COMMUNICATION
DOI: 10.1002/adma.200700763
Controlled Etching of Carbon Nanotubes by Iron-Catalyzed Steam
Gasification**
By Wei Xia, Volker Hagen, Shankhamala Kundu, Yuemin Wang, Christoph Somsen, Gunther Eggeler,
Guoguang Sun, Guido Grundmeier, Martin Stratmann, and Martin Muhler*
Carbon nanotubes are very promising for many potential
applications such as composite materials, catalysis, sensors,
energy devices, and electronics.[1] The large-scale production
of multi-walled carbon nanotubes (MWCNTs) is expected to
start soon in industry.[2] It is frequently necessary to modify
the surface properties for these applications: for example, a
surface treatment is required to improve the dispersion of
nanotubes and their interaction with polymer matrices in
composites.[3] Sensor applications involve the binding of
chemical moieties or the immobilization of proteins with spe-
cific recognition sites to the nanotube surface.[4] As catalyst
support anchoring sites such as surface functional groups or
defects are necessary for the deposition of foreign atoms.[5]
Recently, carbon has been frequently studied as non-metallic
catalyst for various reactions such as the oxygen reduction in
fuel cells and the oxidative dehydrogenation of ethylben-
zene.[6] The active sites, although not yet clearly established,
are believed to be related to surface defects, especially to edge
planes.[7] To our knowledge, all the reported surface modifica-
tions of carbon nanotubes are based on direct oxidation by,
e.g., nitric acid, oxygen plasma, supercritical fluids, air, ozone,
CO2, etc.[8] These oxidation methods are mainly designed to
purify the nanotubes[9] and to enhance the surface oxygen
content,[10] although some of them can also cause visible phys-
ical modifications at arbitrary positions.[11] Here, we report a
localized etching route to selectively modify carbon nano-
tubes in a pre-determined manner.[12] The etching, based on
the catalytic steam gasification of carbon,[13] occurs only at
the interface between the nanotubes and the iron nanoparti-
cles. Different etching patterns can be obtained by tailoring
– (Eq. 1). The iron particles can be deactivated by coking very
[*] Prof. M. Muhler, Dr. W. Xia, Dr. V. Hagen, S. Kundu, Dr. Y. Wang
Laboratory of Industrial Chemistry, Ruhr University Bochum
44780 Bochum (Germany)
E-mail: muhler@techem.ruhr-uni-bochum.de
Dr. C. Somsen, Prof. G. Eggeler
Institut für Werkstoffe, Ruhr-Universität Bochum
44780 Bochum (Germany)
G. Sun, Prof. G. Grundmeier, Prof. M. Stratmann
Max-Planck Institute for Iron Research
40237 Düsseldorf (Germany)
[**] W. Xia and S. Kundu thank the IMPRS of Surface and Interface Engi-
neering in Advanced Materials (SurMat) for financial support. Sup-
porting Information is available online from Wiley InterScience or
from the authors.
3648 © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
the size and the spatial distribution of the iron particles. The
areal density of surface defects such as edge planes, which are
believed to be the main active centers in catalysis, is signifi-
cantly enhanced. Only water and iron as readily available
chemicals are employed in this eco-friendly process producing
hydrogen and carbon monoxide as major components of syn-
thesis gas.
The novel localized etching method of MWCNTs is summa-
rized in Scheme 1. The nanotubes are first functionalized by
oxidation to introduce oxygen-containing groups, which are
necessary for the anchoring of foreign species. Iron is subse-
quently deposited on the nanotubes either from the gas phase
(chemical vapor deposition, CVD) or by impregnation. Fol-
lowing the post-deposition treatment of the iron nanoparti-
cles, etching is performed at elevated temperatures by intro-
ducing water vapor. The walls of the nanotubes are selectively
destructed as a result of the etching. Finally, the iron nanopar-
ticles are removed by washing with diluted acid, and nano-
tubes with etching patterns are obtained. The etching reaction
is described by the following equation:
C ‡ H2 O Fe
! CO ‡ H2 (1)
The as-received nanotubes are characterized by smooth
surfaces on the nanometer scale (Supporting Information,
Fig. 1). After functionalization and deposition, the iron-
loaded nanotubes were reduced and annealed in hydrogen at
500 °C for 1 h before etching. When changing to water vapor,
the formation of CO and the consumption of H2O were de-
tected by online mass spectroscopy (MS) above 600 °C (Sup-
porting Information, Fig. 2). Due to the presence of CO as re-
action product in the gas phase, the deposition of carbon
occurs simultaneously as the reverse reaction of the etching
soon during etching. Hydrogen was therefore added to the gas
stream to keep the iron catalysts active. Although deactiva-
tion can still be observed from the beginning of the etching,
the reaction actually ceases after about 100 min, as indicated
by the acceleration of the deactivation denoted by the slope
change of the CO and H2O signals (Supporting Information,
Fig. 2).
The iron particle size after annealing, which is determined
mainly by the loading, was found to be critical for the etching.
Iron loadings of 1–2 wt % achieved by CVD of ferrocene cor-
responded to particle sizes of 1–2 nm. Although particle
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 COMMUNICATION
removal of
iron by acid
functionalization
by oxidation etching
with water
H2O H2 + CO
–O*
–O*
–O*
–O*
–O*
–O*
–O*
–O*
deposition
of iron
–O*
–O*
–O*
–O*
–O*
–O*
–O*
–O*

