Efficient high-entropy alloy electrocatalyst by rapid microwave synthesis for glycerol-assisted hydrogen evolution

Electrochemical glycerol oxidation reaction (GOR) is an attractive alternative reaction to oxygen evolution reaction (OER) of water electrolysis due to the lower oxidation potential and value-added oxidation products. Developing high-efficient bifunctional electrocatalysts toward anodic GOR and cathodic hydrogen evolution reaction (HER) still faces a grand challenge. Herein, we have constructed high-entropy alloy (HEA) nanoparticles supported on hierarchical N-doped carbon nanocages (hNCNC) by a facile and rapid microwave synthesis. The optimal catalyst exhibits excellent performance in the glycerol-assisted water electrolysis, with an ultralow cell voltage of 0.373 V at 10 mA·cm⁻² and a long-term stability over 50 h with nearly 100% Faradaic efficiency for H₂. The superior performance is ascribed to the increased capability of C–C cleavage and anti-poisoning for GOR and the multiple active sites for HER due to the high-entropy effect, as well as high dispersion and enhanced stability of HEA nanoparticles on hNCNC. This study not only demonstrates an effective approach for constructing advanced bifunctional electrocatalysts for GOR and HER, but also provides new ideas for energy-efficient hydrogen generation by glycerol-assisted water electrolysis