Dynamic Stability in Intermittent Seawater Electrolysis Via Frustrated Lewis Pair Engineering

The Frustrated Lewis Pair concept guides the design strategy of Cr‐NiCoPv@NF to address dual limitations in intermittent alkaline seawater electrolysis. 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‐NiCoPv@NF (Pv: 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. The Frustrated Lewis Pair concept guides the design strategy of Cr-NiCoP v @NF to address dual limitations in intermittent alkaline seawater electrolysis. 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. Advanced Science, EarlyView.