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Molecules 2021, 26, 2144 25 of 37 organic molecules. They can be relatively easily obtained by selective dissolution of the active phase from the alloy-dealloying process. For example, TiCu amorphous alloys are de-alloyed in nitric acid solution [166]. This material was additionally treated at high- temperature. The final material shows significant activity towards EGOR in both acidic and alkaline media. Untreated TiCu alloy shows no catalytic activity in alkaline media and low activity in alkaline solution. Heat-treated nanoporous materials show better results in terms of both catalytic activity and stability, which is probably related to less homogenous and larger pore sizes. Larger pores enable the diffusion process, which enhances the overall reaction rate [166]. 3.4. Propanols The term propanols refer to two isomers: 1-propanol and 2-propanol, also called isopropanol. Both are clear liquids with characteristic smells and low vapor pressure. This last feature has promoted their use as solvents on an industrial scale. Other applications of propanols include anti-freezing agents, biocidal agents and substrates in organic syntheses, such as the production of esters or amines. The larger production scale of isopropanol is linked to its larger industrial signifi- cance [92]. Additionally, isopropanol can be obtained from biomass materials, making it more environmentally friendly than the linear isomer [59,193]. Both propanol isomers on an industrial scale are produced by hydrogenation—isopropanol is a result of the hy- drogenation of acetone (reaction (36)), and propanol is obtained by the hydrogenation of propanal (reaction (37)) [92]: CH3C(O)CH3 + H2 → CH3CH(OH)CH3 (35) CH3CH2CHO + H2 → CH3CH2CH2OH (36) Saturated C3 alcohols, especially isopropanol, which is the smallest secondary alcohol, have been of great interest as potential fuels for fuel cells. They are less toxic than methanol, and the direct alcohol fuel cells that use them for electricity production perform better than DMFCs because of the much lower crossover current, which is limited due to the size of C3 alcohol molecules, which are larger than methanol [59,193–197]. Electrooxidation of propanol is possible in both acidic and alkaline media on palladium- or platinum-based catalysts. Platinum shows greater activity towards propanol oxidation, while palladium gives better results as an anodic material for isopropanol oxidation [130]. The main product of propanol oxidation is propanal, and the isopropanol product stream consists of almost only acetone. The presence of these high molecular weight products is related to the high stability of inter-carbon bonds, which are very difficult to break on the surface of the electrode [135,161,195,197–199]. The oxidation of both propanol isomers is possible with the use of a PdAg catalyst. Even though both isopropanol and propanol undergo oxidation on their surface, a higher current density is observed for primary al- cohols [178]. This difference is probably linked to the conformation of these alcohols. The presence of silver in palladium-based catalysts results in weaker adsorption strength holding oxidation intermediates on the surface of the electrode, which results in higher immunity to CO intermediate poisoning in the final electrocatalytic material [178]. The oxidation of aliphatic alcohols results mainly in the corresponding aldehydes and CO2 [135]. The overall 1-propanol electrooxidation reaction can be expressed as follows [135]: CH3CH2CH2OH → CH3CH2CHO + 2 H+ + 2 e− (37) CH3CH2CH2OH+5H2O→3CO2 +18H+ +18e− (38) As visible in reaction (37), the usage of a feed stream that consists only of propanol results in propanal as a product and a small anodic current. For full propanol oxidation towards carbon dioxide (reaction (38)), the presence of water in the feed stream is necessary.PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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