Innovative Purification Method to Extract Magnetic

Carbon Nanotubes from Arc-discharged Single-walled

Carbon Nanotubes
Chuan He
1
, Yuzhi Hao
1
, James Z. Xing
4
, Jie Chen
1,2,3
1 Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta, Canada
2Department of Biomedical Engineering, University of Alberta, Edmonton, Alberta, Canada
3 National Institute for Nanotechnology, Edmonton, Alberta, Canada
4 Department of Laboratory Medicine & Pathology, University of Alberta, Edmonton, Alberta, Canada
AbstractThe discovery of carbon nanotubes has opened the
door to numerous cutting-edge nanoscaleresearch fields
including microelectronic devices, and biomedical
application. Although pure nanotubes suffice for most
purposes, highly pure magnetic carbon nanotubes are more
suitable for specialized applications such as gene delivery.
The conventional purification methods of carbon nanotubes
are too harsh for the nanotubes to retain any magnetic
characteristics, hence to enable the nanotubes be sensitive to
magnetic field. It requiresthe reloading of metallic particles
inside or on the surface of each tube. Instead, this paper
proposes an innovative purification method to extract
magnetic carbon nanotubes from arc-discharged single-
walled carbon nanotube material. The procedure is easy to
execute and time-saving. TEM and AFM images are used to
monitor the purification process and prove that the carbon
nanotube retain magnetic characteristics after the
purification process.
I. INTRODUCTION
Since S. Iijima discovered carbon nanotubes in 1991
[1], interest in utilizing has been increased exponentially.
Current research areas include microelectronics [2], energy
storage [3], and biomedical application [4]. In most cases,
purified carbon nanotubes are required. For some special
cases, such as gene delivery, D. Pantarotto has reported
increased gene delivery efficiency by applying carbon
nanotubes as proper transporter [3], while J. Chen has
shown that magnetic carbon nanotubes enhance guided
penetration into the hard-to-deliver cell lines, such as stem
cells [5]. To regain carbon nanotubes with magnetic
characteristics, G. Korneva tries to load magnetic particles
inside the tubes [6], but this method requires the diameter
of the carbon nanotube to be around 200nm which is too
large for the cells. Instead, we describe an innovative
purification method to obtain magnetic carbon nanotube
from arc-discharged SWNTs. Metal catalyst nanoparticles
such as nickel, used in single-walled carbon nanotube
(SWNT) production always accompany the final SWNT
product as impurities;some scattered around the SWNT,
and others are attached onto theSWNT, wrapped by
amorphous carbon which is a by-product [7]. Traditional
purification methods, such as oxidation, acid treatment,
annealing, ultrasonication, micro-filtration or any
combinations of the above are so efficient, that they
effectively remove all impurities, including the magnetic
nickel particles [8]. Our developed method enables nickel
particles to remain attached to the SWNT after purification,
while separated nickel particles and amorphous carbon are
largely removed. The nickel particles retained on the
SWNT surface will enable the SWNT to respond to
magnetic fields. To ensure the efficiency of every step,
transmission electronic microscopy (TEM) and atomic
force microscopy (AFM) are used to monitor the
purification process. Since the processed SWNTs are very
small and dispersed in 95% ethanol, it is very difficult to
directly observe magnetic characteristics through human
eye. Again, TEM is used to prove we obtain magnetic
SWNTs in the end.
II. PURIFICATION METHODS
SWNTs were purchased from Sigma Aldrich

