Zhou Peng, Hou Xingang, Chao Yuguang, Yang Wenxiu, Zhang Weiyu, Mu Zijie, Lai Jianping, Lv Fan, Yang Kuan, Liu Yuxi, Li Jiong, Ma Jingyuan, Luo Jun, Guo Shaojun
Department of Materials Science and Engineering , Peking University , Beijing 100871 , China . Email:
Center for Electron Microscopy , Tianjin Key Laboratory of Advanced Functional Porous Materials , Institute for New Energy Materials & Low-Carbon Technologies , School of Materials , Tianjin University of Technology , Tianjin 300384 , China.
Chem Sci. 2019 Apr 25;10(23):5898-5905. doi: 10.1039/c9sc00658c. eCollection 2019 Jun 21.
Sub-nanometer noble metal catalysts, especially single atom (SA), are a new class of catalytic materials for boosting catalysis and possess unique catalytic properties and high atomic utilization efficiency. Exploring the interaction between two neighboring atom monomers has great potential to further improve the performance of SA catalysts and deepen the understanding on the catalytic mechanism of heterogeneous catalysis at the atomic level. Herein, we demonstrate that the synergetic effect between neighboring Pt and Ru monomers supported on N vacancy-rich g-CN promotes the catalytic CO oxidation. The experimental observation and theoretical simulation reveal that the N vacancy in the g-CN structure builds an optimized triangular sub-nanometer cavity for stabilizing the neighboring Pt-Ru monomers by forming Pt-C and Ru-N bonds. The mechanistic studies based on the IR spectrum and theoretical simulation confirm that the neighboring Pt-Ru monomers possess a higher performance for optimizing O activation than Ru-Ru/Pt-Pt monomers or isolated Ru/Pt atoms by balancing the energy evolution of reaction steps in the catalytic CO oxidation. The discovery of the synergetic effect between neighboring monomers may create a new path for manipulating the catalytic properties of SA catalysts.
亚纳米级贵金属催化剂,尤其是单原子(SA)催化剂,是一类用于促进催化作用的新型催化材料,具有独特的催化性能和高原子利用效率。探索两个相邻原子单体之间的相互作用对于进一步提高单原子催化剂的性能以及在原子水平上深化对多相催化反应机理的理解具有巨大潜力。在此,我们证明了负载在富含氮空位的g-CN上的相邻铂和钌单体之间的协同效应促进了催化CO氧化反应。实验观察和理论模拟表明,g-CN结构中的氮空位通过形成Pt-C和Ru-N键构建了一个优化的三角形亚纳米级空腔,用于稳定相邻的Pt-Ru单体。基于红外光谱和理论模拟的机理研究证实,相邻的Pt-Ru单体在催化CO氧化反应中通过平衡反应步骤的能量演化,比Ru-Ru/Pt-Pt单体或孤立的Ru/Pt原子具有更高的优化氧活化性能。相邻单体之间协同效应的发现可能为调控单原子催化剂的催化性能开辟一条新途径。