The oxidation and reduction of CuZn nanoparticles was studied using X-ray photoelectron spectroscopy (XPS) and in situ transmission electron microscopy (TEM). CuZn nanoparticles with a narrow size distribution were produced with a gas-aggregation cluster source in conjunction with mass-filtration. A direct comparison between the spatially averaged XPS information and the local TEM observations was thus made possible. Upon oxidation in O2, the as-deposited metal clusters transform into a polycrystalline cluster consisting of separate CuO and ZnO nanocrystals. Specifically, the CuO is observed to segregate to the cluster surface and partially cover the ZnO nanocrystals. Upon subsequent reduction in H2 the CuO converts into metallic Cu with ZnO nanocrystal covering their surface. In addition, a small amount of metallic Zn is detected suggesting that ZnO is reduced. It is likely that Zn species can migrate to the Cu surface forming a Cu–Zn surface alloy. The oxidation and reduction dynamics of the CuZn nanoparticles is of great importance to industrial methanol synthesis for which the direct interaction of Cu and ZnO nanocrystals synergistically boosts the catalytic activity. Thus, the present results demonstrate a new model approach that should be generally applicable to address metal–support interactions in coprecipitated catalysts and multicomponent nanomaterials.
In heterogeneous catalysis, identifying the active site for key reaction steps is an important contribution for the optimization of industrial synthesis. The structure sensitivity of CO dissociation on a metal catalyst, which is the rate-limiting step for the methanation and the Fischer–Tropsch processes under certain conditions, has been debated for years. Here, scanning tunneling microscopy (STM) and density functional theory (DFT) are used to clarify the role of monatomic steps in the splitting of CO on a stepped Ru(0 1 54) crystal, which displays alternating steps with either 4-fold or 3-fold symmetry. After CO doses at elevated temperatures, the STM images reveal step decorations characteristic of atomic oxygen resulting from CO dissociation on every second step. The comparison of the STM images with the results of DFT calculations shows that the step decoration occurs on the steps displaying the 4-fold symmetry. We conclude that the active sites for CO dissociation on ruthenium are located on the 4-fold symmetry monatomic steps.
Colloidal chemistry, in combination with nanoparticle (NP)/support epitaxial interactions is used here to synthesize shape-selected and thermodynamically stable metallic NPs over a broad range of NP sizes. The morphology of three-dimensional palladium and platinum NPs supported on TiO 2 (110) was investigated using scanning tunneling microscopy. Well-defined Pd and Pt NPs were synthesized via inverse micelle encapsulation. The initially spherical NPs were found to become faceted and form an epitaxial relationship with the support after high-temperature annealing (e.g., 1100 °C). Shape selection was achieved for almost all Pd NPs, namely, a truncated octahedron shape with (111) top and interfacial facets. The Pt NPs were however found to adopt a variety of shapes. The epitaxial relationship of the NPs with the support was evidenced by the alignment of the cluster's edges with TiO 2 (110)-[001] atomic rows and was found to be responsible for the shape control. The ability of synthesizing thermally stable shape-selected metal NPs demonstrated here is expected to be of relevance for applications in the field of catalysis, since the activity and selectivity of NP catalysts has been shown to strongly depend on the NP shape.
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