Construction of Co‐Se‐W at Interfaces of Phase‐Mixed Cobalt Selenide via Spontaneous Phase Transition for Platinum‐Like Hydrogen Evolution Activity and Long‐Term Durability in Alkaline and Acidic Media

Abstract Cost‐effective transition metal chalcogenides are highly promising electrocatalysts for both alkaline and acidic hydrogen evolution reactions (HER). However, unsatisfactory HER kinetics and stability have severely hindered their applications in industrial water electrolysis. Herein, a nanoflowers‐shaped W‐doped cubic/orthorhombic phase‐mixed CoSe 2 catalyst ((c/o)‐CoSe 2 ‐W) is reported. The W doping induces spontaneous phase transition from stable phase cubic CoSe 2 (c‐CoSe 2 ) to metastable phase orthorhombic CoSe 2 , which not only enables precise regulation of the ratio of two phases but also realizes W doping at the interfaces of two phases. The (c/o)‐CoSe 2 ‐W catalyst exhibits a Pt‐like HER activity in both alkaline and acidic media, with record‐low HER overpotentials of 29.8 mV (alkaline) and 35.9 mV (acidic) at 10 mA cm −2 , respectively, surpassing the vast majority of previously reported non‐precious metal electrocatalysts for both alkaline and acidic HER. The Pt‐like HER activities originate from the formation of Co–Se–W active species on the c‐CoSe 2 side at the phase interface, which effectively modulates electron structures of active sites, not only enhancing H 2 O adsorption and dissociation at Co sites but also optimizing H * adsorption to Δ G H* ≈ 0 at W sites. Benefiting from the abundant phase interfaces, the catalyst also displays outstanding long‐term durability in both acidic and alkaline media.