Exploring Pd adsorption, diffusion, and nucleation on bilayer SiO$_{\mathrm{2}}$/Ru as a function of hydroxylation and precursor environment: From UHV to catalyst preparation

The hydroxylation-dependent permeability of bilayer SiO$_{\mathrm{2}}$~supported on Ru(0001) was investigated by XPS and TDS studies in a temperature range of 100~K to 600~K. For this, the thermal behavior of Pd evaporated at 100~K, which results in surface and sub-surface (Ru-supported) binding arrangements, was examined relative to the extent of pre-hydroxylation. Samples containing only defect-mediated hydroxyls showed no effect on Pd diffusion through the film at low temperature. If, instead, the concentration of strongly bound hydroxyl groups and associated weakly bound water molecules was enriched by an electron-assisted hydroxylation procedure, the probability for Pd diffusion through the film is decreased via a pore-blocking mechanism. Above room temperature, all samples showed similar behavior, reflective of particle nucleation above the film and eventual agglomeration with any metal atoms initially binding beneath the film. When depositing Pd onto the same SiO$_{\mathrm{2}}$/Ru model support via adsorption of [Pd(NH$_{\mathrm{3}})_{\mathrm{4}}$]Cl$_{\mathrm{2}}$~from alkaline (pH~12) precursor solution, we observe notably different adsorption and nucleation mechanisms. The resultant Pd adsorption complexes follow established decomposition pathways to produce model catalyst systems compatible with those created exclusively within UHV despite lacking the ability to penetrate the film due to the increased size of the initial Pd precursor groups.