Wang Teng, Yang Chao, Liu Yijiang, Yang Mei, Li Xufeng, He Yan, Li Huaming, Chen Hongbiao, Lin Zhiqun
College of Chemistry and Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, Xiangtan University, Xiangtan 411105, Hunan Province, China.
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
Nano Lett. 2020 Aug 12;20(8):5639-5645. doi: 10.1021/acs.nanolett.0c00081. Epub 2020 Jul 10.
The rational design and facile synthesis of metal organic framework (MOF)-derived carbon materials with high oxygen reduction reaction (ORR) activity still remains challenging. Herein, we report on a simple yet robust route to dual-shelled Co, N, and S co-doped hollow carbon nanocages (denoted Co-N/S-DSHCN) with outstanding ORR performance. The concurrent compositional and structural engineering of the zeolitic imidazolate framework (ZIF-67), enabled by its coating with trithiocyanuric acid (TCA), yields core-shelled precursor particles which are subsequently carbonized into Co-N/S-DSHCN. Notably, Co-N/S-DSHCN-3.5 outperforms the commercial Pt/C, representing a +25 mV onset potential () and a +43 mV half-wave potential () in 0.1 M KOH and a comparable to Pt/C in 0.5 M HSO, respectively. Such impressive ORR activities of Co-N/S-DSHCN-3.5 originate from the effective synergy of Co, N, and S co-doping (i.e., a compositional tuning) in conjunction with a unique dual-shelled hollow architecture containing hierarchical porosity (i.e., a structural tailoring).
合理设计并轻松合成具有高氧还原反应（ORR）活性的金属有机框架（MOF）衍生碳材料仍然具有挑战性。在此，我们报道了一种简单而稳健的路线，用于制备具有出色ORR性能的双壳层钴、氮和硫共掺杂空心碳纳米笼（表示为Co-N/S-DSHCN）。通过用三聚硫氰酸（TCA）包覆沸石咪唑酯框架（ZIF-67）实现的同时进行的成分和结构工程，产生了核壳结构的前驱体颗粒，随后将其碳化成为Co-N/S-DSHCN。值得注意的是，Co-N/S-DSHCN-3.5在性能上优于商业Pt/C，在0.1 M KOH中起始电位（）提高了25 mV，半波电位（）提高了43 mV，在0.5 M HSO中与Pt/C相当。Co-N/S-DSHCN-3.5如此令人印象深刻的ORR活性源于钴、氮和硫共掺杂（即成分调节）与包含分级孔隙率的独特双壳层空心结构（即结构剪裁）的有效协同作用。
