Institute of Advanced Energy Kyoto University , Gokasho Uji, Kyoto 611-0011, Japan.
Department of Chemistry, National University of Singapore , 3 Science Drive 3, Singapore 117543.
Langmuir. 2017 Oct 10;33(40):10439-10445. doi: 10.1021/acs.langmuir.7b01862. Epub 2017 Sep 29.
The orientation and electronic structure of multilayered graphene nanoribbons with an armchair-edge (AGNRs) were determined by low-temperature scanning tunneling microscopy in this study. The orientation of AGNRs was found to be an edge-on structure when positioned as a top layer, while previous reports showed a face-on structure for monolayered AGNRs on Au(111). According to density functional theory calculations, AGNRs in a top layer preferentially form as edge-on structures rather than face-on structures due to the balance of CH-π and π-π interactions between AGNRs. Scanning tunneling spectroscopy and density functional theory calculations revealed that the electronic structures of multilayered AGNRs are similar to those in a gas-phase due to the lack of interaction between AGNRs and the Au(111) substrate. The observation of AGNRs in mutilayers might suggest the conformation-assisted mechanism of dehydrogenation when there is no contact with the Au(111) substrate.
本研究通过低温扫描隧道显微镜确定了具有扶手椅边缘(AGNRs)的多层石墨烯纳米带的取向和电子结构。当 AGNRs 作为顶层放置时,其取向被发现为边缘结构,而之前的报告表明单层 AGNRs 在 Au(111)上为面内结构。根据密度泛函理论计算,由于 AGNRs 之间的 CH-π 和 π-π 相互作用的平衡,顶层的 AGNRs 优先形成边缘结构而不是面内结构。扫描隧道光谱和密度泛函理论计算表明,由于 AGNRs 与 Au(111)基底之间没有相互作用,多层 AGNRs 的电子结构类似于气相中的结构。在没有与 Au(111)基底接触的情况下,观察到多层 AGNRs 可能表明存在脱氢的构象辅助机制。