. The
purification process consists of three steps: sodium dodecyl
sulfate (SDS) treatments, organic solvent treatment and
H
2
O
2
treatment. The procedural flow chart is listed in Fig.
1, followed by detailed information on each step:
Figure 1. Flow chart outlining our purification process
This research is funded by NSERC and CIHR joint CHRP grant, and
NSERC engagement grant
Carbon nanotube
raw material
SDS + sonication
+ filtration
Organic solvent
treatment
H
2
O
2
treatment
75 978-1-4577-0422-2/11/$26.00 c 2011 IEEE
A. SDS Treatment
(i) 26.2mg SWNT was weighed and dispersed in a
solution of 10mL 20% concentration SDS plus 150mL DI
water. The container was gently agitated, after which the
sample solution was sonicated for 2 hours.
(ii) After sonication, sample solution was transferred
into a centrifuge tube and centrifuged at 10000rpm for 10
minutes. Sediment was discarded; supernatant was filtered
through a polytetrafluoroethylene (PTFE) membrane with
0.45m pore size.
(iii) In order to completely remove the SDS after
filtration, DI water was used to wash the SWNTs
remaining on the filter membrane over several rinse cycles.
(iv) Finally SWNTs remaining on the PTFE membrane
was suspended in 95% ethanol.
Sample solution was stored at room temperature for
TEM and AFM analysis and next purification step.
B. Organic Solvent Treatment
(i) Before organic solvent treatment, sample solution
needs to be completely dried. After the drying process,
SWNTs were suspended in 100mL N, N-
dimethylformamide (DMF), after which the sample
solution was refluxed at 130C for 98 hours.
(ii) After the reflux process, sample solution was
filtered again through PTFE membrane with 0.45m pore
size. DI water was used to wash away the remaining DMF.
SWNT remaining on PTFE membrane was suspended in
95% ethanol and stored properly for TEM and AFM
analysis and next purification step.
C. H
2
O
2
Treatment
(i) Before H
2
O
2
treatment, sample solution needs to be
completely dried. After the drying process, 22mL of H
2
O
2
was added to suspend SWNTs. The sample solution was
then sonicated for a total duration of 4 hours. To ensure
enough oxidant was supplied, 10mL of H
2
O
2
was
supplemented into the solution at two hour intervals.
(ii) After H
2
O
2
treatment, samples undergo the same
filtration process as previously described.
(iii) Finally, SWNT was stored in 95% ethanol
solution.
D. TEM Sample Preparation
Sample solution was sonicated for 10 minutes and
immediately transferred dropwise onto the TEM mesh
grid. The TEM sample grid was dried overnight at room
temperature. TEM images are photographed using JEOL

TEM on the next day.

E. AFM Sample Preparation
Firstly, the pH value of the sample solution was
adjusted to approximately 7.0. Then a small amount of
sample solution was directly transferred dropwise onto the
silicon wafer. The sample was dried overnight at room
temperature. AFM images were taken the next day using
Veeco

Multimode V SPM working under contact mode.

III. RESULTS
TEM and AFM images were obtained at each
purification step. The aim is to monitor the process and
check the change of morphology and state after the
respective purification process.
The SWNT material purchased from Sigma

is
supposed to have a purity of 50%.
In the top left corner of Fig. 2 (a), some SWNTs are
visible in separated state, but in Fig. 2 (b), SWNTs are
difficult to locate. We hypothesized that most of the
SWNTs are encased by amorphous carbon (grey block) and
surrounded by nickel particles (dark points). The AFM
image shows similar result. As Fig. 3 shows, it is
impossible to differentiate SWNT from the impurities.
(a)
(b)
Figure 2. TEM images of SWNT from Sigma Aldrich

Figure 3. AFM image of SWNT from Sigma Aldrich

76 2011 IEEE/NIH Life Science Systems and Applications Workshop (LiSSA)

