DOI: 10.1126/science.1087691. Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization

Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization

10.1126/science.1087691

Crossref journal-article

American Association for the Advancement of Science (AAAS)

Science (221)

Abstract

Diazonium reagents functionalize single-walled carbon nanotubes suspended in aqueous solution with high selectivity and enable manipulation according to electronic structure. For example, metallic species are shown to react to the near exclusion of semiconducting nanotubes under controlled conditions. Selectivity is dictated by the availability of electrons near the Fermi level to stabilize a charge-transfer transition state preceding bond formation. The chemistry can be reversed by using a thermal treatment that restores the pristine electronic structure of the nanotube.

Bibliography

Strano, M. S., Dyke, C. A., Usrey, M. L., Barone, P. W., Allen, M. J., Shan, H., Kittrell, C., Hauge, R. H., Tour, J. M., & Smalley, R. E. (2003). Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization. Science, 301(5639), 1519â1522.

Authors 10

Michael S. Strano (first)
Christopher A. Dyke (additional)
Monica L. Usrey (additional)
Paul W. Barone (additional)
Mathew J. Allen (additional)
Hongwei Shan (additional)
Carter Kittrell (additional)
Robert H. Hauge (additional)
James M. Tour (additional)
Richard E. Smalley (additional)

References 23 Referenced 1,194

10.1021/ar010152e
M. S. Dresselhaus G. Dresselhaus P. C. Eklund Science of Fullerenes and Carbon Nanotubes (Academic Press San Diego CA 1996). (10.1016/B978-012221820-0/50003-4)
10.1116/1.1380721
R. Saito G. Dresselhaus M. S. Dresselhaus Physical Properties of Carbon Nanotubes (Imperial College Press London 1998). (10.1142/p080)
10.1166/jnn.2003.194
10.1126/science.1072631
10.1126/science.1078727
10.1021/nl034196n
10.1039/b201013p
10.1021/ar010155r
10.1002/cphc.200390015
10.1038/nmat877
10.1021/ja028599l
10.1103/PhysRevB.62.4273
10.1021/la9708142
10.1021/ja0289806
10.1021/ja010462s
A recirculating flow reactor was used to transfer sodium dodecyl sulfate–suspended carbon nanotubes at pH = 10 at a flow rate of 150 ml/min through a cuvette with inlet and outlet ports. Continuous UV-vis-nIR spectra were generated after the addition of a metered amount of diazonium aryl chloride tetrafluoroborate. Addtions were made in 0.05 mM increments after the system had reached steady state.
M. S. Strano et al., J. Phys. Chem. B107, 6979 (2002). / J. Phys. Chem. B (2002)
10.1021/nl0156639
Increasing the ionic strength of the surfactant-suspended nanotubes screens the charged repulsion of the sulfate head groups and causes the adsorbed layer to adopt a configuration that allows greater access of water to the surface. This causes a characteristic red shift of the absorption transitions that is most prominent for the v1→c1 transitions of the semiconductors. Because of the convolution of the transitions in the spectrum this shifting is seen as a change in intensity of one region in particular. The results can be qualitatively duplicated by the addition of 100 mM NaCl to the solution.
Thermogravimetricanalysis as well as absorption and Raman spectra of the reacted and thermally restored material are available as supporting material on Science Online.
We thank J. White for assistance with Raman spectroscopy M.S.S. acknowledges the financial support of the University of Illinois School of Chemical Sciences. Support at Rice University was provided by the NSF Focused Research Group on Fullerene Nanotube Chemistry (DMR-0073046) the NSF Center for Biological and Environmental Nanotechnology (EEC-0118007) NASA URETI NCC-01-0203 Air Force Office of Scientific Research (F49620-01-1-0364) and the Office of Naval Research Polymer Division. Support from NASA (NCC9-77) for development of the HiPco method is also gratefully acknowledged.

Dates

Type	When
Created	21 years, 11 months ago (Sept. 12, 2003, 1:03 a.m.)
Deposited	1 year, 7 months ago (Jan. 9, 2024, 11:05 p.m.)
Indexed	1 week, 2 days ago (Aug. 12, 2025, 6:12 p.m.)
Issued	21 years, 11 months ago (Sept. 12, 2003)
Published	21 years, 11 months ago (Sept. 12, 2003)
Published Print	21 years, 11 months ago (Sept. 12, 2003)

Funders 0

None

BibTeX

@article{Strano_2003, title={Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization}, volume={301}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1087691}, DOI={10.1126/science.1087691}, number={5639}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Strano, Michael S. and Dyke, Christopher A. and Usrey, Monica L. and Barone, Paul W. and Allen, Mathew J. and Shan, Hongwei and Kittrell, Carter and Hauge, Robert H. and Tour, James M. and Smalley, Richard E.}, year={2003}, month=sep, pages={1519–1522} }

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