Dynamic chemical processes on ZnO surfaces tuned by physisorption under ambient conditions

The catalytic properties of non-reducible metal oxides have intrigued continuous interest in the past decades.Often time,catalytic studies of bulk non-reducible oxides focused on their high-temperature applications owing to their weak interaction with small molecules.Hereby,combining ambient-pressure scanning tunneling microscopy(AP-STM),AP X-ray photoelectron spectroscopy(AP-XPS)and density functional theory(DFT)calculations,we studied the activation of CO and CO_(2)on ZnO,a typical nonreducible oxide and major catalytic material in the conversion of C1 molecules.By visualizing the chemical processes on ZnO surfaces at the atomic scale under AP conditions,we showed that new adsorbate structures induced by the enhanced physisorption and the concerted interaction of physisorbed molecules could facilitate the activation of CO and CO_(2)on ZnO.The reactivity of ZnO towards CO could be observed under AP conditions,where an ordered(2×1)–CO structure was observed on ZnO(1010).Meanwhile,chemisorption of CO_(2)on ZnO(1010)under AP conditions was also enhanced by physisorbed CO_(2),which minimizes the repulsion between surface dipoles and causes a(3×1)–CO_(2)structure.Our study has brought molecular insight into the fundamental chemistry and catalytic properties of ZnO surfaces under realistic reaction conditions.

Evolution of surface of Pd-Rh bimetallic nanocubes and its correlation with CO oxidation

Typically, varying pretreatment conditions probably results in the different catalytic performances for the bimetallic catalysts, and this originates from the surface evolution of catalysts during catalytic process. Hence, it is crucial to correlate surface chemistry(e.g., composition, chemical valence, etc.) of bimetallic nanocatalysts with their corresponding performances upon different pretreatments for the fundamental understanding of catalysis. Herein, compositionvaried(100) facet terminated Pd-Rh nanocubes(NCs) with the similar shape and sizes were prepared by a facile one-pot hydrothermal method to exclude the possible size and shape effect. Surface composition and valence state of these Pd0.8 Rh0.2, Pd0.6 Rh0.4, and Pd0.2 Rh0.8 NCs were tracked under different reaction conditions and during catalysis using a homebuilt ambient pressure X-ray photoelectron spectrometer(APXPS). The correlation of active surface of Pd-Rh NCs and their corresponding catalytic performance was established.

Grain boundary boosting the thermal stability of Pt/CeO_(2)thin films

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.