P-doped binary Ni/Fe-N-C for enhanced oxygen electrocatalysis performance.

Adjusting the micro-environment of highly dispersive metals on carbon supports has been proved to be effective for achieving enhanced electrocatalysis performance. Herein, we delicately design a phosphorus-doped binary NiFe-nitrogen-carbon material (denoted as P-NiFe-NC), taking advantage of the coupling reaction between phenylphosphonamide (P dopant) and formamide (the carbon and nitrogen sources). The XPS N 1s fine scan reveals the strong interplay of N and P by the positively shifted binding energy of pyridinic N species after P incorporation, and the chemical state of Fe species is influenced accordingly. In addition, the P doping can enlarge the specific surface area and increase the meso/macroporosity of NiFe-NC, thus contributing to the enhancement of mass transfer inside the pores. The P-NiFe-NC sample exhibits favorable bifunctional oxygen electrocatalysis performance, rendering an ORR half-wave potential of 0.85 V and an OER potential of 1.69 V@10.0 mA cm, superior to those of P-free NiFe-NC. Assembled into Zn-air batteries, P-NiFe-NC delivers a high specific power of 161.36 mW cm and stable charge/discharge for over 100 h (corresponding to 300 cycles).