Corrosion-Driven Ni3S4 Gradient in NiFe-LDH Enables Durable Industrial-Scale Water Electrolysis.

Abstract

Designing low-cost yet highly efficient oxygen evolution reaction (OER) electrocatalysts is essential to enable sustainable green hydrogen generation. However, synthesis complexity, slow kinetics, and poor durability hinder industrial use. In this study, we present a corrosion-driven gradient engineering approach for the rapid, energy-free synthesis of Ni3S4/NiFe-LDH heterostructures on iron foam (IF) under ambient conditions. During spontaneous IF corrosion, a compositional and gradient structure forms, with Ni3S4 dominating the surface and NiFe-LDH enriching the core, establishing a continuous pathway for rapid electron transport. The catalyst exhibits superior OER performance, achieving low overpotentials of 297 mV in 1 M KOH and 326 mV in simulated seawater at 500 mA cm-2. Notably, in pure-water anion exchange membrane water electrolyzer, the catalyst demonstrates industrial-grade performance, sustaining 1 A cm-2 at 1.85 V with remarkable stability over 1,000 h of continuous operation. Operando spectroscopic studies unveil that SO4 2- leaching from surface Ni3S4 in the gradient structure provides dual protection against metal dissolution and chloride corrosion. Furthermore, the in situ formation of FeOOH synergistically stabilizes the catalytically critical Ni3+ species in NiOOH through strong Fe─O─Ni interfacial bonding, contributing to the exceptional durability. This work provides fundamental insights into corrosion-mediated catalyst design, offering a scalable pathway for developing industrial-grade electrocatalysts.