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Molecules 2021, 26, 2144 19 of 37 reaction [91,154,161,163]. At room temperature, the yield of ethylene glycol oxidation to CO2 does not exceed several percent, which makes it negligible [91]. The non-poisonous way leads to formation of oxalate (reaction (26)) [88]: (CH2OH)2 + 10 OH− → C2O42− + 8 H2O +8 e− (26) and a poisonous path leads to the formation of CO intermediates, such as glyco- lates (reaction (27)) and formate (reaction (28)), that are further oxidized into anode poisoning species [25,88,102,154,163]. The formation of glycolate is a four-electron reaction in which the C–C bond remains unbroken [163]: (CH2OH)2 +5OH− →CH2COO− +4H2O+4e− (27) Another possible product, formate, is generated in a 6 electron reaction that involves the cleavage of the C–C bond [163]: (CH2OH)2 +8OH− →2HCOO− +6H2O+6e− (28) The final nonpoisonous product is oxalate because of the absence of catalytic materials that are capable of oxidation with proper reaction kinetics [33,163]. Other products obtained during nonpoisonous EG oxidation include glycolate and glyoxalate, depending on the reaction pH, which is further oxidized to oxalate [88,154,163]. When EG is oxidized into oxalate species, 8 moles of electrons are obtained from one mole of EG (reaction (26). When we compare this to the maximum possible electron income from complete EG oxidation (reactions (24) and (25))—10 moles of electrons from one mole of EG—we obtain 80% current efficiency compared to full EG oxidation to carbon dioxide [88]. Fortunately, the partial oxidation of ethylene glycol can be advantageous. C2 interme- diates, such as formates, glycolates or oxalates, are valuable organic compounds. Therefore, the lower energetic value of the partial oxidation process is compensated by the production of valuable chemicals that can be isolated from the product stream and further used in other industries for, for example, medicine, pesticides and organic synthesis [102,154]. Most of the established technologies for DAFCs are based on anodes made of platinum and its alloys [31,85,91,108,144,163,167–171]. Because of their popularity, their manufactur- ing process is well established, and the control of the metal ratio, alloy level and surface morphology is possible [115,162]. This well-established production technology makes platinum-based anodes perfect candidates for electrocatalytic materials and is the main rea- son for studying their catalytic activity towards the oxidation of various alcohols [115,162]. The electrooxidation of C2 alcohols, such as ethanol and ethylene glycol, with platinum- based anodes, can show low efficiency. This phenomenon is linked to the high sensitivity of Pt towards poisoning with carbon intermediates rather than to its inability to break the C–C bonds [91,154,161,163] and to favorable kinetics of partial oxidation to C2 intermediates compared to full oxidation to carbon dioxide [91,162]. To minimize the harmful influence of reaction products on platinum electrodes, anodic materials are doped with additives that significantly increase their immunity to poisoning. The doping of platinum anodes with other metals leads to modification of Pt geometric and electronic structures by Pt–M interactions, where M can be Sn [15,91,144,168], Pd [88], Au [167,172], Ru [85,108,163,173,174], Ni [163,169], Pb [161], Bi [88], Co [171], etc. and thus to changes in catalytic activities [161,162]. As mentioned, catalyze is a surface process. A bigger area of contact between the solution and the electrode enhances the reaction rate thanks to a higher amount of active sites accessible for alcohol particles and better conditions for their transport, enabling the diffusion towards the electrode [170]. To enhance its catalytic activity towards EGOR, different forms of anodic materials have been examined from solid electrodes, mesh [49] or aerogels [175] to immobilized nanoparticles, both mono- [144,174,176] and multimetallicPDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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