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Computational study on the reactions of H 2 O 2 on TiO 2 anatase (101) and rutile (110) surfaces
Author(s) -
Huang WenFei,
Raghunath P.,
Lin M. C.
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21686
Subject(s) - rutile , anatase , adsorption , density functional theory , exothermic reaction , oxygen , chemistry , activation energy , crystallography , materials science , catalysis , computational chemistry , photocatalysis , organic chemistry
This study investigates the adsorption and reactions of H 2 O 2 on TiO 2 anatase (101) and rutile (110) surfaces by first‐principles calculations based on the density functional theory in conjunction with the projected augmented wave approach, using PW91, PBE, and revPBE functionals. Adsorption mechanisms of H 2 O 2 and its fragments on both surfaces are analyzed. It is found that H 2 O 2 , H 2 O, and HO preferentially adsorb at the Ti 5c site, meanwhile HOO, O, and H preferentially adsorb at the (O 2c )(Ti 5c ), (Ti 5c ) 2 , and O 2c sites, respectively. Potential energy profiles of the adsorption processes on both surfaces have been constructed using the nudged elastic band method. The two restructured surfaces, the 1/3 ML oxygen covered TiO 2 and the hydroxylated TiO 2 , are produced with the H 2 O 2 dehydration and deoxidation, respectively. The formation of main products, H 2 O(g) and the 1/3 ML oxygen covered TiO 2 surface, is exothermic by 2.8 and 5.0 kcal/mol, requiring energy barriers of 0.8 and 1.1 kcal/mol on the rutile (110) and anatase (101) surface, respectively. The rate constants for the H 2 O 2 dehydration processes have been predicted to be 6.65 × 10 −27 T 4.38 exp(−0.14 kcal mol −1 /RT) and 3.18 × 10 −23 T 5.60 exp(−2.92 kcal mol −1 /RT) respectively, in units of cm 3 molecule −1 s −1 . © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011.