MoNi4/MoO2异质结构实现安倍级电流环己酮电氧化-产氢反应

doi:10.1016/S1872-2067(25)64858-3

催化学报 ›› 2026, Vol. 81: 344-354.DOI: 10.1016/S1872-2067(25)64858-3

MoNi₄/MoO₂异质结构实现安倍级电流环己酮电氧化-产氢反应

杨瑞^a, 韩子敏^a, 高音^a, 冯国庆^a, 刘怀志^a, 黄艺吟^b(), 汪钟凯^a(), 王要兵^c()

^a 安徽农业大学材料与化学学院, 生物质分子工程中心, 安徽省汽车用高性能纤维制品工程研究中心, 安徽合肥 230036
^b 福建师范大学物理与能源学院, 福建省量子调控与新能源材料重点实验室, 福建福州 350117
^c 中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福建省纳米材料重点实验室, 光电子材料化学与物理重点实验室, 福建福州 350002

收稿日期:2025-08-25 接受日期:2025-09-02 出版日期:2026-02-18 发布日期:2025-12-26
通讯作者: *电子信箱: wangyb@fjirsm.ac.cn (王要兵),wangzk6@ahau.edu.cn (汪钟凯),hyy@fjnu.edu.cn (黄艺吟).
基金资助:
国家自然科学基金(22175036);三峡实验室开放课题基金(SK240007);安徽省自然科学基金(2408085QE132);安徽省高等学校科学研究项目(2024AH050435);福建省自然科学基金(2022J01181)

Charge-mediated cyclohexanone enrichment and intermediate stabilization at MoNi₄/MoO₂ heterostructures enable paired cyclohexanone electrooxidation-hydrogen production at ampere-level current

Rui Yang^a, Zimin Han^a, Yin Gao^a, Guoqing Feng^a, Huaizhi Liu^a, Yiyin Huang^b(), Zhongkai Wang^a(), Yaobing Wang^c()

^a School of Materials and Chemistry, Anhui Agricultural University, Biomass Molecular Engineering Center, Engineering Research Center for High-Performance Fiber Products for Automobile of Anhui Province, Hefei 230036, Anhui, China
^b College of Physics and Energy, Fujian Normal University, Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials, Fuzhou 350117, Fujian, China
^c Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, State Key Laboratory of Structural Chemistry, Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China

Received:2025-08-25 Accepted:2025-09-02 Online:2026-02-18 Published:2025-12-26
Contact: *E-mail: wangyb@fjirsm.ac.cn (Y. Wang),wangzk6@ahau.edu.cn (Z. Wang),hyy@fjnu.edu.cn (Y. Huang).
Supported by:
National Natural Science Foundation of China(22175036);Open and Innovation Fund of Hubei Three Gorges Laboratory(SK240007);Anhui Provincial Natural Science Foundation(2408085QE132);University Natural Science Research Project of Anhui Province(2024AH050435);Natural Science Foundation of Fujian Province(2022J01181)

摘要/Abstract

摘要：

电催化氧化环己酮制备己二酸是一种绿色、高附加值的合成路径, 并且它可耦合产氢反应, 替代传统高能耗的析氧反应, 从而显著降低电解水制氢的能耗. 然而, 环己酮在水相电解质中溶解度低、吸附能力弱, 导致反应动力学缓慢、产物收率有限, 严重制约其实际应用. 近年来, 异质结构工程因其可调控界面电子结构、增强反应物吸附和中间体稳定性, 成为提升电催化性能的有效策略. 因此, 构建具有强电子耦合效应的异质结构, 实现环己酮高效电氧化与产氢协同进行, 具有重要的科学意义与应用前景.

