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Molecules 2021, 26, 2144 20 of 37 ones [51,177,178]. Because of very promising results, most of the researchers have focused on developing catalytic nanoparticles. Thanks to their high surface-to-volume ratio, small catalytic particles show high reactivity related to increased mass and electron transport, which are usually the rate-limiting steps during alcohol electrooxidation [170]. Another advantage of this type of anodic material is its higher durability than that of a classic Pt/C electrode. The influence of support material on such properties cannot be omitted; Pt/r-GO/Nb4N5 is a material with high electrical conductivity and a large electroactive area because of the presence of carbon nanocompounds and niobium nitride. This material remains stable after cycling for 6000 s because of the protection of the r-GO layer [100]. One of the disadvantages of nanoscale catalytic materials is the fact that the perfor- mance of anodes based on nanoparticles can be easily influenced by changing the catalyst loading. The reaction potential remains constant because this change does not influence the reaction mechanism but rather accelerates the reaction by providing more active centers. As a consequence, greater catalyst loading often leads to an increase in the peak current, but in some cases, a greater loading of nanoparticles decreases the peak current because of the agglomeration of deposited nanoparticles, thus lowering the electroactive surface and consequently decreasing the reaction efficiency [88]. Similar to previous substances, ethylene glycol electrooxidation is sensitive to the geometric structure of the anodic material. The highest activity for EGOR is observed for platinum materials with a (111) plane structure, which is characterized by a low number of structural defects, which lowers the affinity of COads to the electrode surface and eases their desorption. This enables high activity towards the oxidation of adsorbed carbon-based in- termediates, thus improving the electrode immunity from catalyst poisoning [144,161,170]. The geometric structure is not the only property of the catalytic material that can strongly influence the EGOR. Other electrode material characteristics, such as the number of active reaction centers on the electrode surface and the electronic structure, which changes the rate of charge transfer, strongly influence the reaction rate. As mentioned, the carbon intermediates produced during EG oxidation can reduce the number of active centers available for EG particles by adsorption on the anode and thus decrease the reaction kinetics and efficiency [91,154,161,163]. Fortunately, the carbon intermediates can be desorbed from the electrode surface through their further oxidation to carbon dioxide during the second step of the EGOR. This reaction requires the presence of adsorbed hydroxide ions on the surface of the electrode. Oxophilic elements, such as Ru [85,162], Ir [108], Sn [15,91], Pd [88], Co [37] and Ni [108], enable water dissociation at potentials lower than that of pure platinum (0.35 V for Ru and 0.6 V for Pt); thus, this kind of catalytic material shows a bifunctional mechanism: alcohol is adsorbed on the platinum surfaces, and water is split on the surface of the ruthenium, which is presented below [85,108,161,162,179]: + 4 H2O + Pt + (CH2OH)2 → Pt(CH2OH)2 (ads) → 2 Pt(: CHO) → 2 Pt(HCOOH) (ads) + 4 H + 4 e Pt(HCOOH) (ads) → Pt(CO)2 (ads) − H2O Pt+H2O→Pt(OH)ads +H+ +e− Ru+H2O→Ru(OH)ads +H+ +e− Pt(OH)ads + Pt(CO)ads → Pt + CO2 + H+ + e− Ru(OH)ads + Pt(CO)ads → Pt + Ru + CO2↑ + H+ + e− − (30) (31) (32) (33) (34) Although pure ruthenium shows no catalytic properties towards ethylene glycol oxidation at room temperature [162], it is still one of the most popular doping elements for Pt electrodes [108,162,163]. EGOR on the surface of a PtRu catalyst is controlled by the kinetics of adsorption of the fuel molecules on the anode and the desorption of the (29)PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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