Fluidized-Bed Synthesis of Sub-Millimeter-Long Single Walled Carbon Nanotube Arrays
Fluidized-Bed Synthesis of Sub-Millimeter-Long Single Walled Carbon Nanotube Arrays
Fluidized-Bed Synthesis of Sub-Millimeter-Long Single Walled Carbon Nanotube Arrays
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5 authors, including:
Hisashi Sugime
Suguru Noda
Waseda University
Waseda University
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Available at www.sciencedirect.com
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
A R T I C L E I N F O
A B S T R A C T
Article history:
The rapid growth method for vertically aligned, single walled carbon nanotube (SWCNT)
arrays on flat substrates was applied to a fluidized-bed, using ceramic beads as catalyst
lysts were deposited on the surface of Al2O3 beads by sputtering and SWCNTs were grown
on the beads by chemical vapor deposition (CVD) using C2H2 as a feedstock. Scanning electron microscopy and transmission electron microscopy showed that SWCNTs of 24 nm in
diameter grew and formed vertically aligned arrays of 0.5 mm in height. Thermogravimetric analysis showed that the SWCNTs had a catalyst impurity level below 1 wt.%. Furthermore, they were synthesized at a carbon yield as high as 65 at.% with a gas residence time
as short as <0.2 s. Our fluidized-bed CVD, which efficiently utilizes the three-dimensional
space of the reactor volume while retaining the characteristics of SWCNTs on substrates,
is a promising option for mass-production of high-purity, sub-millimeter-long SWCNT
arrays.
2011 Elsevier Ltd. All rights reserved.
1.
Introduction
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2.
Experimental
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3.
3.1.
Synthesis of VA-SWCNT arrays by fluidized bed CVD
using the sputtered beads with a fixed catalyst thickness
CARBON
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3.2.
Effect of the catalyst thickness on the structure and
yield of VA-SWCNT arrays
SWCNTs with a rather large diameters of around 24 nm.
Most existed as individual SWCNTs or small-sized bundles
without catalyst particles.
The VA-SWCNT arrays were separated from the beads by
shaking in a sample bottle by hand and analyzed by TGA
(Fig. 5). The VA-SWCNT arrays had a high carbon purity over
99 wt.%, with only minor contamination (catalysts below
Fig. 3 SEM images of the pretreated bead (a) and the beads after fluidized-bed CVD (be). The SWCNT arrays on the bead (e)
are shown at a higher magnification in (f).
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Fig. 4 TEM images of sub-millimeter-long VA-SWCNT arrays, transferred from a bead to a microgrid using tweezers, without
purification. The insets show enlarged images and the histogram of the diameter distribution of the SWCNTs.
CARBON
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Fig. 6 Characterization of VA-SWCNT arrays on the Al2O3 beads. (a) A side-view schematic for the Raman measurement of
VA-SWCNT arrays on a bead. (bd) Top-view optical microscope images and Raman spectra (left: RBM region, right D-band
and G-band) of the VA-SWCNT arrays on the beads. The nominal Fe thicknesses were (b) 0.8 nm, (c) 1.0 nm, and (d) 1.5 nm.
a higher C2H2 partial pressure shortens the lifetime, especially for Fe catalysts with smaller nominal thickness [9].
The amount of Fe catalyst particles in a reactor of similar volume (30 cm3) is much larger in a fluidized bed CVD than a flat
substrate because of the much larger surface-to-volume ratio
of the catalyst support in the former. Therefore, C2H2 at a
higher partial pressure (1.1 kPa) was fed at a larger flow rate
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Fig. 7 Amounts and carbon yields of the synthesized SWCNTs (a) and average lengths of the VA-SWCNT arrays on the beads
(b) for different nominal Fe thicknesses of 0.8, 1.0, and 1.5 nm. Insets in (b) are SEM images of the VA-SWCNT arrays on the
beads, with a scale bar of 0.5 mm.
(3.16 slm) in this work than for CVD on flat substrates in previous work (0.10.6 kPa and 0.5 slm, respectively) [9]. Such a
high carbon feed can easily deactivate the catalyst by carbonization [9] and therefore water vapor at a higher partial pressure (0.06 kPa) was used than that in previous work (0
0.03 kPa) [9]. However, the excess carbon feed possibly shortened the lifetime of the small Fe particles with the thinner Fe
catalytic layer, resulted in a shorter final length and smaller
overall yield of VA-SWCNTs.
3.3.
Effects of H2O vapor on the yield and structure of
SWCNTs
Then we examined the effect of H2O vapor on the yield and
structure of SWCNTs. SWCNTs were grown at a slightly higher temperature (1113 K) to improve the quality of SWCNTs
than the experiments above while preventing sooting, with
decreasing feed of H2O vapor from 0.06 to 0 kPa (Fig. 8). The
IG/ID ratio was improved from 1.73 (B in Fig. 6b) to 2.29 (A in
Fig. 8b) with an increase in temperature by 20 K. RBM peaks
appeared at around 200 cm 1 (corresponding to 1.25 nm in
SWCNT diameter) with 0.06 kPa H2O, and they appeared at
higher wavenumbers of 200260 cm 1 with decreasing H2O
feed (Fig. 8a). The IG/ID ratio decreased from 2.29 to 1.65
(Fig. 8b and c), the average length of the SWCNT arrays decreased from 0.3 to 0.1 mm (Fig. 8d), and carbon yield decreased from 40 to 10 at.% (Fig. 8d) with decreasing H2O
feed. These results suggest that the decreased H2O feed activated small Fe particles to grow SWCNTs of smaller diameters
while it resulted in shorter growth lifetimes and degraded
SWCNT qualities. As we previously reported for flat substrates [9], H2O inhibits the SWCNT growth from thin catalytic
layer and thus small catalyst particles, possibly by oxidizing
the small catalyst particles and/or small diameter SWCNTs
of lower stability. At the same time, H2O prolongs the catalyst
lifetime when C2H2 is fed at high partial pressures [9], possibly
by removing the carbon by-products covering the catalyst particles [24]. There is a trade off in the productivity (higher
productivity with higher C2H2 and H2O feed) and SWCNT
quality (higher IG/ID ratio and smaller diameter with lower
C2H2 and H2O feed), and therefore the CVD conditions should
be chosen case by case.
3.4.
Prospects for continuous production of millimeterlong VA-SWCNT arrays
By applying a sputtered catalyst in a fluidized bed CVD, we
succeeded in synthesizing sub-millimeter-long VA-SWCNT
CARBON
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4.
Conclusions
Acknowledgements
We gratefully thank Ms. Asuka Tashiro for her help in some
experiments. This work is financially supported by Nanotech
Challenge (No. 07005623-0) by NEDO, Japan, by cooperative research project with Hitachi Chemical, Co., Ltd., Japan, by
KAKENHI (Nos. 18686062 and 21686074), by MEXT, Japan,
and by ALCA by JST, Japan.
R E F E R E N C E S
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