NiMoO4同质结d带工程促进选择性电化学氮还原制氨

doi:10.1016/S1872-2067(26)64978-9

催化学报 ›› 2026, Vol. 85: 216-225.DOI: 10.1016/S1872-2067(26)64978-9

NiMoO₄同质结d带工程促进选择性电化学氮还原制氨

任宇曦, 许堡荣, 靳瑜, 肖航, 牛冉冉, 刘威, 欧鸿辉(), 杨贵东()

西安交通大学化学工程与技术学院, 氟氮化工新材料全国重点实验室, 陕西西安 710049

收稿日期:2025-09-18 接受日期:2025-11-06 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: ouhonghui@xjtu.edu.cn (欧鸿辉),
guidongyang@xjtu.edu.cn (杨贵东).
基金资助:
国家重点研发计划(2020YFA0710000);国家自然科学基金联合基金(U22A20391);陕西省创新能力支撑计划(2023-CX-TD-26);高等学校学科创新引智计划(B23025);陕西省重点研发计划(2023GXLH-004);榆林市科技计划基金(CXY-2022-148)

Homojunction-driven d-band engineering in NiMoO₄ for selective electrochemical nitrogen reduction to ammonia

Yuxi Ren, Baorong Xu, Yu Jin, Hang Xiao, Ranran Niu, Wei Liu, Honghui Ou(), Guidong Yang()

State Key Laboratory of Fluorine & Nitrogen Chemicals, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China

Received:2025-09-18 Accepted:2025-11-06 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: ouhonghui@xjtu.edu.cn (H. Ou),
guidongyang@xjtu.edu.cn (G. Yang).
Supported by:
National Key R&D Program of China(2020YFA0710000);Joint Funds of the National Natural Science Foundation of China(U22A20391);Innovation Capability Support Program of Shaanxi(2023-CX-TD-26);Program of Introducing Talents of Discipline to Universities(B23025);Key Projects in Shaanxi Province(2023GXLH-004);Science and Technology Plan Fund of Yulin City(CXY-2022-148)

摘要/Abstract

摘要：

电催化氮还原反应(eNRR)利用电能在常温常压下直接将氮气(N₂)与水中的质子耦合转化为氨(NH₃). 相比传统的能源密集型Haber-Bosch工艺, 这项新型合成氨技术不仅避免了高碳排放, 还与可持续发展的目标高度契合. 然而, 快速发生的竞争性析氢反应(HER)与结构稳定的N≡N键(945 kJ mol^-1)限制了eNRR反应效率: 电解质中的质子在催化剂表面将被优先还原为H₂而非参与N₂还原, 导致产氨法拉第效率(FE)低. 因此, 需要合理设计高选择性合成氨电催化剂以打破技术瓶颈.

催化剂对反应物的吸附与活化效率受其d带电子结构的直接影响. 通常d带中心越高, 催化剂对反应物的吸附能力更强. 当d带中心非常接近于费米能级时, 催化剂与质子强烈的相互作用将促进HER发生, 导致氮还原合成氨反应的选择性降低. 因此, 高效的氮还原催化剂需具备处于适当能级的d带电子, 使其可以在吸附活化N₂的同时抑制竞争性的HER. 本研究通过简单的温度调控策略, 为氮还原反应定制了具有适配d带的α/β-NiMoO₄异相同质结(根据合成温度, 样品命名为NMO-500), 实现了高选择性合成氨. 紫外光电子能谱结果表明, 在同质结界面的驱动下, NMO-500催化剂的d带中心相比单相β-NiMoO₄(NMO-450)适度下移. 通过气相色谱收集反应过程中的产氢量, NMO-500的产氢量相比NMO-450催化剂明显降低, 说明下移的d带中心削弱了催化剂与质子的相互作用, 从而抑制了竞争性的HER反应. 电化学测试结果显示, 在常温常压的反应环境中, NMO-500催化剂在-1.1 V vs. Ag/AgCl的外加电压驱动下展现出更高的合成氨产率(63.9 μg h^-1 mg^-1)及高达33.5%的法拉第效率, 同时还具备良好的循环稳定性. NMO-500催化剂的合成氨性能明显超越其对应的单相催化剂NMO-450(β-NiMoO₄)和α-NMO(α-NiMoO₄), 证实了在同质结驱动下的d带调控策略可以显著提升催化剂NRR活性和选择性. 通过密度泛函理论计算确认活性位点时发现, N₂分子优先在界面处β相的钼位点发生吸附和活化. 原位傅里叶变换红外光谱进一步检测到了N₂在NMO-500催化剂表面被还原时产生的中间体和产物, 其信号随反应时间累积增强, 证实了氮还原反应在催化剂表面发生. 根据吉布斯自由能计算结果, N₂在NMO-500表面以交替路径加氢时吉布斯自由能更有利, 说明N₂在NMO-500催化剂表面还原时将优先选择交替反应机制.

