Methanol Electrochemical Thermal Desorption

Different experimental approaches were applied in the past [6, 45] and in recent years [23, 46] to study the nature of the organic residue. But the results or their interpretation have been contradictory. Even at present, the application of modem analytical techniques and optimized electrochemical instruments have led to different results and all three particles given above, namely HCO, COH and CO, have been recently discussed as possible methanol intermediates [14,15,23,46,47]. We shall present here the results of recent investigations on the electrochemical oxidation of methanol by application of electrochemical thermal desorption mass spectroscopy (ECTDMS) on-line mass spectroscopy, and Fourier Transform IR-reflection-absorption spectroscopy (SNIFTIRS). 

Iwasita et used the similar techniques and confirmed that the adsorbate contains a proton atom but concluded that the adsorbate is C-OHad ie same group executed electrochemical thermal desorption mass spectroscopy, in which the methanol absorbing electrode was washed by the supporting electrolyte, transferred to the UHV environment, heated to desorb the adsorbates to analyze them by mass spectroscopy. They found hydrogen molecules in the desorbed gas as well as CO and the ratio of hydrogen to CO decreased as the concentration of methanol increased. 

Much of the effort on the electrooxidation of ethanol has been devoted mainly to identifying the adsorbed intermediates on the electrode and elucidating the reaction mechanism by means of various techniques, as differential electrochemical mass spectrometry, in situ Fourier transform infrared spectroscopy, and electrochemical thermal desorption mass spectroscopy. The established major products include CO2, acetaldehyde, and acetic acid, and it has been reported that methane and ethane have also been detected. Surface-adsorbed CO is still identified as the leading intermediate in ethanol electrooxidation, as it is in the methanol electrooxidation. Other surface intermediates include various Ci and C2 compounds such as ethoxy and acetyl [102]. There is general agreement that ethanol electrooxidation proceeds via a complex multi-step mechanism, which involves a number of adsorbed intermediates and also leads to different byproducts for incomplete ethanol oxidation, as shown in Figure 1.22. 

However, the important criteria for WC to be implemented in fuel cells are its surface area, phase, and porosity. Ganesan and Lee reported that WC with a surface area of 170 m /g was obtained by thermal method, but the product tuned to be containing more sub-tungsten carbide (W2C) [70]. The latter was used to support Pt catalyst for methanol oxidation reaction. No test was done for ORR. Nevertheless, authors believed that oxide layer formed on carbide support is the key player in promoting alcohol oxidation by providing oxygen species as indicated by the decrease in desorption temperature of CO. In a different study carried out by the same group, mesoporous WC was synthesized and used as a support for Pt [71]. The mesoporosity was introduced by addition of surfactant like cetyltrimethylammonium bromide (CTABr). Catalyst performance was evaluated under identical conditions as previously stated however, no statement has been reported on ORR activity and electrochemical stability in both cases [70, 71]. 

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