本研究通过原位相分离策略, 在镍泡沫上成功构建了MoNi₄/MoO₂异质结构催化剂. 首先采用水热法合成NiMoO₄前驱体, 随后在500 °C下H₂/Ar气氛中进行还原处理, 诱导MoNi₄与MoO₂两相自发分离并形成紧密界面. 通过多种表征手段证实了异质结构的成功构建及其界面电子结构的调控作用. 电化学测试表明, MoNi₄/MoO₂在1.0 mol L⁻¹ KOH + 0.4 mol L⁻¹环己酮电解液中表现出优异的环己酮氧化性能, 在1.40 V vs. RHE下即可达到200 mA cm^-2的电流密度, 远优于单一组分的MoNi₄和MoO₂. 己二酸的法拉第效率高达85%, 产率达到2.08 mmol h⁻¹ cm⁻², 分别是MoNi₄和MoO₂的6倍和10倍. 机理研究表明, MoNi₄与MoO₂之间存在0.2 eV的功函数差, 诱导界面电荷重新分布, 形成电子缺位的Ni位点和电子富集的MoO₂区域, 显著增强了环己酮的吸附能力. 开路电位和差分电容曲线测试进一步证实了环己酮在异质界面上的富集行为. 原位拉曼光谱和电化学阻抗谱表明, Ni³⁺物种在反应中作为活性中心. 该物种的生成电位降低, 且反应过程中无NiOOH积累, 说明环己酮可自发还原NiOOH, 促进反应的进行. 密度泛函理论计算结果表明, 异质结构降低了关键中间体C₆H₁₀O₂和C₆H₁₀O₃的吸附能, 并将决速步能垒从MoNi₄的2.6降至1.85 eV, 显著提升了反应效率. 为进一步验证其实际应用潜力, 本文构建了双电极膜电极组装电解槽, 以MoNi₄/MoO₂同时作为阳极和阴极. 在1 A电流下运行8 h, 可生成12.1 mmol己二酸和3.34 L氢气, 系统在3 A下稳定运行56 h无性能衰减, 展现出其优异的工业应用前景.

综上, 本研究通过异质结构工程成功实现了环己酮的高效电氧化与产氢协同过程, 为低溶解度生物质分子的高电流电催化转化提供了新思路. 未来可通过进一步调控界面电子结构、拓展底物范围、优化反应器设计等方式, 推动该类双功能催化剂在绿色合成与能源转换中的实际应用.

关键词: MoNi₄/MoO₂异质结, 环己酮电氧化, 电荷重分布, 强吸附, 稳定中间体

Abstract:

Electrocatalytic oxidation of cyclohexanone (KOR) to adipic acid provides a sustainable and value-added pathway for coupled hydrogen evolution (HER). However, the weak adsorption of the reactants and intermediates leads to poor reaction kinetics and product yield. Herein, we synthesized MoNi₄/MoO₂ heterostructures via phase conversion to engineer a large work function difference that optimizes the Ni electronic structure. This design enhances cyclohexanone adsorption and regulates intermediates, achieving 85% Faradaic efficiency for production of adipic acid and a 2 mmol h^-1 cm^-2 production rate, along with an ampere-level current. In a membrane electrode assembly electrolyzer for KOR-assisted HER, this catalyst displays 1 A current with 12.1 mol adipic acid production and 3.34 L H₂ generation over 8 h, maintaining stability for 56 h at 3 A. Optimized Ni electronic structure achieved through heterojunction-induced charge redistribution strengthens cyclohexanone adsorption and lowers the energy barriers for key intermediates (C₆H₁₀O₂^* and C₆H₁₀O₃^*), boosting oxidation activity. This study presents a novel heterojunction engineering strategy that synergistically enhances reactant adsorption and optimizes intermediate reaction kinetics, offering a tailored approach for efficient catalytic systems.

Key words: MoNi₄/MoO₂ heterostructures, Cyclohexanone electrooxidation, Charge redistribution, Strengthen adsorption, Intermediate stabilization

杨瑞, 韩子敏, 高音, 冯国庆, 刘怀志, 黄艺吟, 汪钟凯, 王要兵. MoNi₄/MoO₂异质结构实现安倍级电流环己酮电氧化-产氢反应[J]. 催化学报, 2026, 81: 344-354.

Rui Yang, Zimin Han, Yin Gao, Guoqing Feng, Huaizhi Liu, Yiyin Huang, Zhongkai Wang, Yaobing Wang. Charge-mediated cyclohexanone enrichment and intermediate stabilization at MoNi₄/MoO₂ heterostructures enable paired cyclohexanone electrooxidation-hydrogen production at ampere-level current[J]. Chinese Journal of Catalysis, 2026, 81: 344-354.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64858-3

https://www.cjcatal.com/CN/Y2026/V81/I2/344

图/表 6

Fig. 1. Structural and morphological characterization. (a) Schematic of the process for the preparation of MoNi4/MoO2/NF. SEM image (inset: size distribution) (b), HRTEM image (c), XRD pattern (d), and corresponding elemental mapping images (e?h) of MoNi4/MoO2 electrocatalysts.

