Energy‐Efficient Hydrogen Evolution via Glycerol‐Assisted Electrolysis Enabled by Bi ₂ Se ₃ @g‐C ₃ N ₄ Electrocatalyst

ABSTRACT Developing energy‐efficient strategies for hydrogen production is crucial to advance sustainable energy technologies. Herein, we report a bismuth selenide–graphitic carbon nitride hybrid (Bi 2 Se 3 @g‐C 3 N 4 ) electrocatalyst for glycerol‐assisted water electrolysis in alkaline medium. The synergistic integration of conductive Bi 2 Se 3 nanosheets with nitrogen‐rich graphitic carbon nitride facilitates efficient charge transfer, greater exposure of active sites, and superior catalytic performance. When tested in 1 M KOH with 0.2 M glycerol, the system achieves glycerol oxidation at a much lower anodic potential of 1.30 V to deliver 10 mA cm −2 , outperforming the conventional oxygen evolution reaction, which requires 1.80 V under identical conditions. On the cathodic side, the electrocatalyst requires only 157 mV overpotential to drive hydrogen evolution at the same current density. The Bi 2 Se 3 @g‐C 3 N 4 catalyst also demonstrates robust durability and favorable reaction kinetics, as evidenced by impedance and Tafel analysis. These results underscore the promise of Bi 2 Se 3 @g‐C 3 N 4 as a bifunctional electrocatalyst for hybrid electrolysis, enabling simultaneous hydrogen production along with a value‐added product.