Understanding the dispersion of Ag on high surface area TiO2 supports using XPS intensity ratios

Silver-titania (Ag/TiO2) adsorbents, in the range of 4 wt% Ag, display high selectivity toward sulfur heterocyclic compounds from complex fuel streams containing other aromatics. An experimental investigation of Ag on TiO2 has been undertaken to understand the state of dispersion and growth of Ag. XPS is one of the more promising characterization tools for the state of dispersion. Silver loading from 1 wt% to 20 wt% on 150 m2/g titania was investigated. Ag/Ti intensity ratios increased linearly with Ag content up to 4 wt% and increased less significantly thereafter from 8 wt% to 20 wt% indicating nucleation and growth of Ag crystallites. Inelastic mean free path (IMFP) calculations were used to estimate Ag crystallite size based on the attenuation of the Ag signal, realizing in this regime there is insufficient Ag to attenuate background titania. At 4, 8, 12, and 20 wt% the estimated average crystallite sizes were 0.35, 0.71, 0.84, and 1.11 nm respectively. Ag loadings up to 4 wt% were present in the form of Ag+1 adatoms presumably occupying TiO2 surface defects. Saturation of surface TiO2 defects is in good agreement with quantitative sulfur heterocycle adsorption.