Synthesis of boron nitride nanotubes from carbon nanotubes by a substitution reaction

Article abstract of DOI:10.1063/1.122680

A method involving carbon nanotubes substituted reaction was developed for the synthesis of mass quantities of boron nitride nanotubes. Boron oxide vapor was reacted with nitrogen gas in the presence of carbon nanotubes to form boron nitride nanotubes, whose diameters and lengths are similar to those of the starting carbon nanotubes. It is proposed that carbon atoms of carbon nanotubes can be fully substituted by boron and nitrogen atoms through a general chemical reaction. The results suggest that the synthesis methodology developed here may also be extended to form nanotubes from other novel materials.

Full text of DOI:10.1063/1.122680

Synthesis of boron nitride nanotubes from carbon nanotubes by a substitution reaction
Weiqiang Han, Yoshio Bando, Keiji Kurashima, and Tadao Sato
Citation: Applied Physics Letters 73, 3085 (1998); doi: 10.1063/1.122680
View online: http://dx.doi.org/10.1063/1.122680
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APPLIED PHYSICS LETTERS
VOLUME 73, NUMBER 21
23 NOVEMBER 1998
Synthesis of boron nitride nanotubes from carbon nanotubes
by a substitution reaction
Weiqiang Han,a) Yoshio Bando,b) Keiji Kurashima, and Tadao Sato
National Institute for Research in Inorganic Materials, Tsukuba Ibaraki 305, Japan
͑
Received 10 August 1998; accepted for publication 24 September 1998͒
A method involving carbon nanotubes substituted reaction was developed for the synthesis of mass
quantities of boron nitride nanotubes. Boron oxide vapor was reacted with nitrogen gas in the
presence of carbon nanotubes to form boron nitride nanotubes, whose diameters and lengths are
similar to those of the starting carbon nanotubes. It is proposed that carbon atoms of carbon
nanotubes can be fully substituted by boron and nitrogen atoms through a general chemical reaction.
The results suggest that the synthesis methodology developed here may also be extended to form
nanotubes from other novel materials. © 1998 American Institute of Physics.
͓
S0003-6951͑98͒02447-4͔
Boron nitride nanotubes ͑BN-NTs͒, whose electronic
diameters of approximately 10 nm used here were prepared
by a metal-catalyzed chemical vapor deposition ͑CVD͒
method. The crucible was held in a flowing nitrogen atmo-
sphere at 1773 K for 0.5 h.
After the crucible from the furnace was recovered, the
starting black carbon nanotubes were found to have turned
into a grey colored layer of a wool-like product. The product
and the starting CNTs were characterized with Ragaku RINT
properties are independent of helicity and the number of lay-
1
ers according to theoretical predictions offer highly promis-
ing for the creation of nanostructure electronic devices. BN-
2,3
NTs have recently been synthesized by arc-discharge high
4
5
pressure laser heating and oven-laser ablation, but these
methods have only resulted in low yields. Here we show that
a simple and easily accessible technique involving a carbon
nanotubes ͑CNTs͒ substituted reaction can generate mass
quantities of BN-NTs.
2
000 x-ray diffractometer ͑XRD͒ with Cu K␣ radiation. Fig-
6
ure 2͑a͒ is an XRD pattern of the product, which is identified
as a mixture of hexagonal BN (h-BN) ͑two-layered repeat-
ing units͒ and the rhombohedral BN (r-BN) ͑three-layered
repeating units͒. As can be seen from Fig. 2͑a͒, the intensity
of the peak assigned to ͑100͒ h-BN is almost the same with
that of the peak assigned to ͑101͒ r-BN, indicating that the
content of the h-BN is almost the same with that of r-BN in
the product. For the product the strongest peak correspond-
ing to both ͑002͒ h-BN and ͑003͒ r-BN has a distinguished
lower value ͑0.335 nm͒ compared to that ͑0.345 nm͒ of the
starting CNTs ͓Fig. 2͑b͔͒. It was also clear that the degree of
crystallization of the BN product is better than that of the
starting CNTs.
Since the discovery of CNTs, this hollow nanostructure
has been used as a template to produce new one dimensional
7
–9
9,10
nanoscale materials by filling,
reaction ͑carbide
coating,
and confined
͒ ͑Fig. 1͒. In
1
1,12
13–15
and nitride nanorods
the present study, we claim that CNTs could be exploited as
templates to prepare other nanotubes. We call this method
CNTs substituted reaction, which means that through this
chemical reaction the carbon atoms of CNTs are substituted
by other atoms to form nanotubes. The CNTs substituted
reaction is quite different from the CNTs confined reaction13
because the latter results in solid rod-like nanostructures,
rather than hollow nanotubes.
For confirming the speculated CNTs substituted reac-
tion, BN-NTs were chosen to be synthesized because BN-
NTs have the same layered structure and also close lattice
constants compared with CNTs. The designed reaction can
be expressed as
B O ϩ3C ͑nanotubes͒ϩN →2BN ͑nanotubes͒ϩ3CO.
2
3
2
It was expected that boron oxide gas generated from the
B O powder would flow up towards the region containing
2
3
the carbon nanotubes and react with the nanotubes and the
nitrogen (N ) gas.
2
The reaction was carried out in an induction-heating sys-
tem with susceptors made of graphite. B O powder was
2
3
placed in an open sintered graphite crucible and then covered
with CNTs. Relatively pure multishell CNTs with typical
FIG. 1. Schematic illustrations of carbon nanotubes as a template to produce
new one dimensional nanoscale materials by ͑a͒ filling, ͑b͒ coating, ͑c͒
carbon nanotubes confined reaction to produce carbide and nitride nanorods,
and ͑d͒ carbon nanotubes substituted reaction to produce boron nitride
nanotubes.
a͒
Electronic mail: whan@nirim.go.jp
To whom correspondence should be addressed.
b͒
Electronic mail: bando@nirim.go.jp
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003-6951/98/73(21)/3085/3/$15.00 3085 © 1998 American Institute of Physics
70.140.26.180 On: Sun, 25 May 2014 11:57:45
0
1

