In the last decade, transition metal carbides, particularly based of molybdenum and tungsten, have emerged as novel materials with promising catalytic properties toward several important practical electrochemical reactions. In this presentation, the activity of such materials will be discussed for the following electrochemical approaches/reactions: i) the electrocatalysis of oxygen reduction reaction (ORR) in acid media on Pt- and Pt₂Ni-nanoparticles supported on carbon forming composites with tungsten and molybdenum carbides with cubic (α) and hexagonal (β) structures; ii) the hydrogen evolution reaction (HER) in acid and alkaline media on TM-modified molybdenum carbide (TM-Mo₂C) catalysts, where TM is a transition metal, such as, Fe, Co, Ni and Cu; iii) the CO₂ and CO electro-reduction reactions in 0.1 M NaClO₄ and 0.5 and 1 M KHCO₃ solutions on carbon supported tungsten and molybdenum carbides. Syntheses of the carbide-based catalysts have been conducted employing different procedures, after which the produced material are characterized by X-Ray diffraction (XRD), energy dispersive X-ray spectroscopy, (EDS), X-ray photoelectron spectroscopy (XPS), in situ X-ray absorption near edge structure (XANES), and transmission electron microscopy (TEM). Cyclic voltammetry and polarization measurements on stationary and rotation disk electrodes have been employed for the electrochemical investigations. For the CO/CO₂ reduction, reaction products were analyzed by differential electrochemical mass spectrometry (DEMS) and high performance liquid chromatography (HPLC) analyses.

Enhanced mass and specific ORR activities are seen for Pt–molybdenum carbide-derived composites compared to Pt-α-WC/C, which in turn presents specific activity for the ORR similar to that of a standard carbon supported Pt catalyst (Pt/C). For Pt-β-WC_1-x/C composites, the specific activity is also higher than that of Pt/C when a carbide-to carbon load of 40 wt.% is used. In the case of the HER, high activities are observed for all TM-Mo₂C catalysts in acid and alkaline media. Nonetheless, while in acid there is a decrease in the activity upon metal doping, with an activity trend of α-Mo₂C > Fe-Mo₂C > Co-Mo₂C > Ni‑Mo₂C > Cu-Mo₂C, the opposite tendency is found in alkaline solutions. In situ near-edge X-ray adsorption analysis reveals different oxidation states of the TM inside the carbide in both solutions. In acid, a positive charge of the TM in the materials in the electrochemical environment is possibly at the origin of the deleterious effect of Fe, Co, Ni and Cu. In addition, catalysts stability against dissolution in acid media is increased by doping of molybdenum carbide with TM. Regarding of CO and CO₂ electro-reductions in 0.1 M NaClO₄ and 0.5 and 1 M KHCO₃ solutions, results suggest that neither molybdenum nor tungsten carbides can be considered as active catalysts, in contrast to reported results in gas phase. It appears that both the aqueous environment and their activity toward the HER surpass the reactivity toward these latter reactions.

Acknowledgements: Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP - Procs. 2013/16930-7 and 2014/23486-9) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) (Procs. 1423454), Brazil, for financial supports.