Distinct from inert bulk gold, nanoparticulate gold has been found to possess remarkable catalytic activity towards oxidation reactions. The catalytic performance of nanoparticulate gold strongly depends on size and support, and catalytic activity usually cannot be observed at characteristic sizes larger than 5 nm. Interestingly, significant catalytic activity can be retained in dealloyed nanoporous gold (NPG) even when its feature lengths are larger than 30 nm. Here we report atomic insights of the NPG catalysis, characterized by spherical-aberration-corrected transmission electron microscopy (TEM) and environmental TEM. A high density of atomic steps and kinks is observed on the curved surfaces of NPG, comparable to 3-5 nm nanoparticles, which are stabilized by hyperboloid-like gold ligaments. In situ TEM observations provide compelling evidence that the surface defects are active sites for the catalytic oxidation of CO and residual Ag stabilizes the atomic steps by suppressing {111} faceting kinetics.

The particle size effect of Pd nanoparticles supported on alumina with various crystalline phases on methane combustion was investigated. Pd/θ, α-Al O with weak metal-support interaction showed a volcano-shaped dependence of the catalytic activity on the size of Pd particles, and the catalytic activity of the strongly interacted Pd/γ-Al O increased with the particle size. Based on a structural analysis of Pd nanoparticles using CO adsorption IR spectroscopy and spherical aberration-corrected scanning/transmission electron microscopy, the dependence of catalytic activity on Pd particle size and the alumina crystalline phase was due to the fraction of step sites on Pd particle surface. The difference in fraction of the step site is derived from the particle shape, which varies not only with Pd particle size but also with the strength of metal-support interaction. Therefore, this interaction perturbs the particle size effect of Pd/Al O for methane combustion.

The hydrogen oxidation reaction (HOR) in alkaline electrolyte was conducted on carbon-supported Ru nanoparticles (Ru/C) of which size was controlled in the range from approximately 2 to 7 nm. The HOR activity of Ru/C normalized by the metal surface area showed volcano shaped dependence on the particle size with a maximum activity at approximately 3 nm. The HOR activity of approximately 3 nm Ru/C was higher than commercially available Pt nanoparticles (ca. 2 nm) supported on carbon. The structural analysis of Ru/C using Cs-corrected scanning transmission electron microscopy with atomic resolution revealed the unique structural change of Ru/C different from Pt/C: Ru nanoparticle structure changed from amorphous-like structure below 3 nm to metal nanocrystallite with roughened surface at approximately 3 nm and then to that with well-defined facets above 3 nm, although Pt/C kept well-defined facets even at approximately 2 nm. It is proposed that the generation of unique structure observed on approximately 3 nm Ru nanoparticles, that is, long bridged coordinatively unsaturated Ru metal surface atoms on its nanocrystallite, is a key to achieve high HOR activity.

Carbon nitride nanosheets (NS-C N ) were found to undergo robust binding with a binuclear ruthenium(II) complex (RuRu') even in basic aqueous solution. A hybrid material consisting of NS-C N (further modified with nanoparticulate Ag) and RuRu' promoted the photocatalytic reduction of CO to formate in aqueous media, in conjunction with high selectivity (approximately 98 %) and a good turnover number (>2000 with respect to the loaded Ru complex). These represent the highest values yet reported for a powder-based photocatalytic system during CO reduction under visible light in an aqueous environment. We also assessed the desorption of RuRu' from the Ag/C N surface, a factor that can contribute to a loss of activity. It was determined that desorption is not induced by salt additives, pH changes, or photoirradiation, which partly explains the high photocatalytic performance of this material.

Dealloyed nanoporous metals have attracted much attention because of their excellent catalytic activities toward various chemical reactions. Nevertheless, coarsening mechanisms in these catalysts have not been experimentally studied. Here, we report in situ atomic-scale observations of the structural evolution of nanoporous gold during catalytic CO oxidation. The catalysis-induced nanopore coarsening is associated with the rapid diffusion of gold atoms at chemically active surface steps and the surface segregation of residual Ag atoms, both of which are stimulated by the chemical reaction. Our observations provide the first direct evidence that planar defects hinder nanopore coarsening, suggesting a new strategy for developing structurally stable and highly active heterogeneous catalysts.