Self-Powered Hydrogen Production with Improved Energy Efficiency via Polysulfides Redox

In the pursuit of efficient solar-driven electrocatalytic water splitting for hydrogen production, the intrinsic challenges posed by the sluggish kinetics of anodic oxygen evolution and intermittent sunlight have prompted the need for innovative energy systems. Here, we introduce an approach by coupling the polysulfides oxidation reaction with the hydrogen evolution reaction for energy-saving H₂ production, which could be powered by an aqueous zinc-polysulfides battery to construct a self-powered energy system. This unusual hybrid water electrolyzer achieves 300 mA cm^-2 at a low cell voltage of 1.14 V, saving electricity consumption by 100.4% from 5.47 to 2.73 kWh per m³ H₂ compared to traditional overall water splitting. Benefiting from the favorable reaction kinetics of polysulfides oxidation/reduction, the aqueous zinc-polysulfides battery exhibits an energy efficiency of approximately 89% at 1.0 mA cm^-2. Specially, the zinc-polysulfide battery effectively stores intermittent solar energy as chemical energy during light reaction by solar cells. Under an unassisted light reaction, the batteries could release energy to drive H₂ production through a hybrid water electrolyzer for uninterrupted hydrogen production. Therefore, the aim of simultaneously generating H₂ and eliminating the restrictions of intermittent sunlight is realized by combining the merits of polysulfides redox, an aqueous metal-polysulfide battery, and solar cells. We believe that this concept and utilization of polysulfides redox will inspire further fascinating attempts for the development of sustainable energy via electrocatalytic reactions.