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In this work, graphitized ordered mesoporous carbons (gCMK-3) were employed as support for Pt and Pt–Ru nanoparticles synthesized by different reduction methods. The catalysts displayed metal contents and Pt:Ru atomic ratios close to 20 wt % and 1:1, respectively. A comparison of the physical parameters of Pt and Pt–Ru catalysts demonstrated that Ru enters into the Pt crystal structure, with well-dispersed nanoparticles on the carbon support. The Pt catalysts exhibited similar surface oxide composition, whereas a variable content of surface Pt and Ru oxides was found for the Pt–Ru catalysts. As expected, the Pt–Ru catalysts showed low CO oxidation onset and peak potentials, which were attributed to the high relative abundances of both metallic Pt and Ru oxides. All the studied catalysts exhibited higher maximum current densities than those observed for the commercial Pt and Pt–Ru catalysts, although the current–time curves at 0.6 V vs. reversible hydrogen electrode (RHE) demonstrated a slightly higher stationary current density in the case of the Pt/C commercial catalyst compared with Pt nanoparticles supported on gCMK-3s. However, the stationary currents obtained from the Pt–Ru/gCMK-3 catalysts surpassed those of the commercial Pt–Ru material, suggesting the suitability of the prepared catalysts as anodes for these devices.

The graphitisation of ordered mesoporous carbons (CMK-3) was carried out by thermal treatments under different conditions of temperature and heating rate. The electrochemical characterization in acidic medium of the graphitised CMK-3 showed that such a thermal treatment is effective to decrease the carbon oxidation rate (corrosion) while preserving a good porosity in terms of capacitance. Besides, the graphitisation degree and, in consequence the electrochemical corrosion resistance, can be modulated by an appropriate choice of thermal treatment conditions, where the heating rate and temperature appear as critical parameters. Under certain graphitisation conditions, the carbon corrosion of CMK-3 can be minimized showing lower rates compared to a commercial carbon black (Vulcan XC-72R). Palladium nanoparticles were supported on the most promising graphitised CMK-3 and Vulcan using a method based on impregnation and reduction with borohydride, resulting in suitable metal crystallite sizes. The electrocatalytic activity towards the oxidation of carbon monoxide and formic acid were assessed in aqueous sulphuric acid electrolyte for application at the anode of direct formic acid fuel cells (DFAFCs). The best activity results were obtained for the Pd catalyst supported on a graphitised CMK-3.

Pt-Ru nanoparticles supported on carbon nanofibers (CNF) were synthesized by the sodium borohydride reduction method, using different generation dendrimers (zero, one, two and three generations). After the synthesis process, these materials were submitted to a heat treatment at 350 °C, in order to clean the nanoparticle surface of organic residues. TEM characterization showed that the Pt-Ru nanoparticles size ranged between 1.9 and 5.5 nm. The use of dendrimers did not totally avoid the formation of aggregates, although monodisperse sizes were observed. The heat treatment produces the desired surface cleaning, although promoted the formation of agglomerates and crystalline Ru oxides. The study of the electrochemical activity towards the methanol oxidation displayed some clues about the influence of both the dendrimer generation and the presence of Ru oxides. Moreover, the apparent activation energy Eap for this reaction was determined. The results showed a beneficial effect of the heat treatment on the methanol oxidation current densities for the materials synthesized with the biggest dendrimers, being the methanol deprotonation and COad diffusion the predominant rate determining steps (rds).