Metal-Oxide Interface Sites Created Using Atomic Layer Deposition and Tested for CO Oxidation.

The performance of catalysts made out of Pt supported on TiO₂ thin films grown on SBA-15 (a silica mesoporous material) by atomic layer deposition (ALD) was characterized systematically by combining in situ infrared absorption spectroscopy (IR) with other techniques including electron microscopy and adsorption-desorption isothermal measurements. The titania films in the resulting high-surface-area catalysts were evenly distributed throughout the inner surface of the SBA-15 mesopores, and their thickness could be controlled at a submonolayer level, with 3 to 4 TiO₂ ALD cycles needed for the complete coverage of the silica sites. The titania films could be deposited either before or after adding the metal (Pt), which was dispersed in the form of small nanoparticles (NPs) approximately 4-6 nm in diameter, in order to exert some control on the density and nature of the Pt/TiO₂ interface sites. One important lesson deriving from this work is that such an order of deposition leads to significantly different catalysts in spite of the fact that most of their structural properties are similar. If the Pt is deposited on the titania films, the resulting metal NPs are slightly smaller than those grown on silica and display CO adsorption sites with lower surface Pt coordination numbers. On the other hand, when TiO₂ is deposited on the Pt/SBA-15 starting material, some titania grows on the metal and partially blocks its surface while also creating new interface sites where CO binds more weakly and displays lower C-O stretching frequencies. In terms of catalytic performance, the results from in situ IR CO site titration and kinetic measurements combined suggest a mechanism where CO first adsorbs on Pt atop sites and then migrates to Pt/TiO₂ interface sites, where oxidation takes place. Both types of sites appear to be similar in all the catalysts tested, but catalytic performance could be optimized by tuning their surface densities. Maximum catalytic activity was obtained when the TiO₂ films were deposited first and with TiO₂ coverages of at least half a monolayer, that is, after at least 2 ALD cycles.