Tahara Kazukuni, Ishikawa Toru, Hirsch Brandon E, Kubo Yuki, Brown Anton, Eyley Samuel, Daukiya Lakshya, Thielemans Wim, Li Zhi, Walke Peter, Hirose Shingo, Hashimoto Shingo, De Feyter Steven, Tobe Yoshito
Division of Frontier Materials Science, Graduate School of Engineering Science , Osaka University , Toyonaka , Osaka 560-8531 , Japan.
Department of Applied Chemistry, School of Science and Technology , Meiji University , 1-1-1 Higashimita, Tama-ku , Kawasaki , Kanagawa 214-8571 , Japan.
ACS Nano. 2018 Nov 27;12(11):11520-11528. doi: 10.1021/acsnano.8b06681. Epub 2018 Nov 12.
An approach for nanoscale covalent functionalization of graphite surfaces employing self-assembled molecular monolayers of n-alkanes as templating masks is presented. Linearly aligned aryl groups with a lateral periodicity of 5 or 7 nm are demonstrated utilizing molecular templates of different lengths. The key feature of this approach is the use of a phase separated solution double layer consisting of a thin organic layer containing template molecules topped by an aqueous layer containing aryldiazonium molecules capable of electrochemical reduction to generate aryl radicals which bring about surface grafting. Upon sweeping of the potential, lateral displacement dynamics at the n-alkane terminal edges acts in conjunction with electrochemical diffusion to result in templated covalent bond formation in a linear fashion. This protocol was demonstrated to be applicable to linear grafting of graphene. The present processing described herein is useful for the realization of rationally designed nanoscale materials.
提出了一种利用正构烷烃自组装分子单层作为模板掩膜对石墨表面进行纳米级共价功能化的方法。利用不同长度的分子模板展示了具有5或7 nm横向周期性的线性排列芳基。该方法的关键特征是使用相分离溶液双层，其由包含模板分子的薄有机层和包含能够电化学还原以产生芳基自由基从而实现表面接枝的芳基重氮鎓分子的水层组成。在扫描电位时，正构烷烃末端边缘的横向位移动力学与电化学扩散共同作用，以线性方式导致模板化共价键形成。该方案被证明适用于石墨烯的线性接枝。本文所述的当前工艺对于实现合理设计的纳米级材料很有用。
