| Summary: | Abstract Developing an economical, durable, and efficient electrode that performs well at high current densities and is capable of satisfying large‐scale electrochemical hydrogen production is highly demanded. A self‐supported electrocatalytic “Pt‐like” WC porous electrode with open finger‐like holes is produced through industrial processes, and a tightly bonded nitrogen‐doped WC/W (WC‐N/W) heterostructure is formed in situ on the WC grains. The obtained WC‐N/W electrode manifests excellent durability and stability under multi‐step current density in the range of 30–1000 mA cm−2 for more than 220 h in both acidic and alkaline media. Although WC is three orders of magnitude cheaper than Pt, the produced electrode demonstrates comparable hydrogen evolution reaction performance to the Pt electrode at high current density. Density functional theory calculations attribute its superior performance to the electrode structure and the modulated electronic structure at the WC‐N/W interface.
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