UNSW

The Functionalization of
Carbon Nanotubes
Rongmei Liu,
School of Chemistry
University of New South Wales
Nanotubes in Analytical Chemistry
Direct electron transfer through the
transducer and the redox center of
GOx via CNT.

DNA detection via labelling with

CNT loaded with enzymes

DNA detection via labelling with

CNT loaded with quantum dots

DNA detection via labelling with

CNT loaded with enzymes

Immunosensing via antibody

labelling with CNT loaded with
enzymes

Merkoci A., Microchim Acta 152, 157-174 (2006)

 Nanotubes in Sensitive Imaging

X = functional groups of substrate

surface

Covalently functionalized nanotubes as nanometer-sized

probes in chemistry and biology
Wong, S.S., et al.,. Nature (London), 1998. Vol. 394(6688): p. 52-55
 Issues
• Tubes are insoluble in many solvents due to van der
Waals and π- π interactions; There are impurities in
the pristine tubes.
• How to solubilize CNTs individually into solvents
for further application?
 Project Strategy
Pristine tubes

Cut tubes

Covalent Non-covalent
functionalization with functionalization with
organic molecules organic molecules

Introduce spectroscopic /fluorescent labels to monitor

functionalization

Self-assembly of functionalized CNTs on

Si(100) for device applications
 Structure and Properties of CNTs

What are CNTs ?

•CNTs are tubular structures of nanometer diameter and many
microns in length, like Rolled-up graphene sheets.

• There are two types of carbon tubes: Single-walled carbon

nanotubes (SWCNTs) and Multi-walled carbon nanotubes
(MWCNTs).
Structure and Properties of CNTs

• The bonding in CNTs is similar to

that of graphite. Curvature produces a
local strain in the π–ring systems;
• CNTs are expected to be more
reactive than a flat graphene sheet.
•MWCNTs are regarded as metallic
conductors. SWCNTs are a mixture of
metallic and semiconductiong
material, depending sensitively on
their geometrical structures.
 Properties of carbon nanotubes
Attribute Assessment

Thermal conductivity: ∼ 6000 W M-1 K-1 >Diamond

Young’s modulus: ∼1 TPa Stiffer than any other

material

Tensile strength: 150 GPa ∼ 100 times the strength of

steel

Maximal supported electrical current ∼100 times greater than

density: >109 A/cm2 for copper wires

Carrier mobility: ∼ 105 cm2/V s (room > Hole mobility in Si

temperature)
 Characterization of Pristine CNTs by Raman Spectroscopy
Energy excited 514 nm
RBM
202 260
500
243
Radial Breathing Mode (RBM):
182
Presence of 5 peaks indicative of a
Intensity

300 225
wide range of tube diameters.

100
100 160 220 280
Wavenumber (cm-1) G (graphitic) band (sp2 C): Expect
2
two modes for semiconducting
G (sp C)
D/G Band
phases at 1542 and 1515 cm-1, and
two modes at 1592, 1564 cm-1 for
Intensity/counts

3
10x10

metallic phase;

5
D (diamond) band (sp3 C):
3
D (sp C) indicative of surface defects.
1200 1400 1600 1800
-1
wavenumber /cm
Dresselhaus et al., Advances in Physics, 2002, Vol., 49, 705
Characterization of Pristine SWCNTs—Raw SWCNTs

XPS
X-ray Photoelectron
Metal
15x10
3 C 1s C–C
O 1s oxides
spectroscopy (XPS):
3500

10 • Hydroxyls (C-OH) and

Counts

Counts
3000
quinones (C=O) exist at
5 C=O
C–OH
2500
defect sites;
• Metallic (Fe, Co, Ni)
2000
290 285 280 540 535 530
Binding energy /eV
Binding energy /eV
oxides present.

•Impurities exist
0.87
Intensity (a. u.)

0.72
M 11 Near IR:
S22 S11
0.57 Electronic transitions due to metallic
(M11) and semiconducting (S11 and
0.42
400 700 1000 1300 1600 S22) phases have been shown.
Wavelength (nm)
 Cut CNTs - Oxidation

• Cutting (oxidation) of tubes allows:

(1) Purification (removes amorphous carbon and metallic oxides)
(2) Opens up tube ends, shorten tube lengths and functionalizes ends
with carboxyl and carbonyl groups;
(3) increased solubility in solvents for further chemical modification.

