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Molecules 2021, 26, 2144 26 of 37 The amount of released electrons is nine times higher than that in the case of pure propanol oxidation. This difference is caused by the presence of oxygen atoms in water molecules, which is necessary for carbon dioxide formation [135]. Isopropanol can be electrochemically oxidized in both acidic and alkaline media [195,198]. Its electrooxidation in acidic media results in obtaining higher current densities than MOR in the same conditions [200]. For alkaline solutions, observed peak current densities are even higher because the higher pH value of the electrolyte enhances the oxygen reduction reaction that takes place on the cathodic site of the fuel cell [198,201]. The overall 2-propanol electrooxidation reaction, despite the reaction environment, can be expressed as [135,161,195,198,202]: CH3CH(OH)CH3 → CH3C(O)CH3 + 2 H+ + 2 e− (39) CH3C(O)CH3 +16OH− →3CO2 +11H2O+16e− (40) As shown in reactions (39) and (40), acetone formation strongly prevails during 2-propanol electrooxidation. In the products stream, only a little amount of CO2 is de- tected [161,198]. The absence of CO and its intermediates is one of the greatest advantages of isopropanol as a fuel because it lowers the chances of occurring of the phenomenon of self-poisoning of the system with CO intermediates and allows power generation without carbon dioxide emission [197,199]. Additionally, isopropanol’s oxidation to acetone takes place in a lower potential region than its complete oxidation to CO intermediates and further to carbon dioxide, which makes it more efficient [198,199]. Oxidation to acetone, instead of full oxidation to carbon dioxide, is one of the greatest advantages of direct isopropanol fuel cells. Because of the lack of CO2 emissions, this kind of fuel cell is carbon neutral and thus is even more environmentally friendly than other fuel cell technologies [197,199]. Additionally, because of this reaction, the isopropanol and acetone system can act as a liquid hydrogen carrier—a pair of hydrogen-rich (iso- propanol) and hydrogen lean (acetone) molecules that can be used as hydrogen sources with repeated catalytic hydrogenation and dehydrogenation cycles. In the fuel cell, the role of the catalyst is played by the electrocatalytic materials, from which the electrodes are made. Such a solution can be very convenient because hydrogen as a fuel has many interesting features, such as high gravimetric energy storage, and enables fully de-fossilized energy production [197,199]. Because classical approaches to hydrogen storage, such as compression or cooling, do not seem to be effective, other methods of hydrogen storage must be developed. Liquid hydrogen carriers combined with fuel cells can be an elegant solution to this problem—in one device and on one electrocatalytic material, both reactions (protonation and deprotonation) can take place, which allows better usage of space and lower investment costs. Additionally, using electrocatalytic materials for the deprotonation of organic molecules in fuel cells results in protons instead of hydrogen molecules, which increases the system’s safety [197,199]. The cell reactions using this system can be described as [197]: (A): CH3CH(OH)CH3 → CH3COCH3 + 2H+ + 2e− (41) (C)2H+ + 12 O2 +2e− →H2O (42) The summary reaction is as follows: H3CH(OH)CH3 + 12 O2 → CH3COCH3 + H2O (43) The theoretical potential of such a cell (1.1 V) is 13 mV lower than that for the classic hydrogen fuel cell (1.113 V) but is higher than the potentials obtained for other direct alcohol fuel cells fed methanol or ethanol [197].PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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