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Chemistry of Carbon Nanostructures: Functionalization of Carbon Nanotubes and Synthesis of Organometallic Fullerene Derivatives
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry, Physical Organic Chemistry. (Helena Grennberg)
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based on two main parts. The first part concerns purification and functionalization of carbon nanotubes (papers I-III), and the second part is related to the synthesis of organometallic fullerene derivatives (papers IV-VII):

Two oxidative methods involving aqueous nitric acid were compared with respect to their capability to introduce carboxylic groups into single walled carbon nanotubes, and several literature methods for esterification and amidation of these groups have been evaluated with focus on efficiency and reproducibility in forming covalently functionalized products soluble in organic media. Amidation proceeding via a SWNT-(COCl)n intermediate yielded the expected covalent product, whereas carboxylate salt formation dominated with other attempted methods. Esterification was achieved via the acyl chloride method and via alkylation of SWNT-(COO)n, the latter being the more efficient method.

A new, reagent-free method for purification of single- and multi walled carbon nanotubes has been developed. Microwave treatment dissociates non-nanotube carbon and disperses it into an organic solvent, resulting in very pure carbon nanotubes within a few minutes of heating, without the involvement of acidic/oxidative reagents. According to thermogravimetric analysis, Raman and IR spectroscopy, as well as SEM, the process yields nanotubes with a low degree of defects.

A non-covalent approach has been employed to prepare nanotubes functionalized with glycosides. Derivatives of galactose and lactose were covalently linked to a pyrene moiety and the thus formed pyrene-glycosides were non-covalently attached to single- and multi walled carbon nanotubes by π-π interactions. Fluorescence titrations have been used to quantify the formed supramolecular assemblies, which for SWNTs exhibits increased water solubility.

A fulleropyrrolidine-(tricarbonyl)chromium complex was synthesized and fully characterized. IR spectroelectrochemistry was used to probe the redox state of the fullerene and provided evidence for electronic communication between the two electroacive moieties. A C60-ferrocene-C60 triad system was synthesized and characterized. Cyclic voltammetry and fluorescence studies suggested electronic communication between ferrocene and the two fullerenes. Finally, the synthesis and initial characterization of short fullerene-ferrocene oligomers are presented.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2011. , 62 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 859
Keyword [en]
Carbon nanotubes, Fullerenes, Purification, Functionalization, Organometallic complexes
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-159315ISBN: 978-91-554-8170-4 (print)OAI: oai:DiVA.org:uu-159315DiVA: diva2:444118
Public defence
2011-11-10, B7:101a, BMC, Husargatan 3, Uppsala, 09:30 (English)
Opponent
Supervisors
Available from: 2011-10-19 Created: 2011-09-27 Last updated: 2011-11-04Bibliographically approved
List of papers
1. Reproducibility and efficiency of carbon nanotube end-group generation and functionalization
Open this publication in new window or tab >>Reproducibility and efficiency of carbon nanotube end-group generation and functionalization
2009 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, Vol. 26, 4421-4428 p.Article in journal (Refereed) Published
Abstract [en]

In a systematic fashion, several methods for esterification and  amidation of single-walled carbon nanotubes have been evaluated with   focus on efficiency and reproducibility in forming covalently   functionalized products soluble in organic media. The outcome of   transformations was determined using IR, Raman and NMR spectroscopy and   by thermogravimetric analysis (TGA). Amidation proceeding via a   SWNT-(COCl)(n) intermediate yielded the expected covalent product,  whereas carboxylate salt formation dominated with other attempted   methods. Esterification was achieved via the acyl chloride method and   via alkylation of SWNT-(COO-)(n), the latter being the more efficient   method. A non-covalent solubilizing interaction was obtained for RNH2   but not for ROH (R = octadecyl), proving that the most important   non-covalent interaction between oxidatively cleaned SWNTs and   octadecylamine is a salt formation. The outcome of the secondary   functionalization of carboxyl units is highly reproducible for   experiments carried out on the same batch of SWNT-(COOH)(n). Normalization of the outcome of the secondary functionalization to the   composition of the different batches of starting materials reveals an overall high reproducibility of the secondary function alizations. The   differences in outcome related to different commercial SWNT batches   from the same synthetic procedure is negligible compared to that   resulting from differences in overall carboxyl content after the   primary HNO3 oxidative cleaning step. Hence, the composition of   purified SWNT starting materials always needs to be assessed, in particular before drawing any conclusions concerning differences in   outcome from reaction systems involving different sources of SWNT  material.

Keyword
Nanotubes, Nanotechnology, Functionalization, Esterification, Amidation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-112369 (URN)10.1002/ejoc.200900534 (DOI)000270014700006 ()
Available from: 2010-01-13 Created: 2010-01-13 Last updated: 2017-12-12Bibliographically approved
2. The reagent-free, microwave-assisted purification of carbon nanotubes
Open this publication in new window or tab >>The reagent-free, microwave-assisted purification of carbon nanotubes
Show others...
2010 (English)In: New Journal of Chemistry, ISSN 1144-0546, E-ISSN 1369-9261, Vol. 34, no 10, 2275-2280 p.Article in journal (Refereed) Published
Abstract [en]

We have developed a microwave-assisted, reagent-free method for the efficient primary purification of MW and SW carbon nanotubes that is extremely fast compared to previously reported processes. The treatment dissociates and disperses non-nanotube carbon in an organic solvent to yield very pure carbon nanotubes within a few minutes of heating and a simple filtration, without the involvement of acidic/oxidative reagents. According to thermogravimetric analysis, Raman and IR spectroscopy, as well as scanning and transmission electron microscopy, the process yields pure nanotubes with a low degree of defects.

