Nanometer-sized metal clusters are prime candidates for photoactivated catalysis, based on their unique tunable optical and electronic properties, combined with a large surface-to-volume ratio. Due to the very small optical cross sections of such nanoclusters, support-mediated plasmonic activation could potentially make activation more efficient. Our support is a semi-transparent gold film, optimized to work in a back-illumination geometry. It has a surface plasmon resonance excitable in the 510-540 nm wavelength range. Pt clusters (size distribution peaked at n = 46 atoms) have been deposited onto this support and investigated for photoactivated catalytic performance in the oxidative decomposition of methylene blue. The Pt cluster catalytic activity under illumination exceeds that of the gold support by more than an order of magnitude per active surface area. To further investigate the underlying mechanism of plasmon-induced catalysis, the clusters have been imaged with optically-assisted scanning tunneling microscopy under illumination. The photoactivation of the Pt clusters via plasmonic excitation of the support and subsequential electronic excitation of the clusters can be imaged with nanometer resolution. The light-induced tunneling current on the clusters is enhanced relative to the gold film support.
Time resolution is one of the most severe limitations of scanning probe microscopies (SPMs), since the typical image acquisition times are in the order of several seconds or even few minutes. As a consequence, the characterization of dynamical processes occurring at surfaces (e.g. surface diffusion, film growth, self-assembly and chemical reactions) cannot be thoroughly addressed by conventional SPMs. To overcome this limitation, several years ago we developed a first prototype of the FAST module, an add-on instrument capable of driving a commercial scanning tunneling microscope (STM) at and beyond video rate frequencies. Here we report on a fully redesigned version of the FAST module, featuring improved performance and user experience, which can be used both with STMs and atomic force microscopes (AFMs), and offers additional capabilities such as an atom tracking mode. All the new features of the FAST module, including portability between different commercial instruments, are described in detail and practically demonstrated.
Metal clusters are partway between molecular and bulk systems and thus exhibit special physical and chemical properties. Atoms can rearrange within a cluster to form different structural isomers. Internal degrees of freedom and the interaction with the supportwhich both are dependent on cluster sizecan promote diffusion across a support. Here, we show how fast scanning tunneling microscopy (FastSTM) can be used to investigate such dynamical behavior of individual clusters on the example of Pdn (1≤n≤19) on a hexagonal boron nitride nanomesh on Rh(111), in particular pertaining to minority species and rare events. By tuning the cluster size and varying the temperature to match the dynamics to the FastSTM frame rate, we followed steady state diffusion of clusters and atoms inside the nanomesh pore and reversible cluster isomerization in situ. While atoms diffuse along the rim of a pore, a small cluster experiences a corrugation in the potential energy landscape and jumps between six sites around the center of the pore. The atom and cluster diffusion between pores is strongly influenced by defects.
In this work, ethanol is used as a chemical probe to study the passivation of molecular beam epitaxy-grown GaN(0001) by surface oxidation. With a high degree of oxidation, no reaction from ethanol to acetaldehyde in temperature-programmed desorption experiments is observed. The acetaldehyde formation is attributed to a mechanism based on α-H abstraction from the dissociatively bound alcohol molecule. The reactivity is related to negatively charged surface states, which are removed upon oxidation of the GaN(0001) surface. This is compared with the GaO(2¯01) single crystal surface, which is found to be inert for the acetaldehyde production. These results offer a toolbox to explore the surface chemistry of nitrides and oxynitrides on an atomic scale and relate their intrinsic activity to systems under ambient atmosphere.
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