Nature of Catalytic Behavior of Cobalt Oxides for CO2 Hydrogenation

Kailang Li; Xianghong Li; Lulu Li; Xin Chang; Shican Wu; Chengsheng Yang; Xiwen Song; Zhi-Jian Zhao; Jinlong Gong

doi:10.1021/jacsau.2c00632

Nature of Catalytic Behavior of Cobalt Oxides for CO₂ Hydrogenation

JACS Au. 2023 Feb 1;3(2):508-515. doi: 10.1021/jacsau.2c00632. eCollection 2023 Feb 27.

Authors

Kailang Li¹, Xianghong Li¹, Lulu Li¹, Xin Chang¹, Shican Wu¹, Chengsheng Yang¹, Xiwen Song¹, Zhi-Jian Zhao¹, Jinlong Gong^{1

2

3

4}

Affiliations

¹ Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University; Collaborative Innovation Center for Chemical Science and Engineering, Tianjin 300072, China.
² Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, China.
³ Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China.
⁴ National Industry-Education Platform of Energy Storage, Tianjin University, 135 Yaguan Road, Tianjin 300350, China.

Abstract

Cobalt oxide (CoO _x ) catalysts are widely applied in CO₂ hydrogenation but suffer from structural evolution during the reaction. This paper describes the complicated structure-performance relationship under reaction conditions. An iterative approach was employed to simulate the reduction process with the help of neural network potential-accelerated molecular dynamics. Based on the reduced models of catalysts, a combined theoretical and experimental study has discovered that CoO(111) provides active sites to break C-O bonds for CH₄ production. The analysis of the reaction mechanism indicated that the C-O bond scission of *CH₂O species plays a key role in producing CH₄. The nature of dissociating C-O bonds is attributed to the stabilization of *O atoms after C-O bond cleavage and the weakening of C-O bond strength by surface-transferred electrons. This work may offer a paradigm to explore the origin of performance over metal oxides in heterogeneous catalysis.