综上, 本研究通过构筑异相同质结修饰d带电子结构, 成功削弱了催化剂与H的相互作用以抑制竞争性析氢反应, 显著提升了氮还原反应选择性, 为开发高效的氮还原电催化剂提供了新的视角.

关键词: 电催化, 异相同质结, d带修饰, 抑制析氢反应, 固氮

Abstract:

The selectivity of the electrochemical nitrogen reduction reaction (eNRR) is predominantly influenced by the d-band electronic structure of the catalyst. An effective catalyst requires d-band electrons at appropriate energy levels to activate N₂ while simultaneously suppressing the competitive hydrogen evolution reaction (HER). In this study, an α/β-NiMoO₄ heterophase homojunction with tailored d-band was constructed by a facile temperature-controlled strategy for selective electrochemical N₂ to NH₃ conversion. Experimental and theoretical results demonstrate that forming an α/β-NiMoO₄ heterophase homojunction induced moderate downshift of the d-band center and weakened the metal-hydrogen interaction, thereby effectively suppressing the competitive HER. Electrochemical measurements reveal that the optimized NMO-500 catalyst exhibits a boosted ammonia yield rate (63.9 μg h^-1 mg^-1) with a high efficiency of 33.5% at -1.1 V vs. Ag/AgCl under ambient conditions, outperforming its single-phase NiMoO₄ counterpart. Homojunction-driven d-band engineering stands out as a facile, effective, and rational strategy for developing high-performance eNRR catalysts.

Key words: Electrocatalysis, Heterophase homojunction, d-Band modification, Suppress hydrogen evolution reaction, Nitrogen fixation

任宇曦, 许堡荣, 靳瑜, 肖航, 牛冉冉, 刘威, 欧鸿辉, 杨贵东. NiMoO₄同质结d带工程促进选择性电化学氮还原制氨[J]. 催化学报, 2026, 85: 216-225.

Yuxi Ren, Baorong Xu, Yu Jin, Hang Xiao, Ranran Niu, Wei Liu, Honghui Ou, Guidong Yang. Homojunction-driven d-band engineering in NiMoO₄ for selective electrochemical nitrogen reduction to ammonia[J]. Chinese Journal of Catalysis, 2026, 85: 216-225.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)64978-9

https://www.cjcatal.com/CN/Y2026/V85/I6/216

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Fig. 1. (a) Schematic diagram of the temperature-controlled strategy to construct α/β-NiMoO4 heterophase homojunction. TEM images of NMO-450 (b), NMO-500 (c), and NMO-600 (d). The corresponding HRTEM images of NMO-450 (e), NMO-500 (f), and NMO-600 (g).

Fig. 2. XRD patterns (a) and Raman spectra (b) of NMO-450, NMO-500, and NMO-600. (c) Detail information of the NMO-450 in (b). (d) FTIR spectra of NMO-pre, NMO-450, NMO-500, and NMO-600. XPS spectra of Mo 3d (e) and Ni 2p (f) of NMO-450, NMO-500, and NMO-600.

Fig. 3. (a) UV-vis absorption spectra of electrolyte obtained before test, and after 1-hour test under N2/Ar condition. Ammonia yield rate (b) and corresponding FE (c) of NMO-450, NMO-500, and NMO-600 at different potentials. Chronoamperometry test for NMO-500 under N2 condition at 1.1 V for 6 cycles (d) and the corresponding activity (e). (f) NRR performance comparison with a series of reported catalyst.

Fig. 4. The work functions of α-NiMoO4 (a) and β-NiMoO4 (b). (c) Schematic diagram of the work function-driven electrons transfer. UPS spectra corresponding to the work function of NMO-450 (d) and NMO-500 (e). (f) FE of HER at -0.35 mA cm-2 on NMO-450 and NMO-500. (g) Schematic diagram of the HER suppression by d-band modulation. (h) In-situ FTIR spectra of NMO-500 at 1.1 V under N2 atmosphere.

Fig. 5. Charge density differences (Blue region represents charge depletion, while yellow region represents accumulation. Sphere represents atoms: Purple represents Mo, red represents O, light grey represents Ni and light blue represents N) (a) and electronic location function (ELF) (b) of the adsorbed N2 on NMO-500. (c) The pCOHP of the free N2 and the adsorbed N2 on NMO-500. (d) Gibbs free energy for N2 reduction pathway on NMO-500.

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NiMoO₄同质结d带工程促进选择性电化学氮还原制氨

Homojunction-driven d-band engineering in NiMoO₄ for selective electrochemical nitrogen reduction to ammonia

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