CoW Bimetallic Carbide Nanocatalysts: Computational Exploration, Confined Disassembly-Assembly Synthesis and Alkaline/Seawater Hydrogen Evolution.

Earth-abundant tungsten carbide exhibits potential hydrogen evolution reaction (HER) catalytic activity owing to its Pt-like d-band electronic structure, which, unfortunately, suffers from the relatively strong tungsten-hydrogen binding, deteriorating its HER performance. Herein, a catalyst design concept of incorporating late transition metal into early transition metal carbide is proposed for regulating the metal-H bonding strength and largely enhancing the HER performance, which is employed to synthesize CoW bi-metallic carbide Co6 W6 C by a "disassembly-assembly" approach in a confined environment. Such synthesized Co6 W6 C nanocatalyst features the optimal Gibbs free energy of *H intermediate and dissociation barrier energy of H2 O molecules as well by taking advantage of the electron complementary effect between Co and W species, which endows the electrocatalyst with excellent HER performance in both alkaline and seawater/alkaline electrolytes featuring especially low overpotentials, elevated current densities, and much-enhanced operation durability in comparison to commercial Pt/C catalyst. Moreover, a proof-of-concept Mg/seawater battery equipped with Co6 W6 C-2-600 as cathode offers a peak power density of 9.1 mW cm-2 and an open-circuit voltage of ≈1.71 V, concurrently realizing hydrogen production and electricity output.