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The behavior of supported alloyed and de-alloyed platinum-copper catalysts, which contained 14–27% wt. of Pt, was studied in the reactions of methanol electrooxidation (MOR) and oxygen electroreduction (ORR) in 0.1 M HClO4 solutions. Alloyed PtCux/C catalysts were prepared by a multistage sequential deposition of copper and platinum onto a Vulcan XC72 dispersed carbon support. De-alloyed PtCux−y/C catalysts were prepared by PtCux/C materials pretreatment in acid solutions. The effects of the catalysts initial composition and the acid treatment condition on their composition, structure, and catalytic activity in MOR and ORR were studied. Functional characteristics of platinum-copper catalysts were compared with those of commercial Pt/C catalysts when tested, both in an electrochemical cell and in H2/Air membrane-electrode assembly (MEA). It was shown that the acid pretreatment of platinum-copper catalysts practically does not have negative effect on their catalytic activity, but it reduces the amount of copper passing into the solution during the subsequent electrochemical study. The activity of platinum-copper catalysts in the MOR and the current-voltage characteristics of the H2/Air proton-exchange membrane fuel cell MEAs measured in the process of their life tests were much higher than those of the Pt/C catalysts.

Electrooxidation of methanol, ethanol, and formic acid was studied on three platinum-containing electrocatalysts: PtCu/C, Pt/(SnO2/C), and Pt/C, Pt content being about 20 wt%. In all reactions, the integral specific activity of the catalysts, estimated from the results of cyclic voltammetry, grows in the Pt/C < Pt/(SnO2/C) < PtCu/C row. The influence of the reagent nature subjected to electrooxidation is manifested both in the difference of the absolute rate values of the corresponding reactions, decreasing in the order CH3OH > HCOOH > C2H5OH, and in the different ratio of these rates on different catalysts and at different potentials. Pt/(SnO2/C) catalyst containing SnO2 nanoparticles is the most active among the studied catalysts in methanol and formic acid electrooxidation reactions under potentiostatic conditions at the E = 0.60 V. Moreover, in formic acid electrooxidation reaction it is significantly superior to even the PtRu/C commercial catalyst. The reasons for the positive influence of Cu atoms and SnO2 nanoparticles on the catalytic activity of platinum are presumably associated with different effects: Interaction of the d-orbitals of copper and platinum atoms in bimetallic nanoparticles and implementation of the bifunctional catalysis mechanism on the adjacent platinum and tin dioxide nanoparticles.

A carbon supported PtCux/C catalyst, which demonstrates high activity in the oxygen electroreduction and methanol electrooxidation reactions in acidic media, has been obtained using a method of chemical reduction of Pt (IV) and Cu (2+) in the liquid phase. It has been found that the potential range of the preliminary voltammetric activation of the PtCux/C catalyst has a significant effect on the de-alloyed material activity in the oxygen electroreduction reaction (ORR). High-resolution transmission electron microscopy (HRTEM) demonstrates that there are differences in the structures of the as-prepared material and the materials activated in different potential ranges. In this case, there is practically no difference in the composition of the PtCux-y/C materials obtained after activation in different conditions. The main reason for the established effect, apparently, is the reorganized features of the bimetallic nanoparticles’ surface structure, which depend on the value of the limiting anodic potential in the activation process. The effect of the activation conditions on the catalyst’s activity in the methanol electrooxidation reaction is less pronounced.

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