Ordered epitaxial ZrO2 films were grown on Pt(111) and characterized by low energy electron diffraction (LEED), synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The ...Ordered epitaxial ZrO2 films were grown on Pt(111) and characterized by low energy electron diffraction (LEED), synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The films were prepared by vapor deposition of zirconium in an O2 atmosphere followed by annealing under ultra high vacuum. At low coverages, the films grew as discontinuous two-dimentional islands with ordered structures. The size and structure of these islands were dependent on the coverage of ZrO2 films. At coverage <0.5 monolayer (ML), ( 19^(1/2) × 19^(1/2)) R23.4° and (5×5) structures coexisted on the surface. As the coverage increased, the (19^(1/2) × 19^(1/2) ) R23.4° structure developed with increasing degree of long-range order, while the (5×5) structure gradually faded. When the coverage reached >6 ML, a continuous ZrO2(111) film was formed with a (1×1) surface LEED pattern coexisting with a (2×2) pattern. These ordered thin ZrO2 films provide good model surfaces of bulk ZrO2 and can be used for further fundamental studies of the surface chemistry of ZrO2 using modern surface science techniques.展开更多
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Fundamental Research Funds for the Central Universities(DUT16LAB11)Opening Project of Key Laboratory of Inorganic Coating Materials,Chinese Academy of Sciences(KLICM-2014-01)
基金supported by the Specialized Research Fund for the Doctoral Program of Higher Education (SRFDP, 200803580012)the National Natural Science Foundation of China (20873128)+2 种基金the Program for New Century Excellent Talents in University (NCET)the National Basic Research Program of China (2010CB923302)the Hundred Talents Program of the Chinese Academy of Sciences
文摘Ordered epitaxial ZrO2 films were grown on Pt(111) and characterized by low energy electron diffraction (LEED), synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoelectron spectroscopy (XPS). The films were prepared by vapor deposition of zirconium in an O2 atmosphere followed by annealing under ultra high vacuum. At low coverages, the films grew as discontinuous two-dimentional islands with ordered structures. The size and structure of these islands were dependent on the coverage of ZrO2 films. At coverage <0.5 monolayer (ML), ( 19^(1/2) × 19^(1/2)) R23.4° and (5×5) structures coexisted on the surface. As the coverage increased, the (19^(1/2) × 19^(1/2) ) R23.4° structure developed with increasing degree of long-range order, while the (5×5) structure gradually faded. When the coverage reached >6 ML, a continuous ZrO2(111) film was formed with a (1×1) surface LEED pattern coexisting with a (2×2) pattern. These ordered thin ZrO2 films provide good model surfaces of bulk ZrO2 and can be used for further fundamental studies of the surface chemistry of ZrO2 using modern surface science techniques.
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.
