Authors: Shuanglin Hu, Phillipe A. Bopp, Lars Österlund, Peter Broqvist, and Kersti Hermansson
The adsorption and dissociation of a formic acid molecule (HCOO) on a partially reduced rutile TiO2–x (110) surface and the subsequent transformations of the adsorbed fragments are studied via quantumechanical molecular dnamics simulations and climbing-image nudged elastic band (CI-NEB) calculations. The electronic structure methods used are self-consistent-charge density functional tight binding (SCC-DFTB) and DFT+U calculations. We address the apparent lack of consensus in the literature regarding the formic acid adsorbate species that heal the O vacancies, where different experiments have suggested the occurrence of one, two, or no such species types. From our calculations, we propose that the formic acid molecule quickly dissociates on the surface into a formate ion and a proton. If no mechanism exists by which the dissociation products can migrate away from each other, three formate species will coexist on the partially reduced TiO2 surface: one majority species bound to the Ti rows and two minority species healing the O vacancies. However, if such a diffusion mechanism does exist, our barrier calculations show that one of the minority species will transform into the other, and only two adsorbate types can be expected on the surface. We also identify a new adsorbate configuration (which we denote C′), where the formate is located on the row of two-coordinated oxygen atoms, healing an O vacancy and accepting an H-bond from the detached H atom.
J. Phys. Chem. C 118, 14876 (2014).