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Structural dependence of the selectivity of formic acid decomposition on faceted TiO sub 2 (001) surfaces

Journal Article · · Langmuir; (USA)
DOI:https://doi.org/10.1021/la00099a009· OSTI ID:6286862
;  [1]
  1. Univ. of Delaware, Newark (USA)

The reactions of formic acid on TiO{sub 2} (001) single-crystal surfaces were examined by temperature-programmed desorption and x-ray photoelectron spectroscopy. The (011)-faceted and (114)-faceted surfaces were chosen as model surfaces in order to investigate the effects of surface structure and composition upon reaction selectivity and to identify the active sites. Formic acid adsorbed dissociatively at 300 K to yield surface formate species. Approximately 15% of the adsorbed formates was removed from the surface as formic acid at 390 K via recombination with surface hydroxyls. The remaining formates decomposed above 550 K to CO, CO{sub 2}, and formaldehyde, with selectivities toward these products dependent upon the surface structure and composition. On the (011)-faceted surface, which exposes fivefold oxygen-coordinated Ti{sup 4+} cations, adsorbed formates decomposed exclusively via unimolecular reactions to product CO and CO{sub 2}. On the (114)-faceted surface, which exposes four-, five-, and sixfold coordinated cations, the reaction of adsorbed formates to produce formaldehyde was also observed.

OSTI ID:
6286862
Journal Information:
Langmuir; (USA), Journal Name: Langmuir; (USA) Vol. 6:9; ISSN 0743-7463; ISSN LANGD
Country of Publication:
United States
Language:
English