Elucidating the correlation of the polymer precursors and active sites formation of multi-heteroatom doped based carbon for oxygen reduction reaction (ORR) is essential to develop molecular-level design of highly efficient metal-free carbon catalysts. To achieve this goal, herein, two series of N doped and N, S co-doped carbon nanospheres were synthesized via pyrolysis of self-polymerized compounds of three analogous precursors of 2,6-Diaminopyridine, 4, 6-Diaminopyrimidine and 1,3-Diaminobenzene as nitrogen source initiated by hydrogen peroxide and ammonium persulfate as sulfer source respectively. The results demonstrate that nitrogen atoms in the six-membered rings of three precursors play a critical role on the formation of N-doping types and synergistic effects of N and S dopants in their derived carbon nanoshperes for ORR. Among the three precursors, 2,6-Diaminopyrimidine prefers to form the Pyridinic N doped carbon, resulting in the highest activity for ORR in N doped nanospheres, in contrast, 2,6-Diaminopyridine facilitates the formation of more content of Graphitic-N dopant, which has stronger synergy with thiophenic-S dopant in carbon matrix than that of Pyridinic N dopants. This unique characteristic endows 2,6-Diaminopyrimidine derived N, S co-doped nanospheres with excellent ORR activity of higher half-wave potential of 0.87 V vs. RHE in 0.1 M KOH and Zn-Air battery power output performance than that of the same loading of commercial Pt/C catalyst. Revealing the dependence of specific active sites determined by precursors with very similar molecular structures in the work will shed light on the precise design strategy based on the precursors-selecting guidance for the development of advanced multi-heteroatom doped carbon ORR catalysts.

阐明聚合物前体与多杂原子掺杂基碳的氧还原反应（ORR）的相关性对于开发高效的无金属碳催化剂的分子级设计至关重要。为了实现该目标，本文通过热解2,6-二氨基吡啶，4,6-二氨基嘧啶和1,3的三个类似前体的自聚合化合物合成了两个系列的N掺杂和N，S共掺杂的碳纳米球。 -二氨基苯作为氮源，分别由过氧化氢和过硫酸铵作为硫源引发。结果表明，三个前体的六元环中的氮原子在N掺杂类型的形成以及N和S掺杂剂在其衍生的碳纳米级ORR的协同效应中起关键作用。在这三种前体中，2,6-二氨基嘧啶倾向于形成N掺杂的吡啶吡啶碳，从而在N掺杂的纳米球中产生最高的ORR活性，相反，2,6-二氨基吡啶则有助于形成更多含量的Graphitic-N掺杂剂。 ，其与碳N基体中的噻吩S掺杂剂的协同作用比吡啶N掺杂剂的协同作用强。这种独特的特性赋予了2,6-二氨基嘧啶衍生的N，S共掺杂纳米球，具有出色的ORR活性，更高的半波电势为0.87 V 在碳基体中，它与噻吩-S掺杂剂的协同作用比吡啶N掺杂剂的协同作用强。这种独特的特性赋予了2,6-二氨基嘧啶衍生的N，S共掺杂纳米球，具有出色的ORR活性，更高的半波电势为0.87 V 在碳基体中，它与噻吩-S掺杂剂的协同作用比吡啶N掺杂剂的协同作用强。这种独特的特性赋予了2,6-二氨基嘧啶衍生的N，S共掺杂纳米球，具有出色的ORR活性，更高的半波电势为0.87 V 与。RHE在0.1 M KOH和Zn-Air电池中的功率输出性能要高于相同负载的商用Pt / C催化剂。揭示工作中具有非常相似的分子结构的前体所确定的特定活性位点的依赖性，将为基于前体的精确设计策略提供依据，从而为开发先进的多杂原子掺杂碳ORR催化剂的开发提供指导。