Phosphor-doping modulates the d-band center of Fe atoms in Fe-N4 catalytic sites to boost the activity of oxygen reduction

Regulating the electronic structure by phosphor-doping is a preferred strategy to boost the performance of carbon-based catalysts for oxygen reduction reaction (ORR). Here, a porous Fe, P, N-codoped carbon catalyst (PCF-FeTz-900) is designed by a phytic acid-assisted thermal etching strategy, in which P atoms are first doped into the carbon matrix to form a stable P C bond, and then FeN 4 sites are produced from Fe-2,4,6-Tris(2-pyridyl)-s-triazine complex (Fe-TPTz). Theoretical calculations suggest that the electrons are transferred from the doped P atom to the neighboring FeN 4 sites, which facilitates the ORR at the Fe sites by reducing the energy barrier and the adsorption energy of intermediates. Additionally, the P-doped FeN 4 (FeN 4 P) structure manifests a lower free energy difference than that of FeN 4 and the d -band center of Fe is also lowered, which further ensures its higher ORR catalytic ability. As a result, the PCF-FeTz-900 catalyst exhibits superior ORR activity and stability in alkaline electrolyte, and the assembled primary zinc-air battery shows greater performances compared to the commercial Pt/C catalyst. This work can provide an effective pathway for modulating the performance of doped-carbon materials in energy conversion devices.