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Molecules 2021, 26, 2144 6 of 37 Alcohol Methanol Ethanol Ethylene glycol Propanol Gasoline Density (kg m−3) * 786.68 [2] 789.30 [84] 1113.50 [90] 803.60 [92] Boiling Point (◦C) ** 64.70 [84,85] 78.32 [84] 197.60 [85,90] 97.22 [92] Energetic Density (MJ L−1) 17.85 based on [2] 23.49 based on [84,89] 21.23 based on [90] 27.00 based on [92] Heat of Combustion (MJ kg−1) 22.69 [2] 29.76 based on [89] 19.07 [90] 33.60 [92] Theoretical Energetic Density (kWh kg−1) 6.1 [86–88] 8.00 [23,86,87] 5.2 [23,86,88,91] 5.58 [87] 10–11 [87] E◦ Cell (V) 1.213 [87] 1.145 [87] 1.22 [91] 1.029 [87] 1.067 [87] Due to its high energy density (see Table 1), the energy industry uses methanol directly as a fuel, as a fuel additive or as a substrate in biodiesel production [1,70]. Methanol as fuel gained the world’s attention during the Arab oil embargo in 1973 [2,65]. Since then, methanol has been widely used as a fuel additive in diesel engines [1,70,71], biodiesel production [71] and as a fuel alternative in internal combustion engines [1,71]. Because it can be economically produced from the fermentation of biomass or agricultural waste, it is considered to be a renewable fuel [72,73]. Recently, electrochemical methanol oxidation reactions (MOR) have gained researchers’ attention because they can be used as a direct source of electricity with direct methanol fuel cells (DMFCs). In DMFCs, an electrolyte containing a methanol mixture is directly fed to the anode, on which the oxidation process can take place at atmospheric pressure and temperatures lower than 100 ◦C [38,74]. Due to the electrocatalytic properties of anodic materials, electric current related to the chemical reaction can be obtained directly without the use of additional devices, such as vapor turbines [34,38,74–76]. DMFCs are considered a promising energy source because of their low pollution emissions, simple operation and high efficiency of energy conversion [34,54]. Additionally, their unique properties, such as simple configuration, suitability for small and portable applications (e.g., electronics) and higher energy density than the best rechargeable batteries based on lithium compounds, suggest developing DMFCs as a potential replacement for lithium-based batteries [34,77]. Presently, catalysts based on PtRu are widely used for MORs, but slow reaction kinetics still inhibit developing this technology [34,38,77,78]. Unfortunately, this is only one of the prob- lems that DMFC technology must face, and most of them are related to the anode material on which the reaction takes place. One of the most undesired phenomena that can occur in DMFC is carbon monoxide poisoning, which occurs when molecules of CO formed during methanol oxidation irreversibly adsorb on active anode sites [6,34,75,77,79–81]. Platinum- based electrodes are very prone to this phenomenon [34,80,81]. As a result, fewer active sites are available for bulk methanol molecules, leading to a decrease in electrode activity and, consequently, a lower reaction yield [6,16,34,35,75,77,79–83]. For these reasons, devel- oping new anodic materials with electrocatalytic properties towards methanol oxidation is necessary, and researchers are still working on this subject to enable the commercialization of DMFCs. Table 1. Physical properties of mentioned alcohols. * At 20 ◦C, ** for 1013.25 hPa. Different reaction mechanisms may lead to different products, but during electrochem- ical methanol oxidation, different product compositions have been observed for the same reaction conditions. This suggests that reactions can take place through different pathways, such as [81,93,94]: 1. Stepwise dehydrogenation to adsorbed CO and subsequent oxidation to CO2; 2. Reaction along parallel, “direct” paths to CO2; 3. Partial oxidation to formic acid and/or formaldehyde.PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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