A goal in the characterization of supported metal catalysts is to achieve particle-by-particle analysis of the charge state strongly correlated with the catalytic activity. Here, we demonstrate the direct identification of the charge state of individual platinum nanoparticles (NPs) supported on titanium dioxide using ultrahigh sensitivity and precision electron holography. Sophisticated phase-shift analysis for the part of the NPs protruding into the vacuum visualized slight potential changes around individual platinum NPs. The analysis revealed the number (only one to six electrons) and sense (positive or negative) of the charge per platinum NP. The underlying mechanism of platinum charging is explained by the work function differences between platinum and titanium dioxide (depending on the orientation relationship and lattice distortion) and by first-principles calculations in terms of the charge transfer processes.

Nanoporous gold (NPG) with sponge-like structures has been studied by atomic-scale and microsecond-resolution environmental transmission electron microscopy (ETEM) combined with ab initio energy calculations. Peculiar surface dynamics were found in the reaction environment for the oxidation of CO at room temperature, involving residual silver in the NPG leaves as well as gold and oxygen atoms, especially on {110} facets. The NPG is thus classified as a novel self-activating catalyst. The essential structure unit for catalytic activity was identified as Au–AgO surface clusters, implying that the NPG is regarded as a nano-structured silver oxide catalyst supported on the matrix of NPG, or an inverse catalyst of a supported gold nanoparticulate (AuNP) catalyst. Hence, the catalytically active structure in the gold catalysts (supported AuNP and NPG catalysts) can now be experimentally unified in low-temperature CO oxidation, a step forward towards elucidating the fascinating catalysis mechanism of gold.

Metal-oxide nanowires have demonstrated excellent capability in the electrical detection of various molecules based on their material robustness in liquid and air environments. Although the surface structure of the nanowires essentially determines their interaction with adsorbed molecules, understanding the correlation between an oxide nanowire surface and an adsorbed molecule is still a major challenge. Herein, we propose a rational methodology to obtain this information for low-density molecules adsorbed on metal oxide nanowire surfaces by employing infrared p-polarized multiple-angle incidence resolution spectroscopy and temperature-programmed desorption/gas chromatography–mass spectrometry. As a model system, we studied the surface chemical transformation of an aldehyde (nonanal, a cancer biomarker in breath) on single-crystalline ZnO nanowires. We found that a slight surface reconstruction, induced by the thermal pretreatment, determines the surface chemical reactivity of nonanal. The present results show that the observed surface reaction trend can be interpreted in terms of the density of Zn ions exposed on the nanowire surface and of their corresponding spatial arrangement on the surface, which promotes the reaction between neighboring adsorbed molecules. The proposed methodology will support a better understanding of complex molecular transformations on various nanostructured metal-oxide surfaces.

A reversible gas–solid reaction occurs on the tip surface of a positively biased palladium electrode in nitrogen in ETEM apparatus.