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.
We report the synthesis of ultra-low-density three-dimensional macroassemblies of graphene sheets that exhibit high electrical conductivities and large internal surface areas. These materials are prepared as monolithic solids from suspensions of single-layer graphene oxide in which organic sol-gel chemistry is used to cross-link the individual sheets. The resulting gels are supercritically dried and then thermally reduced to yield graphene aerogels with densities approaching 10 mg/cm(3). In contrast to methods that utilize physical cross-links between GO, this approach provides covalent carbon bonding between the graphene sheets. These graphene aerogels exhibit an improvement in bulk electrical conductivity of more than 2 orders of magnitude (∼1 × 10(2) S/m) compared to graphene assemblies with physical cross-links alone (∼5 × 10(-1) S/m). The graphene aerogels also possess large surface areas (584 m(2)/g) and pore volumes (2.96 cm(3)/g), making these materials viable candidates for use in energy storage, catalysis, and sensing applications.
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.
Bimetallic, nanostructured materials hold promise for improving catalyst activity and selectivity, yet little is known about the dynamic compositional and structural changes that these systems undergo during pretreatment that leads to efficient catalyst function. Here we use ozone-activated silver-gold alloys in the form of nanoporous gold as a case study to demonstrate the dynamic behaviour of bimetallic systems during activation to produce a functioning catalyst. We show that it is these dynamic changes that give rise to the observed catalytic activity. Advanced in situ electron microscopy and X-ray photoelectron spectroscopy are used to demonstrate that major restructuring and compositional changes occur along the path to catalytic function for selective alcohol oxidation. Transient kinetic measurements correlate the restructuring to three types of oxygen on the surface. The direct influence of changes in surface silver concentration and restructuring at the nanoscale on oxidation activity is demonstrated. Our results demonstrate that characterization of these dynamic changes is necessary to unlock the full potential of bimetallic catalytic materials.
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