Engineering Multilevel Collaborative Catalytic Interfaces with Multifunctional Iron Sites Enabling High-Performance Real Seawater Splitting.

Given the abundant reserves of seawater and the scarcity of freshwater, real seawater electrolysis is a more economically appealing technology for hydrogen production relative to orthodox freshwater electrolysis. However, this technology is greatly precluded by the undesirable chlorine oxidation reaction and severe chloride corrosion at the anode, further restricting the catalytic efficiency of overall seawater splitting. Herein, a feasible strategy by engineering multifunctional collaborative catalytic interfaces is reported to develop porous metal nitride/phosphide heterostructure arrays anchoring on conductive NiP surfaces with affluent iron sites. Collaborative catalytic interfaces among iron phosphide, bimetallic nitride, and porous NiP supports play a positive role in improving water adsorption/dissociation and hydrogen adsorption behaviors of active Fe sites evidenced by theoretical calculations for hydrogen evolution reactions, and enhancing oxygenated species adsorption and nitrate-rich passivating layers resistant to chloride corrosion for oxygen evolution reaction, thus cooperatively propelling high-performance bifunctional seawater splitting. The resultant material FeP/NiCoN/NiP performs excellently as a self-standing bifunctional catalyst for alkaline seawater splitting. It requires extremely low cell voltages of 1.624 and 1.742 V to afford current densities of 100 and 500 mA/cm in 1 M KOH seawater electrolytes, respectively, along with superior long-term stability, outperforming nearly all the ever-reported non-noble bifunctional electrocatalysts and benchmark Pt/IrO coupled electrodes for freshwater/seawater electrolysis. This work presents an effective strategy for greatly enhancing the catalytic efficiency of non-noble catalysts toward green hydrogen production from seawater electrolysis.