Flow-Based Multiadsorbate Ellipsometric Porosimetry for the Characterization of Mesoporous Pt−TiO2 and Au−TiO2 Nanocomposites

Abstract

Au and Pt nanoparticle distributions within hierarchically ordered mesoporous TiO2 were explored using a combination of techniques including ellipsometric porosimetry (EP) and X-ray photoelectron spectroscopy (XPS). EP studies were used to examine adsorbate-TiO2 interactions and the influence of adsorbate polarity upon adsorption isotherms for mesoporous TiO2 films with and without Pt and Au nanoparticles. In particular, methods are described for modeling EP data to estimate the surface area and porosity of mesoporous TiO2 films and for estimating the pore size distribution (PSD) directly from the ellipsometry parameters Psi and Delta when fitting parameters alone are unable to extract reliable optical constants from the ellipsometry data. This approach reveals that mesoporous TiO2 films of approximately 200 nm thickness and approximately 10 nm pore diameter can be loaded with 1.7 nm diameter Pt and 3.9 nm diameter Au nanoparticles up to 26 and 21 wt %, respectively. The BET surface area of a representative mesoporous TiO2 sample using toluene as the adsorbate was found to be 44 m2/g with a mean pore diameter of 8.8 nm. EP and XPS depth profiling experiments indicate that 1.7 nm diameter Pt nanoparticles are well dispersed through the mesoporous TiO2 film, while 3.9 nm diameter Au nanoparticles are concentrated at the top of the film, blocking a significant portion of the available TiO2 pore volume. UV irradiation of the TiO2 films indicates that adsorbate-TiO2 interactions and surface wetting effects can play a critical role in the resulting isotherm and in evaluation of PSD.