Highly efficient sulfur-doped Ni3Fe electrocatalysts for overall water splitting: Rapid synthesis, mechanism and driven by sustainable energy

Designing efficient electrocatalysts and insight into their electrocatalytic mechanisms are significantly important for storing and converting the intermittent sustainable energy sources into clean hydrogen. In this study, we synthesize the bifunctional sulfur-doped Ni3Fe (NiFeS) electrocatalysts by a simple electrodeposition method only taking 30 s. After optimizing the components, it was found that the synthesized NiFeS electrocatalysts exhibit the excellent hydrogen and oxygen evolution reaction performances in 1.0 M potassium hydroxide solution. The results of experimental and theoretical calculations reveal that the introduced sulfur could optimize the electronic distribution, which make Ni electron-rich and Fe electron-deficient, thereby weakening the energy barriers of potential-determining steps, i.e. the absorption of H2O molecule on Ni sites for HER and formation of *OOH on Fe sites for OER, respectively. Besides, the NiFeS electrocatalysts are used as the bifunctional electrodes to water splitting, which only need 1.51 V to reach 10 mA·cm-2, and exhibits excellent durability and a >95% Faraday efficiency. Furthermore, the intermittent kinetic, wind and solar energies are used to power the assembled electrolyzer with NiFeS bi-electrodes to verify their great application potential. This work not only proved a deep insight into mechanism of the boosted electrocatalytic activities of NiFeS, but also the synthesized NiFeS electrocatalysts have great application prospect in the conversion of intermittent and sustainable energy sources into hydrogen by water electrocatalysis.