物理化学学报2025，Vol.41Issue(12)：111-121,11.DOI:10.1016/j.actphy.2025.100159
Ni诱导的Pt 5d-H 1s反键轨道调控以增强析氢和尿素氧化
Ni-induced modulation of Pt 5d-H 1s antibonding orbitals for enhanced hydrogen evolution and urea oxidation
摘要
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.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Key words
Hydrogen evolution reaction/Urea oxidation reaction/Pt@PtNi3 core@shell alloy/Asymmetric acid-alkaline catalysis/Antibonding orbital occupancy分类
化学化工引用本文复制引用
Ruyan Liu,Zhenrui Ni,Olim Ruzimuradov,Khayit Turayev,Tao Liu,Luo Yu,Panyong Kuang..Ni诱导的Pt 5d-H 1s反键轨道调控以增强析氢和尿素氧化[J].物理化学学报,2025,41(12):111-121,11.基金项目
This work was supported by the National Key Research and Development Program of China(2022YFB3803600),National Natural Science Foundation of China(22272153,22479132,22238009,U23A20102,22361142704,22309168),the Natural Science Foundation of Hubei Province of China(2022CFA001),and Key R&D Program Projects in Hubei Province(2023BAB113). 国家重点研发计划项目(2022YFB3803600),国家自然科学基金(22272153,22479132,22238009,U23A20102,22361142704,22309168),湖北省自然科学基金(2022CFA001)和湖北省重点研发计划项目(2023BAB113)资助.感谢安徽创谱仪器科技有限公司提供的XAFS测试及相关分析支持 （2022YFB3803600）
