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Molecules 2021, 26, 2144 14 of 37 carbon intermediates and provides pertinent dilatation of the lattice parameter so that the C–C bond can be broken [16,144]. With increasing tin content, the current density obtained by ethanol oxidation increases, but only towards a specific maximum value. An Sn content that is too high leads to a decrease in active platinum sites or weakens the adsorption of alcohols on the Pt surface [16,136,144]. Unfortunately, the optimal ratio varies depending on the reaction temperature, potential range and catalyst type. The optimal tin content for ethanol oxidation in 0.5 M H2SO4 at room temperature reported by researchers varies from 10 to 50% depending on the electrode preparation procedure [15,16,143–145]. Figure 5. Bifunctional mechanism of ethanol oxidation reaction (EOR) on the PtSn (Pt—brown, Sn—blue) catalyst surface, reprinted with permission of American Chemical Society [15]. Tin in the form of SnO2 also enhances the catalytic properties of platinum electrodes. Generally, metal oxides mixed with Pt alter its electronic structure and enhance the removal of adsorbed carbon oxide intermediates from active platinum sites. One of the greatest advantages of tin and its compounds as doping agents is that the required processing is minimal [140]. Other forms of platinum–tin catalysts based on nanoparticles have also been devel- oped. Ultrathin nanofibers of PtSn3 [15], PtSn nanospheres [143] or Pt–Sn nanostructured catalyst [16,144] have shown enhanced stability and activity towards ethanol electrooxida- tion. Especially platinum-based nanofibers are interesting from a fuel cell point of view because they are characterized by good structural foundations, such as flexibility, conduc- tivity, large electroactive surfaces and inherent anisotropic morphologies. Additionally, this type of nanomaterial is less prone to aggregation or other structural deformation types that could cause serious damage during fuel cell operation [15]. In acidic media, some catalyst materials show even higher peak current densities for ethanol oxidation than for methanol oxidation, which is compliable with the theoretical assumption that ethanol can be a better current source than menthol. Pt-Sn catalysts show a tendency of increasing ability to oxidize alcohols as the tin content increases with increasing oxidized compound carbon atom number [16]. Among other oxophilic elements, nickel has shown interesting properties as a dopant in Pt electrodes. The obtained electrocatalytic material has higher activity than pure platinum, is less prone to CO poisoning and has a lower carbon dioxide to acetic acid ratio [138]. PtNi octahedrons are more specific towards the breaking of the C–C bondPDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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