Dynamic transformation between bilayer islands and dinuclear clusters of Cr oxide on Au(111) through environment and interface effects.

SignificanceFor oxide catalysts, it is important to elucidate and further control their atomic structures. In this work, well-defined CrO2 bilayer islands and Cr2O7 dinuclear clusters have been grown on Au(111) and unambiguously identified by scanning tunneling microscopy and theoretical calculations. Upon cycled redox treatments, the two kinds of oxide nanostructures can be reversibly transformed. It is interesting to note that both Cr oxides do not exist in bulk but need to be stabilized by the metal surface and the specific environment. Our results suggest that both redox atmosphere and interface confinement effects can be used to construct an oxide nanostructure with the specific chemical state and structure.

Oxide-Metal Interaction Probed by Scanning Tunneling Microscope Manipulation of Cr2O7 Clusters on Au(111).

Interfacial interaction plays a crucial rule in catalysis over supported catalysts, and the catalyst-support interaction needs to be explored at microscopic scale. Here, we use the scanning tunneling microscope (STM) tip to manipulate Cr2O7 dinuclear clusters on Au(111) and find that the Cr2O7-Au interaction can be weakened by an electric field in the STM junction, facilitating rotation and translation of the individual clusters at the imaging temperature (78 K). Surface alloying with Cu makes the manipulation of the Cr2O7 clusters hard due to the enhanced Cr2O7-substrate interaction. Density functional theory calculations reveal that barrier for translation of a Cr2O7 cluster on the surface can be increased by surface alloying, influencing the tip manipulation. Our study demonstrates that the oxide-metal interfacial interaction can be probed by STM tip manipulation of supported oxide clusters, which provides a new method to investigate the interfacial interaction.

Periodic Arrays of Metal Nanoclusters on Ultrathin Fe-Oxide Films Modulated by Metal-Oxide Interactions.

Rational design of highly stable and active metal catalysts requires a deep understanding of metal-support interactions at the atomic scale. Here, ultrathin films of FeO and FeO2-x grown on Pt(111) are used as templates for the construction of well-defined metal nanoclusters. Periodic arrays of Cu clusters in the form of monomers and trimers are preferentially located at FCC domains of FeO/Pt(111) surface, while the selective location of Cu clusters at FeO2 domains is observed on FeO2-x /Pt(111) surface. The preferential nucleation and formation of well-ordered Cu clusters are driven by different interactions of Cu with the Fe oxide domains in the sequence of FeO2-FCC > FeO-FCC > FeO-HCP > FeO-TOP, which is further validated by density functional theory calculations. It has been revealed that the p-band center as a reactivity descriptor of surface O atoms determines the interaction between metal adatoms and Fe oxides. The modulated metal-oxide interaction provides guidance for the rational design of supported single-atom and nanocluster catalysts.