Engineering interfacial sulfur migration in transition-metal sulfide enables low overpotential for durable hydrogen evolution in seawater.

Hydrogen production from seawater remains challenging due to the deactivation of the hydrogen evolution reaction (HER) electrode under high current density. To overcome the activity-stability trade-offs in transition-metal sulfides, we propose a strategy to engineer sulfur migration by constructing a nickel-cobalt sulfides heterostructure with nitrogen-doped carbon shell encapsulation (CN@NiCoS) electrocatalyst. State-of-the-art ex situ/in situ characterizations and density functional theory calculations reveal the restructuring of the CN@NiCoS interface, clearly identifying dynamic sulfur migration. The NiCoS heterostructure stimulates sulfur migration by creating sulfur vacancies at the Ni 3 S 2 -Co 9 S 8 heterointerface, while the migrated sulfur atoms are subsequently captured by the CN shell via strong C-S bond, preventing sulfide dissolution into alkaline electrolyte. Remarkably, the dynamically formed sulfur-doped CN shell and sulfur vacancies pairing sites significantly enhances HER activity by altering the d-band center near Fermi level, resulting in a low overpotential of 4.6 and 8 mV at 10 mA cm -2 in alkaline freshwater and seawater media, and long-term stability up to 1000 h. This work thus provides a guidance for the design of high-performance HER electrocatalyst by engineering interfacial atomic migration.