Synthesis of TiO2 nanoparticles on the Au(111) surface

The growth of titanium oxide nanoparticles on reconstructed Au(111) surfaces 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. Titanium oxide clusters were synthesized by subsequent exposure to O{sub 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 these titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO{sub 2} nanocrystals as judged by the observed XPS binding energies. Nano-dispersed TiO{sub 2} on Au(111) is an ideal system to test the various models explaining 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

Our contribution to the Faraday Discussion on Gold Nanoporous gold: a new gold catalyst with tunable properties

Abstract Nanoporous gold (np-Au) represents a novel nanostructured bulk material with very interesting 10 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 20 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

Dynamic Control Over Electronic Transport in 3D Bulk Nanographene via Interfacial Charging

Electrochemical surface charge-induced variation of physical properties in interface-dominated bulk materials is a rapidly emerging field in material science. The recently developed three-dimensional bulk nanographene (3D-BNG) macro-assemblies with ultra-high surface area and chemical inertness offer new opportunities in this area. Here, the electronic transport in centimeter-sized 3D-BNG monoliths can be dynamically controlled via electrochemically induced surface charge density. Specifically, a fully reversible variation in macroscopic conductance up to several hundred percent is observed with ≤1 V applied gate potential. The observed conductivity change can be explained in the light of the electrochemically-induced accumulation or depletion of charge carriers in combination with a large variation in the carrier mobility; the latter, being highly affected by the defect density modulations resulting from the interfacial charge injection, sharply decreases with an increase in defect concentrations. The phenomenon presented in this study is believed to open the door to novel applications of bulk graphene materials such as, for example, low voltage and high power tunable resistors

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

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