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Molecules 2021, 26, 2144 7 of 37 All are presented in Figure 3. Regardless of the reaction path, the conversion rate towards carbon dioxide ranges from 90 to 100% [95]. Figure 3. Proposed mechanism of methanol oxidation via direct and indirect way. Reprinted with permission of American Chemical Society [94]. Methanol oxidation can take place in both acidic and alkaline environments, but the mechanism of the reaction varies depending on the pH of the feed media. Since the anodic material should be immune to corrosion, during the process and without polarization, with a change in the supporting electrolyte, different anodic materials must be used. Below, different electrocatalytic materials are described with partitioning based on the pH of the supporting electrolyte. In acidic solution, most of the catalytic materials are platinum-based. Because of platinum nobility, they remain stable in reaction conditions, but high-affinity of carbon monoxide derivatives to the platinum surface can lead to catalyst poisoning by permanent adhesion of oxidation products with electrode [19,21,96–99]. To prevent such a situation, different modifications of platinum electrodes have been proposed. Usually, good results are observed for bimetallic systems, where the addition of second metal leads to syner- gic [100–102], electronic (ligand) [59,78,103,104] or geometric effect [19,21] that changes the strength of adsorption of reaction products to platinum sites and thus prevent the catalyst poisoning or thanks to bifunctional mechanism increase the amount of adsorbed hydroxide ions, which enhances the further oxidation of COads and thus prevent cat- alyst poisoning [21,99]. Added metals that will be mentioned later in the text usually have a higher affinity to oxygen than platinum and thus enhance the MOR and prevent catalyst poisoning. The bifunctional mechanism of methanol oxidation on Pt-based catalysts can be explained by the example of a PtRu catalyst in acidic solution [7,34,62,78,94,105]: Pt+CH3OH→Pt(CO)ads +4H+ +4e− (1) Ru+H2O→Ru(OH)ads +H+ +e− (2) Pt(CO)ads + Ru(OH)ads →Pt + Ru + CO2 + H+ + e− (3) CH3OH+8OH− →CO32− +6H2O+6e− (4) In alkaline media, platinum also can play the role of anodic material, but because high pH is much less corrosive towards other metallic material, a non-noble catalyst, such as nickel, can be used [14,41,42,106,107]. Elimination of platinum not only reduces the cost of the catalytic material but also prevents catalyst poisoning with COads since used metals have a lower affinity to carbon monoxide derivatives than Pt [41,42,106,107].PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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