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Electrocatalysts based on Pt-M bimetallic nanoparticles deposited on carbon supports have already been used in commercially available Proton Exchanged Membrane Fuel Cells (PEM FC). Nevertheless, production and practical use of such materials faces with the problems caused by the need to combine high specific activity in current-forming reactions and their durability, with the stability of the element's composition during the operation of PEM FC. The suggested stepwise approach to the PtCu/C materials synthesis in the liquid phase is based on the initial deposition of platinum nuclei and their subsequent growth due to the joint or sequential deposition of copper and platinum from the solutions of their precursors. The PtCu/C catalysts, obtained in this way, demonstrated not only higher activity in oxygen reduction reaction compared to the commercial Pt/C catalyst, but also a significantly higher corrosion-morphological stability.

Durability is one of the most important characteristics of electrocatalysts used in low-temperature fuel cells with a proton exchange membrane. The degradation degree of deposited electrocatalysts containing platinum and platinum-copper nanoparticles with Pt-loading of about 20% by weight was assessed by voltammetric stress-testing, which corresponded to different mechanisms of degradation. The differences in the Pt Cu nanoparticles architecture, caused by the peculiarities in their synthesis, affect the catalysts stability and their composition change due to the stress tests. It has been shown that at the close values of Pt-loading and electrochemically active surface area (ESA), the bimetallic catalysts on the Vulcan XC72 carbon carrier demonstrate significantly higher stability compared to commercial Pt/C catalysts. In this case, the “gradient” catalyst obtained by successive multi-stage copper and platinum deposition showed the highest residual activity in ORR, as well as resistance to stress testing and to the copper selective dissolution.

The architecture of bimetallic nanoparticles has strong influence on durability and activity of PtM/C electrocatalysts in the oxygen electroreduction (ORR) and the methanol electrooxidation reactions (MOR). In the present study the Pt0.8(Cu)/C electrocatalyst was obtained by the methods of successive multistage reduction of platinum and copper from the solutions of their precursors while platinum concentration in the matrix solution was increasing step by step. The composition, structural characteristics and electrochemical behavior of this material were compared with the Pt1.0Cu/C catalyst based on the nanoparticles of a solid solution, which was obtained by the combined single-step chemical reduction of precursors, as well as with a commercial Pt/C sample with the same Pt-loading (20% by weight). The catalyst based on the Pt–Cu gradient nanoparticles demonstrated the highest corrosion-morphological stability in the stress-test, as well as the highest activity in ORR and MOR in the HClO4 solutions. Both of the studied bimetallic catalysts lose a significant amount of copper during the standardizing cycling and the stress-test. In the stabilized composition of the “gradient catalyst” the residual copper content, however, is considerably higher than that of the catalyst with the solid solution nanoparticles. The positive features of the electrochemical behavior of Pt0.8(Cu)/C catalyst arise apparently due to the faster formation of a durable protective layer of platinum on the surface of nanoparticles in the process of functioning, compared to the analogue based on the nanoparticles of the solid solution. High stability and activity of Pt0.8(Cu)/C compared to the Pt/C analogue are associated with the larger size of the nanoparticles and the promoting influence of residual copper on the catalytical activity of platinum.

The sequential chemical reduction of metals (copper or silver) and platinum was used to prepare M@Pt/C electrocatalysts that contain a high content of platinum on the surface of bimetallic nanoparticles. The compositions, microstructures and electrochemical behaviors of these electrocatalysts were studied using X-ray diffraction, thermogravimetry, X-ray fluorescence analysis, TEM and cyclic voltammetry. Depending on the composition and mode of synthesis, the obtained electrocatalysts have electrochemically active surface areas ranging from 35 to 61 m2 g−1 (Pt). The presence of nanoparticles with a core-shell structure was directly confirmed for Cu0.9Pt0.1@Pt/C sample. Copper-containing electrocatalysts exhibited better stability during voltammetric cycling compared to a similar composition of commercial Pt/C electrocatalyst and Ag0.9Pt0.1@Pt/C systems, but one of Ag0.9Pt0.1@Pt/C electrocatalysts has shown the highest specific activity in ORR.