北京航空航天大学郭林团队报道了氮掺杂非晶单原子层碳。相关研究成果于2024年9月25日发表于国际一流学术期刊《自然》。

单原子层状碳材料，如石墨烯和非晶单层碳，由于其前所未有的物理性质和广泛的有前景的应用，激发了人们对基础和应用研究的热情。到目前为止，这些材料主要是通过化学气相沉积生产的，与溶液相合成相比，化学气相淀积通常需要严格的反应条件。

该文中，研究人员展示了通过在可移除的层状双氢氧化物模板的受限层间腔内聚合吡咯，制备具有混合五元、六元和七元（5-6-7-元）环的独立氮掺杂非晶单层碳的溶液。

结构表征和第一性原理计算表明，氮掺杂的无定形单层碳是通过吡咯在α、β和N位点的自由基聚合形成的，受到反应空间的限制，这使得键能够通过斯通-威尔士变换重新排列。

空间限制抑制了聚合过程中的C-C键旋转和链纠缠，导致原子厚的连续非晶层具有平面内π共轭电子结构。使用固体模板和离子交换策略的空间受限自由基聚合显示出，作为获得二维共价网络的通用合成方法的潜力，例如聚噻吩和聚咔唑单层的成功合成。

附：英文原文

Title: Nitrogen-doped amorphous monolayer carbon

Author: Bai, Xiuhui, Hu, Pengfei, Li, Ang, Zhang, Youwei, Li, Aowen, Zhang, Guangjie, Xue, Yufeng, Jiang, Tianxing, Wang, Zezhou, Cui, Hanke, Kang, Jianxin, Zhao, Hewei, Gu, Lin, Zhou, Wu, Liu, Li-Min, Qiu, Xiaohui, Guo, Lin

Issue&Volume: 2024-09-25

Abstract: Monoatomic-layered carbon materials, such as graphene1 and amorphous monolayer carbon2,3, have stimulated intense fundamental and applied research owing to their unprecedented physical properties and a wide range of promising applications4,5. So far, such materials have mainly been produced by chemical vapour deposition, which typically requires stringent reaction conditions compared to solution-phase synthesis. Herein, we demonstrate the solution preparation of free-standing nitrogen-doped amorphous monolayer carbon with mixed five-, six- and seven-membered (5-6-7-membered) rings through the polymerization of pyrrole within the confined interlayer cavity of a removable layered-double-hydroxide template. Structural characterizations and first-principles calculations suggest that the nitrogen-doped amorphous monolayer carbon was formed by radical polymerization of pyrrole at the α, β and N sites subjected to confinement of the reaction space, which enables bond rearrangements through the Stone–Wales transformation. The spatial confinement inhibits the C–C bond rotation and chain entanglement during polymerization, resulting in an atom-thick continuous amorphous layer with an in-plane π-conjugation electronic structure. The spatially confined radical polymerization using solid templates and ion exchange strategy demonstrates potential as a universal synthesis approach for obtaining two-dimensional covalent networks, as exemplified by the successful synthesis of monolayers of polythiophene and polycarbazole.

DOI: 10.1038/s41586-024-07958-0

Source: https://www.nature.com/articles/s41586-024-07958-0