Quantum chemical elucidation of the mechanism for hydrogenation of TiO{sub 2} anatase crystals
- Center for Interdisciplinary Molecular Science, Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan (China)
Hydrogenation of TiO{sub 2} is relevant to hydrogen storage and water splitting. We have carried out a detailed mechanistic study on TiO{sub 2} hydrogenation through H and/or H{sub 2} diffusion from the surface into subsurface layers of anatase TiO{sub 2} (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT + U). Both H atoms and H{sub 2} molecules can migrate from the crystal surface into TiO{sub 2} near subsurface layer with 27.8 and 46.2 kcal/mol energy barriers, respectively. The controlling step for the former process is the dissociative adsorption of H{sub 2} on the surface which requires 47.8 kcal/mol of energy barrier. Both hydrogen incorporation processes are expected to be equally favorable. The barrier energy for H{sub 2} migration from the first layer of the subsurface O{sub sub1} to the 2nd layer of the subsurface oxygen O{sub sub2} requires only 6.6 kcal. The presence of H atoms on the surface and inside the subsurface layer tends to promote both H and H{sub 2} penetration into the subsurface layer by reducing their energy barriers, as well as to prevent the escape of the H{sub 2} from the cage by increasing its escaping barrier energy. The H{sub 2} molecule inside a cage can readily dissociate and form 2HO-species exothermically ({Delta}H =-31.0 kcal/mol) with only 26.2 kcal/mol barrier. The 2HO-species within the cage may further transform into H{sub 2}O with a 22.0 kcal/mol barrier and 19.3 kcal/mol exothermicity relative to the caged H{sub 2} molecule. H{sub 2}O formation following the breaking of Ti-O bonds within the cage may result in the formation of O-vacancies and surface disordering as observed experimentally under a high pressure and moderately high temperature condition. According to density of states analysis, the projected density of states of the interstitial H, H{sub 2}, and H{sub 2}O appear prominently within the TiO{sub 2} band gap; in addition, the former induces a shift of the band gap position notably towards the conduction band. The thermochemistry for formation of the most stable sub-surface species (2HO and H{sub 2}O) has been predicted. These results satisfactorily account for the photo-catalytic activity enhancement observed experimentally by hydrogenation at high temperatures and high pressures.
- OSTI ID:
- 22105480
- Journal Information:
- Journal of Chemical Physics, Vol. 138, Issue 15; Other Information: (c) 2013 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ADSORPTION
CRYSTALS
DENSITY
DENSITY FUNCTIONAL METHOD
HYDROGEN
HYDROGENATION
INTERACTIONS
LAYERS
PRESSURE RANGE MEGA PA 10-100
SURFACES
TEMPERATURE RANGE 0400-1000 K
TITANIUM OXIDES
VACANCIES