Core–Shell Nanostructured Catalysts
Novel nanotechnologies have allowed great improvements in the syn-thesis of catalysts with well-controlled size, shape, and surface properties. Transition metal nanostructures with specific sizes and shapes, for instance, have shown great promise as catalysts with high selectivities and relative ease of recycling. Researchers have already demonstrated new selective catalysis with solution-dispersed or supported-metal nanocatalysts, in some cases applied to new types of reactions. Several challenges remain, however, particularly in improving the structural stability of the catalytic active phase. Core?shell nanostructures are nanoparticles encapsulated and protected by an outer shell that isolates the nanoparticles and prevents their migration and coalescence during the catalytic reactions. The synthesis and characterization of effective core?shell catalysts has been at the center of our research efforts and is the focus of this Account. Efficient core?shell catalysts require porous shells that allow free access of chemical species from the outside to the surface of nanocatalysts. For this purpose, we have developed a surface-protected etching process to prepare mesoporous silica and titania shells with controllable porosity. In certain cases, we can tune catalytic reaction rates by adjusting the porosity of the outer shell. We also designed and successfully applied a silica-protected calcination method to prepare crystalline shells with high surface area, using anatase titania as a model system. We achieved a high degree of control over the crystallinity and porosity of the anatase shells, allowing for the systematic optimization of their photocatalytic activity. Core?shell nanostructures also provide a great opportunity for controlling the interaction among the different components in ways that might boost structural stability or catalytic activity. For example, we fabricated a SiO2/Au/N-doped TiO2 core-shell photocatalyst with a sandwich structure that showed excellent catalytic activity for the oxidation of organic compounds under UV, visible, and direct sunlight. The enhanced photocatalytic efficiency of this nanostructure resulted from an added interfacial nonmetal doping, which improved visible light absorption, and from plasmonic metal decoration that enhanced light harvesting and charge separation. In addition to our synthetic efforts, we have developed ways to evaluate the accessibility of reactants to the metal cores and to characterize the catalytic properties of the core?shell samples we have synthesized. We have adapted infrared absorption spectroscopy and titration experiments using carbon monoxide and other molecules as probes to study adsorption on the surface of metal cores in metal oxide?shell structures in situ in both gas and liquid phases. In particular, the experiments in solution have provided insights into the ease of diffusion of molecules of different sizes in and out of the shells in these catalysts.