A. Sample after SDS Treatment
(a)
(b)
Figure 4. TEM images of SWNT after SDS treatment
Fig. 4 (a), (b) show the status of SWNTs after SDS
treatment. More SWNTs are observed, supporting our
hypothesis that SWNTs were initially hidden in the
accumulation of impurities. Overall, some large impurity
particles are removed from the sample solution.
B. Sample after Organic Solvent Treatment
After organic solvent treatment, the status of SWNTs
has changed greatly. As Fig. 5 (a), (b) show, compared
with image taken in the last step, the expansive
accumulation block has further divided into smaller pieces,
while many SWNTs act as bridges linking each other. The
area occupied by amorphous carbon now exhibits a loose
structure.
(a)
(b)
Figure 5. TEM images of SWNT after organic solvent treatment
C. Samples after H
2
O
2
Treatment
After H
2
O
2
treatment which is the last purification
stage, it is hypothesized that most amorphous carbon and
separated nickel particles should have been removed, and
SWNT would be free in solution with certain amount of
nickel particles attached onto their surface. Fig. 6 (a), (b)
prove this supposition. Short SWNTs are observed for the
first time and they are evenly distributed in the image.
Most SWNTs have a dark point in the tip indicating the
presence of nickel particles. The AFM image in Fig. 7
provides more straightforward evidence. Unfortunately,
there still remain relative large nickel particles in solution.
Overall, the purification process was successful.
(a)
(b)
Figure 6. TEM images of SWNT after H2O2 treatment
2011 IEEE/NIH Life Science Systems and Applications Workshop (LiSSA) 77
Figure 7. AFM image of SWNT after H2O2 treatment
IV. ANALYSIS
A. Sample after SDS Treatment
SDS is a highly effective surfactant. Because the
original SWNTs purchased from Sigma Aldrich

don`t
dissolve well in DI water, SDS is used here to assist the
dispersion process. Sonication further aids in dispersing
the accumulation of amorphous carbon and nickel
particles.
It is hypothesized that after sonication fragmented the
accumulated block, SDS will quickly surround the
separate particles to make them water soluble. Meanwhile
some impurities are too large and too heavy for SDS to
ensure good solubility. By centrifuging the solution at
10000 rpm, many large impurity particles, especially large
nickel nanoparticles are removed from the sample.
B. Sample after Organic Solvent Treatment
Sometimes DMF is used to disperse SWNT [9]. But
here, its intent is to generate the 'pumping up
phenomenon whereby more and more organic solvent is
adsorbed into the accumulation block, leading to a
loosened accumulation structure. Since amorphous carbon
is no longer packed tightly, it will be easier to free the
SWNTs within.
C. Sample after H
2
O
2
Treatment
Y. Y. Feng has shown that H
2
O
2
could help oxidize
amorphous carbon at room temperature [10]. Here, we
prove that when amorphous carbon is structured in loose
scaffolding, it becomes much easier to achieve the same
result. As Fig. 6 and Fig. 7 show, there is almost no
amorphous carbon accumulation left in the solution.
The formation of short SWNTs is resulted from the
continuous sonication process. Fortunately, some nickel
particles are still attached onto the SWNT after sustaining
prolonged harshness during sonication.
Since the SWNT sample solution was filtered three
times throughout the purification process, most small
nickel particles existing in the filtrate have been discarded.
As SWNTs at some point may block the pores on PTFE
membrane, some of the large nickel particles still remain in
the sample solution. The diameter of the large nickel
particles are measured to be around 170-200nm.
Fortunately, for biomedical application like gene delivery,
particles with size more than 150 nm are difficult to enter
the cells by any possible mechanism. Thus, by applying
proper washing steps, the side effect of large nickel
particles can be minimized.
V. CONCLUSION
In this paper, we demonstrate an innovative
purification method to extract magnetic carbon nanotube
from raw materials. The process is divided into three main
procedures: SDS treatment, organic solvent treatment, and
H
2
O
2
treatment. To ensure the SWNTs retain magnetic
characteristics, we avoid using harsh acids which is
common to traditional oxidation methods because we
intend for some nickel particles to remain. TEM and AFM
images are used to monitor each step in the purification
process, and final results show that the developed method
is efficient and reliable.
ACKNOWLEDGMENT
The authors would like to acknowledge the funding
supports of NSERC and CIHR joint CHRP grant, and
NSERC engagement grant. The authors would also like to
thank Mr. Ray Yang for providing valuable feedbacks of
our paper
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78 2011 IEEE/NIH Life Science Systems and Applications Workshop (LiSSA)