Fang Yarong, Zhang Qi, Zhang Huan, Li Xiaomin, Chen Wei, Xu Jue, Shen Huan, Yang Ji, Pan Chuanqi, Zhu Yuhua, Wang Jinlong, Luo Zhu, Wang Liming, Bai Xuedong, Song Fei, Zhang Lizhi, Guo Yanbing
Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental and Applied Chemistry, College of Chemistry, Central China Normal University, Wuhan, 430079, China.
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
Angew Chem Int Ed Engl. 2022 Nov 25;61(48):e202212273. doi: 10.1002/anie.202212273. Epub 2022 Oct 25.
The in-depth mechanism on the simultaneous activation of O and surface lattice O on one active metallic site has not been elucidated yet. Herein, we report a strategy for the construction of abundant oxygen activation sites by rational design of Cu /TiO single atom catalysts (SACs). The charge transfer between isolated Cu and TiO support generates abundant Cu and 2-coordinated O sites in Cu -O-Ti hybridization structure, which facilitates the chemisorption and activation of O molecules. Simultaneously, the Cu -O-Ti induced TiO lattice distortion activate the adjacent surface lattice O , achieving the dual activation of O and surface lattice O . The Cu -O-Ti active site switches the CO oxidation mechanism from Eley-Rideal (80 °C) to Mars-van Krevelen route (200 °C) with the increase of reaction temperature. The dual activation of O and surface lattice O can by modulating the electron properties of SACs can boost the heterogeneous catalytic oxidation activity.
一个活性金属位点上同时激活O和表面晶格O的深入机制尚未阐明。在此，我们报告了一种通过合理设计Cu/TiO单原子催化剂（SACs）来构建丰富氧活化位点的策略。孤立的Cu与TiO载体之间的电荷转移在Cu-O-Ti杂化结构中产生了丰富的Cu和二配位O位点，这有利于O分子的化学吸附和活化。同时，Cu-O-Ti诱导的TiO晶格畸变激活了相邻的表面晶格O，实现了O和表面晶格O的双重活化。随着反应温度的升高，Cu-O-Ti活性位点将CO氧化机制从Eley-Rideal（80°C）转变为Mars-van Krevelen途径（200°C）。通过调节SACs的电子性质，O和表面晶格O的双重活化可以提高多相催化氧化活性。
