氧化反应

Construction of CoMoNiS_x/NF via Co-Mo Co-Doping for Efficient Sulfur Oxidation Reaction