基于界面工程的NiV-LDH@MoS2异质结构用于高效碱性析氢反应

doi:10.1016/S1872-2067(26)65224-2

催化学报 ›› 2026, Vol. 91: 222-231.DOI: 10.1016/S1872-2067(26)65224-2

基于界面工程的NiV-LDH@MoS₂异质结构用于高效碱性析氢反应

于世浩^a^,^b, 严玥莹^a^,^b, 杨阳^a^,^b, 姚博瀚^a^,^b, 朱子雯^a^,^b, 王德文^a, 邢志财^a^,^*(), 杨秀荣^a^,^b^,^*()

^a 中国科学院长春应用化学研究所, 电分析化学国家重点实验室, 吉林长春 130022
^b 中国科学技术大学应用化学与工程学院, 安徽合肥 230026

收稿日期:2026-01-29 接受日期:2026-04-07 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: xingzc@ciac.ac.cn (邢志财),
xryang@ciac.ac.cn (杨秀荣).
基金资助:
国家自然科学基金(22393930);吉林省科技发展计划(SKL202302029)

Interfacial engineering of an advanced NiV-LDH@MoS₂ heterostructure electrocatalyst for efficient alkaline hydrogen evolution

Shihao Yu^a^,^b, Yueying Yan^a^,^b, Yang Yang^a^,^b, Bohan Yao^a^,^b, Ziwen Zhu^a^,^b, Dewen Wang^a, Zhicai Xing^a^,^*(), Xiurong Yang^a^,^b^,^*()

^a State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China
^b School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2026-01-29 Accepted:2026-04-07 Online:2026-12-18 Published:2026-10-13
Supported by:
National Natural Science Foundation of China(22393930);Science and Technology Development Plan Project of Jilin Province, China(SKL202302029)

摘要/Abstract

摘要：

氢能因其能量密度高、清洁无碳等优势, 被视为替代传统化石燃料的理想能源载体. 利用碱性水电解技术, 可将太阳能、风能等间歇性可再生能源转化为易于储存的氢气, 近年来受到广泛关注. 然而, 碱性介质中的析氢反应(HER)涉及额外的水解离步骤, 动力学过程缓慢. 贵金属铂基催化剂虽活性优异, 但成本高昂、资源稀缺, 难以实现规模化应用. 因此, 开发低成本、高活性且高稳定性的非贵金属碱性析氢电催化剂, 对于推动电解水制氢技术的商业化具有重要意义.
本文提出界面工程协同策略, 通过两步水热法在碳布基底上构建了镍钒层状双金属氢氧化物(NiV-LDH)纳米片修饰硫化钼(MoS₂)纳米片阵列异质结构(NiV-LDH@MoS₂). 该设计利用NiV-LDH优异的水解离能力并通过界面工程调节氢吸附自由能, 同步突破碱性HER的两大动力学限制. X-射线衍射、扫描电子显微镜、透射电镜等表征证实了NiV-LDH成功负载于MoS₂纳米片表面, 且二者形成紧密异质界面. X-射线光电子能谱分析表明, 电子从NiV-LDH向MoS₂定向转移, 有效调控了界面电子结构. 电化学测试结果显示, 优化后的NiV-LDH@MoS₂在1 mol L^-1 KOH中仅需103 mV过电位即可达到10 mA cm^-2电流密度, 远优于NiV-LDH (402 mV)和MoS₂ (152 mV). 其Tafel斜率为76.9 mV dec^-1, 遵循Volmer-Heyrovsky反应路径. 在100 mA cm^-2高电流密度下, 过电位(193 mV)与商业Pt/C (187 mV)相当. 200 mV过电位下转换频率(TOF)值高达11.3 s^-1, 分别为MoS₂和NiV-LDH的5.6倍和2.2倍. 电化学阻抗谱分析证实异质结构电荷转移电阻显著降低. 该催化剂在10 mA cm^-2下连续稳定运行超1000 h. 密度泛函理论计算揭示了协同催化机理: 异质界面形成能为-1.61 eV, 表明界面热力学自发形成. NiV-LDH@MoS₂的水解离自由能降至-0.38 eV, 低于MoS₂ (-0.67 eV)和NiV-LDH (-0.51 eV). 氢吸附自由能(ΔG_H*)优化至-0.13 eV, 趋近热力学中性. 态密度分析显示Ni的d带中心下移, 削弱了氢的过度结合, 利于H₂脱附. 全路径分析表明, NiV-LDH优先催化水解离生成H^*中间体, NiV-LDH@MoS₂界面处加速后续H^*吸脱附与重组, 二者通过串联协同机制实现碱性HER路径的整体加速. 在实际器件验证中, 以NiV-LDH@MoS₂为阴极组装的阴离子交换膜电解池仅需2.26 V即达1 A cm^-2, 并在60 °C下稳定运行超200 h.
综上, 本工作通过界面工程策略成功构建了NiV-LDH@MoS₂异质结构, 实现了对碱性HER中水解离和氢吸脱附步骤的协同优化, 为设计高活性、高稳定性的非贵金属电催化剂提供了新思路. 该研究深化了对异质界面电子协同催化机理的理解, 对推动阴离子交换膜水电解技术从基础研究走向实际应用具有重要参考价值.

