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Molecules 2021, 26, 2144 27 of 37 The efficiency of isopropanol oxidation on platinum- and platinum-based catalysts in alkaline media is very low, mainly because of its lack of stability under reaction condi- tions, high sensitivity to poisoning and lack of ability to break the inter-carbon bonds in isopropanol molecules, which is why, for 2–propanol oxidation, mainly palladium-based catalysts are used [130,161,194,198,203]. Monometallic electrodes show worse results in terms of electrocatalytic effects towards alcohol oxidation and isopropanol oxidation on palladium, which is not an exception to this rule. Even though palladium shows good catalytic properties, such as low onset potential and high current density, acetone, which is the main product of this reaction, can strongly adsorb on the surface of the electrode and thus prevent the adsorption of fresh portions of isopropanol from the bulk solution, which leads to a decrease in the system efficiency [135,194,198,202,203]. Just like in the cases of other catalytic materials, the palladium activity can be improved by doping with other elements that show catalytic properties towards isopropanol oxidation and strong immunity to poisoning, like, for example, nickel [198] or iron [59]. The mechanism of isopropanol oxidation of PdNi catalyst is presented below, in Figure 8. Figure 8. Reaction mechanism for isopropanol oxidation on Pd/Ni electrode reprinted with permis- sion of Elsevier [198]. The addition of iron into palladium-based catalysts also enhances their catalytic and anti-poisoning properties for regimes focused on obtaining CO2 as the main product. Fe can enhance the desorption of carbon oxide-based intermediates from the electrode’s surface, thanks to the electronic (ligand) effect, and therefore, provide higher stability and longer activity to the catalyst [59]. Some researchers have shown different approaches, and instead of palladium-based electrodes, they have developed Pt-based electrodes with other metal additives that signifi- cantly change the poisoning sensitivity and ability to break inter-carbon bonds. Doping with metals, such as lead [161], palladium [130], nickel [198], ruthenium [161,197,199] or gold [161,194,196,201,202] leads to occurrence of bifunctional mechanism. The addition of electron donor molecules, such as Ni2P, to platinum catalysts, provides stability for the resulting material thanks to the occurrence of the electronic (ligand) effect. Ni2P provides electrons that stabilize the platinum atoms and lower the adsorption energy for isopropanol. This results in a final material with higher activity and stability (than the pure Pt/C catalyst). Nickel phosphide also shows the ability to prevent the agglomeration of platinum particles, leading to better utilization of the noble metal used and a higher active area in the final electrode material [193]. Additionally, other non-noble metal-based materials have been investigated, such as rhodium, which shows catalytic properties towards isopropanol electrooxidation on its own, especially when the obtained material is on the nanoscale, like rhodium nanoroses presented in Figure 9, and can be characterized by a high ECSA [204], or titanium dioxide, which shows photocatalytic properties [205]. After doping TiO2 with transition metals,PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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