The oxygen reduction reaction (ORR) is a fundamental reaction for energy storage and conversion. It has mainly relied on platinum-based electrocatalysts, but the chemical doping of carbon-based materials has proven to be a promising strategy for preparing metal-free alternatives. Nitrogen doping in particular provides a diverse range of nitrogen forms. Here, we introduce a new form of nitrogen doping moieties —sp-hybridized nitrogen (sp-N) atoms into chemically defined sites of ultrathin graphdiyne, through pericyclic replacement of the acetylene groups. The as-prepared sp-N-doped graphdiyne catalyst exhibits overall good ORR performance, in particular with regards to peak potential, half-wave potential and current density. Under alkaline conditions it was comparable to commercial Pt/C, and showed more rapid kinetics. And although its performances are a bit lower than those of Pt/C in acidic media they surpass those of other metal-free materials. Taken together, experimental data and density functional theory calculations suggest that the high catalytic activity originates from the sp-N dopant, which facilitates O₂ adsorption and electron transfer on the surface of the catalyst. This incorporation of chemically defined sp-N atoms provides a new synthetic route to high-performance carbon-based and other metal-free catalysts.

氧还原反应（ORR）是能量存储和转化的基本反应。它主要依靠铂基电催化剂，但事实证明，对碳基材料进行化学掺杂是制备无金属替代品的一种有前途的策略。氮掺杂尤其提供了多种形式的氮。在这里，我们引入氮掺杂部分的一种新形式的- SP-杂化氮（SP- N）原子成超薄graphdiyne，通过周环更换乙炔基团的化学成分确定的位点。准备好的sp-N掺杂的石墨二炔催化剂表现出总体良好的ORR性能，特别是在峰值电势，半波电势和电流密度方面。在碱性条件下，它可与市售Pt / C相媲美，并显示出更快的动力学。而且，尽管它在酸性介质中的性能略低于Pt / C，但它们却超过了其他不含金属的材料。总之，实验数据和密度泛函理论计算表明，高催化活性源自sp- N掺杂剂，这有助于O ₂在催化剂表面的吸附和电子转移。化学定义的sp N原子的这种结合为高性能的碳基和其他无金属催化剂提供了一条新的合成途径。