College of Chemistry and Chemical Engineering and Provincial Key Lab for Advanced Functional Materials and Excite State, Harbin Normal University, Harbin, People's Republic of China.
J Mol Model. 2012 Jun;18(6):2861-8. doi: 10.1007/s00894-011-1309-8. Epub 2011 Nov 30.
Chemical functionalization of graphene provides a promising route to improve its solubility in water and organic solvents as well as modify its electronic properties, thus significantly expanding its potential applications. In this article, by using density functional theory (DFT) methods, we have studied the effects of the chemical functionalization of graphenes via aryne cycloaddition on its properties. We found that the adsorption of an isolated aryne group on the graphene sheet is very weak with the adsorption energy of -0.204 eV, even though two new single C-C interactions are formed between the aryne group and the graphene. However, the interaction of graphene with the aryne group can be greatly strengthened by (i) substituting the H-atoms in aryne group with F-, Cl-, -NO(2) (electron-withdrawing capability), or CH(3)-group (electron-donating capability), and (ii) increasing the coverage of the adsorbed aryne groups on the graphene sheet. As expected, the strongest bonding is found on the graphene edges, in which the adsorbed aryne groups prefer to be far away from each other. Interestingly, chemical functionalization with aryne groups leads to an opening of the band gap of graphene, which is dependent on the coverage of the adsorbed aryne groups. The present work provides an insight into the modifications of graphene with aryne groups in experiment.
通过芳炔环加成反应对石墨烯进行化学功能化，提供了一种改善其在水和有机溶剂中溶解度以及修饰其电子性质的有前途的途径，从而显著扩大了其潜在应用。在本文中，我们通过使用密度泛函理论（DFT）方法，研究了芳炔环加成反应对石墨烯性质的影响。我们发现，孤立芳炔基团在石墨烯片上的吸附非常弱，吸附能为-0.204 eV，尽管芳炔基团和石墨烯之间形成了两个新的 C-C 单键。然而，通过（i）用 F-、Cl-、-NO2（吸电子能力）或 CH3-（供电子能力）取代芳炔基团中的 H 原子，以及（ii）增加吸附在石墨烯片上的芳炔基团的覆盖率，可以大大增强石墨烯与芳炔基团的相互作用。正如预期的那样，最强的键合发生在石墨烯边缘，在这些边缘处，吸附的芳炔基团彼此之间更喜欢保持距离。有趣的是，芳炔基团的化学功能化导致石墨烯带隙的打开，这取决于吸附的芳炔基团的覆盖率。本工作为实验中芳炔基团对石墨烯的修饰提供了深入的了解。