关键词: 析氢反应, 层状双氢氧化物, 二硫化钼, 异质结构, 水裂解

Abstract:

The development of efficient and stable non-noble-metal electrocatalysts is crucial for alkaline water electrolysis toward hydrogen production. Herein, a heterostructure comprising NiV-LDH decorated MoS₂ nanosheet arrays on carbon cloth (NiV-LDH@MoS₂) is fabricated via a facile two-step hydrothermal method. The catalyst exhibits outstanding hydrogen evolution reaction (HER) performance in 1 mol L^-1 KOH, requiring an overpotential of only 103 mV to deliver a current density of 10 mA cm^-2, with a Tafel slope of 76.9 mV dec^-1 and exceptional stability surpassing 1000 h. The characterizations combined with theoretical calculations reveal that the heterointerface induces electron transfer from NiV-LDH to MoS₂, effectively modulating the electronic structure. This synergy significantly lowers the water-dissociation energy barrier and optimizes the hydrogen adsorption free energy, thereby collectively accelerating the alkaline HER kinetics. Furthermore, an anion-exchange membrane water electrolyzer assembled with this catalyst achieves a high current density of 1 A cm^-2 at 2.26 V and maintains stable operation for over 200 h, underscoring its practical potential. This work provides an effective interfacial-engineering strategy for designing high-performance, low-cost electrocatalysts for the alkaline HER.

Key words: Hydrogen evolution reaction, Layered double hydroxide, MoS₂, Heterostructure, Water splitting

于世浩, 严玥莹, 杨阳, 姚博瀚, 朱子雯, 王德文, 邢志财, 杨秀荣. 基于界面工程的NiV-LDH@MoS₂异质结构用于高效碱性析氢反应[J]. 催化学报, 2026, 91: 222-231.

Shihao Yu, Yueying Yan, Yang Yang, Bohan Yao, Ziwen Zhu, Dewen Wang, Zhicai Xing, Xiurong Yang. Interfacial engineering of an advanced NiV-LDH@MoS₂ heterostructure electrocatalyst for efficient alkaline hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 91: 222-231.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65224-2

https://www.cjcatal.com/CN/Y2026/V91/I12/222

图/表 6

Fig. 1. Schematic illustration for the synthesis of the NiV-LDH@MoS2 heterostructure.

Fig. 2. XRD patterns (a), SEM image (b), STEM image (c), HRTEM image (d), HAADF-STEM image (e), and EDS elemental mapping images (f) of the NiV-LDH@MoS2 heterostructure.

Fig. 3. High-resolution XPS spectra: Ni 2p (a) and V 2p (b) of NiV-LDH and NiV-LDH@MoS2; Mo 3d (c) and S 2p (d) of MoS2 and NiV-LDH@MoS2.

Fig. 4. Electrochemical HER performance of NiV-LDH@MoS2, MoS2, NiV-LDH, and Pt/C in 1 mol L-1 KOH. LSV curves (a), Tafel plots (b), comparison of overpotentials at 10 and 100 mA cm-2 (c), ECSA-normalized polarization curves (d), Nyquist plots with the equivalent circuit (inset) (e), comparison of overpotentials at 10 mA cm-2 with recently reported non-noble-metal catalysts (f), and chronopotentiometry curve of NiV-LDH@MoS2 at 10 mA cm-2 (g).

Fig. 5. DFT calculations. (a) Atomic structure model and proposed HER pathway on NiV-LDH@MoS2. (b) ΔG(H*) on Ni and V sites. (c) PDOS of Ni 3d orbitals. (d) Free energy diagrams for the HER on MoS2, NiV-LDH, and NiV-LDH@MoS2 surfaces.

Fig. 6. (a) Schematic diagram of the AEMWE cell. (b) Polarization curve of the AEM electrolyzer at 60 °C. (c) Chronopotentiometry curve of the NiFe-LDH||NiV-LDH@MoS2 electrolyzer at 1 A cm-2 and 60 °C.

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基于界面工程的NiV-LDH@MoS₂异质结构用于高效碱性析氢反应

Interfacial engineering of an advanced NiV-LDH@MoS₂ heterostructure electrocatalyst for efficient alkaline hydrogen evolution

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