Oxidants

Different conditions

Hirsch, A. Angew. Chem. Int. Ed. 2002, 41, No. 11

Covalently functionalized CNTs

The covalent functionalization of CNTs allows

functional groups to be attached to tube end or side
walls. Covalent side wall functionalization forms sp3
carbon sites on the tubes, which disrupts band-to-
band transitions of π electrons, and may cause loss
of properties of CNTs, such as their high conductivity
and remarkable mechanical properties.
End wall covalent functionalization

A: Covalent chemistry at the open ends of SWCNTs

B: Zwitterionic functionalization of SWCNTs

Dai et al., Chem. Rev. 2006, Vol 106, 1105

Side wall covalent functionalization
b.Cycloaddition c.Nitrene
dichlorocarbene cycloaddition

a.1,3-Dipolar
cycloaddition PhHgCCl2 Br/toluene
or CHCl3/NaOH
hv
O T
DMF, 130oC HO

RNHCH2COOH/(CH2O)n N3

e. Fluorination+ further derivatization

d. Bingel reaction + subsequent
attachment to Au EtOOC COOEt

Br

MeS
OH

Dai et al., Chem. Rev. 2006, Vol 106, 1105

Covalent Functionalization of SWNTs
(a) NO2 NO2 NO2

SWCNTs + +

N2BF4 SWCNTs
•Maximum
(b)
NO2 functionalization was
O2N
NO2 NO2 NO2
occurred for R=COOH,
suggested that multi-
layers can be formed.
SWCNTs

(c) NO2
•Covalent
NO2 NO2
NO2 functionalization of CNTs:
to remove metallic
character, change
NO2

NO2
NO2 O2 N
NO2 NO2
structure, increase
solubility and gain control
over tube assembly.

SWCNTs
Noncovalent functionalization

The tube surface via van

der Waals forces and π-
π interactions can be
modified by adsorption
of polynuclear aromatic
Example: compounds, surfactants,
polymers and
biomolecules.

Dai et. al., J. Am. Chem. Soc. 2001, 123, 3838

 Noncovalent functionalization

Advantages:
• attaching chemical handles without affecting the
structure and electronic network of the tubes;

• simple preparation procedure;

• applicable to as-produced full-length CNTs. The

solubility of CNTs in a solvent depends on the type and
concentration of the molecules adsorbed on the tube
surface.
Functionalization with surfactants
(a)

(b)

J. Nanosci. Nanotechnol. 2006, Vol. 6, No.1

Noncovalent Functionalization - Pyrene derivatives
Pyrenes can help tubes to be soluble into some organic
solvents and H2O
NH3+Cl COOH NaO3S SO3Na
COOH

HO SO 3Na

TEM Images
Tubes Pyrene+tubes
 Noncovalent Functionalization - Pyrene derivatives
Fluorescence spectroscopy study

Py-MeNH3 Cl + MWCNTs + DMF

•Free and bound pyrenes are

not distinguished;
Intensity

•Decrease in intensity ⇒
quenching due to tube
attachment;

360 410 460 510 560

Wavelength (nm)
 UV-Vis and Near-IR spectroscopy study
Py-MeNH3 Cl + MWCNTs + DMF

Near-IR Uv-Visable
0.065 Pyrene+MWCNTs 0.3 Pyrene+MWCNTs
abs

0.045
0.15

abs
0.025
0
1000 1200 1400 1600
Wavelength (nm) 260 360 460 560 660
0.105 Wavelength (nm)
MWCNTs
Non-covalent functionalization:
0.1
Abs

• Solubility is increased.
0.095
•There is no change in Near-IR.
0.09 • Pyrene in UV does not distinguish
1000 1200 1400 1600 free and bound pyrenes.
Wavelength (nm)
 Reversibility of Functionalization

NMR Dialysis
Pyrene+tubes

Pyrene

Dialysis
membrane

After non-covalently functionalization, Soluble tubes gradually

the peaks are broader;
Pyrene gradually released from the
tubes as temperature increases;
Therefore, pyrene attachment is
temperature dependant.
precipitate from the solution as
dialysis time increases; Pyrene
derivatives are released from
the tubes into dialysis solvent.
Therefore, pyrene attachment is
reversible.
X-ray Photoelectron Spectroacopy Study on the Reversed Tubes
MWCNTs (2 h cut)

C=C
Intensity (a. u.)

