Arne Wittstock

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.

Ultralow Loading Pt Nanocatalysts Prepared by Atomic Layer Deposition on Carbon Aerogels

Using atomic layer deposition (ALD), we show that Pt nanoparticles can be deposited on the inner surfaces of carbon aerogels (CA). The resultant Pt-loaded materials exhibit high catalytic activity for the oxidation of CO even at loading levels as low as approximately 0.05 mg Pt/cm2. We observe a conversion efficiency of nearly 100% in the 150-250 degrees C temperatures range, and the total conversion rate seems to be limited only by the thermal stability of the CA support in ambient oxygen. The ALD approach described here is universal in nature, and can be applied to the design of new catalytic materials for a variety of applications, including fuel cells, hydrogen storage, pollution control, green chemistry, and liquid fuel production.

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.

Oxygen-mediated coupling of alcohols over nanoporous gold catalysts at ambient pressures.

Heterogeneous catalysis is a key technology to address the ever-increasing demand for the cost-effective and environmentally friendly production of commodity and fine chemicals. A major challenge is the development of catalytic processes that operate at low temperatures with high conversion and high selectivity for the desired product. Achieving this goal would be facilitated by the rational design of catalysts based on a molecular-level understanding of the reactive processes that occur on the catalyst surface. However, the transfer of insights from model studies at low pressure to the complex environment of practical catalytic systems—the so-called “material” and “pressure gaps”— often proves challenging. For catalysis based on metallic gold such a correlation is feasible, opening the possibility of the directed preparation of catalysts. This is because most molecules, including H2O, bind weakly to metallic gold. Hence, the steady-state concentrations of surface species remain low—conditions that can be mimicked in ultrahigh vacuum (UHV) on metallic gold. This strong correspondence between model studies at very low pressure and the actual working catalyst was previously demonstrated for the selective oxidative coupling of methanol to give methyl formate, which was studied on metallic Au(111) containing atomic O and over nanoporous Au (npAu) catalysts using O2 as an oxidant. [4] These experiments demonstrated an astonishing correlation between the two regimes, thus making it possible to understand the reactivity and selectivity of npAu on a molecular level. In the present study, we pursued the question of whether the transferability of UHV-based insight is more universal and can be extended to the oxidation of other alcohols as well. The structure of npAu consists of a three-dimensional network of gold ligaments in the range of a few tens of nanometers (typically 30 to 50 nm, Figure 1) with a high surface area of approximately 10 m g . The surprising

Macroscopic 3D nanographene with dynamically tunable bulk properties.

Polymer-derived, monolithic three-dimensional nanographene (3D-NG) bulk material with tunable properties is produced by a simple and inexpensive approach. The material is mass-producible, and combines chemical inertness and mechanical strength with a hierarchical porous architecture and a graphene-like surface area. This provides an opportunity to control its electron transport and mechanical properties dynamically by means of electrochemical-induced interfacial electric fields.

Catalysis by Unsupported Skeletal Gold Catalysts

Catalysis is one of the key technologies for the 21st century for achieving the required sustainability of chemical processes. Critical improvements are based on the development of new catalysts and catalytic concepts. In this context, gold holds great promise because it is more active and selective than other precious metal catalysts at low temperatures. However, gold becomes only chemically and catalytically active when it is nanostructured. Since the 1970s and 1980s, the first type of gold catalysts that chemists studied were small nanoparticles on oxidic supports. With the later onset of nanotechnology, a variety of nanostructured materials not requiring a support or organic stabilizers became available within about the last 10 years. Among these are gold nanofoams generated by combustion of gold compounds, nanotube membranes prepared by electroless deposition of gold inside a template, and corrosion-derived nanoporous gold. Even though these materials are macroscopic in their geometric dimensions (e.g., disks, cubes, and membranes with dimensions of millimeters), they are comprised of gold nanostructures, for example, in the form of ligaments as small as 15 nm in diameter (nanoporous gold, npAu). The nanostructure brings about a high surface to volume ratio and a large fraction of low coordinated surface atoms. In this Account, we discuss how unsupported materials are active catalysts for aerobic oxidation reaction in gas phase (oxidation of CO and primary alcohols), as well as liquid phase oxidation and reduction reactions. It turns out that the bonding and activation of molecular oxygen for gas phase oxidations strongly profits from trace amounts of an ad-metal residue such as silver. It is noteworthy that these catalysts still exhibit the special gold type chemistry, characterized by activity at very low temperatures and high selectivity for partial oxidations. For example, we can oxidize CO over these unsupported catalysts (npAu, nanotubes, and powder) at temperatures well below waters freezing point (-30 °C) and with turnover frequencies up to 0.5 s(-1) (at 30 °C). Yet, we can anticipate the surface chemistry of these unsupported and extended gold surfaces based on model experiments under UHV conditions. We have demonstrated this for the selective oxidation of primary alcohols at low temperatures employing npAu catalysts. Chemists have paid growing interest to oxidation and reduction reactions in liquid phase catalysis, most suitable for synthetic organic chemistry. Early work on the aerobic oxidation of d-glucose in 2008 using Raney type npAu already showed the potential of this type of catalyst for liquid phase reactions. Since then, researchers have investigated further oxidation reactions (silanes to silanols) and reduction reactions of alkynes, as well as C-C coupling reactions ([4 + 2] benzannulation) and azo compound decomposition, with likely several more reactions to be reported in the next years. The advantage of this unsupported skeletal type of catalyst is its recyclability and retrievability without leaching of gold into the reaction medium, owing to its monolithic structure. Even though these materials contain nanoscopic structures, they are macroscopic in their geometric dimensions and pose no threat to the environment or health as discussed for other nanomaterials.

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.

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.

Effect of surface chemistry on the stability of gold nanostructures.

Understanding the role of surface chemistry in the stability of nanostructured noble-metal materials is important for many technological applications but experimentally difficult to access and thus little understood. To develop a fundamental understanding of the effect of surface chemistry on both the formation and stabilization of self-organized gold nanostructures, we performed a series of controlled-environment annealing experiments on nanoporous gold (np-Au) and ion-bombarded Au(111) single-crystal surfaces. The annealing experiments on np-Au in ambient ozone were carried out to study the effect of adsorbed oxygen under dynamic conditions, whereas the ion-bombarded Au single-crystal surfaces were used as a model system to obtain atomic-scale information. Our results show that adsorbed oxygen stabilizes nanoscale gold structures at low temperatures whereas oxygen-induced mobilization of Au surface atoms seems to accelerate the coarsening under dynamic equilibrium conditions at higher temperatures.