Anna Katharina Müller, Stefan Loos, Christian Immanuel Bernäcker, Aaron B. Naden, Felix Heubner, Thomas Weißgärber
High Resolution Image Download MS PowerPoint Slide The development of efficient and cost-effective electrocatalysts for alkaline water electrolysis is crucial for advancing hydrogen production technologies. Herein, we report the synthesis and characterization of a highly active, platinum-group-metal-free electrocatalyst for the hydrogen evolution reaction in alkaline media. The catalyst is obtained via the exsolution of Ni–Mo alloy nanoparticles anchored on MoO 2 during the reduction of a NiMoO 4 precursor grown on porous nickel substrates. It demonstrates high catalytic activity, achieving benchmark performance with an overpotential of −89 mV and a cell voltage of 1.71 V at a current density of 1 A/cm 2 . Electrochemical testing, including operation at high current densities under industrially relevant conditions (80 °C, 30 wt % KOH, flowing electrolyte), validates its suitability for large-scale applications. Importantly, structural analysis reveals the presence of Ni-rich Ni 10 Mo particles on MoO 2 rather than the often-proposed Ni 4 Mo alloy, providing insight into the actual active phase of Ni–Mo catalysts. This distinction advances the fundamental understanding of Ni–Mo chemistry and offers guidance for the rational design of high-performance, platinum-group-metal-free catalysts for hydrogen evolution.