Developing cost-efficient multifunctional electrocatalysts is highly critical for the integrated electrochemical energy-conversion systems such as water electrolysis based on hydrogen/oxygen evolution reactions (HER/OER) and metal-air batteries based on OER/oxygen reduction reactions (ORR). The core-shell structured materials with transition metal phosphide as the core and nitrogen-doped carbon (NC) as the shell have been known as promising HER electrocatalysts. However, their oxygen-related electrocatalytic activities still remain unsatisfactory, which severely limits their further applications. Herein an effective strategy to improve the core and shell performances of core-shell Co2 P@NC electrocatalysts through secondary metal (e.g., Fe, Ni, Mo, Al, Mn) doping (termed M-Co2 P@M-N-C) is reported. The as-synthesized M-Co2 P@M-N-C electrocatalysts show multifunctional HER/OER/ORR activities and good integrated capabilities for overall water splitting and Zn-air batteries. Among the M-Co2 P@M-N-C catalysts, Fe-Co2 P@Fe-N-C electrocatalyst exhibits the best catalytic activities, which is closely related to the configuration of highly active species (Fe-doping Co2 P core and Fe-N-C shell) and their subtle synergy, and a stable carbon shell for outstanding durability. Combination of electrochemical-based in situ Fourier transform infrared spectroscopy with extensive experimental investigation provides deep insights into the origin of the activity and the underlying electrocatalytic mechanisms at the molecular level.
Keywords: Zn-air batteries; core-shell electrocatalysts; in situ Fourier transform infrared; overall water splitting; secondary metal doping.
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