4.7 Article

Operando study of ethanol oxidation on Pt(111) by infrared spectroscopy at near-ambient pressure

Journal

APPLIED SURFACE SCIENCE
Volume 615, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apsusc.2023.156373

Keywords

Heterogeneous catalysis; Reaction mechanism; Ethanol oxidation; Platinum; Surface carbonate

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The oxidation of ethanol on a Pt(1 1 1) single crystal surface was investigated using PM-IRRAS at near-ambient pressures. The study monitored reaction intermediates and the main reaction products in the gas phase, as well as adsorbed species on the platinum surface, during stepwise heating from room temperature to 600 K. The results showed that ethanol oxidation starts at 330 K, with acetaldehyde, acetic acid, CO2, and water detected as gas-phase products. Surface intermediates such as adsorbed acetaldehyde and ethoxy-groups were observed at low temperatures, while carbonates were the only surface intermediates at higher temperatures.
The oxidation of ethanol on the surface of a Pt(1 1 1) single crystal was studied at near-ambient pressures using polarization-modulation reflection absorption infrared spectroscopy (PM-IRRAS). Reaction intermediates adsorbed on the platinum surface as well as ethanol and the main reaction products in the gas phase were followed by PM-IRRAS simultaneously in a batch reactor during stepwise heating from room temperature to 600 K. The experiments were carried out at two different ethanol/oxygen molar ratios, modeling stoichiometric and oxygen-rich conditions. It was shown that the oxidation of ethanol begins already at 330 K. Acetaldehyde, acetic acid, CO2, and water were detected as products in the gas phase. Adsorbed acetaldehyde and ethoxy-groups were distinguished as reaction intermediates on the platinum surface at low temperatures. At higher temperatures between 450 and 600 K, the only surface intermediates were carbonates, indicating their stability and ability to block the catalyst surface. No adsorbed CO was detected in the whole temperature range. The overall mechanism of the oxidation of ethanol on platinum is discussed.

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