物理化学学报 >> 2025, Vol. 41 >> Issue (12): 100159.doi: 10.1016/j.actphy.2025.100159

论文 上一篇    下一篇

Ni诱导的Pt 5d-H 1s反键轨道调控以增强析氢和尿素氧化

柳如艳1,†, 倪振瑞1,†, RuzimuradovOlim2,3, TurayevKhayit4, 刘涛1, 余罗1, 邝攀勇1,*()   

  1. 1 中国地质大学(武汉)材料与化学学院, 太阳燃料实验室, 湖北 武汉 430078
    2 Alfraganus University, Yuqori Karakamish Street 2a, Tashkent 100190, Uzbekistan
    3 Turin Polytechnic University in Tashkent, Kichik khalqa yoli 17, Tashkent 100095, Uzbekistan
    4 Termez State University, Barkamol Avlod Street 43, Termez 190111, Uzbekistan
  • 收稿日期:2025-07-24 修回日期:2025-08-12 录用日期:2025-08-14 发布日期:2025-10-23
  • 通讯作者: Email: kuangpanyong@cug.edu.cn (邝攀勇)
  • 作者简介:

    † These authors contributed equally to this work

  • 基金资助:
    国家重点研发计划项目(2022YFB3803600); 国家自然科学基金(22272153); 国家自然科学基金(22479132); 国家自然科学基金(22238009); 国家自然科学基金(U23A20102); 国家自然科学基金(22361142704); 国家自然科学基金(22309168); 湖北省自然科学基金(2022CFA001); 湖北省重点研发计划项目(2023BAB113)

Ni-induced modulation of Pt 5d-H 1s antibonding orbitals for enhanced hydrogen evolution and urea oxidation

Ruyan Liu1, Zhenrui Ni1, Olim Ruzimuradov2,3, Khayit Turayev4, Tao Liu1, Luo Yu1, Panyong Kuang1,*()   

  1. 1 Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan 430078, Hubei Province, China
    2 Alfraganus University, Yuqori Karakamish Street 2a, Tashkent 100190, Uzbekistan
    3 Turin Polytechnic University in Tashkent, Kichik khalqa yoli 17, Tashkent 100095, Uzbekistan
    4 Termez State University, Barkamol Avlod Street 43, Termez 190111, Uzbekistan
  • Received:2025-07-24 Revised:2025-08-12 Accepted:2025-08-14 Published:2025-10-23
  • Contact: Email: kuangpanyong@cug.edu.cn (Panyong Kuang)
  • Supported by:
    the National Key Research and Development Program of China(2022YFB3803600); National Natural Science Foundation of China(22272153); National Natural Science Foundation of China(22479132); National Natural Science Foundation of China(22238009); National Natural Science Foundation of China(U23A20102); National Natural Science Foundation of China(22361142704); National Natural Science Foundation of China(22309168); the Natural Science Foundation of Hubei Province of China(2022CFA001); Key R&D Program Projects in Hubei Province(2023BAB113)

RichHTML

12

PDF

236

赞

补充材料

1

摘要：

尽管氢气具有高能量密度、环境友好性和可再生性等优势，但其高效生产受限于析氧反应(Oxygen Evolution Reaction，OER)的缓慢动力学。本研究报道了一种Pt@PtNi3核壳合金电催化剂，通过引入Ni元素调控Pt 5d反键轨道占据，同步提升析氢反应(Hydrogen Evolution Reaction，HER)与尿素氧化反应(Urea Oxidation Reaction，UOR)活性。对于HER，优化后的Pt@PtNi3-500在酸性条件下实现10 mA cm-2电流密度仅需21 mV的低过电位，同时在碱性条件下的UOR起始电位为1.27 V，性能均优于单金属Pt和Ni催化剂。当被应用于酸碱非对称电解(HER/UOR)时，相较于传统碱性水分解(HER/OER)，Pt@PtNi3-500的制氢能耗降低了68.3%。机理研究表明Pt@PtNi3中适量的Ni掺杂增加了Pt 5d–H 1s反键轨道占据，既强化了H+吸附又削弱了过强的H*结合，同时还降低了*NH2脱氢能垒，从而协同促进了氢气生成与尿素分解。该研究为高效生物质氧化辅助制氢合金电催化剂设计提供了新思路。

关键词: 析氢反应, 尿素氧化反应, Pt@PtNi3核壳合金, 酸碱非对称催化, 反键轨道占据

Abstract:

While H2 features high energy density, environmental friendliness, and renewability, its efficient production is limited by the sluggish kinetics of the oxygen evolution reaction (OER). Here, we report a Pt@PtNi3 core@shell alloy electrocatalyst that, through Ni incorporation, modulates the occupancy of Pt 5d antibonding orbitals and simultaneously enhances both hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) activities. The optimized Pt@PtNi3-500 delivers an ultralow overpotential of 21 mV at 10 mA cm-2 for HER under acidic conditions and a low onset potential of 1.27 V for UOR under alkaline conditions, surpassing monometallic Pt and Ni counterparts. When employed in an asymmetric acid-alkaline electrolyzer (HER/UOR), Pt@PtNi3-500 achieves a 68.3% reduction in electrical energy consumption for H2 production compared to traditional alkaline water splitting (HER/OER). Mechanistic investigations reveal that appropriate Ni incorporation in Pt@PtNi3 increases the occupancy of Pt 5d–H 1s antibonding orbitals, which not only reinforces H+ adsorption but also weakens the overly strong H* binding. Simultaneously, it reduces the energy barrier for *NH2 dehydrogenation, thereby synergistically accelerating both H2 generation and urea decomposition. This work provides new insights into the design of alloy electrocatalysts for high-efficiency H2 production.

Key words: Hydrogen evolution reaction, Urea oxidation reaction, Pt@PtNi3 core@shell alloy, Asymmetric acid-alkaline catalysis, Antibonding orbital occupancy