Understanding NO x chemistry at titania nanoparticle surfaces is important for photocatalytic environmental remediation processes. We focus on this problem and put forward an experimental-computational approach based on vibrational spectroscopy grounds. Temperature-dependent IR experiments of NO x adsorption on shape-engineered nanoparticle (101) anatase surfaces are paired with power spectra obtained from Born-Oppenheimer trajectories. Then, the harmonic versus anharmonic vibrational frequencies of several adsorption scenarios are directly compared with the IR experiments. We conclude that molecules are adsorbed mainly by the N-end side and both the intermolecular interactions between adsorbed molecules and (NO)2 dimer formation are responsible for the main NO adsorption spectroscopic features. We also investigate the spectroscopy and the mechanism of formation on defective anatase surfaces of the long-lived greenhouse gas N2O.
© 2022 The Authors. Published by American Chemical Society.