Developing efficient metal-free carbon-based electrocatalysts for the oxygen reduction reaction (ORR) is significant and challenging to reduce the cost of fuel cells and metal–air batteries for large-scale applications. Herein, a novel metal-free N, B, F ternary-doped carbon electrocatalyst (FBNC^Δ(1:6)-950) exhibited an excellent ORR performance with half-wave potential of 0.858 V vs. reversible hydrogen electrode (RHE) via an almost exclusively four-electron transfer pathway in 0.1 M KOH, even better than the commercial Pt/C (20 %). Moreover, the FBNC^Δ(1:6)-950-based zinc–air battery (ZAB) shown an excellent power density of 147 mW·cm⁻² and long-term stability of 100 h. The FBNC^Δ(1:6)-950 was constructed via pyrolyzing zeolite imidazole framework (ZIF-8) precursor containing ${\text{BF}}_4^{–}$ at 950 °C under N₂ to volatilize the Zn. According to the structural characterization and theoretical calculations, B and F from ${\text{BF}}_4^{–}$ not only increased the number of active sites of pyridine-N by etching intact carbon matrix, but also co-modified part of pyridine-N to further optimize the electronic structure and reduce the adsorption energy of *OH, both of which together result in the excellent performance of FBNC^Δ(1:6)-950. This work provides a fresh perspective on the advancement of highly active metal-free carbon-based electrocatalysts for the ORR and ZAB.

开发用于氧还原反应（ORR）的高效无金属碳基电催化剂对于降低大规模应用的燃料电池和金属空气电池的成本具有重要意义和挑战性。在此，一种新型无金属N、B、F三元掺杂碳电催化剂（FBNC ^Δ（1：6）-950）表现出优异的ORR性能，与可逆氢电极（RHE）相比，半波电位为0.858 V 0.1 M KOH 中几乎完全是四电子转移途径，甚至比商业 Pt/C (20%) 更好。此外，FBNC ^Δ (1:6)-950基锌空气电池（ZAB）表现出147 mW·cm ^-2的优异功率密度和100 h的长期稳定性。 FBNC ^Δ (1:6)-950 是通过热解沸石咪唑骨架 (ZIF-8) 前体构建的，其中含有${\text{BF}}_4^{–}$_{在N 2}下于950℃使Zn挥发。根据结构表征和理论计算，B和F由${\text{BF}}_4^{–}$不仅通过蚀刻完整的碳基质来增加吡啶-N的活性位点数量，而且还对部分吡啶-N进行共修饰以进一步优化电子结构并降低*OH的吸附能，两者共同导致FBNC ^Δ (1:6)-950的优异性能。这项工作为 ORR 和 ZAB 的高活性无金属碳基电催化剂的发展提供了新的视角。