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Molecules 2021, 26, 2144 3 of 37 cancy and number of neighboring metal atoms, are responsible for the chemical and electrochemical reactivity of electrodes [10]. One of the methods to enhance the overall electrode reactivity is doping. The addition of other metallic elements and the creation of bi- or trimetallic systems changes the crucial electrode properties, such as conductivity or surface activity [11–14]. Especially the electrocatalytic activity of noble metals can be enhanced by a synergistic effect between noble and transition metals thanks to the elec- tronic (ligand) effect [15]., which happens in multimetallic systems because of different electronegativity of their components [16]. Such difference results in charge transfer from less electronegative transition metals to unoccupied valence orbitals of more electronega- tive noble metals, which changes the properties, such as adsorption strength, of the final material [16]. Easier desorption leads to higher catalytic activity because more active centers are accessible for the reaction. Additionally, alloys consisting of these metals show and show different intermetallic surfaces than pure, noble metals [16–21]. The properties of alloys can be designed by coupling their ingredients in the right proportions, which provides wide opportunities for tailoring alloy functions and enhancing their application performance [10–12]. Moreover, some metals can be present on the electrode surface in the form of oxides, preventing the poisoning by carbon monoxide that can occur during the oxidation of organic compounds [10]. Doping is not the only way to improve the performance of catalytic materials. Other properties that can be easily influenced and strongly change by the electrooxidation process include the properties of the electrode–electrolyte interface and the active surface of the cat- alytic material. The electrode surface area (ESA) can be influenced by changing the size of the catalytic particles. One of the most popular methods for increasing the ESA is the usage of catalytic material in the form of nanoparticles because of their high surface-to-volume ra- tio, which results in higher activity and immunity to poisoning in the final material [22–24]. There are almost endless possibilities regarding the shapes of nanomaterials, but the most popular ones are one-dimensional nanomaterials (nanowires) [25,26], nanocubes [24,27], nanocrystals [23,28–31], spheres [23,32] and hexagons. Core–shell materials, like core–shell nanorods presented in Figure 2, are a special part of nanomaterials because their specific structure strongly changes the reactivity of the final material. Figure 2. Compositional mapping images of PdAg@Pd core–shell structures, reprinted with permis- sion of Elsevier [26]. They consist of a core material that does not have direct contact with the batch solution and shell material that is responsible for the reactivity of such molecules. Because catalysis is a surface process, the presence of catalytically active material is crucial only on the surface of the material [26,28]. Core–shell materials take advantage of this property—cheaper metal is usually used as a core material, so the cost of the whole system can be lowered by reducing the usage of the expensive, active metal [26,28,32,33]. Additionally, nanocages, because of their porous walls and characteristic hollow structure, allow maximum efficiency in surface atom utilization, and the control of the surface structures can optimize the active catalyst centers [24].PDF Image | Effect of Anode Material on Electrochemical Oxidation of Alcohols
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