Insights into CO Oxidation in Cu/CeO₂ Catalysts: O₂ Activation at the Dual‐Interfacial Sites

Abstract

Cu clusters supported on CeO 2 have been reported as a promising and active catalyst for CO oxidation. However, the identification of interfacial interactions and active sites is still a great challenge. In this work, we demonstrated that interfacial chemistry can be understood and predicted by using a simple descriptor of adsorbate-surface interactions that uncovers structure-activity relationships. The catalytic activity of CeO 2 supported Cu clusters for CO oxidation was studied by density functional theory. The CuÀ Ce dual site mechanism enables the Cu/CeO 2 catalyst to have a much lower reaction energy barrier than the Mars-van Krevelen (M-vK) mechanism and the Cu-only mechanism. The reaction energy barriers of Cu/CeO 2-x with an oxygen vacancy on the CeO 2 surface were 0.10, 0.37 and 0.77 eV, respectively. The excellent performance of Cu/CeO 2 catalysts is related to the interfacial interaction between Cu and CeO 2 and their synergistic redox behaviors, and oxygen vacancies facilitate the generation and stabilization of active Cu + species through the interaction with Cu clusters. And we have identified the binding energy of O 2 * can describe the CO oxidation activity of Cu/CeO 2 . Our study provides insight into the nature of active sites for Cu/CeO 2 catalysts and guidance for high-performance.

Intelligent Structure Searching and Designs for Nanoclusters: Effective Units in Atomic Manufacturing

“…[ 181–184 ] Ji et al studied the minimum energy structure of Cu 8 cluster anchored on the CeO 2 (111) and CeO 2− x (111) surface by CALYPSO code (shown in Figure 21B) and revealed the interfacial effect on the catalytic activity for CO oxidation. [ 185 ] Sub‐nano Ni cluster supported on substrate is also important for catalysis application. Zhao et al by CALYPSO code investigated the structure of sub‐nano Ni cluster (Ni n , n = 2–21) in vacuum, on ZnO(000) and γ‐Al 2 O 3 (100) surfaces and unique magic numbers are revealed in vacuum and on substrates.…”

“…[ 178 ] B) The schematic illustration of the formation process of Cu 8 cluster on perfect and oxygen‐vacancy CeO 2 (111) surface. [ 185 ] C) The schematic of the zigzag edge reconstruction of graphene. [ 189 ] D) a) The flowchart of surface structure prediction of CALYPSO.…”

“…A) The schematic of the borophene structures controlled by substrate [178]. B) The schematic illustration of the formation process of Cu 8 cluster on perfect and oxygen-vacancy CeO 2(111) surface [185]. C) The schematic of the zigzag edge reconstruction of graphene [189].…”

Effect of Copper Particle Size on the Surface Structure and Catalytic Activity of Cu–CeO2 Nanocomposites Prepared by Mechanochemical Synthesis in the Preferential CO Oxidation in a H2-Rich Stream (CO-PROX)

“…The Cu-containing catalysts based on ceria are widely used for different industrially and ecologically important processes. For example, oxidation of volatile organic compounds [1], soot of various genesis [2,3], direct and reverse Water-Gas Shift reaction [4,5], low-temperature CO oxidation, and preferential CO oxidation in a H 2 -rich stream [6,7]. A zero CO 2 emission policy assumes hydrogen, a clean and zero-carbon fuel, as the main fuel resource.…”