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Molecules 2021, 26, 2144 11 of 37 Usage of nickel and cobalt together shows interesting results [106,126,131–134]. This effect is a result of the reaction between these two hydroxides: Ni(OH)2 + CoOOH → NiOOH + Co(OH)2 (12) The presence of both of these metals in electrode material leads to an increased number of active sites for methanol oxidation on the electrode surface enhances the reaction kinetics [106,126,131–134]. Additionally, systems containing three active components have been tested, such as Pd-Cu-Co [128] and NiCoPO [106]. The addition of cobalt to the Ni–PO system lowers the onset potential even more, depending on the cobalt-nickel proportions [106]. 3.2. Ethanol Oxidation Despite mentioned advantages, direct methanol fuel cells still have some obstacles to overcome. The most important factors are the high overpotential of the methanol oxidation reaction (even with the usage of catalytic anode materials) [135,136], carbon monoxide catalyst poisoning for platinum-based materials [136] and the high methanol crossover rate, which impede cathodic performance [135,136]. To overcome these problems, new electrocatalytic materials should be prepared, or other low molecular weight alcohols can be used as liquid fuels for fuel cells Among other liquid fuels for direct fuel cells, ethanol has the greatest chance for practical application. It has an even higher energy density than methanol (8,27 kWh/kg; see Table 1) and is a nontoxic liquid with high permeability [32,136]. The concept of using ethanol as a fuel has been known for years, and the idea of using agricultural alcohol as a fuel has been considered for a long time. For example, after the Bolshevik Revolution, this idea was strongly supported by leaders, but it met strong resistance from citizens, who did not want their beloved vodka to be “misused” [66]. In some countries, i.e., Brazil, ethanol is already used as a fuel for combustion engines. In these cases, the fast application of direct fuel cells as an energy source in vehicles would be simple because no changes in existing infrastructure would be necessary [83,135]. The production of ethanol is one of the oldest biochemical processes used on an industrial scale. It can easily be produced in large quantities by fermentation of any plant-based material [1,32,135]; these materials can be divided into two main feed streams: starch-based feedstocks (corn, grain, and barley) and sugar-based feedstocks (sugarcane and cane citrus molasses) [1]. Moreover, for industrial purposes, ethanol can be obtained by the direct and indirect hydration of ethylene with phosphoric or sulfuric acid as a catalyst [1]. Ethanol molecule consists of two carbon atoms that are connected by a strong inter- carbon bond. To fully oxidize this molecule, not only the bond between oxygen and hydrogen, as in the case of methanol, must be broken, but also this strong C–C bond. The durability of this bond is responsible for ethanol’s stability, which makes it a perfect fuel; however, at the same time, it is the main source of the challenges to using ethanol’s full potential as a current source [83,100]. The electrochemical ethanol oxidation reaction (EOR) is more problematic than the MOR because the strong bond between two carbon atoms must be destroyed in addition to the bond between hydrogen and oxygen. Electrooxidation of ethanol occurs through different pathways and thus results in different products depending on the reaction regime—the electrode potentials, feed stream composition and temperature [135,137]. The complete oxidation of ethanol to carbon dioxide is a 12 electron reaction, so it should be twice as efficient in terms of current income as methanol oxidation. Complete oxidation, where carbon dioxide is the main carbon-based product, represents the so-called C1 mechanism and is the goal of DEFCs [135,137,138]. Complete oxidation allows the maximum usage of oxidized fuel by providing the highest number of electrons from one molecule of the fuel [7]: CH3CH2OH+3H2O→CO2 +12H+ +12e− (13)PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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