Imperial College London
Alternate

Prof Milo Shaffer

Faculty of Natural Sciences, Department of Chemistry

Professor of Materials Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5825m.shaffer Website

 
 
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Assistant

 

Mr John Murrell +44 (0)20 7594 2845

 
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Location

 

401BMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Clancy:2019:10.1039/c8sc04970j,
author = {Clancy, A and Sirisinudomkit, P and Anthony, D and Thong, A and Greenfield, J and Salaken, Singh MK and Shaffer, M},
doi = {10.1039/c8sc04970j},
journal = {Chemical Science},
pages = {3300--3306},
title = {Real-time mechanistic study of carbon nanotube anion functionalisation through open circuit voltammetry},
url = {http://dx.doi.org/10.1039/c8sc04970j},
volume = {10},
year = {2019}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - The mechanism of the functionalisation of reduced single walled carbon nanotubes with organobromides was monitored byopen circuit voltammetry throughout the reaction and further elucidated through a series of comparative reactions. Thedegree of functionalisation was mapped against the reagent reduction potential, degree of electron donation of substituents(Hammett parameter), and energies calculated, ab initio, for dissociation and heterolytic cleavage of the C-Br bond. Incontrast to the previously assumed reduction/homolytic cleavage mechanism, the reaction was shown to consist of a rapidassociation of carbon-halide bond to the reduced nanotube as a complex, displacing surface-condensed countercations,leading to an initial increase in the net nanotube surface negative charge. The complex subsequently slowly degradesthrough charge transfer from the reduced single-walled carbon nanotube to the organobromide, utilizing charge, and thecarbon-halide bond breaks heterolytically. Electron density on the C-Br bond in the initial reagent is the best predictor fordegree of functionalisation, with more electron donating substituents increasing the degree of functionalisation. Both themechanism and the new application of OCV to study such reactions are potentially relevant to wide range of related systems.
AU  - Clancy,A
AU  - Sirisinudomkit,P
AU  - Anthony,D
AU  - Thong,A
AU  - Greenfield,J
AU  - Salaken,Singh MK
AU  - Shaffer,M
DO  - 10.1039/c8sc04970j
EP  - 3306
PY  - 2019///
SN  - 2041-6520
SP  - 3300
TI  - Real-time mechanistic study of carbon nanotube anion functionalisation through open circuit voltammetry
T2  - Chemical Science
UR  - http://dx.doi.org/10.1039/c8sc04970j
UR  - http://hdl.handle.net/10044/1/67302
VL  - 10
ER  -
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