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Adsorption and photooxidation of CH{sub 3}CN on TiO{sub 2}

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
DOI:https://doi.org/10.1021/jp991040w· OSTI ID:691305
; ;  [1]
  1. Univ. of Pittsburgh, PA (United States)

The adsorption and photooxidation of CH{sub 3}CN chemisorbed on TiO{sub 2} has been investigated using infrared spectroscopy. It was found that CH{sub 3}CN forms an ice layer on TiO{sub 2} at 126 K and above 126 K CH{sub 3}CN diffusion into TiO{sub 2} occurs. At 200 K, the adsorption of CH{sub 3}CN on both isolated Ti-OH groups and on the Ti{sup 4+} Lewis acid site was observed. Under UV irradiation (350 {+-} 50 nm; hv = 3.10--4.13 eV), CH{sub 3}CN was oxidized in the presence of O{sub 2} to form H{sub 2}O, CO{sub 2}, surface CO{sub 3}{sup 2{minus}} and an intermediate partially oxidized isocyanate species, NCO, which was identified by various isotopic experiments. Photooxidation of the CH{sub 3} moiety in adsorbed CH{sub 3}CN occurs more readily than does the CN moiety in CH{sub 3}CN. Lattice oxygen of TiO{sub 2} was found to preferentially form adsorbed NCO, compared to oxygen from adsorbed O{sub 2}. A mechanism of the formation of NCO species was postulated.

OSTI ID:
691305
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 33 Vol. 103; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English

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