New insights into methanol and formic acid electro-oxidation on Pt: Simultaneous DEMS and ATR-SEIRAS study under well-defined flow conditions and simulations of CO spectra

Methanol and formic acid electro-oxidation on Pt has been studied under well-defined flow conditions by a spectroscopic platform that combines differential electrochemical mass spectrometry (DEMS) and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. The volatile soluble products from methanol and formic acid oxidation on Pt have been detected by DEMS, while adsorbed intermediates have been identified with ATR-FTIR spectroscopy. Besides CO2 and methylformate, which were detected by DEMS, other non-volatile soluble intermediates such as formaldehyde and formic acid were also generated during methanol oxidation on Pt. Besides water adsorption bands, linearly bonded CO, bridge-bonded CO, adsorbed formate, adsorbed formic acid, and adsorbed CHO bands were observed by ATR-FTIR spectroscopy during methanol and formic acid oxidation on Pt. Formic acid adsorption suppressed the formate and water adsorption. Our results suggest that formate could be an inactive adsorbed species, rather than an active intermediate, for both methanol and formic acid oxidation. Pb modification of Pt significantly enhanced formic acid oxidation through the direct pathway due to the third-body effect and electronic effects. Formic acid oxidation took place mainly at Pb modified low-coordinated defect sites at low potentials. Formic acid decomposition to form adsorbed CO occurred only in the hydrogen region, and Pb modification also slightly enhanced the successive oxidation of adsorbed CO. A double-peak infrared band was observed for linearly bound CO on the Pt film and was simulated with the Fresnel equations and Bruggeman effective medium theory.