Preparation of Yolk-Shell-Structured Cox Fe1-x P with Enhanced OER Performance.

The design and development of low-cost, highly efficient, and stable electrocatalysts to take the place of noble-metal catalysts for the oxygen evolution reaction (OER) remain a significant challenge. Herein, the synthesis of yolk-shell-structured binary transition metal phosphide Cox Fe1-x P with different Co/Fe ratios by phosphidation of a cobalt ferrite precursor is reported. The as-synthesized Cox Fe1-x P catalysts were used for the OER. All yolk-shell Cox Fe1-x P catalysts with different Co/Fe ratios showed much better performance than the corresponding solid catalyst. The formation of Co oxides on the catalyst surface during OER and the optimal Co/Fe ratio were found to be critical to their activity. Among the as-prepared Cox Fe1-x P catalysts, that with a Co/Fe ratio of 0.47/0.53 (Co0.47 Fe0.53 P) exhibited the best performance. Co0.47 Fe0.53 P has an overpotential of 277 mV at a current density of 10 mA cm-2 , a Tafel slope of 37 mV dec-1 , and superior stability in alkaline medium. The outstanding performance is partly ascribed to the transfer of valence electrons from Co to P and Fe. The Co0.47 Fe0.53 P matrix with excellent conductivity and Fe phosphate that is stable on the surface of the catalyst are also helpful for the OER performance. In addition, the yolk-shell structure of Co0.47 Fe0.53 P increases the contact area between electrolyte and catalyst. These characteristics of Co0.47 Fe0.53 P greatly improve its OER performance. This optimized binary transition metal phosphide provides a new approach for the design of nonprecious-metal electrocatalysts.