催化学报

催化学报 ›› 2026, Vol. 89: 232-245.DOI: 10.1016/S1872-2067(26)65155-8

• 论文 • 上一篇    下一篇

自驱动力介导组装:分层杂化电催化剂中构建单原子结构的一般策略

李婷a, 陈晓慧a, 李晓林a, 肖琦b,*(), 李念兵a,*(), 罗红群a,*()   

  1. a西南大学化学化工学院,重庆 400715
    b南宁师范大学化学与材料学院,广西南宁 530001
  • 收稿日期:2026-01-07 接受日期:2026-03-12 出版日期:2026-10-18 发布日期:2026-09-01
  • 通讯作者: *电子信箱: qi.xiao@nnnu.edu.cn (肖琦),
    luohq@swu.edu.cn (罗红群),
    linb@swu.edu.cn(李念兵).
  • 基金资助:
    国家自然科学基金(21675131);重庆市自然科学基金(cstc2020jcyj-zdxmX0003);重庆市自然科学基金(CSTB2023NSCQ-MSX0924)

Autogenous force-mediated assembly: A general strategy for constructing single-atom architectures in hierarchical hybrid electrocatalysts

Ting Lia, Xiaohui Chena, Xiaolin Lia, Qi Xiaob,*(), Hongqun Luoa,*(), Nianbing Lia,*()   

  1. aSchool of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China
    bSchool of Chemistry and Materials, Nanning Normal University, Nanning 530001, Guangxi, China
  • Received:2026-01-07 Accepted:2026-03-12 Online:2026-10-18 Published:2026-09-01
  • Contact: *E-mail:qi.xiao@nnnu.edu.cn(Q. Xiao),luohq@swu.edu.cn (H. Luo),linb@swu.edu.cn(N. Li).
  • Supported by:
    National Natural Science Foundation of China(21675131);Natural Science Foundation of Chongqing(cstc2020jcyj-zdxmX0003);Natural Science Foundation of Chongqing(CSTB2023NSCQ-MSX0924)

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摘要：

随着全球能源结构转型的深化, 氢能作为实现碳中和目标的清洁能源载体, 其高效、低成本制备成为关键. 然而, 当前高效催化剂普遍面临贵金属用量与催化活性、稳定性难以兼顾的核心矛盾: 降低载量易导致活性位点团聚失活, 而提升性能则推高成本. 单原子催化剂(SACs)以其极限的原子利用率, 为破解这一困境提供了理论可能, 但其实际应用仍受限于合成过程中金属原子易迁移团聚、与载体作用弱以及宽pH条件下稳定性不足等瓶颈. 在此背景下,如何在原子尺度上精准构筑同时兼具高活性、高稳定性及宽pH适应性的单原子催化体系, 成为该领域亟待突破的焦点难题.

本文提出了一种自驱动力介导的动态合成新范式, 通过设计独特的非对称管状前驱体, 巧妙地利用其内部自发产生的毛细力与化学势梯度作为唯一驱动力, 一步实现了Co的定向迁出、Co3O4基质的原位构筑与Ru单原子的同步晶格限域锚定, 成功创制出具有明确“内金属核-外单原子壳”空间与功能分区的一体化催化剂, 该策略避免了传统合成中对复杂步骤与苛刻条件的依赖, 其自限制的动态过程确保了Ru的原子级分散. 具体而言, 首先设计了一端封闭、一端开口且内部封装Co纳米颗粒的氮掺杂碳纳米管作为自组装模板. 然后将其浸没在含Ru溶液中, 利用管内毛细作用与Co2+离子浓度梯度共同形成的自发驱动力, 实现了Co物种由内向外的定向迁移, 并在管外表面原位形成Co3O4基底, 同步锚定Ru物种形成原子级分散的活性位点, 该动态迁移-沉积过程有效抑制了Ru物种团聚, 确保了Ru单原子的均匀分散与稳定锚定. 所制得的催化剂在碱性与酸性电解液中均表现出优异的析氢反应活性与稳定性, 其性能优于大多数已报道的催化剂. 实验表征与理论计算表明, 优异的催化性能源于Ru单原子与Co3O4基质之间的强电子金属-载体相互作用以及Co@NCNTs内核的高导电性之间的有效协同. 此外, 该制备方法也可以应用至其他贵金属单原子催化剂的制备, 为单原子催化剂的可控合成提供了全新的内建驱动思路.

综上, 本工作通过自驱动力介导的合成策略, 成功构筑了内外协同、晶格限域的Ru单原子催化剂, 在原子尺度实现了高效、稳定、宽pH普适的析氢催化. 并进一步通过实验与理论揭示了此类“自组装-限域”机制下独特的电子协同与稳定性根源, 为设计下一代高性能催化材料建立了新的设计思路, 对推动高性能电催化剂设计与可再生能源转换技术具有重要意义.

关键词: 单原子催化剂, 析氢反应, 金属-载体相互作用, 碳纳米管, 三维分层材料

Abstract:

The design of efficient and pH-universal ruthenium (Ru) single-atom catalysts (SACs) remains a pivotal challenge for hydrogen economy systems. Here, inspired by tubular capillary phenomena, a novel approach is introduced—autogenous force-mediated assembly—enabled by a unique asymmetric N-doped carbon nanotubes (NCNTs) scaffold with a Co-embedded sealed end. The confined geometry drives a spontaneous, directional outward migration of Co2+ species at room temperature, which deposit as amorphous or poorly crystalline cobalt-based compounds at the outer surface while concurrently capturing and stabilizing Ru species in single-atom configurations. And these precursors transform into well-crystallized Co3O4 anchored with Ru single-atom upon calcination. This process yields a precisely organized three-dimensional architecture where metallic Co nanoparticles remain confined within the NCNTs, while atomically dispersed Ru sites are firmly anchored on the exterior Co3O4 lattice. The gradual migration-deposition process is inherently self-limiting, ensuring uniform dispersion of Ru single-atoms (SAs). The resulting lattice confinement induces a strong electronic metal-support interaction (EMSI), which effectively suppresses atomic aggregation and optimizes the electronic structure of the active sites. The integrated system—coupling the conductive Co@NCNT with the EMSI-enhanced Ru-Co3O4 interface—delivers outstanding hydrogen evolution reaction performance. This work establishes a generalizable synthesis paradigm that leverages internally generated forces for the precise spatial organization of active components, presenting a versatile route toward high-performance SACs for sustainable energy conversion.

Key words: Single-atom catalysts, Hydrogen evolution reaction, Metal-support interaction, Carbon nanotubes, Three-dimensional hierarchical, material