Noble Metal Nanoparticle-loaded Mesoporous Oxide Microspheres for Catalysis

Noble metal nanoparticles/nanocrystals have attracted much attention as catalysts due to their unique characteristics, including high surface areas and well-controlled facets, which are not often possessed by their bulk counterparts. To avoid the loss of their catalytic activities brought about by their size and shape changes during catalytic reactions, noble metal nanoparticles/nanocrystals are usually dispersed and supported finely on solid oxide supports to prevent agglomeration, nanoparticle growth, and therefore the decrease in the total surface area. Moreover, metal oxide supports can also play important roles in catalytic reactions through the synergistic interactions with loaded metal nanoparticles/nanocrystals. In this thesis, I use ultrasonic aerosol spray to produce hybrid microspheres that are composed of noble metal nanoparticles/nanocrystals embedded in mesoporous metal oxide matrices. The mesoporous metal oxide structure allows for the fast diffusion of reactants and products as well as confining and supporting noble metal nanoparticles.;I will first describe my studies on noble metal-loaded mesoporous oxide microspheres as catalysts. Three types of noble metals (Au, Pt, Pd) and three types of metal oxide substrates (TiO2, ZrO2, Al 2O3) were selected, because they are widely used for practical catalytic applications involved in environmental cleaning, pollution control, petrochemical, and pharmaceutical syntheses. By considering every possible combination of the noble metals and oxide substrates, nine types of catalyst samples were produced. I characterized the structures of these catalysts, including their sizes, morphologies, crystallinity, and porosities, and their catalytic performances by using a representative reduction reaction from nitrobenzene to aminobenzene. Comparison of the catalytic results reveals the effects of the different noble metals, their incorporation amounts, and oxide substrates on the catalytic abilities. For this particular reaction, I found that Pd nanoparticles supported on mesoporous TiO2 exhibit the best catalytic performance. The demonstrated low-cost and high-productivity preparation method can be extended to other catalysts, which can contain various metals and oxide substrates and will have high potential for industrial applications. Our preparation method also provides a platform for the studies of the synergetic catalytic effects between different oxide substrates and metals.;I further fabricated hollow mesoporous microspheres containing differently shaped noble metal nanocrystals. Hollow structures are strongly desired in many applications because of their high pore volumes, surface areas, and possible light-trapping effect. In my study, the hollow structures were obtained by simply dispersing polystyrene (PS) nanospheres into the precursor solution for aerosol spray. The PS spheres were removed by thermal calcination to produce hollow mesoporous microspheres. In my first study, the noble metal salts were dissolved in the precursor solutions, and the noble metal nanoparticles were obtained through thermal calcination. In this way, the size and shape of the metal nanoparticles cannot be well controlled. In my second study, I first grew noble metal nanocrystals and then incorporated them into the oxide supports. This preparation route allowed me to incorporate metal nanocrystals with controlled sizes, shapes, and compositions into the oxide matrices. The metal nanocrystals I used in this experiment included Pd nanocubes, Au nanorods, and Au core–Pd shell nanorods. These nanocrystals were functionalized with thiol-terminated methoxypoly(ethylene glycol) . The surface functionalization allowed them to adsorb on the PS spheres. After thermal calcination, the noble metal nanocrystals were left inside and adsorbed on the inner surface of the hollow mesoporous metal oxide microspheres. I investigated the catalytic activities of the Pd nanocube-embedded hollow mesoporous TiO2 and ZrO2 microspheres for the reduction of 4-nitrophenol to 4-aminophenol. I also examined the recyclability of the Pd nanocube-embedded hollow mesoporous ZrO2 microsphere catalysts. The results showed that the combination of the noble metal nanocrystals and oxides prevents the aggregation of the nanostructures and reduces the loss of the catalysts during the recycling processes, leading to the remarkable recyclability of the hybrid catalyst. This method for the preparation of noble metal nanostructure-embedded hollow mesoporous oxide microspheres can greatly facilitate the investigation on the catalytic properties of noble metal nanocrystal and metal oxide hybrid nanostructures and therefore guide the design and fabrication of high-performance catalysts.;Last but not least, I investigated the magnetic mesoporous microspheres to enable a better recyclability of the mesoporous oxide catalysts. Both magnetic nanoparticle-included mesoporous metal oxides and mesoporous magnetic oxides were presented. The successfully syntheses of these microspheres will greatly improve the catalytic performance of the noble metal nanoparticle-loaded mesoporous oxide microspheres.