Gold (Au) is an interesting catalytic material because of its ability to catalyze reactions, such as partial oxidations, with high selectivities at low temperatures; but limitations arise from the low O2 dissociation probability on Au. This problem can be overcome by using Au nanoparticles supported on suitable oxides which, however, are prone to sintering. Nanoporous Au, prepared by the dealloying of AuAg alloys, is a new catalyst with a stable structure that is active without any support. It catalyzes the selective oxidative coupling of methanol to methyl formate with selectivities above 97% and high turnover frequencies at temperatures below 80 degrees C. Because the overall catalytic characteristics of nanoporous Au are in agreement with studies on Au single crystals, we deduced that the selective surface chemistry of Au is unaltered but that O2 can be readily activated with this material. Residual silver is shown to regulate the availability of reactive oxygen.

https://science.sciencemag.org/content/sci/327/5963/319.full.pdf

Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature

Gold Nanomaterials at Work in Biomedicine

Metallic nanostructures attract much interest as an efficient media for surface-enhanced Raman scattering (SERS). Significant progress has been made on the synthesis of metal nanoparticles with various shapes, composition, and controlled plasmonic properties, all critical for an efficient SERS response. For practical applications, efficient strategies of assembling metal nanoparticles into organized nanostructures are paramount for the fabrication of reproducible, stable, and highly active SERS substrates. Recent progress in the synthesis of novel plasmonic nanoparticles, fabrication of highly ordered one-, two-, and three-dimensional SERS substrates, and some applications of corresponding SERS effects are discussed.

Nanostructured Surfaces and Assemblies as SERS Media

Noble metal nanomaterials: Controllable synthesis and application in fuel cells and analytical sensors

The understanding and management of strain is of fundamental importance in the design and implementation of materials. The strain properties of nanocrystalline materials are different from those of the bulk because of the strong influence of their surfaces and interfaces, which can be used to augment their function and introduce desirable characteristics. Here we explain how new X-ray diffraction techniques, which take advantage of the latest synchrotron radiation sources, can be used to obtain quantitative three-dimensional images of strain. These methods will lead, in the near future, to new knowledge of how nanomaterials behave within active devices and on unprecedented timescales.

Coherent X-ray diffraction imaging of strain at the nanoscale.

Recent nanomechanical tests on submicron metal columns and wires have revealed a dramatic increase in yield strength with decreasing sample size. Here, we demonstrate that nanoporous metal foams can be envisioned as a three-dimensional network of ultrahigh-strength nanowires, thus bringing together two seemingly conflicting properties: high strength and high porosity. Specifically, we characterized the size-dependent mechanical properties of nanoporous gold using a combination of nanoindentation, column microcompression, and molecular dynamics simulations. We find that nanoporous gold can be as strong as bulk Au, despite being a highly porous material, and that the ligaments in nanoporous gold approach the theoretical yield strength of Au.

Size effects on the mechanical behavior of nanoporous Au.

Scaling equation for yield strength of nanoporous open-cell foams

A comprehensive study on the relationship between yield strength, relative density and ligament sizes is presented for nanoporous Au foams. Depth-sensing nanoindentation tests were performed on nanoporous foams ranging from 20 to 42% relative density with ligament sizes ranging from 10 to 900 nm. The Gibson and Ashby yield strength equation for open-cell macro-cellular foams is modified in order to incorporate ligament size effects. This study demonstrates that at the nanoscale, foam strength is governed by ligament size, in addition to relative density. Furthermore, we present the ligament length scale as a new parameter to tailor foam properties and achieve high strength at low densities.

Scaling Equation for yield strength of nanoporous open-cell foams

Monolithic nanoporous copper was synthesized by dealloying Mn0.7Cu0.3 by two distinct methods: potentiostatically driven dealloying and free corrosion. Both the ligament size and morphology were found to be highly dependent on the dealloying methods and conditions. For example, ligaments from 16 nm–125 nm were obtained by dealloying either electrochemically or by free corrosion, respectively. Optimization of the starting Mn–Cu alloy microstructure allowed us to synthesize uniform porous structures; but we found cracking to be unavoidable. Despite the presence of unavoidable defects, the nanoporous material still exhibits higher than expected yield strength.

Monolithic nanoporous copper by dealloying Mn–Cu

Colloidal solutions of metal nanoparticles are currently among the most studied substrates for sensors based on surface-enhanced Raman scattering (SERS). However, such substrates often suffer from not being cost-effective, reusable, or stable. Here, we develop nanoporous Au as a highly active, tunable, stable, biocompatible, and reusable SERS substrate. Nanoporous Au is prepared by a facile process of free corrosion of AgAu alloys followed by annealing. Results show that nanofoams with average pore widths of ∼250nm exhibit the largest SERS signal for 632.8nm excitation. This is attributed to the electromagnetic SERS enhancement mechanism with additional field localization within pores.

Joel Hayes

Papers

Size effects on the mechanical behavior of nanoporous Au.

Scaling equation for yield strength of nanoporous open-cell foams

Scaling Equation for yield strength of nanoporous open-cell foams

Monolithic nanoporous copper by dealloying Mn–Cu

Surface-enhanced Raman scattering on nanoporous Au