Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-sit...Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.展开更多
基金The APXPS experiments were performed at BL02B01 of SSRF with the approval of the Proposal Assessing Committee of SiP.ME2 platform project(Proposal No.2019-SSRF-PT-011613)the Natural Science Foundation of China(No.11227902)the Shanghai Key Research Program(No.20ZR1436700).
文摘Understanding how defect chemistry of oxide material influences the thermal stability of noble metal dopant ions plays an important role in designing high-performance heterogeneous catalytic systems.Here we use in-situ ambient-pressure X-ray photoemission spectroscopy(APXPS)to experimentally determine the role of grain boundary in the thermal stability of platinum doped cerium oxide(Pt/CeO_(2)).The grain boundaries were introduced in Pt/CeO_(2)thin films by pulsed laser deposition without significantly change of the surface microstructure.The defect level was tuned by the strain field obtained using a highly/low mismatched substrate.The Pt/CeO_(2)thin film models having well defined crystallographic properties but different grain boundary structural defect levels provide an ideal platform for exploring the evolution of Pt–O–Ce bond with changing the temperature in reducing conditions.We have direct demonstration and explanation of the role of Ce^(3+)induced by grain boundaries in enhancing Pt2+stability.We observe that the Pt^(2+)–O–Ce^(3+)bond provides an ideal coordinated site for anchoring of Pt^(2+)ions and limits the further formation of oxygen vacancies during the reduction with H_(2).Our findings demonstrate the importance of grain boundary in the atomic-scale design of thermally stable catalytic active sites.
