Atomically dispersed metal catalysts supported on the rigidly hollow matrix are promising materials for developing carbon-neutral technologies. Herein, we develop an elaborate multistep templating approach to fabricate cobalt single-atom-decorated nitrogen-doped carbon macroporous fibers (Co SAs@NCMFs). During the thermal reduction, the cobalt nanoparticles derived from the sintered Co²⁺ ions are formed at 600°C, which can be further transformed into unevenly loaded atomically dispersed cobalt sites at 1,000°C. The Co SAs@NCMF catalyst delivers excellent CO Faradaic efficiency (98.4%) and turnover frequency (38,390 h⁻¹) at −1.0 V versus reversible hydrogen electrode for CO₂ electroreduction. Furthermore, benefiting from the multiple advantageous features, including rigidly hollow structure, high specific surface area, and accessible active sites, the Co SAs@NCMF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-CO₂ batteries.

负载在刚性空心基质上的原子分散金属催化剂是开发碳中和技术的有前途的材料。在此，我们开发了一种精细的多步模板方法来制造钴单原子装饰的氮掺杂碳大孔纤维（Co SAs@NCMFs）。^{在热还原过程中，由烧结的 Co 2+}离子衍生的钴纳米颗粒在 600 ℃下形成，在 1000 ℃下可进一步转化为不均匀负载的原子分散钴位点。Co SAs@NCMF 催化剂在 -1.0 V 时提供出色的 CO 法拉第效率 (98.4%) 和周转频率 (38,390 h ^{-1 ) 与 CO} ₂的可逆氢电极相比电还原。此外，得益于刚性空心结构、高比表面积和可接近的活性位点等多种优势特性，Co SAs@NCMF 电极在水系 Zn-CO ₂电池中表现出出色的可充电性和稳定的循环寿命。