Surface Oxygen Vacancies Confined by Ferroelectric Polarization for Tunable CO Oxidation Kinetics

Surface oxygen vacancies have been widely discussed to be crucial for tailoring the activity of various chemical reactions from CO, NO, to water oxidation by using oxide‐supported catalysts. However, the real role and potential function of surface oxygen vacancies in the reaction remains unclear because of their very short lifetime. Here, it is reported that surface oxygen vacancies can be well confined electrostatically for a polarization screening near the perimeter interface between Pt {111} nanocrystals and the negative polar surface (001) of ferroelectric PbTiO3. Strikingly, such a catalyst demonstrates a tunable catalytic CO oxidation kinetics from 200 °C to near room temperature by increasing the O2 gas pressure, accompanied by the conversion curve from a hysteresis‐free loop to one with hysteresis. The combination of reaction kinetics, electronic energy loss spectroscopy (EELS) analysis, and density functional theory (DFT) calculations, indicates that the oxygen vacancies stabilized by the negative polar surface are the active sites for O2 adsorption as a rate‐determining step, and then dissociated O moves to the surface of the Pt nanocrystals for oxidizing adsorbed CO. The results open a new pathway for tunable catalytic activity of CO oxidation. Surface oxygen vacancies are well confined near the interface between Pt {111} nanocrystals and the negative polar surface (001) of ferroelectric PbTiO3 nanoplate. The vacancies are stabilized electrostatically by ferroelectric polarization, giving rise to tunable catalytic CO oxidation kinetics from 200 °C to near room temperature. A new pathway of CO oxidation via polarization‐stabilized oxygen vacancies accounts for the tunable reaction activity.