(764c) Nanobowls: A Platform for Selective Acid Catalysis on External Oxide Surfaces

Ardagh, A., Northwestern University
Thornburg, N. E., Northwestern University
Bo, Z., Northwestern University
Nauert, S., Northwestern University
Notestein, J. M., Northwestern University
Metal oxide catalysts are workhorse materials in the production of petroleum products and fine chemicals. Crystalline, microporous materials (zeolites) have long dominated catalysis in these industries since being introduced in 1960. Zeolites act as shape selective solid acid catalysts and often possess both strong Brønsted and Lewis acidity. As the chemical industry looks to switch over to biomass and tar sands feedstocks, reactant diffusion and catalyst stability issues have arisen. These problems could be addressed by running these same reactions over (somehow) selective, non-porous metal oxides. In addition, using bulk oxides for zeolite chemistry would open the door to tunable materials development covering a wide array of elemental compositions. Therefore, we propose the Nanobowls approach as an alternative, highly tunable synthesis method to create selective acid catalysts. In this approach, we construct 1-2 nm diameter cavities on the surface of nonporous oxides. The Nanobowls approach has been applied to both major types of acid catalysts: those with Brønsted sites and those with Lewis sites.

In the Brønsted acidic case, spherical Al2O3 particles were overcoated with SiO2 in the liquid phase using TEOS as the Si precursor. These overcoated materials were calcined at 650 oC with a high ramp rate, 20 oC/min, that lead to the formation of strong Brønsted acid sites contained within a thin, accessible microporous overcoat. Their performance in a Brønsted acidity probe reaction, the vapor phase catalytic cracking of Triisopropylbenzene (TIPB) was on par with industry standard amorphous SiO2-Al2O3 and slightly less active than zeolite H-Y on a surface area basis. In the Lewis acidic case, shape selective Ti sites were synthesized on SiO2 spheres by grafting Cp*TiCl3, calcining off the ligands at 550 oC, overcoating with SiO2 using the same liquid phase deposition technique, and recalcining the material at 550 oC with a high ramp rate of 10 oC/min. This lead to the formation of strong Lewis acid sites contained within a thin, accessible microporous overcoat. Their shape selectivity performance is being tested in several Lewis acidity probe reactions including competitive Tetrahydropyranylation of Benzyl alcohol and 2,4,6-Trimethylbenzyl alcohol, competitive MPV reduction of Acetophenone and 2,4,6-Trimethylacetophenone, and Limonene Epoxidation.

Overall, we have demonstrated this approach as a highly tunable synthetic pathway to alternative selective Brønsted and Lewis acidic oxide materials. Future materials development will include application to bifunctional catalysis such as biomass conversion reactions and the synthesis of shape selective Brønsted sites via sulfation of Al2O3 or TiO2 within 1-2 nm SiO2 cavities.