Abstract

Preparing cost-effective and highly active catalysts for electrocatalytic hydrogen evolution reaction is crucial for developing hydrogen-based technologies. Hence, four conductive polyanilines, prepared by the environmentally-friendly approach using Fe3O4 nanoparticles/H2O2 as the catalyst/main oxidant system (PANI/Fe3O4), were investi¬gated for the first time as electrocatalysts for hydrogen evolution reaction (HER) in acidic media (0.1 M H2SO4) by using voltammetry and chronoamperometry. PANI/Fe3O4 electrodes exhibited Tafel slope values in the -171 to -246 mV dec-1 range depending on the synthesis conditions ‒ Fe3O4/aniline mass ratio and polymerization time. The sample PANI/Fe3O4-II(3) prepared with shorter reaction time and higher Fe3O4/aniline mass ratio showed the best electrocatalytic behaviour reflected in the lowest onset potential (-0.286 V), the lowest overpotential to reach a current density of -10 mA cm-2, the highest current density, the lowest HER activation energy (10 kJ mol-1), and the lowest charge-transfer resistance (5.3 Ω) under HER conditions. Materials were characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray photo¬electron spectroscopy and electrochemical impedance spectroscopy, and differences in their electrocatalytic HER performance were explained by differences in their content of Fe3O4, surface and electrical properties. Moreover, the possibility of using PANI/Fe3O4-II(3) as HER electrocatalyst in a wider range of pH (i.e. in alkaline media as well) and as a bifunc¬tional electrocatalyst, i.e., for oxygen evolution reaction beside HER, was also examined.

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