Abstract:The mechanical properties of ordinary materials degrade substantially with reduced density, due to the bending of their structural elements under applied load. We report a class of micro-architected materials that maintain a nearly constant stiffness per unit mass density, even at ultra-low density. This performance derives from a network of nearly isotropic microscale unit cells with high structural connectivity and nanoscale features, whose structural members are designed to carry loads in tension or compression. Production of these microlattices, with constituent materials ranging from polymers to metals and ceramics, is made possible by using projection microstereolithography, an additive micromanufacturing technique, combined with nanoscale coating and postprocessing. We found that these materials exhibit ultra-stiff properties across more than three orders of magnitude in density, regardless of the constituent material. One Sentence Summary:We report a class of micro-architected materials that change their stiffness linearly with reduced density.Main Text: Nature has found a way to achieve mechanically efficient materials by evolving cellular structures. Natural cellular materials, including honeycomb (1) (wood, cork) and foamlike structures, such as trabecular bone (2), plant parenchyma (3), and sponge (4), combine low weight with superior mechanical properties. For example, lightweight balsa has a stiffness-toweight ratio comparable to that of steel along the axial loading direction (5). Inspired by these naturally occurring cellular structures, manmade lightweight cellular materials fabricated from a wide array of solid constituents are desirable for a broad range of applications including structural components (6, 7), energy absorption (8, 9), heat exchange (10, 11), catalyst supports (12), filtration (13,14), and biomaterials (15,16). However, the degradation in mechanical properties can be drastic as density decreases (17,18). A number of examples among recently reported low-density materials include graphene elastomers (19), metallic micro-lattices (20), carbon nanotube foams (21), and silica aerogels (22,23). For instance, the Young's modulus of low-density silica aerogels (22, 23) decreases to 10 kPa (10 -5 % of bulk ) at a density of less than 10 mg/cm 3 (< 0.5% of bulk). This loss of mechanical performance is because most natural and engineered cellular solids with random porosity, particularly at relative densities less than 0.1%, exhibit a quadratic or stronger scaling relationship between Young's modulus and density as well as between strength and density. Namely, E/E s ~ (/ s ) n and  y  ys ~ (/ s ) n , where E is Young's modulus,  is density,  y is yield strength, and s denotes the respective bulk value of the solid constituent material property. The power n of the scaling relationship between relative material density and the relative mechanical property depends on the material's microarchitecture. Conventional cellular foam materials with stochastic porosity are known to...

Despite the general inertness of gold, finely dispersed gold nanoparticles on suitable oxide supports can demonstrate remarkable catalytic activity for the epoxidation of propene or the oxidation of CO, for example. [1][2][3][4][5][6][7] Gold-based catalysts have potential applications in automotive emission control, because unlike platinum or palladium catalysts, they remain active at low temperatures (room temperature).[8] While various support materials, particle synthesis routes, and deposition techniques have been investigated over the years, [9,10] the mechanisms responsible for the catalytic activity are still under debate, because of the complexity of the particle-support interactions and the reaction pathways.Research to date has shown that the particle size, type of support material, and particle-support contact structure play major roles. [6,11,12] In contrast to supported gold catalyst systems, unsupported systems, such as gold powder, have not yet drawn much attention, although remarkably high catalytic activity for CO oxidation has been attained with such systems. [13] Moreover, unsupported gold catalysts allow the relevant catalytic mechanisms to be more easily understood and also make new applications accessible. Herein, we demonstrate that high catalytic activity is not necessarily linked to the presence of finely dispersed particles. Nanoporous gold with a spongelike morphology, formed through the selective leaching of silver from a gold-silver alloy, [14][15][16] has an unexpectedly high catalytic activity for CO oxidation at ambient pressures and temperatures down to À20 8C. Sintering can hamper the catalytic applications of gold particles; in contrast, nanoporous gold has good thermal stability, and its morphology can be easily reproduced.The spongelike morphology of the nanoporous gold used herein consists of interconnecting ligaments with diameters[*] Dr.

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry-driven actuation can be realized in high-surface-area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes of the order of a few tenths of a per cent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into a mechanical response, thus opening the door to surface-chemistry-driven actuator and sensor technologies.

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The unique properties of gold especially in low temperature CO oxidation have been ascribed to a combination of various effects. In particular, particle sizes below a few nanometers and specific particle−support interactions have been shown to play important roles. In contrast, recent reports revealed that monolithic nanoporous gold (npAu) prepared by leaching a less noble metal, such as Ag, out of the corresponding alloy can also exhibit a remarkably high catalytic activity for CO oxidation, even though no support is present. Therefore, it was claimed to be a pure and unsupported gold catalyst. We investigated npAu with respect to its morphology, surface composition, and catalytic properties. In particular, we studied the reaction kinetics for low temperature CO oxidation in detail, taking the mass transport limitation due to the porous structure of the material into account. Our results reveal that Ag, even if removed almost completely from the bulk, segregates to the surface, resulting in surface concentrations of up to 10 atom %. Our data suggest that this Ag plays a significant role in activating of molecular oxygen. Therefore, npAu should be considered a bimetallic catalyst rather than a pure Au catalyst.

Since Au turned out to be an active catalyst for CO oxidation at low temperatures, CO adsorption on various Au surfaces has been in the scope of numerous surface science studies. Interestingly, supported particles as well as stepped and rough single-crystal surfaces exhibit very similar adsorption behavior. To elucidate the origin of these similarities, we have performed temperature-programmed desorption and infrared absorption spectroscopy for a whole range of Au surfaces from nanoparticles grown on HOPG to Au(111) surfaces roughened by argon ion bombardment. In line with previous results, we have observed two desorption states at ∼130-145 and ∼170-185 K, respectively, and one infrared peak at around 2120 cm -1 in all cases. In addition to the experiments, we have carried out theoretical studies of CO adsorption on Au(332). The calculations show that CO desorption states above 100 K may be located at step-edges but not on terrace sites. Reducing the coordination of Au atoms further leads to successively higher binding energies with an unchanged anharmonic frequency. Therefore, we conclude that both desorption peaks belong to CO on low-coordinated Au atoms at steps and kinks. For the sputtered Au(111) surface, scanning tunneling microscopy reveals a rough pit-and-mound morphology with a large number of such sites. In annealing experiments we observe that the loss of these sites coincides with the loss of CO adsorption capacity, corroborating our conclusions.

Nanoporous metals have many technologically promising applications, but their tendency to coarsen limits their long-term stability and excludes high temperature applications. Here, we demonstrate that atomic layer deposition (ALD) can be used to stabilize and functionalize nanoporous metals. Specifically, we studied the effect of nanometer-thick alumina and titania ALD films on thermal stability, mechanical properties, and catalytic activity of nanoporous gold (np-Au). Our results demonstrate that even only 1 nm thick oxide films can stabilize the nanoscale morphology of np-Au up to 1000°C, while simultaneously making the material stronger and stiffer. The catalytic activity of np-Au can be drastically increased by TiO2 ALD coatings. Our results open the door to high-temperature sensor, actuator, and catalysis applications and functionalized electrodes for energy storage and harvesting applications.

We review different routes for the generation of nanoporous metallic foams and films exhibiting well-defined pore size and short-range order. Dealloying and templating allows the generation of both two-and threedimensional structures which promise a well defined plasmonic response determined by material constituents and porosity. Viewed in the context of metamaterials, the ease of fabrication of samples covering macroscopic dimensions is highly promising, and suggests more in-depth investigations of the plasmonic and photonic properties of this material system for photonic applications.