Exploring low-cost and high-performance electrocatalysts for multifunctional activities is highly desirable but challenging. It is a convenient way to couple late transition metals (Fe, Co, Ni) with carbon nanomaterials, as their proximity not only improves the catalytic performance through their synergistic effect but also provides a cost-effective preparation process compared with precious metals (e.g., Pt, Ru, and Ir). Herein, FeCoNi alloy nanoparticles embedded in a nitrogen-doped carbon shell (NC) were synthesized via a simple one-step chemical reaction of three metal salts (Fe, Co, and Ni) and two organic linkers (2-methylimidazole and 2,6-naphthalene dicarboxylic acid dipotassium) followed by pyrolysis. The as-synthesized catalyst with an optimized composition (Fe_1.0Co_1.1Ni_1.4–NC) required overpotentials of 270 mV and 175 mV for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively, to deliver a current density of 10 mA cm⁻² in 1.0 M KOH electrolyte. Moreover, the catalyst demonstrated ethanol oxidation reaction (EOR) activity by achieving a 9% less positive onset potential than for the OER in 1.0 M KOH + 1.0 M C₂H₅OH electrolyte. The high catalytic activity of Fe_1.0Co_1.1Ni_1.4–NC was intrinsically associated with the presence of Fe⁺³ species as revealed by X-ray photoelectron spectroscopy. When the catalyst Fe_1.0Co_1.1Ni_1.4–NC comprised both the anode and cathode in a prototype electrolytic cell for overall water splitting, it required 1.52 V vs. RHE to reach a 10 mA cm⁻² current density in 1.0 M KOH, outperforming the benchmark IrO₂ (or RuO₂)‖Pt/C coupled cells.

By means of in situIR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li⁺ < Na⁺ < K⁺) is reflected in the increase in the ratio between carbonate and oxalate produced.

As in the case of most small organic molecules, the electro-oxidation of methanol to CO₂ is believed to proceed through a so-called dual pathway mechanism. The direct pathway proceeds via reactive intermediates such as formaldehyde or formic acid, whereas the indirect pathway occurs in parallel, and proceeds via the formation of adsorbed carbon monoxide (CO_ad). Despite the extensive literature on the electro-oxidation of methanol, no study to date distinguished the production of CO₂ from direct and indirect pathways. Working under, far-from-equilibrium, oscillatory conditions, we were able to decouple, for the first time, the direct and indirect pathways that lead to CO₂ during the oscillatory electro-oxidation of methanol on platinum. The CO₂ production was followed by differential electrochemical mass spectrometry and the individual contributions of parallel pathways were identified by a combination of experiments and numerical simulations. We believe that our report opens some perspectives, particularly as a methodology to be used to identify the role played by surface modifiers in the relative weight of both pathways—a key issue to the effective development of catalysts for low temperature fuel cells.