超越地方协调:全球结构如何设计单原子催化剂对CO2的选择性
Yu Cui1,2, Yilei Wu1, Chunjin Ren1
1Key Laboratory of Quantum Materials and Devices of Ministry of Education, School of Physics, Southeast University, Nanjing, 211189, China.
Angewandte Chemie (International ed. in English)
|November 5, 2025
概括
单原子催化剂 (SAC) 的催化性能取决于本地活性点和全球结构. 全球结构工程,结合局部灵敏度,通过影响电子安置和反应能量学来决定性能.
科学领域:
- 材料科学 材料科学 材料科学
- 催化剂是一种催化剂.
- 表面化学 表面化学
背景情况:
- 活性位点的局部结构传统上被认为是催化性能的主要决定因素.
- 这种模式经常失败,特别是在基于碳的单原子催化剂 (SAC) 中,不同的基质 (例如,N-化碳与酸) 产生不同的性能,尽管具有相同的活性中心 (MN4).
研究的目的:
- 揭示一种内在的全球-本地相互作用机制,控制SACs的催化性能.
- 阐明全球结构变化和本地站点敏感性如何共同影响催化结果.
主要方法:
- 研究了局部活性位结构,全球基质结构和SAC中的催化性能之间的关系.
- 分析了d波段中心,反应热力学,零电荷 (PZC) 潜力,电子容纳和界面水方向.
- 评估了不同金属中心 (Co,Fe,Ni) 局部电荷对全球结构变化的敏感性.
主要成果:
- 类似的局部活性点 (MN4) 导致可比的d频段中心和反应热力学.
- 不同的全球结构导致了显著不同的零电荷 (PZC) 潜力,影响了电子的安置和水的方向.
- 当地活性站点的电荷对全球结构变化的敏感性对催化性能进行了关键调节.
- 与Fe和Ni SAC相比,Co SACs在N-doped碳和phthalocyanine基底之间表现出相反的选择性,这是由于相比Fe和Ni SACs的灵敏度更高.
结论:
- 在SAC中,催化性能是由全球结构和本地站点灵敏度之间的相互作用决定的,超越了传统的本地站点范式.
- 全球结构工程对于通过影响电子属性和接口行为来优化SAC性能至关重要.
- 活性部位对全球结构变化的敏感性是决定对催化物的全球影响程度的关键因素.
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