Carbon-Supported Mo₂C for Oxygen Reduction Reaction Electrocatalysis

Molybdenum carbide (Mo₂C)-based electrocatalysts were prepared using two different carbon supports, commercial carbon nanotubes (CNTs) and synthesised carbon xerogel (CXG), to be studied from the point of view of both capacitive and electrocatalytic properties. Cation type (K⁺ or Na⁺) in the alkaline electrolyte solution did not affect the rate of formation of the electrical double layer at a low scan rate of 10 mV s^-1. Conversely, the different mobility of these cations through the electrolyte was found to be crucial for the rate of double-layer formation at higher scan rates. Molybdenum carbide supported on carbon xerogel (Mo₂C/CXG) showed ca. 3 times higher double-layer capacity amounting to 75 mF cm^-2 compared to molybdenum carbide supported on carbon nanotubes (Mo₂C/CNT) with a value of 23 mF cm^-2 due to having more than double the surface area size. The electrocatalytic properties of carbon-supported molybdenum carbides for the oxygen reduction reaction in alkaline media were evaluated using linear scan voltammetry with a rotating disk electrode. The studied materials demonstrated good electrocatalytic performance with Mo₂C/CXG delivering higher current densities at more positive onset and half-wave potential. The number of electrons exchanged during oxygen reduction reaction (ORR) was calculated to be 3, suggesting a combination of four- and two-electron mechanism.