高效电催化固氮: 基于轨道耦合差异化响应解耦竞争反应

doi:10.1016/S1872-2067(26)65043-7

催化学报 ›› 2026, Vol. 86: 181-190.DOI: 10.1016/S1872-2067(26)65043-7

高效电催化固氮: 基于轨道耦合差异化响应解耦竞争反应

王德志^a^,^b, 杨松华^a, 杨刘熠懿^a, 彭需发^a, 刘芳洋^c, 费浩^d^,^*(), 吴壮志^a^,^b^,^*()

^a 中南大学材料科学与工程学院, 湖南长沙 410083
^b 中南大学粉末冶金研究院国家重点实验室, 湖南长沙 410083
^c 中南大学冶金与环境学院, 湖南长沙 410083
^d 香港城市大学能源及环境学院, 香港 999077

收稿日期:2025-10-22 接受日期:2025-12-16 出版日期:2026-07-05 发布日期:2026-06-12
通讯作者: ^*电子信箱: haofei2@cityu.edu.hk (费浩),
zwu@csu.edu.cn (吴壮志).
基金资助:
国家自然科学基金(52374407)

Decoupling competitive reactions by their differential orbital-coupling response to vacancy engineering for efficient electrocatalytic nitrogen reduction

Dezhi Wang^a^,^b, Songhua Yang^a, Yiyi Yangliu^a, Xufa Peng^a, Fangyang Liu^c, Hao Fei^d^,^*(), Zhuangzhi Wu^a^,^b^,^*()

^a School of Materials Science and Engineering, Central South University, Changsha 410083, Hunan, China
^b State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, Hunan, China
^c School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan, China
^d School of Energy and Environment, City University of Hong Kong, Kowloon, Hong Kong, SAR 999077, China

Received:2025-10-22 Accepted:2025-12-16 Online:2026-07-05 Published:2026-06-12
Supported by:
National Natural Science Foundation of China(52374407)

摘要/Abstract

摘要：

氨作为现代工农业的核心化工原料及极具潜力的无碳能源载体, 其绿色可持续合成对产业升级与能源结构转型意义重大. 传统哈伯-博施法能耗高、碳排放量大, 电催化氮还原反应(NRR)成为极具前景的替代方案, 但该反应面临N≡N键活化困难与析氢反应(HER)竞争剧烈的双重挑战, 导致催化活性与选择性难以兼顾. 缺陷工程作为调控催化剂电子结构的有效手段, 在优化催化性能方面展现出巨大潜力, 而精准调控空位浓度以破解NRR与HER的竞争关系, 是当前该领域亟待解决的关键问题.

本文提出了一种创新策略, 通过精准调控1T相二硫化钼(1T-MoS₂)中的硫空位(V_S)浓度, 利用NRR与HER对轨道耦合的差异性响应, 实现了二者的有效解耦, 从而突破了传统催化剂活性-选择性权衡瓶颈. 采用溶剂热与液相刻蚀相结合的方法, 以醋酸为结构导向剂、硼氢化钠为刻蚀剂, 通过调控硼氢化钠用量(50−200 mg)制备了系列不同V_S浓度的1T-MoS₂催化剂(MoS₂-X, X为硼氢化钠用量), 系统探究了V_S浓度对催化性能的影响机制. 表征结果显示, MoS₂-100样品的V_S浓度优化至9.38%, 其层间距因V_S积累导致范德华力减弱而扩展至0.93 nm, 1T相含量达66%且Mo与S元素分布均匀; X-射线衍射与拉曼光谱证实, 刻蚀后样品结晶度降低, 但1T相结构稳定, 电子顺磁共振与X-射线光电子能谱进一步验证了V_S浓度的可调控性. 电化学测试表明, 该优化催化剂在N₂饱和的0.1 mol L^-1 K₂SO₄电解液中表现出卓越性能: −0.7 V vs. RHE时氨产率达64.50 μg h^-1 mg^-1, −0.5 V时法拉第效率为15.25%, 较未刻蚀样品分别提升3.3倍和5.5倍, 性能优于多数已报道电催化剂. 稳定性测试显示, 该催化剂经24 h连续电解及6次循环后, 电流密度、氨产率与法拉第效率均无显著衰减, 结构与相组成保持稳定. 机理研究表明, 优化的V_S浓度通过两种途径提升催化性能: (1)增强Mo与N₂间的d-σ轨道耦合, 使N≡N键活化能垒降至0.28 eV, 显著促进N₂吸附与活化; (2)利用MoN₂(d-σ耦合)与Mo-H(d-s耦合)对V_S浓度的差异化响应进行调控, 使NRR能垒呈摆线型变化, 而HER能垒呈单调变化, 从而构建了NRR热力学优势窗口. 原位拉曼光谱捕捉到N−H, *NH₂及NH₃等中间体信号, 证实MoS₂-100可高效促进反应进程: 密度泛函理论计算揭示, 9.38%的V_S浓度使催化剂费米能级附近电子态富集, 通过“电子捐赠-反馈”机制削弱N≡N键, 同时N₂吸附能(−0.89 eV)显著低于H⁺, 实现选择性提升.

