Partially sintered copper\u2012ceria as excellent catalyst for the high-temperature reverse water gas shift reaction

Hao-Xin Liu,Chao Ma,Chun-Jiang Jia,Wu-Jun Zhang,Shan-Qing Li,Wei-Wei Wang,Wen-Zhu Yu

doi:10.1038/s41467-022-28476-5

Abstract

For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts. Herein, we report the construction of sufficient and stable copper clusters in the copper‒ceria catalyst with high Cu loading (15 wt.%) for the high-temperature reverse water gas shift (RWGS) reaction. Under very harsh working conditions, the ceria nanorods suffered a partial sintering, on which the 2D and 3D copper clusters were formed. This partially sintered catalyst exhibits unmatched activity and excellent durability at high temperature. The interaction between the copper and ceria ensures the copper clusters stably anchored on the surface of ceria. Abundant in situ generated and consumed surface oxygen vacancies form synergistic effect with adjacent copper clusters to promote the reaction process. This work investigates the structure-function relation of the catalyst with sintered and inhomogeneous structure and explores the potential application of the sintered catalyst in C1 chemistry.

Highlights

For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts
Structural characterization and density functional theory (DFT) calculations confirmed that abundant active surface oxygen vacancies were in situ generated and consumed circularly during the reaction, which combined with adjacent copper clusters to promote the activation of CO2 and catalytic efficiency
The catalytic performance in the reverse water gas shift (RWGS) reaction over various catalysts was evaluated at various temperatures under a high space velocity of 400,000 mL·gcat−1·h−1

Summary

Introduction

For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts. We report the construction of sufficient and stable copper clusters in the copper‒ceria catalyst with high Cu loading (15 wt.%) for the high-temperature reverse water gas shift (RWGS) reaction. Under very harsh working conditions, the ceria nanorods suffered a partial sintering, on which the 2D and 3D copper clusters were formed This partially sintered catalyst exhibits unmatched activity and excellent durability at high temperature. We report a partially sintered Cu/CeO2 catalyst with Cu loading up to 15 wt.% which exhibits extraordinarily high activity and stability for the RWGS reaction under very harsh conditions (600 °C, space velocity of 400,000 mL·gcat−1·h−1). Two-dimensional (2D) and three-dimensional (3D) copper clusters are formed and firmly anchored on the surface of ceria under the reaction conditions due to the interaction between copper and ceria, through which abundant stable active sites were constructed. The partially sintered catalyst with excellent catalytic performance breaks the conventional impression that catalysts are severely deactivated upon sintering and shows great potential in the utilization of CO2

Methods

Results

Conclusion