Jürgen Biener

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

Methanol Coupling Catalyzed with Gold Gold surfaces can be effective catalysts for partial oxidation reactions, in part because lower interaction strengths of molecules absorbed on gold allow products to desorb before further unwanted oxidations occur. One challenge in these reactions is the low rate of formation of reactive atomic surface oxygen. Wittstock et al. (p. 319; see the Perspective by Christensen and Nørskov) created high–surface area gold catalysts by leaching silver from gold-silver alloys. This material proved to be an effective catalyst for partial oxidative coupling of methanol, yielding methyl formate. Residual silver appears to play a key role in activating the dissociation of molecular oxygen. Leaching of gold-silver alloys creates a highly active catalyst for partial oxidation reactions. 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°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.

Surface-chemistry-driven actuation in nanoporous gold

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.

Surface-enhanced Raman scattering on nanoporous Au

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.

ALD Functionalized Nanoporous Gold: Thermal Stability, Mechanical Properties, and Catalytic Activity

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 1,000°C, while simultaneously making the material stronger and stiffer. The catalytic activity of np-Au can be drastically increased by TiO(2) ALD coatings. Our results open the door to high-temperature sensor, actuator, and catalysis applications and functionalized electrodes for energy storage and harvesting applications.

Atomic layer deposition of ZnO on ultralow-density nanoporous silica aerogel monoliths

We report on atomic layer deposition of an ∼2-nm-thick ZnO layer on the inner surface of ultralow-density (∼0.5% of the full density) nanoporous silica aerogel monoliths with an extremely large effective aspect ratio of ∼105 (defined as the ratio of the monolith thickness to the average pore size). The resultant monoliths are formed by amorphous-SiO2 core/wurtzite-ZnO shell nanoparticles which are randomly oriented and interconnected into an open-cell network with an apparent density of ∼3% and a surface area of ∼100m2g−1. Secondary ion mass spectrometry and high-resolution transmission electron microscopy imaging reveal excellent uniformity and crystallinity of ZnO coating. Oxygen K-edge and Zn L3-edge soft x-ray absorption near-edge structure spectroscopy shows broadened O p- as well as Zn s- and d-projected densities of states in the conduction band.

Mechanisms of atomic layer deposition on substrates with ultrahigh aspect ratios.

Atomic layer deposition (ALD) appears to be uniquely suited for coating substrates with ultrahigh aspect ratios (> or similar 10(3)), including nanoporous solids. Here, we study the ALD of Cu and Cu3N on the inner surfaces of low-density nanoporous silica aerogel monoliths. Results show that Cu depth profiles in nanoporous monoliths are limited not only by Knudsen diffusion of heavier precursor molecules into the pores, as currently believed, but also by other processes such as the interaction of precursor and reaction product molecules with pore walls. Similar behavior has also been observed for Fe, Ru, and Pt ALD on aerogels. On the basis of these results, we discuss design rules for ALD precursors specifically geared for coating nanoporous solids.

Diamond spheres for inertial confinement fusion

The National Ignition Facility (NIF) will allow scientists to prove the feasibility of inertial confinement fusion (ICF). The success of ICF experiments at NIF will critically depend on the availability of robust targets. Guided by computer simulations, we generated a new target design that takes advantage of the extreme atomic density of synthetic diamond, and developed a process that allows us to produce large quantities of these ultrahigh precision diamond targets via a low-cost batch process. Computer simulations were used to assess the performance and the robustness of these diamond targets. The results demonstrate that diamond has the potential to outperform other target materials in terms of energy efficiency and implosion stability, thus making successful ignition more likely.

Nanoporous gold: a new gold catalyst with tunable properties.

Nanoporous gold (np-Au) represents a novel nanostructured bulk material with very interesting perspectives in heterogeneous catalysis. Its monolithic porous structure and the absence of a support or other stabilizing agents opens up unprecedented possibilities to tune structure and surface chemistry in order to adapt the material to specific catalytic applications. We investigated three of these tuning options in more detail: change of the porosity by annealing, increase of activity by the deposition of oxides and change of activity and selectivity by bimetallic effects. As an example for the latter case, the effect of Ag impurities will be discussed. The presence and concentration of Ag can be correlated to the availability of active oxygen. While for the oxidation of CO the activity of the catalyst can be significantly enhanced when increasing the content of Ag, we show for the oxidation of methanol that the selectivity is shifted from partial to total oxidation. In a second set of experiments, two different metal-oxides were deposited on np-Au, praseodymia and titania. In both cases, the surface chemistry changed significantly. The activity of the catalyst for oxidation of CO was increased by up to one order of magnitude after modification. Finally, we used adsorbate controlled coarsening to tune the structure of np-Au. In this way, even gradients in the pore- and ligament size could be induced, taking advantage of mass transport phenomena.

Synthesis of TiO2 nanoparticles on the Au(111) surface

The growth of titanium oxide nanoparticles on reconstructed Au(111) was investigated by scanning tunneling microscopy and x-ray photoelectron spectroscopy. Ti was deposited by physical-vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. The titanium oxide nanoclusters were synthesized by subsequent exposure to O(2) at 300 K. Two-and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated 110-oriented step-edge morphology suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of the titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO(2) nanocrystals as judged by the Ti(2p) binding energies measured in the x-ray photoelectron data. The nanodispersed TiO(2) on Au(111) is an ideal system to test the various models proposed for the enhanced catalytic reactivity of supported Au nanoparticles.

Surface Chemistry in Nanoscale Materials

Although surfaces or, more precisely, the surface atomic and electronic structure, determine the way materials interact with their environment, the influence of surface chemistry on the bulk of the material is generally considered to be small. However, in the case of high surface area materials such as nanoporous solids, surface properties can start to dominate the overall material behavior. This allows one to create new materials with physical and chemical properties that are no longer determined by the bulk material, but by their nanoscale architectures. Here, we discuss several examples, ranging from nanoporous gold to surface engineered carbon aerogels that demonstrate the tuneability of nanoporous solids for sustainable energy applications.