Integration of heteroatom doped carbon material and metal phosphide is an ideal strategy for bifunctional oxygen reduction and evolution catalysis. In this work, heteroatoms doped carbon nanotubes, together with cobalt phosphide (Co₂P/doped-CNTs) are prepared with a simultaneous phosphorization and carbonization strategy. It is revealed that the in-situ generated Co₂P weakens the catalytic graphitization effect of metallic Co during the carbonization process, thus bringing about large numbers of defects, which is conducive to generating more pyridinic-N species in the carbon nanotube. As a result, the ORR-active pyridinic-N species and the OER-active Co₂P are enriched in the carbon nanotube after the introduction of phosphorus, therefore providing dual active sites. The resultant Co₂P/doped-CNTs catalyst shows outstanding ORR and OER performances, which are comparable to those of the commercial counterparts. The bifunctional activity makes Co₂P/doped-CNTs an effective air–cathode catalyst for the rechargeable zinc-air batteries, showing a high power density and prominent cycling stability. This work abandons the traditional post-treatment phosphating method and realizes the integration of simplicity, safety and high efficiency.

杂原子掺杂碳材料和金属磷化物的整合是双功能氧还原和析出催化的理想策略。在这项工作中，杂原子掺杂的碳纳米管与磷化钴（Co ₂ P/掺杂的CNT）一起采用同时磷化和碳化策略制备。结果表明，原位生成的Co ₂ P削弱了金属Co在碳化过程中的催化石墨化作用，从而带来了大量的缺陷，有利于在碳纳米管中生成更多的吡啶-N物种。因此，ORR 活性吡啶 N 物种和 OER 活性 Co ₂P在引入磷后富集在碳纳米管中，因此提供了双重活性位点。所得的 Co ₂ P/掺杂的 CNTs 催化剂表现出出色的 ORR 和 OER 性能，与商业同类产品相当。双功能活性使 Co ₂ P/掺杂碳纳米管成为可充电锌空气电池的有效空气阴极催化剂，表现出高功率密度和突出的循环稳定性。本工作摒弃了传统的后处理磷化方法，实现了简单、安全、高效的一体化。