Department of Chemistry and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA.
Phys Chem Chem Phys. 2011 Jun 28;13(24):11766-72. doi: 10.1039/c1cp20534j. Epub 2011 May 20.
We have studied non-covalent functionalization of boron nitride nanotubes (BNNTs) with benzene molecule and with seven other different heterocyclic aromatic rings (furan, thiophene, pyrrole, pyridine, pyrazine, pyrimidine, and pyridazine, respectively). A hybrid density functional theory (DFT) method with the inclusion of dispersion correction is employed. The structural and electronic properties of the functionalized BNNTs are obtained. The DFT calculation shows that upon adsorption to the BNNT, the center of aromatic rings tend to locate on top of the nitrogen site. The trend of adsorption energy for the aromatic rings on the BNNTs shows marked dependence on different intermolecular interactions, including the dispersion interaction (area of the delocalized π bond), the dipole-dipole interaction (polarization), and the electrostatic repulsion (lone pair electrons). The DFT calculation also shows that non-covalent functionalization of BNNTs with aromatic rings can give rise to new impurity states within the band gap of pristine BNNTs, suggesting possible carrier doping of BNNTs via selective adsorption of aromatic rings.
我们研究了苯分子和其他七种不同杂环芳烃（呋喃、噻吩、吡咯、吡啶、吡嗪、嘧啶和哒嗪）对氮化硼纳米管（BNNTs）的非共价功能化。采用包含色散校正的杂化密度泛函理论（DFT）方法。得到了功能化 BNNTs 的结构和电子性质。DFT 计算表明，吸附到 BNNT 上后，芳环的中心倾向于位于氮位的顶部。芳环在 BNNTs 上的吸附能趋势明显取决于不同的分子间相互作用，包括色散相互作用（离域π键的面积）、偶极-偶极相互作用（极化）和静电排斥（孤对电子）。DFT 计算还表明，芳环对 BNNTs 的非共价功能化可以在原始 BNNTs 的能带隙内产生新的杂质态，这表明通过选择性吸附芳环可以对 BNNTs 进行载流子掺杂。
