Zhao Zaiwang, Duan Linlin, Zhao Yujuan, Wang Lipeng, Zhang Junye, Bu Fanxing, Sun Zhihao, Zhang Tengsheng, Liu Mengli, Chen Hanxing, Yang Yi, Lan Kun, Lv Zirui, Zu Lianhai, Zhang Pengfei, Che Renchao, Tang Yun, Chao Dongliang, Li Wei, Zhao Dongyuan
Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, iChEM and State Key Laboratory of Molecular Engineering of Polymers, College of Chemistry and Materials, Fudan University, Shanghai 200433, P. R. China.
Centre for High-Resolution Electron Microscopy (ChEM), School of Physical Science and Technology, Shanghai Tech University, 393 Middle Huaxia Road, Pudong, Shanghai 201210, P. R. China.
J Am Chem Soc. 2022 Jul 6;144(26):11767-11777. doi: 10.1021/jacs.2c03814. Epub 2022 Jun 22.
Constructing hierarchical three-dimensional (3D) mesostructures with unique pore structure, controllable morphology, highly accessible surface area, and appealing functionality remains a great challenge in materials science. Here, we report a monomicelle interface confined assembly approach to fabricate an unprecedented type of 3D mesoporous N-doped carbon superstructure for the first time. In this hierarchical structure, a large hollow locates in the center (∼300 nm in diameter), and an ultrathin monolayer of spherical mesopores (∼22 nm) uniformly distributes on the hollow shells. Meanwhile, a small hole (4.0-4.5 nm) is also created on the interior surface of each small spherical mesopore, enabling the superstructure to be totally interconnected. Vitally, such interconnected porous supraparticles exhibit ultrahigh accessible surface area (685 m g) and good underwater aerophilicity due to the abundant spherical mesopores. Additionally, the number (70-150) of spherical mesopores, particle size (22 and 42 nm), and shell thickness (4.0-26 nm) of the supraparticles can all be accurately manipulated. Besides this spherical morphology, other configurations involving 3D hollow nanovesicles and 2D nanosheets were also obtained. Finally, we manifest the mesoporous carbon superstructure as an advanced electrocatalytic material with a half-wave potential of 0.82 V (vs RHE), equivalent to the value of the commercial Pt/C electrode, and notable durability for oxygen reduction reaction (ORR).
构建具有独特孔结构、可控形态、高可及表面积和吸引人功能的分级三维（3D）介观结构在材料科学中仍然是一个巨大挑战。在此，我们首次报道了一种单胶束界面受限组装方法来制备一种前所未有的3D介孔氮掺杂碳超结构。在这种分级结构中，一个大的中空部分位于中心（直径约300 nm），并且一层超薄的球形介孔（约22 nm）单层均匀分布在中空壳上。同时，在每个小球形介孔的内表面也形成了一个小孔（4.0 - 4.5 nm），使超结构完全相互连接。至关重要的是，由于丰富的球形介孔，这种相互连接的多孔超粒子表现出超高的可及表面积（685 m²/g）和良好的水下亲气性。此外，超粒子的球形介孔数量（70 - 150个）、粒径（22和42 nm）以及壳厚度（4.0 - 26 nm）都可以精确控制。除了这种球形形态外，还获得了涉及3D中空纳米囊泡和2D纳米片的其他构型。最后，我们证明这种介孔碳超结构是一种先进的电催化材料，其半波电位为0.82 V（相对于可逆氢电极），与商业Pt/C电极的值相当，并且对氧还原反应（ORR）具有显著的耐久性。
