Energy-saving hydrogen production from sulfion oxidation-hybrid seawater splitting enabled by superwettable corrosion-resistant NiFe layered double hydroxide/FeNi2S4 heterostructured nanoarrays

Electrochemical seawater splitting is a sustainable pathway towards hydrogen production independent of scarce freshwater resources. However, the high energy consumption and harmful chlorine-chemistry interference still pose major technological challenges. Herein, thermodynamically more favorable sulfion oxidation reaction (SOR) is explored to replace energy-intensive oxygen evolution reaction (OER), enabling the dramatically reduced energy consumption and the avoidance of corrosive chlorine species in electrocatalytic systems of NiFe layered double hydroxide (LDH)/FeNi2S4 grown on iron foam (IF) substrate. The resulting NiFe-LDH/FeNi2S4/IF with superwettable surfaces and favorable heterointerfaces can effectively catalyze SOR and hydrogen evolution reaction (HER), which greatly reduces the operational voltage by 1.05 V at 50 mA cm- 2 compared to pure seawater splitting and achieves impressively low electricity consumption of 2.33 kW h per cubic meter of H2 at 100 mA cm- 2. Significantly, benefitting from the repulsive effect of surface sulfate anions to Cl-, the NiFe-LDH/ FeNi2S4/IF exhibits outstanding long-term stability for SOR-coupled chlorine-free hydrogen production with sulfion upcycling into elemental sulfur. The present study uncovers the "killing two birds with one stone" effect of SOR for energy-efficient hydrogen generation and value-added elemental sulfur recovery in seawater electrolysis without detrimental chlorine chemistry.