Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 116, Issue 20, Pages 11200-11205Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp303011a
Keywords
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Funding
- Academy of Sciences of the Czech Republic [IAAX00100903, IAA 400400804, KAN200100801]
- Grant Agency of the Czech Republic [P208/10/1678]
- Czech Ministry of Education, Youth and Sports [OC09044, MP0702]
- EC [NMP-246124]
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The photoinduced isotope exchange between O-18 atoms in the lattice of vacuum-calcinated solid (TiO2)-O-18 and O-16 atoms of formic acid and its photoproducts was studied with gas-phase high-resolution Fourier transform infrared absorption spectroscopy. The rotation-vibration absorption spectra of all products from the photochemical reactions of formic acid were measured over a broad infrared spectral range and used to quantify the time-dependent isotope exchange between the oxygen atoms on solid (TiO2)-O-18 and the oxygen atoms in gaseous (HCOOH)-O-16-O-16 and the isotopologues of CO2, CO, and H2O. It was found that formic acid did not exchange oxygen with titania during adsorption and decomposition processes; strongly bonded formate species blocked active sites and thereby inhibited the exchange between CO2 and (TiO2)-O-18. Similar blocking was observed by adsorbed water. The isotopologues (COO)-O-16-O-18 and (CO2)-O-18 are the products of the spontaneous exchange of oxygen atoms in (CO2)-O-16 and the active sites on (TiO2)-O-18 that are unblocked during the irradiation of the surface by UV photons. The (CO)-O-18 molecules are a product of the UV decomposition of (COO)-O-16-O-18 or (CO2)-O-18 that is formed during the spontaneous exchange process.
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