Promoted surface reconstruction of pentlandite via phosphorus-doping for enhanced oxygen evolution reaction.

ABSTRACT

The pentlandite Fe5Ni4S8(abbreviated as FNS) is not efficient for water splitting because of its inferior performance for the oxygen evolution reaction (OER). This issue originates from the low activity and instability of FNS during the OER process but can be solved through appropriate doping. Herein, a P-doping strategy based on annealing in the presence of NaH2PO2as a phosphorus source upstream was employed on FNS to enhance its activity and stability toward OER. The results demonstrated fine-tuned electronic structures of Fe and Ni in FNS through P-doping, resulting in suppressed Fe leaching,improved electrical conductivity of FNS, and easier formation of NiOOH on the surface of the catalyst. In turn, these features enhanced the OER activity and stability. The optimal P-doped FNS catalyst FNSP-40 exhibited a 4-fold greater electrochemical surface area compared to that of FNS, accompanied by an overpotential of 235 mV at 10 mA cm-2. The optimized FNSP-40 catalyst was used as an anode, and platinum-decorated FNS was used as a cathode. This combination demonstrated an electrolysis performance with a cell voltage of 1.57 V, reaching a current density of 100 mA cm-2,which indicates efficient operation. The advantages of P-doping engineering were also verified in simulated seawater with enhanced OER performance. Overall, the proposed strategy looks promising for the fabrication of pentlandite-structured catalysts for efficient alkaline water and seawater oxidation.