Nanoporous Gold: From Structure Evolution to Functional Properties in Catalysis and Electrochemistry.

Nanoporous gold (NPG) is characterized by a bicontinuous network of nanometer-sized metallic struts and interconnected pores formed spontaneously by oxidative dissolution of the less noble element from gold alloys. The resulting material exhibits decent catalytic activity for low-temperature, aerobic total as well as partial oxidation reactions, the oxidative coupling of methanol to methyl formate being the prototypical example. This review not only provides a critical discussion of ways to tune the morphology and composition of this material and its implication for catalysis and electrocatalysis, but will also exemplarily review the current mechanistic understanding of the partial oxidation of methanol using information from quantum chemical studies, model studies on single-crystal surfaces, gas phase catalysis, aerobic liquid phase oxidation, and electrocatalysis. In this respect, a particular focus will be on mechanistic aspects not well understood, yet. Apart from the mechanistic aspects of catalysis, best practice examples with respect to material preparation and characterization will be discussed. These can improve the reproducibility of the materials property such as the catalytic activity and selectivity as well as the scope of reactions being identified as the main challenges for a broader application of NPG in target-oriented organic synthesis.

Self-Detachment and Subsurface Densification of Dealloyed Nanoporous Thin Films.

Experiment shows thin films of dealloyed nanoporous gold (NPG) spontaneously detaching from massive gold base layers. NPG can also densify near its external surface. This is naturally reproduced by kinetic Monte Carlo (KMC) simulation of dealloying and coarsening and so appears generic for nanoscale network materials evolving by surface diffusion. Near the porous layer's external surface and near its interface with the base layer, gradients in the depth-profile of a laterally averaged mean surface curvature provide driving forces for diffusion and cause divergences of the net fluxes of matter, leading to accretion/densification or to erosion/disconnection. As a toy model, the morphology evolution of substrate-supported nanopillars by surface diffusion illustrates and confirms our considerations. Contrary to cylindrical nanowires, the ligaments in nanoporous materials exhibit pre-existing gradients in the mean curvature. The Plateau-Rayleigh long-wavelength stability criterion is then not applicable and the disconnection accelerated.

Plastic Poisson's Ratio of Nanoporous Metals: A Macroscopic Signature of Tension-Compression Asymmetry at the Nanoscale.

The suggestion, based on atomistic simulation, of a surface-induced tension-compression asymmetry of the strength and flow stress of small metal bodies so far lacks experimental confirmation. Here, we present the missing experimental evidence. We study the transverse plastic flow of nanoporous gold under uniaxial compression. Performing mechanical tests in electrolyte affords control over the surface state. Specifically, the surface tension, γ, can be varied in situ during plastic flow. We find that decreasing γ leads to an increase of the effective macroscopic plastic Poisson ratio, νP. Finite element simulations of a network with surface tension confirm the notion that νP of nanoporous gold provides a signature for a local tension-compression asymmetry of the nanoscale struts that form the network. We show that γ promotes compression while impeding tensile elongation. Because the transverse strain is partly carried by the elongation of ligaments oriented normal to the load axis, the surface-induced tension-compression asymmetry acts to reduce νP. Our experiment confirms a decisive contribution of the surface tension to small-scale plasticity.

Semiordered Hierarchical Metallic Network for Fast and Large Charge-Induced Strain.

Nanoporous metallic actuators for artificial muscle applications are distinguished by combining the low operating voltage, which is otherwise reserved for polymer-based actuators with interesting values of strain amplitude, strength, and stiffness that are comparable of those of piezoceramics. We report a nanoporous metal actuator with enhanced strain amplitude and accelerated switching. Our 3D macroscopic metallic muscle has semiordered and hierarchical nanoporous structure, in which µm-sized tubes align perpendicular with the sample surface, while nm-sized ligaments consist of the tube walls. This nanoarchitecture combines channels for fast ion transportation with large surface area for charge storage and strain generation. The result is a record reversible strain amplitude of 1.59% with a strain rate of 8.83 × 10-6 s-1 in the field of metallic based actuators. A passive hydroxide layer is self-grown on the metal surface, which not only contributes a supercapacitive layer, but also stabilizes the nanoporous structure against coarsening, which guarantees sustainable actuation beyond ten-thousand cycles.