界面结构调控提高酸性介质中MoxOy/Co3O4电催化氧析出反应的性能

doi:10.1016/S1872-2067(26)65083-8

催化学报 ›› 2026, Vol. 88: 295-306.DOI: 10.1016/S1872-2067(26)65083-8

界面结构调控提高酸性介质中Mo_xO_y/Co₃O₄电催化氧析出反应的性能

唐祺^a^,¹, 王博邈^a^,¹, 王崇太^b^,^*(), 吴道雄^c, 程子鸣^a, 韩慧敏^a, 韩雷云^a, 陈华夏^a^,^*(), 华英杰^a^,^*()

^a 海南师范大学化学与化工学院, 海南省电化学储能与能量转换重点实验室, 海口市电化学储能与光能转换材料重点实验室, 海南海口 571158
^b 海南科技职业大学化工与材料工程学院, 海南海口 571126
^c 海南大学海洋科学与工程学院, 南海海洋资源利用国家重点实验室, 海南海口 570228

收稿日期:2025-12-09 接受日期:2026-01-26 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: 521000hua282@sina.com (华英杰),
chenhx@hainnu.edu.cn (陈华夏),
oehy2014@163.com (王崇太).
基金资助:
国家自然科学基金(22462008);国家自然科学基金(22562011);海南省院士创新平台专项(YSPTZX202508);海南省孙世刚院士团队创新中心;海南省教育厅(HnKy2024-11)

The regulation of interface structure improves the performance of the Mo_xO_y/Co₃O₄ electrocatalytic oxygen evolution reaction in acidic media

Qi Tang^a^,¹, Bomiao Wang^a^,¹, Chongtai Wang^b^,^*(), DaoXiong Wu^c, Ziming Cheng^a, Huimin Han^a, Leiyun Han^a, Huaxia Chen^a^,^*(), Yingjie Hua^a^,^*()

^a Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province, Key Laboratory of Electrochemical Energy Storage and Energy Conversion Materials of Haikou City, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, Hainan, China
^b College of Chemical and Materials Engineering, Hainan Vocational University of Science and Technology, Haikou 571126, Hainan, China
^c School of Marine Science and Engineering, State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan University, Haikou 570228, Hainan, China

Received:2025-12-09 Accepted:2026-01-26 Online:2026-09-18 Published:2026-09-05
About author:First author contact:1 共同第一作者.
1 Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22462008);The National Natural Science Foundation of China(22562011);The Grants for the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202508);The Innovation Center of Academician Sun Shigang’s Team in Hainan Province;The Education Department of Hainan Province(HnKy2024-11)

