Designing and preparing oxygen reduction reaction (ORR) catalysts with low cost, high activity and strong stability play a crucial function in the application of fuel cells and metal-air batteries. In this work, we use pristine graphite and carbon nanotubes (CNT) mixture as initial carbon source, and for the first time successfully prepare N, S-co-doped carbon nanotubes/graphene/MnS ternary hybrid (NSCNT/NSG/MnS) by modified Hummers' method followed by a pyrolysis process. The morphology, structure, composition and ORR performance of the obtained sample are measured by scanning electron microscope, X-ray diffraction and lots of other techniques. The results show that the successful synthesis of NSCNT/NSG/MnS is achieved by the combination of effective exploitation of residual Mn and S species and strong reducibility of carbon under high temperature. Besides, we find that the resultant NSCNT/NSG/MnS can not only effectively stabilize and disperse MnS nanoparticles, but also possess large specific surface area, high N content and unique 3D architecture. Compared to other counterparts, the obtained 3D NSCNT/NSG/MnS exhibits superior ORR performance (the onset potential moves positively to 1.00 V; limiting-current density achieves 4.93 mA/cm²; ORR electron transfer number is close to four), which is proven to approach that of commercial Pt/C catalyst.

低成本，高活性和强稳定性的设计和制备氧还原反应（ORR）催化剂在燃料电池和金属空气电池的应用中起着至关重要的作用。在这项工作中，我们使用原始石墨和碳纳米管（CNT）的混合物作为初始碳源，并首次成功地通过以下方法成功制备了N，S共掺杂的碳纳米管/石墨烯/ MnS三元杂化物（NSCNT / NSG / MnS）。改进的Hummers方法，然后进行热解工艺。通过扫描电子显微镜，X射线衍射和许多其他技术来测量所获得样品的形态，结构，组成和ORR性能。结果表明，通过有效地利用残余的Mn和S物种以及在高温下强大的碳还原能力，可以成功合成NSCNT / NSG / MnS。此外，我们发现所得的NSCNT / NSG / MnS不仅可以有效地稳定和分散MnS纳米颗粒，而且具有较大的比表面积，高的N含量和独特的3D结构。与其他同类产品相比，获得的3D NSCNT / NSG / MnS表现出优异的ORR性能（起始电位正向移动至1.00 V；极限电流密度达到4.93 mA / cm² ; ORR电子转移数接近4），已证明接近商业Pt / C催化剂。