Dual Activation of Molecular Oxygen and Surface Lattice Oxygen in Single Atom Cu1/TiO2 Catalyst for CO Oxidation

• Published in: Angewandte Chemie International Edition 2022-11, Vol.61 (48), p.e202212273-n/a
• Main Authors: 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
• Format: Article
• Language: English
• Subjects: Activated Surface Lattice Oxygen; Carbon monoxide; Catalysts; Charge transfer; Chemisorption; Copper; Cu/TiO2 Catalyst; Dual Activation; Hybridization; Molecular Oxygen; Oxidation; Oxygen; Single Atom Catalyst; Single atom catalysts; Switches; Titanium; Titanium dioxide
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202212273

The in‐depth mechanism on the simultaneous activation of O2 and surface lattice O2− 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 Cu1/TiO2 single atom catalysts (SACs). The charge transfer between isolated Cu and TiO2 support generates abundant CuI and 2‐coordinated Olat sites in Cu1−O−Ti hybridization structure, which facilitates the chemisorption and activation of O2 molecules. Simultaneously, the Cu1−O−Ti induced TiO2 lattice distortion activate the adjacent surface lattice O2−, achieving the dual activation of O2 and surface lattice O2−. The Cu1−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 O2 and surface lattice O2− can by modulating the electron properties of SACs can boost the heterogeneous catalytic oxidation activity. The isolated Cu1+ on Cu1/TiO2 single atom catalysts (SACs) facilitated the simultaneous activation of chemisorbed O2 and 2‐coordinated surface lattice O2−, which triggered the CO oxidation through E‐R (80 °C) and MvK (200 °C) routes synergistically with elevated temperature. This finding provides insights and strategy for the rational design of efficient oxidation catalysts with sufficient reactive oxygen species for practical application.