3086
Appl. Phys. Lett., Vol. 73, No. 21, 23 November 1998
Han et al.
FIG. 2. X-ray diffraction patterns of ͑a͒ product, which is identified as a
mixture of hexagonal and the rhombohedral BN, and ͑b͒ starting carbon
nanotubes.
FIG. 4. A typical EELS core electron K-shell spectrum taken from an indi-
vidual BN-NT.
eters of these nanotubes are a few nanometers and lengths
are up to a few micrometers, which are similar to the diam-
eters and the lengths of starting CNTs. A few of encapsu-
lated nanocages and nanowires were also observed in the
product.
The product was characterized by high resolution lattice
images with the use of a field emission type transmission
electron microscope ͑TEM͒ ͑JEOL-3000F͒, operating at 300
kV, equipped with an apparatus for both energy dispersive
x-ray spectroscopy ͑EDS͒ and parallel recording electron en-
ergy loss spectroscopy ͑EELS͒.16 EELS experiments were
performed by using a stationary focused 1 nm electron probe
with a Gatan spectrometer. Figures 3͑a͒ and 3͑b͒ are typical
high resolution TEM micrographs showing a general view of
the starting CNTS and the product, respectively. Abundant
nanotubes are visible in the product ͓Fig. 3͑b͔͒, and they
appear either as the individual nanotubes or as the bundles.
The interplanar spacing of these nanotubes is approximately
EELS spectra showed that the nanotubes in the product
were all BN-NTs. A typical EELS spectrum from an indi-
2
vidual nanotube corresponds to B-N sp bonds ͑Fig. 4͒. Two
distinct absorption features are revealed, one starting at 188
eV and another at 401 eV, corresponding to the known B-K
and N-K edges, respectively. Noteworthy is the absence of
the feature at 284 eV, the K-edge absorption for carbon. The
B/N ratio of this spectrum is determined to be approximately
1
.02, which is consistent with a stoichiometry of BN ͑due to
0
0
.335 nm, which is consistent with the interplanar distance
.333 nm in both bulk h-BN and r-BN. These nanotubes
uncertainties in background subtraction, the calculated B/N
ratio has an estimated error of 20%͒. The EELS spectra re-
vealed that the nanowires and the nanocage shells were also
BN. EDS measurements showed that the nanoparticles en-
capsulated inside the BN nanocages were iron, which was
used as a catalyst for the synthesis of the starting CNTs and
was encapsulated inside the starting CNTs.
have relative straight fringes indicating a well ordered struc-
ture, which is consistent with the result of XRD. The diam-
In summary, the successful preparation of BN-NTs with
the average diameters and lengths similar to the starting
CNTs confirms the applicability of this method—CNTS sub-
stituted reaction. Although the final BN-NTs nanotubes do
not contain carbon element, CNTs may play an important
role as precursors and in particular supply the skeletons for
the growth of BN-NTs during the substitution reaction. After
fully substituting the carbon atoms of CNTs by B and N
atoms, the B and N atoms of BN-NTs may be involved in a
rearrangement process for more suitable and ordered posi-
tions at high temperature. Although a deeper understanding
of the BN-NTs growth mechanism is clearly needed, we note
that this simple and cheap CNTs substituted reaction tech-
nology could in principle produce BN-NTs of any quantity.
Only sufficient amount of CNT is needed, which have been
synthesized in a large quantity1
7,18
and are commercially
available. The CNTs substituted reaction developed here is
easily accessible to others with an interest in BN-NTs and
may also be extended to form nanotubes of other novel ma-
1
9–21
terials ͑for instance, the B N C
z
or C–BN–C sandwich
x
y
structure22 nanotubes͒. The ready availability of large
amounts of these nanotubes should offer more opportunities
for both new fundamental science and useful nanotechno-
FIG. 3. High resolution TEM images of ͑a͒ starting carbon nanotubes, and
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͑b͒ boron nitride nanotubes.
logical applications.
1
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Appl. Phys. Lett., Vol. 73, No. 21, 23 November 1998
Han et al.
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