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Abstract: This report describes a new family of bimetal carbon nitride (CN) electrocatalysts for the oxygen reduction reaction (ORR) for application in polymer electrolyte membrane fuel cells (PEMFCs). The materials, which bear active sites based on Pt and Rh, are prepared with a three-step protocol consisting of: (1) the synthesis of a homogeneous zeolitic inorganic–organic polymer electrolyte (Z-IOPE) precursor; (2) the pyrolysis of the precursor at a temperature T f =400, 500, 600, 700 or 900°C; (3) the activation, yielding the final product. It is found that T f has a major effect on the structure and the electrochemical properties of these electrocatalysts, as determined from a wide array of independent characterization techniques including: high-resolution thermogravimetry (HR-TGA); Fourier-transform medium infrared (FT-MIR), Fourier-transform far infrared (FT-FIR) and confocal micro-Raman spectroscopies; powder X-ray diffraction (powder XRD); X-ray photoelectron spectroscopy (XPS); and electrochemical investigations carried out with the cyclic voltammetry thin-film rotating disk electrode (CV-TF-RDE) method. All the information is integrated to propose a comprehensive model correlating the effect of T f on the structure of the materials with the corresponding electrochemical performance. The best results in the ORR are obtained with materials prepared at 600≤ T f ≤700°C. These systems present the optimal compromise between the size of the metal-rich nanoparticles, the degree of graphitization of the carbon nitride support and the concentration of ligands blocking the active sites. The best Pt-Rh electrocatalysts exhibit an ORR activity very similar to the Pt/C reference. In addition, the peculiar structure of the proposed materials, which are characterized by active sites supported on the carbon nitride bulky materials, results in a better tolerance toward typical contaminants in the ORR process such as chloride anions with respect to the Pt/C reference. [Copyright &y& Elsevier]

Abstract: In this paper is described the preparation of new platinum-free Pd-Co carbon-nitride electrocatalysts (Pd-Co-CNs) for application in low-temperature fuel cells. Two groups of materials with formula K n [Pd x Co y C z N l H m ] were synthesized, which are grouped in two ensembles: the first is characterized by a molar ratio y/x >1 (I), and the second by y/x <1 (II). K n [Pd x Co y C z N l H m ] materials were prepared through a two-step synthesis protocol. The effect of the Pd/Co molar ratio and of the temperature of the thermal treatments on the structure and properties of the products were studied extensively by thermogravimetry, scanning electron microscopy, and vibrational (FT-IR and micro-Raman) and XPS spectroscopy. Vibrational studies revealed that I and II systems consist of two polymorphs of α- and graphitic-like carbon-nitride nanomaterials. The electrochemical activity towards the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) was measured by cyclic voltammetry measurements with thin-film rotating disk electrode (CV-TF-RDE). The electrochemical performance of Pd-Co-CNs of group I obtained at t f ≥700°C resulted higher than that measured for a platinum-based commercial electrocatalyst in terms of both the activity towards the ORR and the HOR and of the resistance towards the poisoning effect of methanol towards the ORR. [Copyright &y& Elsevier]