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In situ infrared spectroscopy of catalytic solid-liquid interfaces using phase-sensitive detection: Enantioselective hydrogenation of a pyrone over Pd/TiO2

Baiker, Alfons
Published in Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical. 2002, vol. 106, no. 41, p. 10649-10658
Abstract The potential of modulation excitation spectroscopy and phase-sensitive detection in combination with attenuated total reflection (ATR) for in situ infrared spectroscopy of catalytic solid−liquid interfaces is demonstrated. The method is based on the periodic variation of an external parameter such as reactant concentration. The periodically varying signals are subsequently demodulated using a phase-sensitive detection scheme. In this way, the small periodically varying signals are separated from the large static ones, yielding high quality difference spectra. Species, which have different response to the excitation, i.e., species with different kinetics, can easily be separated in the spectra. The method is applied to the enantioselective hydrogenation of 4-methoxy-6-methyl-2-pyrone over a 5 wt % Pd/TiO2 powder catalyst modified by cinchonidine. Upon modulation of the reactant concentration, the ATR spectra exhibit varying signals from dissolved reactant, product as well as from adsorbed species. Part of the signals are associated with carboxylates adsorbed on the TiO2. The kinetics of these species are distinctly different from the one of the primary hydrogenation product. The carboxylates are formed from alcoholysis of the lactone, which is obtained by a second hydrogenation step. The enantiomeric excess was also measured phase sensitive. Its time dependence indicates a negative influence of the carboxylates on enantioselection.
Stable URL http://archive-ouverte.unige.ch/unige:14640
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Deposited on : 2011-03-18

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