National Category
Chemical Sciences Inorganic Chemistry Engineering and Technology
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-134674 (URN)10.1039/c0nj00087f (DOI)000282219600029 ()
Available from: 2010-12-01 Created: 2010-11-30 Last updated: 2017-12-12Bibliographically approved
3. Reversible Non-Covalent Derivatisation of Carbon Nanotubes with Glycosides
Open this publication in new window or tab >>Reversible Non-Covalent Derivatisation of Carbon Nanotubes with Glycosides
2009 (English)In: Soft Matter, ISSN 1744-683X, Vol. 5, no 14, 2713-2716 p.Article in journal (Refereed) Published
Abstract [en]

SWNTs and MWNTs have been non-covalently functionalized with glycosides   in a reversible manner, and fluorescence titrations have been used to   quantify the formed supramolecular assemblies which for SWNTs exhibits   increased water solubility.

Keyword
carbon nanotube
National Category
Chemical Sciences
Identifiers
urn:nbn:se:uu:diva-112366 (URN)10.1039/ B907791J (DOI)000268783500006 ()
Available from: 2010-01-13 Created: 2010-01-13 Last updated: 2011-11-04Bibliographically approved
4. Synthesis and IR Spectroelectrochemical Studies of a [60]Fulleropyrrolidine-(tricarbonyl)chromium Complex: Probing C-60 Redox States by IR Spectroscopy
Open this publication in new window or tab >>Synthesis and IR Spectroelectrochemical Studies of a [60]Fulleropyrrolidine-(tricarbonyl)chromium Complex: Probing C-60 Redox States by IR Spectroscopy
2011 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, no 11, 1744-1749 p.Article in journal (Refereed) Published
Abstract [en]

The synthesis of a new fulleropyrrolidine-(tricarbonyl)chromium complex: 1-methyl-2-(4-methoxyphenyl)-3,4-[60]fulleropyrrolidine-(tricarbonyl)chromium is described together with its characterization by IR, NMR and cyclic voltammetry. IR spectro-electrochemistry has been used to probe the redox level of the fullerene derivative via the relative position of the vibrational bands of the CO ligands, which are sensitive to the electronic state of the complex. Other strategies to incorporate a tricarbonylchromium moiety to fullerene C60 are also briefly discussed and evaluated.

Place, publisher, year, edition, pages
John Wiley & Sons, 2011
Keyword
Fullerenes, Chromium, IR spectroscopy, Cyclic voltammetry, Redox chemistry, Electrochemistry
National Category
Chemical Sciences
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-148456 (URN)10.1002/ejic.201100011 (DOI)000289354900008 ()
Available from: 2011-03-07 Created: 2011-03-07 Last updated: 2017-12-11
5. Synthesis and characterization of a ferrocene-linked bis-fullerene[60] dumbbell
Open this publication in new window or tab >>Synthesis and characterization of a ferrocene-linked bis-fullerene[60] dumbbell
2012 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 41, no 8, 2374-2381 p.Article in journal (Refereed) Published
Abstract [en]

A new [60]fullerene dumbbell consisting of two fulleropyrrolidines connected to a central ferrocene unit by amide linkages has been prepared and fully characterized by elemental analysis, 1H NMR, UV/Vis, fluorescence and mass spectrometry. The electrochemical properties as determined by cyclic voltammetry show ground state electronic communication between the ferrocene and the fullerene units. In addition, the preparaton of a ferrocene building block for an alternative linking approach is presented.

Keyword
Fullerenes, Ferrocene, Dumbbell, Cyclic voltammetry
National Category
Organic Chemistry Inorganic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry; Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-158905 (URN)10.1039/C2DT12097F (DOI)000300186100022 ()
Available from: 2011-09-19 Created: 2011-09-19 Last updated: 2017-12-08Bibliographically approved
6. Short ferrocene-[60]fulleropyrrolidine oligomers. A preliminary account on synthetic studies
Open this publication in new window or tab >>Short ferrocene-[60]fulleropyrrolidine oligomers. A preliminary account on synthetic studies
(English)Manuscript (preprint) (Other academic)
Abstract [en]

A synthetic strategy towards short fullerene based organometallic oligomers is reported. The synthetic approach is based on the secondary functionalization of N-unsubstituted fulleropyrrolidines with ferrocene dicarboxylic acid chloride. Preliminary characterization by mass spectrometry, UV/Vis and NMR suggest a trimer or tetramer structure.

Keyword
Fullerenes / Oligomers / Ferrocene
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-159308 (URN)
Note
preliminärt manuskriptAvailable from: 2011-09-27 Created: 2011-09-27 Last updated: 2011-11-04
7.   Appendix: Experimental details for tricarbonyl chromium complexes
Open this publication in new window or tab >>  Appendix: Experimental details for tricarbonyl chromium complexes
2011 (English)Other (Other academic)
Place, publisher, year, pages
Uppsala: Acta Universitatis Upsaliensis, 2011
National Category
Organic Chemistry
Research subject
Chemistry with specialization in Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-159309 (URN)
Available from: 2011-09-27 Created: 2011-09-27 Last updated: 2011-11-04

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