A catalytic process for the selective formation of cis olefins would help minimize the production of unhealthy trans fats during the partial hydrogenation of edible oils. Here we report on the design of such a process on the basis of studies with model systems. Temperature programmed desorption data on single crystals showed that the isomerization of trans olefins to their cis counterparts is promoted by (111) facets of platinum, and that such selectivity is reversed on more open surfaces. Quantum mechanics calculations suggested that the extra stability of cis olefins seen on hydrogen-saturated Pt(111) surfaces may be due to a lesser degree of surface reconstruction, a factor found to be significant in the adsorption on close-packed platinum surfaces. Kinetic data using catalysts made out of dispersed tetrahedral Pt nanoparticles corroborated the selective promotion of the trans-to-cis isomerization on the (111) facets of the metal. Our work provides an example for how catalytic selectivity may be controlled by controlling the shape of the catalytic particles.

The crystallization of nanometer-scale materials during high-temperature calcination can be controlled by a thin layer of surface coating. Here, a novel silica-protected calcination process for preparing mesoporous hollow TiO 2 nanostructures with a high surface area and a controllable crystallinity is presented. This method involves the preparation of uniform silica colloidal templates, sequential deposition of TiO 2 and then SiO 2 layers through sol-gel processes, calcination to transform amorphous TiO 2 to crystalline anatase, and finally etching of the inner and outer silica to produce mesoporous anatase TiO 2 shells. The silica-protected calcination step allows crystallization of the amorphous TiO 2 layer into anatase nanocrystals, while simultaneously limiting the growth of anatase grains to within several nanometers, eventually producing mesoporous anatase shells with a high surface area (∼311 m 2 g −1 ) and good water dispersibility upon chemical etching of the silica. When used as photocatalysts for the degradation of Rhodamine B under UV irradiation, the as-synthesized mesoporous anatase shells show significantly enhanced photocatalytic activity with greater enhancement for samples calcined at higher temperatures thanks to their improved crystallinity.

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.

In real life applications, supercapacitors (SCs) often can only be used as part of a hybrid system together with other high energy storage devices due to their relatively lower energy density in comparison to other types of energy storage devices such as batteries and fuel cells. Increasing the energy density of SCs will have a huge impact on the development of future energy storage devices by broadening the area of application for SCs. Here, we report a simple and scalable way of preparing a three-dimensional (3D) sub-5 nm hydrous ruthenium oxide (RuO2) anchored graphene and CNT hybrid foam (RGM) architecture for high-performance supercapacitor electrodes. This RGM architecture demonstrates a novel graphene foam conformally covered with hybrid networks of RuO2 nanoparticles and anchored CNTs. SCs based on RGM show superior gravimetric and per-area capacitive performance (specific capacitance: 502.78 F g−1, areal capacitance: 1.11 F cm−2) which leads to an exceptionally high energy density of 39.28 Wh kg−1 and power density of 128.01 kW kg−1. The electrochemical stability, excellent capacitive performance, and the ease of preparation suggest this RGM system is promising for future energy storage applications.

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