Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes

Andrew J. Hilmer, Thomas P. McNicholas, Shangchao Lin, Jingqing Zhang, Qing Wang, Jonathan D. Mendenhall, Changsik Song, Daniel A. Heller, Paul W. Barone, Daniel Blankschtein, Michael S. Strano

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes.

Original languageEnglish (US)
Pages (from-to)1309-1321
Number of pages13
JournalLangmuir
Volume28
Issue number2
DOIs
StatePublished - Jan 17 2012
Externally publishedYes

Fingerprint

Single-walled carbon nanotubes (SWCN)
Surface-Active Agents
Surface active agents
Salts
carbon nanotubes
surfactants
salts
Nanotubes
nanotubes
Sodium
sodium
Sodium Cholate
Carbon Nanotubes
Chemical modification
Bile Acids and Salts
exclusion
Electrostatics
Carbon nanotubes
Taurodeoxycholic Acid
Ions

ASJC Scopus subject areas

  • Electrochemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Materials Science(all)
  • Spectroscopy

Cite this

Hilmer, A. J., McNicholas, T. P., Lin, S., Zhang, J., Wang, Q., Mendenhall, J. D., ... Strano, M. S. (2012). Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes. Langmuir, 28(2), 1309-1321. https://doi.org/10.1021/la204067d

Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes. / Hilmer, Andrew J.; McNicholas, Thomas P.; Lin, Shangchao; Zhang, Jingqing; Wang, Qing; Mendenhall, Jonathan D.; Song, Changsik; Heller, Daniel A.; Barone, Paul W.; Blankschtein, Daniel; Strano, Michael S.

In: Langmuir, Vol. 28, No. 2, 17.01.2012, p. 1309-1321.

Research output: Contribution to journalArticle

Hilmer, AJ, McNicholas, TP, Lin, S, Zhang, J, Wang, Q, Mendenhall, JD, Song, C, Heller, DA, Barone, PW, Blankschtein, D & Strano, MS 2012, 'Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes', Langmuir, vol. 28, no. 2, pp. 1309-1321. https://doi.org/10.1021/la204067d
Hilmer, Andrew J. ; McNicholas, Thomas P. ; Lin, Shangchao ; Zhang, Jingqing ; Wang, Qing ; Mendenhall, Jonathan D. ; Song, Changsik ; Heller, Daniel A. ; Barone, Paul W. ; Blankschtein, Daniel ; Strano, Michael S. / Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes. In: Langmuir. 2012 ; Vol. 28, No. 2. pp. 1309-1321.
@article{a74ce909d8654a6e9d3364172d51da2e,
title = "Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes",
abstract = "Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes.",
author = "Hilmer, {Andrew J.} and McNicholas, {Thomas P.} and Shangchao Lin and Jingqing Zhang and Qing Wang and Mendenhall, {Jonathan D.} and Changsik Song and Heller, {Daniel A.} and Barone, {Paul W.} and Daniel Blankschtein and Strano, {Michael S.}",
year = "2012",
month = "1",
day = "17",
doi = "10.1021/la204067d",
language = "English (US)",
volume = "28",
pages = "1309--1321",
journal = "Langmuir",
issn = "0743-7463",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Role of adsorbed surfactant in the reaction of aryl diazonium salts with single-walled carbon nanotubes

AU - Hilmer, Andrew J.

AU - McNicholas, Thomas P.

AU - Lin, Shangchao

AU - Zhang, Jingqing

AU - Wang, Qing

AU - Mendenhall, Jonathan D.

AU - Song, Changsik

AU - Heller, Daniel A.

AU - Barone, Paul W.

AU - Blankschtein, Daniel

AU - Strano, Michael S.

PY - 2012/1/17

Y1 - 2012/1/17

N2 - Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes.

AB - Because covalent chemistry can diminish the optical and electronic properties of single-walled carbon nanotubes (SWCNTs), there is significant interest in developing methods of controllably functionalizing the nanotube sidewall. To date, most attempts at obtaining such control have focused on reaction stoichiometry or strength of oxidative treatment. Here, we examine the role of surfactants in the chemical modification of single-walled carbon nanotubes with aryl diazonium salts. The adsorbed surfactant layer is shown to affect the diazonium derivatization of carbon nanotubes in several ways, including electrostatic attraction or repulsion, steric exclusion, and direct chemical modification of the diazonium reactant. Electrostatic effects are most pronounced in the cases of anionic sodium dodecyl sulfate and cationic cetyltrimethylammonium bromide, where differences in surfactant charge can significantly affect the ability of the diazonium ion to access the SWCNT surface. For bile salt surfactants, with the exception of sodium cholate, we find that the surfactant wraps tightly enough such that exclusion effects are dominant. Here, sodium taurocholate exhibits almost no reactivity under the explored reaction conditions, while for sodium deoxycholate and sodium taurodeoxycholate, we show that the greatest extent of reaction is observed among a small population of nanotube species, with diameters between 0.88 and 0.92 nm. The anomalous reaction of nanotubes in this diameter range seems to imply that the surfactant is less effective at coating these species, resulting in a reduced surface coverage on the nanotube. Contrary to the other bile salts studied, sodium cholate enables high selectivity toward metallic species and small band gap semiconductors, which is attributed to surfactant-diazonium coupling to form highly reactive diazoesters. Further, it is found that the rigidity of anionic surfactants can significantly influence the ability of the surfactant layer to stabilize the diazonium ion near the nanotube surface. Such Coulombic and surfactant packing effects offer promise toward employing surfactants to controllably functionalize carbon nanotubes.

UR - http://www.scopus.com/inward/record.url?scp=84862908230&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84862908230&partnerID=8YFLogxK

U2 - 10.1021/la204067d

DO - 10.1021/la204067d

M3 - Article

C2 - 22136192

AN - SCOPUS:84862908230

VL - 28

SP - 1309

EP - 1321

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 2

ER -