Developing metal-free oxygen redox catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) to eliminate the risk caused by transition metal based catalysts is highly desirable as promising substitutes for precious metal catalysts for widespread adoption of rechargeable Zn-Air batteries. Herein, N, S co-doped carbon (NS/C) was developed by a molecular-level doping strategy using a new precursor of N and S co-containing bis(imino)-pyridine based polymer, copolymerized by three monomers of 2, 6-Diacetylpyridine (DAP), 1, 5-naphthalenediamine (NDA) and 2, 5-dithiobiurea (DBU) with Schiff base reaction. The results demonstrated that the ratio between the three monomers strongly affects the texture characteristics of the corresponding carbon materials, doping types and contents of N and S, as well their synergetic effects in carbon matrix. The NS/C obtained by the copolymer of DAP_, NDA and DBU with their corresponding molar ratio of 1: 0.5: 0.5 exhibits a small overpotential difference of 0.72 V vs RHE and a remarkable stability in 0.1 M KOH for overall ORR/OER activity, outperforming most of metal-free catalysts reported. Meanwhile, a single rechargeable Zn-Air battery test further identified its excellent activity, in which the battery delivers a maximum power density output of 149 mW·cm⁻², a specific capacity of 769 mAh·g_Zn⁻¹, and long charge-discharge capability at 5 mA·cm⁻² with 600 cycles in 100 h, surpassing that with the mixed Pt/C and IrO₂ (1:1 wt.%) catalysts under the same mass loading. The theoretical calculation results show that the oxygen redox activity of NS/C critically roots in C atoms with positive charge and spin density, induced by the strong interaction between the specific N and S dopants derived from the new designed precursors.

开发用于氧还原反应（ORR）和氧释放反应（OER）的无金属氧氧化还原催化剂以消除过渡金属基催化剂引起的风险是非常可取的，因为它有望成为可贵的Zn-Air电池广泛采用的贵金属催化剂的替代品。本文中，N，S共掺杂碳（NS / C）是通过分子级掺杂策略开发的，使用了一种新的N和S含双（亚氨基）吡啶基聚合物的前驱体，该聚合物由3种2的单体共聚6-二乙酰基吡啶（DAP），1，5-萘二胺（NDA）和2，5-二硫代双脲（DBU）与席夫碱反应。结果表明，三种单体的比例强烈影响相应碳材料的织构特性，掺杂类型和氮，硫含量，以及它们在碳基质中的协同作用。DAP共聚物获得的NS / C_， NDA和DBU为1及其相应的摩尔比为0.5：0.5的展品0.72 V的小的超电势差VS RHE和在0.1M KOH一个显着的稳定性为整体ORR / OER活性，优于大多数的不含金属的催化剂的报道。同时，一次可充电Zn-Air电池测试进一步证明了其出色的性能，该电池提供的最大功率密度输出为149 mW·cm ^-2，比容量为769 mAh·g _Zn ^-1，并且充电时间长。 5 mA·cm ^-2的放电容量，在100 h内进行600次循环，超过了Pt / C和IrO ₂混合气体的放电容量相同质量负载下的（1：1 wt。％）催化剂。理论计算结果表明，由新设计的前体衍生的特定N和S掺杂剂之间的强相互作用导致了NS / C的氧还原活性以C和正电荷和自旋密度为根。