First Principles Insight into H2 Activation and Hydride Species on TiO2 Surfaces

Hu, Guoxiang; Wu, Zili; Jiang, De-en

doi:10.1021/acs.jpcc.8b05251

First Principles Insight into H₂ Activation and Hydride Species on TiO₂ Surfaces

Journal Article · Thu Aug 16 00:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b05251· OSTI ID:1468080

Hu, Guoxiang ^[1]; ^[2]; ^[1]

Univ. of California, Riverside, CA (United States). Department of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division and Center for Nanophase Materials Sciences

Hydrogen interaction with the TiO₂ surfaces is important in many catalytic and photocatalytic reactions. However, the mechanisms of H₂ activation on TiO₂ surfaces remain unclear. Here in this work, we study H₂ activation on the most commonly examined and stable surfaces of different TiO₂ polymorphs, including rutile TiO₂(110), anatase TiO₂(101), and brookite TiO₂(210), by first-principles density functional theory. We find that for all three surfaces, the heterolytic pathway is kinetically more favorable (leading to a hydride and a hydroxyl), even though the homolytic dissociation of H₂ is thermodynamically more favorable (leading to two hydroxyls). For rutile TiO₂(110), the hydride produced by the heterolytic dissociation of H₂ can transfer from Ti to O with an activation energy of 0.99 eV, yielding the homolytic products. For anatase TiO₂(101) and brookite TiO₂(210), the barrier of hydrogen transfer from Ti to O is higher (1.48–1.68 eV). This indicates that hydrides on can be kinetically stabilized on TiO₂ surfaces. In conclusion, our study sheds light on the mechanisms of H₂ dissociation on TiO₂ and provides rational for the existence of hydrides on TiO₂ or other reducible metal oxides which may facilitate hydrogenation reactions.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1468080

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 35 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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