综上, 本文建立了空位浓度-电子结构-催化性能的明确构效关系, 为通过缺陷工程调控竞争电催化反应提供了新范式. 该策略有望拓展至其他多步电催化反应体系, 为设计高活性、高选择性的新型电催化剂提供重要理论指导与技术支撑, 推动NRR技术的实际应用进程.

关键词: 电催化固氮, 电催化析氢, 二硫化钼, 空位工程, 差异化轨道耦合响应

Abstract:

The electrocatalytic nitrogen reduction reaction (NRR) poses formidable challenges, such as competing hydrogen evolution and poor N₂ activation. Herein, we introduce a precise electronic-structure tuning modality through controlled sulfur vacancy (V_S) engineering in 1T-MoS₂. By manipulating the V_S concentration to nearly 9.38%, the optimized catalyst (MoS₂-100) achieves an outstanding NH₃ yield of 64.50 μg h^-1 mg^-1 and a Faradaic efficiency of 15.25%, superior to most electrocatalysts reported. Mechanistic studies reveal that enhanced d-σ orbital coupling between Mo and N₂ significantly promotes N₂ activation, while the distinct orbital-coupling responses of Mo-N₂ and Mo-H to V_S concentration render a potential competition-preponderance window for NRR. This work establishes a novel paradigm for decoupling the competitive reactions by utilizing their differential sensitivity of orbital coupling to vacancy engineering.

Key words: Nitrogen reduction reaction, Hydrogen evolution reaction, Molybdenum disulfide, Vacancy engineering, Differential orbital-coupling response

王德志, 杨松华, 杨刘熠懿, 彭需发, 刘芳洋, 费浩, 吴壮志. 高效电催化固氮: 基于轨道耦合差异化响应解耦竞争反应[J]. 催化学报, 2026, 86: 181-190.

Dezhi Wang, Songhua Yang, Yiyi Yangliu, Xufa Peng, Fangyang Liu, Hao Fei, Zhuangzhi Wu. Decoupling competitive reactions by their differential orbital-coupling response to vacancy engineering for efficient electrocatalytic nitrogen reduction[J]. Chinese Journal of Catalysis, 2026, 86: 181-190.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65043-7

https://www.cjcatal.com/CN/Y2026/V86/I7/181

图/表 5

Fig. 1. (a) HRTEM images of MoS2-100. (b,c) Magnified HRTEM images corresponding to the area framed by the white rectangle in panel (a). (d-f) EDX elemental distribution maps of MoS2-100.

Fig. 2. XRD (a) and Raman patterns (b). (c) EPR intensity of the samples. XPS spectra of Mo 3d (d) and S 2p (e) over the samples. (f) 1T phase and 2H phase concentration of the samples. (g) S/Mo atomic ratio of the samples.

Fig. 3. (a) LSV curves of MoS2-100 in N2- and Ar-saturated 0.1 mol L-1 K2SO4 electrolyte. (b) Properties of MoS2-100. (c) Properties of each sample at different applied potentials. (d) Properties of each sample at −0.7 V. (e) NH3 yield and corresponding UV-vis spectra after 2 h of electrolysis under different operating conditions. (f) 1H NMR spectra with different feeding gas. (g) NRR performance of MoS2-100 under cyclic alternation between N2- and Ar-saturated electrolytes. (h) Current density-time curves and cycle stability test of MoS2-100 at −0.7 V.

Fig. 4. (a) Current density as a function of scanning rate for various samples. (b,c) In-situ EIS Bode phase spectra of MoS2-0 and MoS2-100 measured in N2 and Ar atmospheres. (d,e) The potential-dependent in-situ SERS of MoS2-0 and MoS2-100 at different applied potentials. All spectra were normalized by the peak intensity of SO42- for better comparison. (f) The peak intensities of MoS2-100 at different applied potentials. (g) The difference in peak intensities between MoS2-100 and MoS2-0 at different applied potentials.

Fig. 5. (a) The Gibbs free energy diagram of 3S-FGJ along different NRR pathways. (b) Charge density difference of *N2 on 3S-FGJ. Electron accumulation and depletion are represented by red and cyan isosurfaces, respectively. (c) The COHP of the N≡N in adsorbed N2. (d) The relationship between NRR activity and the corresponding ICOHP of Mo-N. (e) Adsorption energy and Eb contrasts between NRR and HER. (f) The relationship between HER activity and the corresponding ICOHP of Mo-H.

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高效电催化固氮: 基于轨道耦合差异化响应解耦竞争反应

Decoupling competitive reactions by their differential orbital-coupling response to vacancy engineering for efficient electrocatalytic nitrogen reduction

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