摘要/Abstract

摘要：

电解水是制氢的重要技术途径, 质子交换膜(PEM)电解水技术因其效率高和适配间歇性可再生能源电源而备受关注. 然而, PEM电解水需在强酸性环境中运行, 这对析氧反应(OER)催化剂的稳定性是一个挑战. 此外, OER中四电子转移过程的动力学迟缓, 因此, 研发酸性介质中兼具高催化活性和高稳定性的OER电催化剂一直是个热点, 其中, 寻求能替代商业贵金属催化剂的、低成本的过渡金属基催化剂是该领域的主要研究方向. Co基氧化物因其较高的OER性能而成为研究重点, 但仍然面临着提高催化活性和稳定性的问题.
针对酸性OER条件下非贵金属Co基氧化物活性与稳定性难以兼顾的问题, 本文提出多级结构构筑与界面协同调控策略. 以兼具高导电性和三维多孔结构优势的泡沫镍(NF)为基底, 采用电沉积与电氧化相结合的方式, 在NF表面逐层构筑致密d-Co₃O₄、层状h-Co₃O₄以及无定形a-Mo_xO_y助催化层, 成功制备了a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF复合电极. 该多级结构中, 底层致密的d-Co₃O₄有效隔绝了NF与强酸性电解质的直接接触, 显著抑制了基底在工作电位下的电化学腐蚀, 从而保障了三维导电骨架的结构完整性与长期稳定性; 在致密层的基础上, 原位生长的h-Co₃O₄纳米片构建高比表面积的催化活性层, 大幅增加可参与反应的电化学活性位点数量; 最后, 引入的a-Mo_xO_y助催化层通过与Co₃O₄形成紧密界面, 实现对Co活性中心局域电子结构的调控. 电化学性能测试结果表明, a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF在0.5 mol L^‒1 H₂SO₄电解液中表现出优异的酸性OER活性与稳定性, 其在10 mA cm^‒2电流密度下的过电位为254 mV, 对应的塔菲尔斜率为118 mV·dec^‒1, 并可在恒电流条件下稳定运行超过12 h, 表现出良好的反应活性与结构耐久性. 进一步结合原位拉曼光谱、X射线光电子能谱及密度泛函理论计算结果表明, Mo_xO_y-Co₃O₄界面诱导了电子由Co向Mo的定向转移, 降低了Co活性位点的电子云密度, 从而有效调控了OER关键反应中间体(OH*, O*和OOH*)的吸附与脱附行为, 并增强了Co-O键的结构稳定性. 该界面调控机制在提升催化活性的同时有效抑制了Co物种在酸性条件下的溶解, 为非贵金属催化剂在酸性OER体系中的稳定运行提供了重要的结构与机制支撑.
综上, 本研究通过多级结构构筑与界面电子结构调控, 实现了Co基氧化物在酸性OER条件下催化活性与结构稳定性的协同提升, 为非贵金属催化剂在PEM电解水体系中的实际应用提供了新的材料设计思路. 本文所提出的界面调控策略对其他过渡金属氧化物电催化体系同样具有借鉴意义, 有望推动高效、低成本酸性电解水催化材料的发展.

关键词: 电沉积, 电催化, 钴钼氧化物, 界面效应, 酸性析氧反应

Abstract:

This paper proposes a multi-level structure design strategy, a dense cobalt oxide layer (d-Co₃O₄), a cobalt oxide catalytic layer (h-Co₃O₄), and an amorphous molybdenum oxide (a-Mo_xO_y) co-catalytic layer are constructed layer by layer on nickel foam (NF) through the combination of electro-deposition and oxidation. The a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF composite catalyst with both high catalytic activity and high stability was thus prepared. The main function of the d-Co₃O₄ layer is to prevent NF from coming into direct contact with acidic media to stop its electrochemical corrosion. The h-Co₃O₄ catalytic layer thus acquires a larger specific surface area, thereby exposing more active sites. The main function of the a-Mo_xO_y co-catalytic layer is to regulate the electronic structure on the surface of h-Co₃O₄, reduce the electron cloud density of the Co active sites, and thereby promote the adsorption and oxidation of the oxygen in a water molecule on it. The electrochemical test results show that the overpotential of a-Mo_xO_y/h-Co₃O₄/d-Co₃O₄/NF at a current density of 10 mA cm^-2 is 254 mV, the Tafel slope is 118 mV dec^-1, and the stability exceeds 12 h in 0.5 mol L^-1 H₂SO₄. Raman, X-ray photoelectron spectroscopy characterization and theoretical calculations indicate that the a-Mo_xO_y-Co₃O₄ interface promotes the transfer of electrons from Co to Mo, optimizes the electronic structure of the active site, and reduces the adsorption and desorption energy barriers of the reaction intermediates OOH*, OH* and O*, thereby enhancing the oxygen evolution reaction performance of the catalyst. This study provides a new structural design strategy for constructing stable transition metal-based oxide catalysts on NF for acidic oxygen evolution reaction.

Key words: Electrodeposition, Electrocatalysis, Cobalt-molybdenum oxides, Interfacial effect, Acidic oxygen evolution reaction

唐祺, 王博邈, 王崇太, 吴道雄, 程子鸣, 韩慧敏, 韩雷云, 陈华夏, 华英杰. 界面结构调控提高酸性介质中Mo_xO_y/Co₃O₄电催化氧析出反应的性能[J]. 催化学报, 2026, 88: 295-306.

