石墨烯的光化学修饰方法

1. 北京大学纳米化学研究中心 北京大学化学与分子工程学院 北京 100871
• 投稿日期:2013-08-29 发布日期:2013-10-30
• 通讯作者: 刘忠范，E-mail：zfliu@pku.edu.cn E-mail:zfliu@pku.edu.cn
• 基金资助:

项目受科技部国家重点基础研究发展规划（Nos. 2013CB932606，2012CB933404，2011CB933003）和国家自然科学基金（Nos. 51121091，51290272）资助.

Photochemical Modification of Graphene

Zhou Lin, Zhang Liming, Liao Lei, Yang Mingmei, Xie Qin, Peng Hailin, Liu Zhirong, Liu Zhongfan

1. Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871
• Received:2013-08-29 Published:2013-10-30
• Supported by:

Project supported by the National Basic Research Program of China (Nos. 2013CB932606，2012CB933404，2011CB933003) and the National Natural Science Foundation of China (Nos. 51121091, 51290272).

Graphene, a two-dimensional (2D) atomic crystal composed of single-layer hexagonal mesh of carbon atoms, is one of the most exciting materials being investigated today. Graphene chemistry, the covalent functionalization of graphene as a giant molecule, provides a promising approach to controllably engineer graphene's band structure, create novel graphene derivatives and tailor the interfacial characteristics. One of the great challenges for graphene functionalization originates from its strong chemical stability, thus highly reactive chemical species are needed as the reactants. In recent years, we have been working on the photo-induced free radicals-based photochemistry of graphene, targeting the efficient graphene functionalization for its band structure engineering. Various photochemical modification methods have been developed, such as photochemical chlorination, photochemical methylation, photocatalytic oxidation and bifacially asymmetric functionalization of graphene. The homogeneous and nondestructive photochlorination of graphene could remove the conducting π-bands and open up a band gap in graphene. TiO2-based photocatalytic oxidation of graphene could realize photochemical tailoring of graphene, including ribbon cutting, arbitrary patterning on any substrate, layer-by-layer thinning, and localized graphene to graphene oxidation conversion. Using photochemical reaction of graphene as a probe, we have investigated the dimension effects on graphene chemistry, including the thickness, stacking order, single- and double-side, and edge dependent reactivity in graphene. After two-step functionalization of graphene, we have fabricated the thinnest Janus disc named Janus graphene, which comprises two kinds of decorations separated by the one-atom-thick carbon layer. It is found that chemical decorations on one side are capable of affecting both chemical reactivity and wettability of the opposite side, indicative of communication between the two grafted decorations separated by a single-layer graphene. In this review, we select several typical examples to demonstrate such kinds of photochemical graphene engineering and its intrinsic 2D reaction characteristics, together with a brief discussion on the future directions, challenges and opportunities in this research area.