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Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag0.03Au0.97 alloy and their subsequent evolution under steady-state CH3OH oxidation conditions are investigated. Activation using O3 results in AgO and Au2O3, strongly enriching the near-surface region in Ag. These oxides reduce in the O2/CH3OH mixture, yielding CO2 and producing a highly Ag-enriched surface alloy. At the reaction temperature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

Functional porous materials are of increasing importance in energy conversion and catalysis. Improved analysis is needed to guide optimization. Four-dimensional (4D) imaging [chemical mapping in three-dimensional (3D) by spectro-tomography] of an Al2O3 aerogel coated with ZnO by atomic layer deposition was performed using soft X-ray ptychography at the Zn L-edge. A two-dimensional spatial resolution of 14(2) nm was achieved. Visualizations of the 3D chemical structure are provided. The degree of ZnO coverage of the surface of the Al2O3 aerogel framework in two different samples was estimated and found to be both thicker and less homogeneous than expected. Other analyses of the 4D results, including the degree of contact between Al2O3 and ZnO, were extracted from the reconstructed 3D data. This pioneering soft X-ray spectro-ptycho-tomography study will anchor further studies of functional porous materials.

Libraries of nanostructured materials on a single chip are a promising platform for high throughput and combinatorial studies of structure-property relationships in the fields of physics and biology. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a nanostructured material specifically suited for such studies because of its self-similar thermally induced coarsening behavior. However, traditional heat application techniques for the modification of np-Au are bulk processes that cannot be used to generate a library of different pore sizes on a single chip. Here, laser micro-processing offers an attractive solution to this problem by providing a means to apply energy with high spatial and temporal resolution. In the present study we use finite element multiphysics simulations to predict the effects of laser mode (continuous-wave vs. pulsed) and thermal conductivity of the supporting substrate on the local np-Au film temperatures during photothermal annealing. Based on these results we discuss the mechanisms by which the np-Au network is coarsened. Thermal transport simulations predict that continuous-wave mode laser irradiation of np-Au thin films on a silicon substrate supports the widest range of morphologies that can be created through photothermal annealing of np-Au. Using the guidance provided by simulations, we successfully fabricate an on-chip material library consisting of 81 np-Au samples of 9 different morphologies for use in the parallel study of structure-property relationships.

We report on integrating ultrathin monolithic nanoporous gold (npAu) catalyst coatings for CO2 reduction in a large electrode area (25 cm2) electrochemical membrane reactor with gas diffusion electrodes at 100 mA/cm2. The CO Faraday efficiency increases with increasing thickness, from 65% to 75% and 80% for 1, 5, and 10 layers of npAu leaves where each npAu leaf layer is 100 nm thick. For the one npAu leaf layer configuration, this corresponds to an extremely high CO current density of 955 A/g gold thus demonstrating the potential for commercial applications. By device level optimization of catalyst integration we significantly improved the utilization of gold catalysts for electrochemical CO2 reduction to syngas at industrial relevant current densities of 100 mA/cm2. [ABSTRACT FROM AUTHOR]

The 3D chemical structure (4D spectromicroscopy) of nanoporous Al2O3 aerogels coated with ZnO by atomic layer deposition (ALD) was studied by multienergy scanning transmission X-ray microscopy. These materials are representative of a class of designer catalysts in which the nanoporous support is prepared separately from the active catalyst material, which is subsequently introduced by ALD, thereby allowing independent optimization of the morphology, chemistry, and spatial distribution of the support and catalyst. The samples studied were prepared by Ga ion and Xe plasma focused ion beam (FIB) milling as well as drop casting from water suspension. Zn L and Al K edge spectra of six samples with three different ZnO loadings were measured to investigate how loading and different sample preparation methods affect the 3D distribution of the ZnO and Al2O3. Scanning transmission X-ray microscopy (STXM) and ptychographic imaging at two energies each at the Zn L3 and Al K edge were measured. The ptychography data were analyzed by using the SHARP reconstruction code to generate quantitative 2D chemical maps of the Al2O3 and the ZnO. The STXM and ptychography maps were then measured at a sequence of tilt angles, covering up to 160° of rotation. The 3D structure of the ZnO and Al2O3 was derived from the tilt series data by tomographic reconstruction using a compressed sensing algorithm. A two-dimensional spatial resolution (half-period) of 6 nm, measured by Fourier ring correlation, and a 3D spatial resolution (half-period) of 9 nm, measured by Fourier shell correlation, were achieved when using the COSMIC beamline at the Advanced Light Source (ALS). The results show that for all of the ZnO loadings studied there is nonuniform coverage of the ZnO on the Al2O3 aerogel framework. In addition, we found that both FIB methods create sample artifacts, although the distortion was less with Xe plasma than Ga ion FIB. [ABSTRACT FROM AUTHOR]

