Abstract
The photoinduced isotope exchange between 18O atoms in the lattice of vacuum-calcinated solid Ti18O2 and 16O 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 Ti18O2 and the oxygen atoms in gaseous HC16O16OH 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 Ti18O2. Similar blocking was observed by adsorbed water. The isotopologues C16O18O and C18O2 are the products of the spontaneous exchange of oxygen atoms in C16O2 and the active sites on Ti18O2 that are unblocked du...
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