Unraveling the Geometric Structure Induced Electronic Structure‐Activity Insights of Highly Stable Pt/CeO 2 Catalysts for Water–Gas Shift Reaction

Abstract Herein, a coherent study of the intrinsic kinship between electronic and geometric structures was performed using Pt/CeO 2 catalysts. CeO 2 ‐supported Pt nanoclusters (1.7 nm) were synthesized with two distinct exposed crystal facets, CeO 2 (110) and CeO 2 (100), and catalytic activity was tested by a water–gas shift reaction. The CO conversion was achieved higher using the Pt/CeO 2 (110) catalyst (83%) with a rate of the reaction and turnover frequency of 26.87 mol CO /g Pt /h and 3.20 s −1 at 275 °C, respectively. The long‐term stability using the Pt/CeO 2 (110) catalyst was performed for 120 h, and the results show that the Pt/CeO 2 (110) catalyst is still stable without significant CO conversion drop. The physicochemical characterization reveals a moderately embedded structure at the interface of the metal and support, and Pt atoms move into within three to four atomic layers of the crystal lattice of CeO 2 (110). Consequently, the electron density in the Pt species decreases, and the formation of Pt δ+ ‐O v ‐Ce 3+ interfacial sites increases. The theoretical studies integrated with experimental study evidence that the stronger charge movement interfacial species (Pt δ+ ‐O v ‐Ce 3+ ) and higher oxygen vacancy concentration in Pt/CeO 2 (110) catalyst regulated by the inter‐embedded interface structure maximize the adsorption of CO and trigger the H 2 O dissociation, responsible for the exceptional catalytic performance.