催化学报

催化学报 ›› 2026, Vol. 91: 365-375.DOI: 10.1016/S1872-2067(26)65207-2

• 论文 • 上一篇    下一篇

配位重构镍单原子实现规模化光热氨分解制氢

王亚川a,1, 雷如楠a,1, 王薇a,1, 吴琦璇a,1, 康楷雯b,c,1, 袁大超d, 张志波c, 唐沅a,*(), 高琳洁a,*(), 李亚光a,*(), 叶金花a,e,f,*()   

  1. a 河北大学光驱动碳中和研究中心, 教育部零碳能源建筑与计量技术教育部工程研究中心, 物理科学与技术学院, 生命科学与绿色发展研究院, 河北保定 071002, 中国
    b 燕山大学亚稳材料全国重点实验室, 河北秦皇岛 066004, 中国
    c 西南交通大学材料科学与工程学院, 四川成都 611756, 中国
    d 河北农业大学机电工程学院, 河北省畜禽养殖智能装备与新能源利用重点实验室, 河北保定 071001, 中国
    e 天津大学材料科学与工程学院先进催化材料研究中心, 天津 300072, 中国
    f 日本国立材料研究所WPI-MANA研究中心, 茨城县筑波市, 日本
  • 收稿日期:2026-01-15 接受日期:2026-03-19 出版日期:2026-12-18 发布日期:2026-10-13
  • 通讯作者: *电子信箱: tangyuan@tju.edu.cn (唐沅),
    linjiegao@hbu.edu.cn (高琳洁),
    liyaguang@hbu.edu.cn (李亚光),
    Jinhua.ye@hbu.edu.cn (叶金花).
  • 作者简介:1共同第一作者.
  • 基金资助:
    国家自然科学基金(52371220);国家自然科学基金(U23A20139);河北省自然科学基金(B2023204034);河北省自然科学基金(B20232011107);河北省自然科学基金(2023HBQZYCXY001)

Coordination reconfigured Ni single-atoms for scaled photothermal COx free hydrogen production from ammonia

Yachuan Wanga,1, Runan Leia,1, Wei Wanga,1, Qixuan Wua,1, Kaiwen Kangb,c,1, Dachao Yuand, Zhibo Zhangc, Yuan Tanga,*(), Linjie Gaoa,*(), Yaguang Lia,*(), Jinhua Yea,e,f,*()   

  1. a Research Center for Solar Driven Carbon Neutrality, Engineering Research Center of Zero-carbon Energy Buildings and Measurement Techniques, Ministry of Education, The College of Physics Science and Technology, Institute of Life Science and Green Development, Hebei University, Baoding 071002, Hebei, China
    b State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, Hebei, China
    c School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 611756, Sichuan, China
    d College of Mechanical and Electrical Engineering, Key Laboratory Intelligent Equipment and New Energy Utilization of Livestock and Poultry Breeding, Hebei Agricultural University, Baoding 071001, Hebei, China
    e Advanced Catalytic Materials Research Center, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
    f International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
  • Received:2026-01-15 Accepted:2026-03-19 Online:2026-12-18 Published:2026-10-13
  • About author:1Contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China(52371220);National Natural Science Foundation of China(U23A20139);Natural Science Foundation of Hebei Province(B2023204034);Natural Science Foundation of Hebei Province(B20232011107);Natural Science Foundation of Hebei Province(2023HBQZYCXY001)

