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Probing the Chemical Functionalization of Single‐Walled Carbon Nanotubes with Multiple Carbon Ad‐Dimer Defects
Author(s) -
Wang DongLai,
Xu HongLiang,
Su ZhongMin,
Muhammad Shabbir,
Hou DongYan
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100774
Subject(s) - carbon nanotube , dimer , exothermic reaction , chemical stability , binding energy , hydrogen , materials science , carbon fibers , chlorine , surface modification , molecule , hydrogen storage , chemistry , chemical engineering , nanotechnology , organic chemistry , atomic physics , composite material , physics , composite number , engineering
Abstract Drying‐tube‐shaped single‐walled carbon nanotubes (SWCNTs) with multiple carbon ad‐dimer (CD) defects are obtained from armchair ( n , n , m ) SWCNTs ( n =4, 5, 6, 7, 8; m =7, 13). According to the isolated‐pentagon rule (IPR) the drying‐tube‐shaped SWCNTs are unstable non‐IPR species, and their hydrogenated, fluorinated, and chlorinated derivatives are investigated. Interestingly, chemisorptions of hydrogen, fluorine, and chlorine atoms on the drying tube‐shaped SWCNTs are exothermic processes. Compared to the reaction energies for binding of H, F, and Cl atoms to perfect and Stone–Wales‐defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and Stone–Wales‐defective nanotubes. The reaction energy for per F 2 addition is between 85 and 88 kcal mol −1 more negative than that per H 2 addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.98–2.52 to 0.80–1.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying‐tube‐shaped SWCNTs with multiple CD defects are substantially increased to 1.65–3.85 eV. Furthermore, analyses of thermodynamic stability and nucleus‐independent chemical shifts (NICS) are performed to analyze the stability of these molecules.