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Molecules 2021, 26, 2144 18 of 37 via hydrolysis of ethylene oxide, with an annual production of 7 million tons (for 2012) [90]. Such large-scale production means that the supply chains are well developed, which simplifies the adaptation to the role of fuel for current sources [25,90,162]. Even though EG is a simple diol, its complete electrooxidation to carbon dioxide is quite complicated. Its full oxidation can be presented as follows [7,88,162,163]: (CH2OH)2 +2H2O→2CO2 +10H+ +10e− (23) (CH2OH)2 + 10 OH− → 2CO2 + 8 H2O +10 e− (24) (CH2OH)2 + 14 OH− → 2CO32− + 10 H2O +12 e− (25) The complete oxidation of one molecule of ethylene glycol to carbon dioxide results in a gain of 10 electrons (in comparison, complete MOR results in a gain of 6 electrons, and EOR results in a gain of 12 electrons) [91]. The EGOR is a very sensitive reaction, and the process conditions, such as the temper- ature or acidity, can strongly influence its reaction rate. An alkaline environment provides better conditions for EGOR from a kinetic point of view because such conditions enable the higher activity of EGOR molecules [164,165]. Furthermore, better results observed for EGOR in the base environment can be related to the easier electron transfer in the presence of hydroxide ions [166]. Free OH− ions in the feed stream can be adsorbed on the surface of the electrodes [86]. Since hydroxide ions are present in the solution, they do not need to be produced in situ by water activation in the same amount as that in the acidic environment, which simplifies the overall process [86,91,162]. Hydroxide adsorbed on the surface of the electrocatalytic material enhances the oxidation of the poisonous CO intermediates and thus enhances the overall reaction efficiency [86,161,165]. The release of the adsorbed carbon oxide derivatives prevents the poisoning of the electrode and thus enhances the overall electrode reaction yield because more free active sites on the electrode surface area available for newly delivered fuel molecules. Therefore, the higher the amount of oxygen-containing species on the surface of the electrode is, the better the CO poisoning immunity of the electrode and, consequently, the better the system performance [161,165,167]. The oxidation of ethylene glycol in alkali media can go through two paths: poisonous and non-poisonous [25,154], depending on the catalytic material used and the process conditions (i.e., pH and temperature) [154]. In the non-poisonous pathway, the main prod- uct of EGOR is oxalate, while for the poisonous one, products are formed during further oxidation of initially obtained formates [25,154]. Only some ethylene glycol molecules are fully oxidized, so the EGOR leads to a large number of intermediates containing two car- bon atoms—C2 intermediates—including glycolic acid, glyoxal, glyoxylic acid, oxalic acid, glycolaldehyde and glyoxal [88,91,161–163,165] (Figure 6). The scheme of EG oxidation to C2 intermediates can be written as shown in Figure 6 [162]. Figure 6. Mechanism of ethylene glycol oxidation to C2 intermediates based on [162]. The electrooxidation of ethylene glycol takes place in two steps. First, ethylene glycol molecules are adsorbed on the surface of the anode and dehydrogenated, which leads to the formation of C2 adsorbed products. This step is common for both the poisonous and nonpoisonous paths [154,161–163]. The second step of the EGOR is the oxidation of the formulated intermediates [25,154,161–163], and because they are less prone to oxidation than the original compound, this is the rate-determining step for the whole oxidationPDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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