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摘要：

氢能被认为是支撑未来低碳能源体系的重要载体, 但现阶段氢源供应仍面临制备过程能耗高、运输与储存成本大等现实问题. 氨因具有17.6 wt%的高储氢密度、易液化储运以及现有基础设施较为成熟等优势, 被视为极具潜力的储氢和运氢介质. 同时, 氨分解可直接生成不含CO和CO2的高纯氢气, 能够有效避免COx对燃料电池的毒化作用, 因此在分布式供氢场景中具有重要应用前景. 然而, 传统热催化氨分解需要消耗20–26 kWh电能才能制得1 kg氢气, 巨大的二次能耗严重制约了其实际推广. 本文构建了自然太阳光驱动的光热氨分解体系, 并通过调控镍单原子催化剂的局域配位结构, 实现了高效、低能耗的无COx制氢, 为太阳能驱动绿色供氢技术提供了新的研究思路.
本文以采用溶胶-凝胶法制备的铈锆固溶体负载镍单原子催化剂(SA Ni/CexZr1–xO2)为核心, 提出了“固溶体组分调控 → 单原子配位重构 → 光热系统耦合强化”的设计策略. 表征结果表明, Ni物种以单原子形式稳定分散于CexZr1–xO2表面. 其中SA Ni/Ce0.5Zr0.5O2表现出最优结构参数, Ni–O配位数降至4.52, Ni–O键长缩短至1.89 Å, 说明Zr的引入有效重构了Ni活性位点的局域几何与电子结构. 在热催化氨分解中, SA Ni/Ce0.5Zr0.5O2在300 °C下的产氢速率达到500.7 mmol g-cat–1 h–1, NH3转化率为68.1%, 并可稳定运行160 h; 其表观活化能仅为25.1 kJ mol–1, 明显低于其他对比样品. 原位漫反射红外光谱检测到NH2*, NH及Ni–N2等中间物种, 证明反应遵循NH3 → NH2 → NH → N的逐步脱氢路径; 密度泛函理论计算进一步表明, Zr调控后NH3在Zr–O–Ni–O–Ce位点上的吸附-脱附强度趋于适中, SA Ni/Ce0.5Zr0.5O2(111)上的反应能垒降低至1.10 eV, 较SA Ni/Ce1Zr0O2(111)和Ni(111)分别降低0.11和0.67 eV, 同时d带中心的调变削弱了对NHx中间体的过强吸附, 从而协同促进N-H键断裂和中间体脱附动力学. 基于该高效催化剂, 搭建由Cu反射层、TiC吸光层和真空隔热层组成的自制光热反应器, 在无外部加热条件下实现太阳光驱动氨分解, 当光照强度为0.4 sun时, 产氢速率为116.5 mmol gcat–1 h–1; 在标准太阳光辐照下, 体系温度升至314 °C, 产氢速率达到298.0 mmol gcat–1 h–1, 太阳能-氢能转化效率达16.1%, 显著优于已报道同类体系. 进一步放大该体系并构建户外光热氨分解系统, 实现了1.019 kg的日产氢量, 即使在冬季户外测试中, 仍可实现每天0.66 kg的氢产量. 经济性分析表明, 光热氨分解制氢的总成本为3.53 $ kg–1, 低于传统热催化氨分解的$ kg–1, 表明该体系在降低二次能耗和综合制氢成本方面具有明显优势.
综上, 本文证实了通过固溶体载体组分调控镍单原子的配位环境, 并与高效光热反应系统相结合, 可实现自然太阳光驱动下高效、低成本、无COx的氨制氢过程. 未来, 太阳光驱动氨分解制氢仍可在催化剂长期户外稳定性、连续运行能力、系统集成与规模化制造等方面进一步优化. 本文从单原子配位结构调控与光热能量利用协同强化的角度, 为无碳高纯氢的低能耗制备提供了新的理论依据和技术路径, 也为面向加氢站应用的分布式绿色供氢系统奠定了重要基础.

关键词: 光热催化, 氨, 氢, 固溶体

Abstract:

Ammonia (NH3) decomposition to produce COx free hydrogen is an ideal supply for hydrogen refueling stations with the drawback of giant secondary energy consumption, which limits its application. Herein, we develop a natural sunlight driven photothermal NH3 decomposition system to achieve a hydrogen evolution rate of 298.0 mmol g-cat–1 h–1 with the solar-to-hydrogen efficiency of 16.1%, outperforming all counterparts. The catalytic activity is attributed to the catalyst of Ni single atoms loaded on a cerium-zirconium solid solution (SA Ni/CexZr1–xO2), that the component regulation of CexZr1–xO2 could modulate the Ni–O coordination number and shorten the Ni–O bond length of Ni single atoms to synergistically optimize the dissociative energy barrier of NH3 molecules and the desorption kinetics of NHx intermediates. Under outdoor sunlight illumination, the enlarged photothermal NH3 decomposition system achieves a record hydrogen production rate of 1 kg per day and the corresponding cost is calculated as $3.53 kg–1, significantly lower than the market price of hydrogen from thermocatalytic NH3 decomposition ($4.26 kg–1). This work provides a new strategy for NH3 decomposition in COx free hydrogen energy system with low energy consumption and cost advantage through the synergistic of coordination structure modulation of catalyst and photothermal system.

Key words: Photothermal catalysis, Ammonia, Hydrogen, Solid solution