Functionalization of Multiwalled Carbon Nanotubes with Cyclic Nitrones for Materials and Composites: Addressing the Role of CNT Sidewall Defects

被引:51
作者
Giambastiani, Giuliano [1 ]
Cicchi, Stefano [2 ]
Giannasi, Alessandra [3 ]
Luconi, Lapo [1 ]
Rossin, Andrea [1 ]
Mercuri, Francesco [4 ,5 ]
Bianchini, Claudio [1 ]
Brandi, Alberto [2 ]
Melucci, Manuela [1 ]
Ghini, Giacomo [1 ]
Stagnaro, Paola [6 ]
Conzatti, Lucia [6 ]
Passaglia, Elisa [7 ,8 ]
Zoppi, Marco [3 ]
Montini, Tiziano [9 ]
Fornasiero, Paolo [9 ]
机构
[1] Ist Chim Composti Organometallici ICCOM CNR, I-50019 Florence, Italy
[2] Univ Florence, Dipartimento Chim U Schiff, I-50019 Florence, Italy
[3] Ist Sistemi Complessi ISC CNR, I-50019 Florence, Italy
[4] Univ Perugia, Ist Sci Tecnol Mol ISTM CNR, I-06123 Perugia, Italy
[5] Univ Perugia, UdR INSTM, Dipartimento Chim, I-06123 Perugia, Italy
[6] UOS Genova, Ist Studio Macromol ISMAC CNR, I-16149 Genoa, Italy
[7] UOS Pisa, Ist Chim Composti Organomet ICCOM CNR, I-56126 Pisa, Italy
[8] Univ Pisa, I-56126 Pisa, Italy
[9] Univ Trieste, Ist Chim Composti Organomet ICCOM CNR, Dipartimento Sci Chim & Farmaceut, I-34127 Trieste, Italy
关键词
MWCNTs; nitrones; 1,3-dipolar cycloaddition; topological defects; Raman; ASA; DFT calculations; AZA-C-DISACCHARIDES; PYRROLINE N-OXIDES; SINGLE-WALL; RAMAN-SPECTROSCOPY; SURFACE CHARACTERIZATIONS; CHEMICAL-MODIFICATION; THIN-FILMS; CYCLOADDITION; GRAPHENE; REACTIVITY;
D O I
10.1021/cm103655y
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An efficient approach to the organic functionalization of multiwalled carbon nanotubes (MWCNTs) for the production of highly soluble/dispersible materials has been accomplished by a class of highly reactive and thermally stable nitrones. Besides the unprecedented solubility in aprotic polar solvents of the functionalized samples (up to 10 mg of f-MWCNTs per mL of DMF), we have demonstrated, for the first time, that the CNT functionalization by nitrones preferentially occurs at the defective CNT sidewalls without any appreciable degradation of their sp(2) network The role of the reticular imperfections on the graphitic lattice of the MWCNTs has been experimentally and theoretically addressed. A complete chemical (TGA-MS, FT-IR, SSA) and morphological (TEM, AFM) characterization of the functionalized materials has accounted for the high degree of CNT functionalization, whereas Raman scattering, in combination with complementary XRPD and active surface area (ASA) measurements, has provided unambiguous evidence of the key role played by the structural "disorder" of the MWCNTs in the nitrone cycloaddition. Density functional theory (DFT) calculations on the reactivity of selected topological defects at the CNT sidewalls have contributed to trace-out a "defect-based" sidewall reactivity trend. The excellent processability of the functionalized MWCNTs has been finally exploited for the preparation of highly homogeneous CNT/polymer nanocomposites with CNT loadings as high as 3 wt %
引用
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页码:1923 / 1938
页数:16
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