The presented study is concerned with a new multi-step method to synthesize PtCo/C materials based on composite Co_xO_y/C that combines the advantages of different liquid-phase synthesis methods. Based on the results of studying the materials at each stage of synthesis with the TG, XRD, TEM, SEI, TXRF, CV and LSV methods, a detailed overview of the sequential changes in catalyst composition and structure at each stage of the synthesis is presented. The PtCo/C catalyst synthesized with the multi-step method is characterized by a uniform distribution of bimetallic nanoparticles of about 3 nm in size over the surface of the support, which result in its high ESA and ORR activity. The activity study for the synthesized PtCo/C catalyst in an MEA showed better current–voltage characteristics and a higher maximum specific power compared with an MEA based on a commercial Pt/C catalyst. Therefore, the results of the presented study demonstrate high prospects for the developed approach to the multi-step synthesis of PtM/C catalysts, which may enhance the characteristics of proton-exchange membrane fuel cells (PEMFCs).

The growing demand for hydrogen–air fuel cells with a proton-exchange membrane has increased interest in the development of scalable technologies for the synthesis of Pt/C catalysts that will allow us to fine-tune the microstructure of such materials. We have developed a new in situ technique for controlling the kinetics of the transformation of a platinum precursor into its nanoparticles and deposited Pt/C catalysts, which might be applicable during the liquid-phase synthesis in concentrated solutions and carbon suspensions. The technique is based on the analysis of changes in the redox potential and the reaction medium coloring during the synthesis. The application of the developed technique under conditions of scaled production has made it possible to obtain Pt/C catalysts with 20% and 40% platinum loading, containing ultra-small metal nanoparticles with a narrow size distribution. The electrochemically active surface area of platinum and the mass activity of synthesized catalysts in the oxygen electroreduction reaction have proved to be significantly higher than those of commonly used commercial analogs. At the same time, despite the small size of nanoparticles, the catalysts’ degradation rate turned out to be the same as that of commercial analogs.

The composition, structure, catalytic activity in the ORR and stability of PtCo/C materials, obtained in two stages and compared with commercial Pt/C analogs, were studied. At the first stage of the synthesis performed by electrodeposition of cobalt on a carbon support, a CoO_x/C composite containing 8% and 25 wt% cobalt oxide was successfully obtained. In the second step, PtCoO_x/C catalysts of Pt1.56Co and Pt1.12Co composition containing 14 and 30 wt% Pt, respectively, were synthesized based on the previously obtained composites. According to the results of the composition and structure analysis of the obtained PtCoO_x/C catalysts by X-ray diffraction (XRD), X-ray fluorescence analysis (XRF), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods, the formation of small bimetallic nanoparticles on the carbon support surface has been proved. The resulting catalysts demonstrated up to two times higher specific catalytic activity in the ORR and high stability compared to commercial Pt/C analogs.

To obtain the PtRu/C electrocatalysts, the surfactant-free (wet) synthesis methods have been used. The structural-morphological characteristics and electrochemical behavior of the catalysts have been studied. The possibility of ranging the crystallite size from 1.2 to 4.5 nm using different reducing agents (ethylene glycol, ethanol, and isopropanol) has been shown. The effect of both the particles’ size and the mass fraction of the metal component on the electrochemical surface area (ESA), activity in the methanol electrooxidation reaction (MOR), and tolerance to its intermediate products has been studied. The simple and scalable surfactant-free synthesis method of the highly active PtRu/C electrocatalysts with a different mass fraction of metals, with their tolerance to intermediate products of the oxidation being 2.3 times higher than the commercial analogue, has been first proposed. The authors have succeeded in obtaining the PtRu/C catalysts with the nanoparticles’ size of less than 2 nm, characterized by the ultranarrow size and uniform spatial distributions over the support surface, thus having the ESA of more than 90 m²g_PtRu⁻¹.