Fig. 2. Atomic and electronic structure characterizations. (a) Ni K-edge XANES spectra. Wavelet transforms (WT) of MoNi4/MoO2 (b) and MoNi4 samples (c). (d) Fourier transform curves. (e) k3×(k) oscillation curves. (f) XPS spectra of MoNi4 and MoNi4/MoO2 samples.

Fig. 3. Cyclohexanone electrooxidation over MoNi4/MoO2, MoNi4 and MoO2 catalysts. (a) LSV curves in 1 mol L?1 KOH with cyclohexanone. (b) Potential of KOR and OER with MoNi4/MoO2 catalyst at different current densities. (c) Tafel slopes for MoNi4/MoO2, MoNi4 and MoO2 catalysts in 1 mol L?1 KOH with cyclohexanone. Faradaic efficiency of adipic acid production over MoNi4/MoO2, MoNi4 and MoO2 catalysts at various potentials (d) and corresponding adipic acid productivity (e). Relative concentration of cyclohexanone and oxidation products during long-term electrocatalysis (f) and corresponding time-dependent HPLC spectra (g). (h) Corresponding Faradaic efficiency and adipic acid productivity for cyclohexanone electrooxidation on MoNi4/MoO2 as a function of number of electrolysis cycles. (i) Comparison with recently reported studies.

Fig. 4. (a) OCP of the MoNi4/MoO2, MoNi4, and MoO2 samples in 1 mol L?1 KOH solution before and after cyclohexanone was injected. In-situ Raman spectra of MoNi4/MoO2 in KOH without (b) and with (c) cyclohexanone. (d) Periodic sampling experiments on MoNi4/MoO2 (at 1.45 V vs. RHE, open-circuit state, and 0.95 V vs. RHE, respectively). In-situ Bode phase plots of MoNi4/MoO2 in KOH without (e) and with (f) cyclohexanone.

Fig. 5. (a) Charge density difference distribution of MoNi4/MoO2. Purple: Mo atoms. Red: O atoms. Gray: Ni atoms. (b) UPS spectra of MoNi4 and MoO2. Φ = hv ? |Ecutoff ? EF|, where hv, Ecutoff, and EF are the energy of the excitation light (21.22 eV), secondary electron cutoff energy, and Fermi energy, respectively. (c) Calculated Gibbs free energy. Blue: Mo atoms. Red: O atoms. Purple: Ni atoms. Gray: C atoms. White: H atoms.

Fig. 6. MEA electrochemical reactor. Schematic (a) and photographs (b) of MEA. (c) LSV curves. (d) Productivity of adipic acid at a current of 1 A (inset: photograph of purified adipic acid). (e) Stability at 3 A after seven cycles, each lasting 8 h.

