光环化反应实现精确可控石墨烯杂化，这一成果由Miao Yu (哈尔滨工业大学)、André Gourdon、Lev Kantorovich和Federico Rosei研究团队经过不懈努力而取得。 相关论文于2020年10月19日发表在《自然—化学》杂志上。

研究组演示了在二维分子网络上的具有空间选择性性的光环加成反应，该二维分子网络具有无缺陷的单层石墨烯基面。在亚分子级别直接观察表明，环加成反应是由紫外线照射在超高真空下引发，不需要石墨烯莫尔条纹的辅助。反应包括[2 + 2]和[2 + 4]环加反应，反应位点对齐到一个二维扩展和秩序井然的阵列，诱导反应石墨烯的能带隙层。这项工作为设计和工程化基于石墨烯的光电和微电子器件提供了坚实的基础。

据悉，将sp2转化为sp3杂化的化学反应已被证明是一个迷人却具有挑战性的功能化石墨烯的路线。迄今为止，在原子/分子尺度上精确地控制反应位点或它们的侧向顺序还无法实现。对于需要长时间浸泡，加热，电脉冲或探针按压的反应，其应用前景受到限制。

附：英文原文

Title: Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition

Author: Miao Yu, Chong Chen, Qi Liu, Cristina Mattioli, Hongqian Sang, Guoqiang Shi, Wujun Huang, Kongchao Shen, Zhuo Li, Pengcheng Ding, Pengfei Guan, Shaoshan Wang, Ye Sun, Jinping Hu, Andr Gourdon, Lev Kantorovich, Flemming Besenbacher, Mingshu Chen, Fei Song, Federico Rosei

Issue&Volume: 2020-10-19

Abstract: Chemical reactions that convert sp2 to sp3 hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press. Here we demonstrate a spatially selective photocycloaddition reaction of a two-dimensional molecular network with defect-free basal plane of single-layer graphene. Directly visualized at the submolecular level, the cycloaddition is triggered by ultraviolet irradiation in ultrahigh vacuum, requiring no aid of the graphene Moiré pattern. The reaction involves both [2+2] and [2+4] cycloadditions, with the reaction sites aligned into a two-dimensional extended and well-ordered array, inducing a bandgap for the reacted graphene layer. This work provides a solid base for designing and engineering graphene-based optoelectronic and microelectronic devices.

DOI: 10.1038/s41557-020-0540-2

Source: https://www.nature.com/articles/s41557-020-0540-2