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.

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.

Nanoporous ultra-high-entropy alloys containing 14 elements (Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti) were obtained by dealloying. The products showed excellent electrocatalytic performance for water splitting in acidic media.

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We use a green sputtering technique to deposit a Pt/Cu alloy target on liquid polyethylene glycol (PEG) to obtain well-dispersed and stable Pt29Cu71 alloy nanoparticles (NPs). The effects of sputtering current, rotation speed of the stirrer, sputtering time, sputtering period, and temperature of PEG on the particle size are studied systematically. Our key results demonstrate that the aggregation and growth of Pt/Cu alloy NPs occurred at the surface as well as inside the liquid polymer after the particles landed on the liquid surface. According to particle size analysis, a low sputtering current, high rotation speed for the stirrer, short sputtering period, and short sputtering time are found to be favorable for producing small-sized single crystalline alloy NPs. On the other hand, varying the temperature of the liquid PEG does not have any significant impact on the particle size. Thus, our findings shed light on controlling NP growth using the newly developed green sputtering deposition technique.

Pt/Au alloy nanoparticles (NPs) in a wide composition range have been synthesized by room-temperature simultaneous sputter deposition from two independent magnetron sources onto liquid PEG (MW = 600). The prepared NPs were alloyed with the face-centered cubic (fcc) structure. In addition, the particle sizes, composition, and shape are strongly correlated but can be tailored by an appropriate variation of the sputtering parameters. No individual particle but large agglomerates with partial alloy structure formed at Pt content of less than 16 atom %. Highly dispersed NPs with no agglomeration were observed in PEG when the quantity of Pt is more than 26 atom %. On the other hand, a small amount of Pt could terminate the agglomeration of Au when sputtering on the grids for transmission electron microscope observation. Our experiment and computer simulation carried out by two different methods indicate that the composition-dependent particle size of Pt/Au can be explained by the atomic concentration, formation energy of the cluster, and interaction between different metal atoms and the PEG molecule.

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We synthesized zirconium oxynitride from yttria-stabilized zirconia (YSZ) in air by applying DC electric fields that produced a controlled electric current in the specimen. When YSZ was heated under an applied DC electric field, the electric current of the specimen steeply increased at a critical temperature, called a flash event, during flash sintering. By keeping the electric current of the specimen constant during the flash event and then holding the specimen at the critical temperature, YSZ was transformed into zirconium oxynitride under the optimal conditions of 50 V/cm, 500 mA, and 1000 °C. We confirmed that zirconium oxynitride formed using high-resolution transmission electron microscopy, electron energy-loss spectroscopy, and energy-dispersive spectrometry. To convert oxides to nitrides, reducing conditions are necessary to form excess oxygen vacancies. Our technique produced the strong reducing conditions necessary to form nitrides from the oxides by delivering a controlled electric current to the specimen.