参考文献

[1]	R. Wang, Y. Kang, J. Wu, T. Jiang, Y. Wang, L. Gu, Y. Li, X. Yang, Z. Liu, M. Gong, Angew. Chem. Int. Ed., 2022, 61, e202214977.
[2]	H. Zhou, Y. Ren, B. Yao, Z. Li, M. Xu, L. Ma, X. Kong, L. Zheng, M. Shao, H. Duan, Nat. Commun., 2023, 14, 5621.
[3]	X. Wu, Y. Wang, Z.-S. Wu, Chem, 2022, 8, 2594-2629.
[4]	J. Li, H. Duan, Chem, 2024, 10, 3008-3039.
[5]	R. Yang, H. Fu, Z. Han, G. Feng, H. Liu, Y. Hu, Y. Huang, Inorg. Chem. Front., 2024, 11, 5987-5996.
[6]	M. Liu, Y. Jiang, Z. Cao, L. Liu, H. Chen, S. Ye, J. Energy Chem., 2024, 96, 464-471.
[7]	R. Yang, X. Zheng, H. Fu, X. Cao, Y. Hu, Y. Huang, ChemSusChem, 2024, 17, e202301771.
[8]	X. Zheng, X. Shi, H. Ning, R. Yang, B. Lu, Q. Luo, S. Mao, L. Xi, Y. Wang, Nat. Commun., 2023, 14, 4209.
[9]	B. V. Lyalin, V. A. Petrosyan, Russ. Chem. Bull., 2004, 53, 688-692.
[10]	H. Zhou, Z. Li, S.-M. Xu, L. Lu, M. Xu, K. Ji, R. Ge, Y. Yan, L. Ma, X. Kong, L. Zheng, H. Duan, Angew. Chem. Int. Ed., 2021, 60, 8976-8982.
[11]	Q. Qian, J. Zhang, J. Li, Y. Li, X. Jin, Y. Zhu, Y. Liu, Z. Li, A. El-Harairy, C. Xiao, G. Zhang, Y. Xie, Angew. Chem. Int. Ed., 2021, 60, 5984-5993.
[12]	B. Zhao, J. Liu, C. Xu, R. Feng, P. Sui, J.-X. Luo, L. Wang, J. Zhang, J.-L. Luo, X.-Z. Fu, Appl. Catal. B, 2021, 285, 119800.
[13]	J. Zhang, T. Wang, D. Pohl, B. Rellinghaus, R. Dong, S. Liu, X. Zhuang, X. Feng, Angew. Chem. Int. Ed., 2016, 55, 6702-6707.
[14]	R. Yang, H. Fu, Z. Han, G. Feng, H. Liu, Y. Gao, Y. Hu, Z. Wang, Y. Huang, J. Colloid Interface Sci., 2025, 686, 107-117.
[15]	S. Zhang, C. Tan, R. Yan, X. Zou, F.-L. Hu, Y. Mi, C. Yan, S. Zhao, Angew. Chem. Int. Ed., 2023, 62, e202302795.
[16]	X. Wang, S. Li, Z. Yuan, Y. Sun, Z. Tang, X. Gao, H. Zhang, J. Li, S. Wang, D. Yang, J. Xie, Z. Yang, Y.-M. Yan, Angew. Chem. Int. Ed., 2023, 62, e202303794.
[17]	Y. Jia, Z. Chen, B. Gao, Z. Liu, T. Yan, Z. Gui, X. Liao, W. Zhang, Q. Gao, Y. Zhang, X. Xu, Y. Tang, J. Am. Chem. Soc., 2024, 146, 1282-1293.
[18]	H. Sun, L. Li, Y. Chen, H. Kim, X. Xu, D. Guan, Z. Hu, L. Zhang, Z. Shao, W. Jung, Appl. Catal. B, 2023, 325, 122388.
[19]	J. Zhang, S. Li, X. Liu, H. Zheng, W. Zhang, R. Cao, ChemSusChem, 2023, 16, e202300709.
[20]	S. Fan, G. Yang, Y. Jiao, Y. Liu, J. Wang, H. Yan, H. Fu, Adv. Mater., 2025, 37, 2502523.
[21]	W. Gao, C. Wang, W. Wen, S. Wang, X. Zhang, D. Yan, S. Wang,, Adv. Mater., 2025, 37, 2503198.
[22]	Y. Liu, L. Wang, R. Hübner, J. Kresse, X. Zhang, M. Deconinick, Y. Vaynzof, I. M. Weidinger, A. Eychmüller, Angew. Chem. Int. Ed., 2024, 63, e202319239.
[23]	Y. Song, S. Jiang, Y. He, Y. Wu, X. Wan, W. Xie, J. Wang, Z. Li, H. Duan, M. Shao, Fundam. Res., 2024, 4, 69-76.
[24]	Y. Jin, X. Yue, C. Shu, S. Huang, P.-K. Shen, J. Mater. Chem. A, 2017, 5, 2508-2513.
