Ceramic electrodes are cost-effective and stable at high current densities. Thus, they are highly considered for industrial hydrogen production. In this study, a novel self-supported MoO2/MoSi2 ceramic electrode, with open finger-like holes and excellent electrochemical performance, was successfully prepared by phase-inversion, the shaping method of tape-casting, and hydrothermal treatment. The obtained MoO2/MoSi2 electrode has a lower overpotential than the Pt/C electrode at current densities greater than 330 and 410 mA cm–2 in an alkaline and acidic environment, respectively. Furthermore, the electrode exhibits excellent stability at 10–1000 mA cm–2 for 260 h in both alkaline and acidic solutions. Density functional theory calculations showed that the MoO2/MoSi2 heterostructure displays the lowest H adsorption free energy and the highest density of states around the Fermi level.
