RESUMO
Quasiclassical trajectory calculations and vibrational-state-selected beam-surface measurements of CH4 chemisorption on Ir(111) reveal a nonthermal, hot-molecule mechanism for C-H bond activation. Low-energy vibrationally excited molecules become trapped in the physisorption well and react before vibrational and translational energies accommodate the surface. The reaction probability is strongly surface-temperature-dependent and arises from the pivotal role of Ir atom thermal motion. In reactive trajectories, the mean outward Ir atom displacement largely exceeds that of the transition-state geometry obtained through a full geometry optimization. The study also highlights a new way for (temporary) surface defects to impact high-temperature heterogeneous catalytic reactivity. Instead of reactants diffusing to and competing for geometrically localized lower barrier sites, transient, thermally activated surface atom displacements deliver low-barrier surface reaction geometries to the physisorbed reactants.
RESUMO
HYPOTHESIS: Heterogeneous nucleation of silver oxide (Ag2O) onto oxide microparticles (OMPs) followed by spontaneous thermal decomposition produce nanostructures made of OMPs decorated with silver nanoparticles (OMP|AgNPs). EXPERIMENTS: Colloidal chemistry methods have been used to produce the decoration of OMPs with silver nanoparticles (AgNPs), by carrying out the Ag2O precipitation/thermal decomposition. The process is driven in water enriched acetone medium containing NaOH, NH3, AgNO3 and SiO2MPs as substrate. Optical and morphological properties of OMP|AgNPs were characterized by using STEM, EDS, HRTEM and Raman spectroscopy. FINDINGS: A new synthetic method to decorate OMPs (TiO2, SiO2) with metallic AgNPs in a single step/single pot reaction is proven effective to produce OMP|AgNPs either in aqueous or water enriched media.