We develop an atomic-scale model for an ordered incommensurate gold sulfide (AuS) adlayer which has previously been demonstrated to exist on the Au(111) surface, following sulfur deposition and annealing to 450 K. Our model reproduces experimental scanning tunneling microscopy images. Using state-of-the-art Wannier-function-based techniques, we analyze the nature of bonding in this structure and provide an interpretation of the unusual stoichiometry of the gold sulfide layer. The proposed structure and its chemistry have implications for related S–Au interfaces, as in those involved in self-assembled monolayers of thiols on Au substrates. [ABSTRACT FROM AUTHOR]

We describe a novel approach to synthesize two-dimensional nanocrystalline TiS2 islands on Au(111). Ti is deposited by physical vapor deposition at room temperature on AuS-covered Au(111) surfaces. Subsequent annealing to temperatures between 670 K and 800 K leads to the formation of single-layer, triangular TiS2 islands. These TiS2 nanocrystallites reflect the structure of bulk TiS2, and are composed of S–Ti–S stacking units with hexagonally close-packed layers of sulfur atoms and titanium occupying the octahedral sites in between. The lattice constant of the hexagonal unit cell is 3.45 Å. A superlattice with a repeat distance of 17.3 Å results from the coincidence of five TiS2 units with six Au atoms and is observed in scanning tunneling microscopy and low energy electron diffraction. The triangular shape of the islands indicates a preference for one of the two possible edge terminations. The observation of two island orientations rotated by 60° with respect to each other can be attributed to the formation of twin-related TiS2 domains. The population of the two different island orientations changes during annealing at 800 K indicating a thermodynamic preference for one of the possible stacking sequences. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The growth of nanocrystalline MoO3 islands on Au(111) using physical vapor deposition of Mo has been studied by scanning tunneling microscopy and low energy electron diffraction. The growth conditions affect the shape and distribution of the MoO3 nanostructures, providing a means of preparing materials with different percentages of edge sites that may have different chemical and physical properties than atoms in the interior of the nanostructures. MoO3 islands were prepared by physical vapor deposition of Mo and subsequent oxidation by NO2 exposure at temperatures between 450 K and 600 K. They exhibit a crystalline structure with a c(4×2) periodicity relative to unreconstructed Au(111). While the atomic-scale structure is identical to that of MoO3 islands prepared by chemical vapor deposition, we demonstrate that the distribution of MoO3 islands on the Au(111) surface reflects the distribution of Mo clusters prior to oxidation although the growth of MoO3 involves long-range mass transport via volatile MoO3 precursor species. The island morphology is kinetically controlled at 450 K, whereas an equilibrium shape is approached at higher preparation temperatures or after prolonged annealing at the elevated temperature. Mo deposition at or above 525 K leads to the formation of a Mo-Au surface alloy as indicated by the observation of embedded MoO3 islands after oxidation by NO2. Au vacancy islands, formed when Mo and Au dealloy to produce vacancies, are observed for these growth conditions.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The structure and rich coordination chemistry of an ordered incommensurate AuS adlayer that forms on Au(111) following the deposition of sulfur and annealing to 450 K are examined. Bonding analysis based on Wannier functions have shown that the model displays rich coordination chemistry corresponding to different Au oxidation states.