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Platinum–carbon catalysts are widely used in the manufacturing of proton-exchange membrane fuel cells. Increasing Pt/C activity and stability is an urgent task and the optimization of their structure seems to be one of the possible solutions. In the present paper, Pt/C electrocatalysts containing small (2–2.6 nm) nanoparticles (NPs) of a similar size, uniformly distributed over the surface of a carbon support, were obtained by the original method of liquid-phase synthesis. A comparative study of the structural characteristics, catalytic activity in the oxygen electroreduction reaction (ORR), and durability of the synthesized catalysts, as well as their commercial analogs, was carried out. It was shown that the uniformity of the structural and morphological characteristics of Pt/C catalysts makes it possible to reduce the negative effect of the small size of NPs on their stability. As a result, the obtained catalysts were significantly superior to their commercial analogs regarding ORR activity, but not inferior to them in terms of stability.

An important feature of this research is the investigation of the de-alloyed catalysts based on the nanoparticles with a simple structure (alloy) and a complex structure (gradient). The resulting samples exhibit the 2–4 times higher mass activity in the ORR compared with the commercial Pt/C. The novelty of this study is due to the application of the express-electrochemical experiment to register the trend of changes in the ORR activity caused by rearranging the structure of bimetallic nanoparticles. The state-of-the-art protocol makes it possible to establish the dependence of properties of the de-alloyed catalysts on the nanoparticles’ structure obtained at the stage of the material’s synthesis. The study shows the possibility of determining the rate of the ongoing reorganization of bimetallic nanoparticles with different architectures. The PtCu/C electrocatalysts for proton-exchange membrane fuel cells presented in this work are commercially promising in terms of both the high functional characteristics and the production by facile one-pot methods.

Electrochemical intercalation of lithium into intermetallic compounds (IMC) MgCd and MgCd3 out of propylene carbonate solutions of LiBF4 is studied. According to chronopotentiometry data, during the intercalation, lithium forms compounds with cadmium: Li3Cd on MgCd or LiCd and Li3Cd on MgCd3. Reactions of solid-phase substitution, which occur on the electrodes, are accompanied by the destruction of initial IMC and generation of magnesium atoms. Chronoamperometry of MgCd–(Li) and MgCd3–(Li) shows the lithium intercalation to be limited by nonstationary diffusion of lithium in the solid phase. The lithium diffusion in MgCd is slower and that in MgCd3 is faster than in Cd. The calculated potential dependences of the diffusion coefficient for lithium in MgCd and MgCd3 are linear in semilogarithmic coordinates. [ABSTRACT FROM AUTHOR]

Phase conversions and kinetics of electrochemical intercalation of lithium from dimethylformamide solutions of LiCl into bulk electrodes of bismuth, indium and their intermetallic compounds InBi and In2Bi are studied using chronopotentiometry and chronoamperometry methods. The intercalation is controlled by non-steady-state lithium diffusion in the solid electrode. In the lithium–intermetallic compound systems, both components of alloys take part in the formation of compounds with lithium. Considerable volume changes, which occur during the intercalation, may lead to disintegration of lithium-containing phase constituents with a high lithium content. The “extremum” shape of cathodic chronoamperograms may be due successive and/or parallel reactions in which various lithium-containing compounds form. Some of these reactions are limited by solid-phase diffusion, while others involve the formation and diffusion-controlled growth of three-dimensional nuclei of a new phase. [ABSTRACT FROM AUTHOR]