Hierarchical Hollow Covalent Organic Frameworks-derived Heteroatom-doped Carbon Spheres for Metal-free Catalysis
Hierarchical Hollow Covalent Organic Frameworks-derived Heteroatom-doped Carbon Spheres for Metal-free Catalysis
复制标题
用于无金属催化的多级中空共价有机骨架前体的杂原子掺杂碳球
DOI：
10.1002/cssc.201700979
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发表时间：
2017
期刊：
影响因子：
8.4
通讯作者：
Ruihu Wang
中科院分区：
文献类型：
--
作者：
Liuyi Li;Lu Li;Caiyan Cui;Hongjun Fan;Ruihu Wang
具有中空结构的共价有机骨架（COFs）在开发新型功能材料方面具有重要的应用前景。在此，我们报道了一种具有分级壳层的中空球形COF，其作为B，N-共掺杂分级中空碳球的有效前体。得益于分级孔隙率、高比表面积和B、N共掺杂的协同效应，所合成的碳球显示出作为硝基芳烃还原中的无金属催化剂的潜在实用性。在理论和实验研究的基础上提出了一个机理假说。硼原子和间位吡啶氮原子被确定为主要的催化活性中心. 反芳香性源于B和吡啶N原子的共掺杂，而不是电荷分布和变形能，被证实在催化反应中起关键作用。
Covalent organic frameworks (COFs) with hollow structures hold great promise for developing new types of functional materials. Herein, we report a hollow spherical COF with a hierarchical shell, which serves as an effective precursor of B,N‐codoped hierarchical hollow carbon spheres. Benefiting from the synergistic effects of hierarchical porosity, high surface area, and B,N‐codoping, the as‐synthesized carbon spheres show prospective utility as metal‐free catalysts in nitroarene reduction. A mechanistic hypothesis is proposed based on theoretical and experimental studies. Boron atoms situatedmetato pyridinic N atoms are identified to be the main catalytic active sites. The anti‐aromaticity originating from the codoping of B and pyridinic N atoms, not charge distribution and deformation energy, is confirmed to play a pivotal role in the catalytic reaction.