[25]	B. Wang, Z. Zhang, S. Zhang, Y. Cao, Y. Su, S. Liu, W. Tang, J. Yu, Y. Ou, S. Xie, J. Li, M. Ma, Electrochim. Acta, 2020, 359, 136929.
[26]	B. Ravel, M. Newville, J. Synchrotron Radiat., 2005, 12, 537-541.
[27]	M. Newville, J. Synchrotron Radiat., 2001, 8, 322-324.
[28]	L. Lv, B. Tang, Q. Ji, N. Li, Y. Wang, S. Feng, H. Duan, C. Wang, H. Tan, W. Yan, Chin. Chem. Lett., 2023, 34, 107524.
[29]	K.-Z. Sun, C.-F. Wen, X. Qu, P.-F. Liu, H.-G. Yang, Small Methods, 2022, 6, 2200484.
[30]	Z. Liu, H. Li, H.-S. Kang, A. T. N’Diaye, M. H. Lee, Chem. Eng. J., 2023, 454, 140403.
[31]	B. Lin, J. Chen, R. Yang, S. Mao, M. Qin, Y. Wang, Appl. Catal. B, 2022, 316, 121666.
[32]	P. Zhou, X. Lv, S. Tao, J. Wu, H. Wang, X. Wei, T. Wang, B. Zhou, Y. Lu, T. Frauenheim, X. Fu, S. Wang, Y. Zou, Adv. Mater., 2022, 34, 2204089.
[33]	W. Jia, B. Liu, R. Gong, X. Bian, S. Du, S. Ma, Z. Song, Z. Ren, Z. Chen, Small, 2023, 19, 2302025.
[34]	S. Jo, S.-W. Park, Y. Shim, Y. Jung, Electrochim. Acta, 2017, 247, 634-645.
[35]	A. G. Anastopoulos, A. D. Papoutsis, A. A. Papaderakis, J. Solid State Electrochem., 2015, 19, 2369-2377.
[36]	F. Liu, X. Gao, R. Shi, J. Xiong, Z. Guo, E. C. M. Tse, Y. Chen, Adv. Funct. Mater., 2024, 34, 2310274.
[37]	R. Ge, Y. Wang, Z. Li, M. Xu, S.-M. Xu, H. Zhou, K. Ji, F. Chen, J. Zhou, H. Duan, Angew. Chem. Int. Ed., 2022, 61, e202200211.
[38]	M. Qin, J. Chen, M. Qi, H. Wang, S. Mao, L. Xi, Y. Wang, ACS Catal., 2024, 14, 8414-8426.
[39]	M. E. G. Lyons, M. P. Brandon, J. Electroanal. Chem., 2009, 631, 62-70.
[40]	R. Yang, Z. Zeng, Z. Peng, J. Xie, Y. Huang, Y. Wang, J. Energy Chem., 2021, 61, 290-296.
[41]	Y. Huang, R. Yang, G. Anandhababu, J. Xie, J. Lv, X. Zhao, X. Wang, M. Wu, Q. Li, Y. Wang, ACS Energy Lett., 2018, 3, 1854-1860.
[42]	Z. Li, X. Li, H. Zhou, Y. Xu, S.-M. Xu, Y. Ren, Y. Yan, J. Yang, K. Ji, L. Li, M. Xu, M. Shao, X. Kong, X. Sun, H. Duan, Nat. Commun., 2022, 13, 5009.
[43]	X. Liu, Y.-Q. Zhu, J. Li, Y. Wang, Q. Shi, A.-Z. Li, K. Ji, X. Wang, X. Zhao, J. Zheng, H. Duan, Nat. Commun., 2024, 15, 7685.
[44]	F. Liu, X. Gao, Z. Guo, E. C. M. Tse, Y. Chen, J. Am. Chem. Soc., 2024, 146, 15275-15285.
[45]	H. Chen, R. Gao, K. Su, Z. Li, L. Wu, L. Wang, Angew. Chem. Int. Ed., 2025, 137, e202501766.
[46]	G. Ren, B. Liu, X. Xu, P. Jing, J. Wu, J. Zhang, Nano Today, 2024, 56, 102315.
[47]	X. Teng, Z. Wang, Y. Wu, Y. Zhang, B. Yuan, Y. Xu, R. Wang, A. Shan, Nano Energy, 2024, 122, 109299.
[48]	T. Shaikh, A. S. Sharma, S. M. Osman, R. Luque, H. Kaur, Catal. Commun., 2022, 168, 106460.

MoNi₄/MoO₂异质结构实现安倍级电流环己酮电氧化-产氢反应

Charge-mediated cyclohexanone enrichment and intermediate stabilization at MoNi₄/MoO₂ heterostructures enable paired cyclohexanone electrooxidation-hydrogen production at ampere-level current

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 0

编辑推荐

Metrics