Quantitative Phase Composition of TiO2-Coated Nanoporous Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic Behavior

Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO2) guest determine the material's performance. New insights into the structure-function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. Here, we demonstrate that crystallographic phase, morphology, and catalytic activity of TiO2-functionalized nanoporous gold (np-Au) can be controlled by a simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of similar to 2 nm thick TiO2 on millimeter-sized samples of np-Au (40-50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. The annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.