Qi Tang, Bomiao Wang, Chongtai Wang, DaoXiong Wu, Ziming Cheng, Huimin Han, Leiyun Han, Huaxia Chen, Yingjie Hua. The regulation of interface structure improves the performance of the Mo_xO_y/Co₃O₄ electrocatalytic oxygen evolution reaction in acidic media[J]. Chinese Journal of Catalysis, 2026, 88: 295-306.

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图/表 9

Scheme 1. Schematic illustration of the controlled growth of diverse Co3O4 morphologies and their subsequent integration with MoxOy to construct the MoxOy/Co3O4 catalyst.

Fig. 1. SEM images of NF (a,b), d-Co3O4/NF (c,d), h-Co3O4/NF (e,f), and cross-sections of h-Co3O4/NF (g) and d-Co3O4/NF (h).

Fig. 2. (a) Raman spectrum, (b) XRD patterns, XPS of (c) Co 2p and (d) O 1s.

Fig. 3. Electrochemical properties of h-Co3O4/NF and d-Co3O4/NF in 0.5 mol L?1 H2SO4: (a) LSV Curve (inset: stability tests), (b) EIS, (c) Tafel Slope, (d) Cdl. CV Curves of d-Co3O4/NF (e) and h-Co3O4/NF (f).

Fig. 4. SEM images of h-Co3O4/d-Co3O4/NF (a,b) and a-MoxOy/h-Co3O4/d-Co3O4/NF (c,d). Cross-sections of h-Co3O4/d-Co3O4/ NF (e) and a-MoxOy/h-Co3O4/d-Co3O4/NF (f). TEM images of h-Co3O4/ d-Co3O4/NF (g) and a-MoxOy/h-Co3O4/d-Co3O4/NF (h).

Fig. 5. Raman spectra (a), XRD patterns (b), and survey XPS spectra (c) of h-Co3O4/d-Co3O4/NF, a-MoxOy/d-Co3O4/NF and a-MoxOy/h-Co3O4/d-Co3O4/NF. XPS spectra of Co 2p (d), O 1s (e), and Mo 3d (f).

Fig. 6. Electrochemical performance of h-Co3O4/d-Co3O4/NF, a-MoxOy/h-Co3O4/d-Co3O4/NF and a-MoxOy/d-Co3O4/NF in 0.5 mol L-1 H2SO4. (a) LSV curve. (b) Chronopotentiometry curves at a current density of 10 mA cm-2. (c) Dissolution amounts of Co and Ni from the catalyst during the acidic OER stability test (0.5 mol L-1 H2SO4, 10 mA cm-2) as a function of time, determined by ICP-MS. (d) Tafel slope. (e) EIS. (f) Cdl. CV Curves of h-Co3O4/d-Co3O4/NF (g) and a-MoxOy/h-Co3O4/d-Co3O4/NF (h). In-situ Raman of h-Co3O4/d-Co3O4/NF (i,j) and a-MoxOy/h-Co3O4/d-Co3O4/NF (k-l), recorded at different applied potentials (vs. RHE).

Fig. 7. Characterization of a-MoxOy/h-Co3O4/d-Co3O4/NF after stability test. (a,b) SEM images. (c) XRD patterns. XPS spectra of Mo 3d (d), O 1s (e), and Co 2p (f).

Fig. 8. Optimized atomic structures for H2O adsorption on MoO3, Co3O4, and MoO3@Co3O4 surfaces (a), and the corresponding adsorption Gibbs free energies (b). (c) Proposed OER reaction pathway mediated by MoO3@Co3O4. (d) Calculated Gibbs free energy profiles for the OER on MoO3, Co3O4, and MoO3@Co3O4. (e) Comparison of the Gibbs free energies for OOH* intermediate adsorption on MoO3, Co3O4, and MoO3@Co3O4.

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界面结构调控提高酸性介质中Mo_xO_y/Co₃O₄电催化氧析出反应的性能

The regulation of interface structure improves the performance of the Mo_xO_y/Co₃O₄ electrocatalytic oxygen evolution reaction in acidic media

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