Unraveling the Geometric Structure Induced Electronic Structure‐Activity Insights of Highly Stable Pt/CeO2 Catalysts for Water‐Gas Shift Reaction

Herein, a coherent study of the intrinsic kinship between electronic and geometric structures was performed using Pt/CeO2 catalysts. CeO2 supported Pt nanoclusters (1.7 nm) were synthesized with two distinct exposed crystal facets, CeO2(110) and CeO2(100), and catalytic activity was tested by a water‐gas shift reaction. The CO conversion was achieved higher using the Pt/CeO2(110) catalyst (83%) with a rate of the reaction and turnover frequency of 26.87 molCO/gPt/h and 3.20 s‐1 at 275 °C, respectively. The long‐term stability using the Pt/CeO2(110) catalyst was performed for 120 h, and results show that the Pt/CeO2(110) catalyst is still stable without significant CO conversion drop. The physicochemical characterization reveals a moderately embedding structure at the interface of the metal and support, and Pt atoms move into within 3 to 4 atomic layers of the crystal lattice of CeO2(110). Consequently, electron density in the Pt species decreases and the formation of Ptδ+‐Ov‐Ce3+ interfacial sites increases. The theoretical study integrated with experimental study evidence that the stronger charge movement interfacial species (Ptδ+‐Ov‐Ce3+) and higher oxygen vacancy concentration in Pt/CeO2(110) catalyst regulated by the inter‐embedding interface structure maximize the adsorption of CO and trigger the H2O dissociation, responsible for the exceptional catalytic performance.