Dynamic Stability in Intermittent Seawater Electrolysis Via Frustrated Lewis Pair Engineering

Abstract Alkaline seawater electrolysis powered by intermittent renewable energy offers a promising pathway for sustainable hydrogen production, yet faces critical challenges in proton supply dynamics and catalyst stability. The dual limitations are addressed through the design of a Cr‐NiCoP v @NF (P v : P vacancy, NF: nickel foam) electrocatalyst featuring frustrated Lewis pairs (FLPs). The metal‐phosphorus FLP architecture demonstrates ultralow overpotentials of 110 mV at the current density of 10 mA cm −2 and 333 mV at an industrial‐grade current density of 1 A cm −2 in a 1.0 m KOH + seawater electrolyte. Key innovation lies in the system's dynamic stability to intermittent operation, maintaining ≈100% activity after 520 h at 0.5 A cm −2 with 12 h start‐shutdown cycles. Combined experimental and theoretical analyzes reveal two crucial mechanisms: 1) FLPs synergistically facilitate H─OH bond dissociation (0.18 eV barrier reduction) and optimize hydrogen desorption energetics (0.13 eV barrier reduction), solving the proton supply limitation. 2) The selective adsorption behavior enables surface‐enriched OH − groups to form a molecular‐level protective shield that repels chlorides through electrostatic effects, effectively mitigating catalyst corrosion. This work establishes a new paradigm for non‐precious metal catalyst design via targeted electronic structure engineering, while providing fundamental insights into the interfacial microenvironment under intermittent operations.