C 1s N 1s N-O

Intensity (a.u.)
N-C
C=O, C-C
C-OH
COOH

292 287 282

Binding energy (eV) 412 407 402 397
Binding energy (eV)

Pyrene 1 modified MWCNTs

C 1s C=C
N 1s
Intensity (a. u.)

N-C N-C, C-HH2

Intensity (a. u.) C-NH2.HCl
C-C
C=O,
COOH C-OH

292 287 282 412 407 402 397

Binding energy (eV) Binding energy (eV)
 MWCNTs (2 h cut)

O 1s O-C Atom concentrations from XPS

Intensity (a. u.)

C% N% O% Cl%
OCOO/
H 2O
O=C
MWCNTs 71.0 1.1 27.9
Modified 76.5 1.5 21.8 0.14
MWCNTs
538 533 528
Binding energy (eV)

Pyrene 1 modified MWCNTs

O-C Cl 2p
O 1s
Intensity (a.u.)

Intensity (a.u.)

OCOO/
O=C
H 2O

538 533 528 203 198 193

Binding energy (eV) Binding energy (eV)
Nonconvalent functionalization with
polymer and bimolecules

J. Nanosci. Nanotechnol. 2006, Vol. 6, 16

Nonconvalent functionalization with
Amino Acids and Peptides
O O O O
H2N CH C NH CH C NH CH C OH H2N CH C OH
CH2 CH2 CH2 CH2
NH NH NH NH

Polytryptophan 1 Tryptophan 2

O O O O
H2 N CH C NH CH C NH CH C OH H2N CH C OH
CH2 CH2 CH2 CH2

Polyphenylalanine 3 Phenylalanine 4
 Solubility/dispersibility of MWCNTs
with peptides
a b a b c a b c
c

( 1) freshly prepared samples (2) after 2 h (3) after 2 days

• MWCNTs/ Polytryptophan in DMF can be stable for 6 months and in

high temperature 378 K.
• MWCNTs/ Tryptophan
(c) MWCNTs/[Ru(bpy)3]Cl2
 Raman Study Peptide Modified Tubes
514 nm 1584 514 nm 2707
Intensity (a. u.)

Intensity (a. u.)

D/G band G' band
MWCNT (a) (b)

1361
1626

1200 1400 1600 1800 2000 2500 3000 3500

Wavenumber (cm -1) Wavenumber (cm -1)

1574 514 nm 2697

514 nm
Intensity (a. u.)

Intensity (a. u.)

G' band
D/G band
MWCNT +
(c) (d)
polytryptophan

1350 1613

1200 1400 1600 1800 2000 2500 3000 3500

Wavenumber (cm-1) Wavenumber (cm -1)

D band (cm- G band (cm- G’ band (cm-1)

1
) 1
)
MWCNTs 1361 1584, 1626 2707

Polytryptophan 1350 1574, 1613 2697

dispersed MWCNTs
 Conclusion - NonConvalent functionalization
• Pyrenes with functional groups + peptides help
CNTs to be soluble in a range of solvents;
• Pyrene + peptides attachment does not alter the
electronic properties of CNTs;
• Pyrenes + peptides attachment to tubes is strong,
but can be reversed.
•A combination of tube cutting and non-covalent
functionalization by pyrenes or peptides enables
tubes to be suspended/dissolved in solvents such as
DMF and ethanol, and significantly allows tubes to
be manipulated for practical device applications.
 Acknowledgements

• Prefessor Justin Gooding

• A/Professor Grainne Moran
• Dr Till BÖcking
• Dr Wenrong Yang
• Mr Barry Ward

• Alison Chou
• Other group members

APA scholarship