基于缺陷曲率对含有V1~V4空位(5,5)单壁碳纳米管[1+1]和[2+1]加成反应的第一性原理研究
收稿日期: 2016-11-29
修回日期: 2017-02-13
网络出版日期: 2017-02-13
基金资助
项目受内蒙古自然科学基金（No.2016MS0513）和内蒙古科技大学青年人才孵化器（No.2014CY012）资助.
[1+1] and [2+1] Additions on a (5,5) Single-Walled Carbon Nanotube with V1~V4 Vacancies Based on Defect Curvature: A First Principles Study
Received date: 2016-11-29
Revised date: 2017-02-13
Online published: 2017-02-13
Supported by
Project supported by the Natural Science Foundation of Inner Mongolia (No. 2016MS0513) and Youth Talent Incubator of Inner Mongolia University of Science and Technology (No. 2014CY012).
本工作使用GGA-PBE方法研究了H和O在含有V1~V4空位（5，5）单壁碳纳米管[1+1]（H/[1+1]）和[2+1]（O/[2+1]）加成反应的结合能、几何和电子结构.基于方向曲率理论提出的缺陷曲率包括原子曲率（KM-def）和键曲率（KD-def）预测了空位缺陷区不同原子和键的加成反应活性.计算结果表明，不管是[1+1]还是[2+1]加成，V1和V3空位缺陷中含有悬空键的C原子化学活性最强，且在[2+1]加成反应中C与O原子形成了羰基；对空位缺陷区其它原子或键，H与（5，5）管V1~V4空位缺陷区的原子结合能随KM-def的增大而增大；O加成在大KD-def的C-C键时，C-C键易被打断，形成C-O-C产物结构，且相应的结合能较大；O加成在小KD-def的C-C键时，C-C键未被打断，形成三元环产物结构.H/[1+1]和O/[2+1]加成反应结合能除了主要受曲率的影响，还受到参与反应的C原子在（5，5）管最高占据分子轨道的电荷密度以及分波态密度的影响.这些研究将为含有空位缺陷碳纳米管的表面修饰提供理论依据.
李磊 , 贾桂霄 , 王晓霞 , 吴铜伟 , 宋希文 , 安胜利 . 基于缺陷曲率对含有V1~V4空位(5,5)单壁碳纳米管[1+1]和[2+1]加成反应的第一性原理研究[J]. 化学学报, 2017 , 75(3) : 284 -292 . DOI: 10.6023/A16110645
Binding energies, geometric and electronic structures for[1+1] (H/[1+1]) and[2+1] (O/[2+1]) additions of H and O atoms on a (5,5) single-walled carbon nanotube with V1~V4 vacancies are studied using a GGA-PBE method in this work. Defect curvature proposed on the basis of directional curvature theory, including atomic curvature (KM-def) and bond curvature (KD-def), is used to predict the reactivities of different atoms and bonds at the defect structural area. We find that the existence of vacancy defects enhances the H and O adsorption ability on the (5,5) tube. The calculated results show that in the V1 and V3 defects the C atoms with two-coordination have the strongest chemical activity for[1+1] and[2+1] additions, and among which the C atoms participated into[2+1] additions form carbonyl groups with O. For other atoms and bonds at the defect structural area, the binding energies of one H atom on the (5,5) tube monotonously increases with the increase of KM-def. When the KD-def of C-C bonds for the O/[2+1] additions are large, the C-C bonds are easily broken, and they are corresponding to adducts with the C-O-C configuration structures and large binding energies. When the KD-def of C-C bonds are small, the C-C bonds are not broken, and they are corresponding to adducts with the closed-3MR (three-member ring) structures. The binding energies for the H/[1+1] and O/[2+1] additions on the (5,5) tube mainly are determined by the curvature and affected by the electronic density in frontier orbital and partial density of state (PDOS) of C atoms participated in the reactions. The large electronic density in the highest occupied molecular orbital (HOMO) and large PDOS of C atoms near the Fermi level strengthen the adsorption of H and O atoms on the (5,5) tube. This study will provide a theoretical basis for surface modifications of carbon nanotubes with vacancy defects.
Key words： carbon nanotubes; vacancies; defect curvature; electronic structures; additions
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