Boosting the overall electrochemical water splitting performance of pentlandites through non-metallic heteroatom incorporation.

We report on synthesis of the heterotrimetallic pentlandite-type material FeCoNiS (FCNS) in presence of suitable phosphorus-(FCNSP) and nitrogen-(FCNSN) donors for the overall electrochemical water splitting. Throughout the experiments, a preferential incorporation of N into the FCNS-lattice is observed whereas the addition of phosphorus generally leads to metal-phosphate-FCNS composites. The obtained FCNSP, FCNSN, and FCNSNP facilitate the oxygen evolution reaction (OER) at 100 mAcm in 1.0M KOH with overpotentials of 479, 440, and 427 mV, respectively, outperforming the benchmark IrO (564 mV) and commercial Ni metal powder (>600 mV). Likewise, FCNSN and FCNSNP reveal an improved performance toward the hydrogen evolution reaction (HER) in 0.5M HSO outperforming the pristine FCNS. All materials revealed high stability and morphological robustness during OER and HER. Notably, DFT calculation suggests that N and P doping boost the OER activity of the pristine FCNS, whereas N doping enhances the HER activity.