multi-walled nanotube

Scheme 1. Schematic illustration of the four major steps involved in the etching process. The multi-walled nanotubes are first functionalized by con-
centrated nitric acid to introduce oxygen-containing groups, followed by the deposition of iron particles from the gas phase or by impregnation. The
subsequent catalytic etching is performed at 670 °C with diluted water vapor. The metal particles are finally removed by washing with diluted acid at
room temperature.

Figure 1. SEM images of the carbon nanotubes after etching at 670 °C with 1 vol % water in helium (89 vol %) and hydrogen (10 vol %). a) 5 wt % Fe
by CVD, with iron nanoparticles; b) 5 wt % Fe by CVD, after dissolving the iron nanoparticles in acid; c) 5 wt % Fe by impregnation, with iron nanopar-
ticles; d) 5 wt % Fe by impregnation, after dissolving the iron nanoparticles in acid.

growth was observed due to annealing at 500 °C in reducing
atmosphere, the particle size was still too small to achieve a
sustained etching. A loading of 5 wt % Fe was found to be
suitable for continuous etching for up to 2 h at 670 °C with
1 vol % water vapor. In case of impregnation with ammonium
ferric citrate, iron loadings of 4–6 wt % were achieved. Calci-
nation was performed in air at 350 °C to remove organic resi-
dues prior to reduction and annealing at 500 °C. The total
active time was around 1 h, i.e., shorter than that of the CVD
catalyst, which may be attributed to differences in particle
sizes. The iron particles obtained by impregnation were gener-
ally larger than those by CVD, as shown below by TEM.
After the etching the iron nanoparticles are covered by
deposited carbon. These carbonaceous layers have to be re-
moved, because otherwise the iron nanoparticles cannot be
washed off in diluted acid. Therefore, air was introduced to
the reactor at 450 °C. An apparent delay of the oxygen signal
(m/e = 32) compared with that of nitrogen (m/e = 28) was ob-
served by online mass spectrometry, indicating the consump-
tion of oxygen by reaction with the deposited carbon layers
on the iron catalyst particles as well as on the nanotube sur-
faces (Supporting Information, Fig. 3). Correspondingly, the
formation of carbon dioxide (m/e = 44) was detected. These
observations provide further evidence that the deactivation of
the iron catalysts during the etching is mainly due to coking.
The morphology of the MWCNTs resulting from the etch-
ing using CVD-deposited iron particles is shown in Figure 1a
and b. The iron oxide nanoparticles are embedded in the walls
of the nanotubes after etching (Fig. 1a). The diameter of the
particles is in the range from 5 to 12 nm. Restricted move-
ment of iron particles obviously occurred during the reaction
resulting in etching pits larger than the particle size. The area

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COMMUNICATION

Clearly, the active center of the etching reaction is localized

at the interface between iron and carbon. Transient formation
(1) as-received of carbide is highly likely at the solid–solid interface. How-
250 (2) CVD + etching
(3) impregnation + etching
ever, the presence of stable carbides can be excluded, other-
wise the reaction would not proceed, as is known from the
catalytic growth of carbon nanotubes.
200 The traditional oxidation treatment aims at the purification
Adsorption volume (cm g )
-1

and functionalization of the nanotubes, whereas the catalytic

3

etching can significantly modify the bulk properties by ex-

150
100
50
(3)
(2)
(1)
0 (BJH method). Because the as-received nanotubes are open-
0.0 0.2 0.4 0.6
Relative pressure
Figure 2. Nitrogen physisorption isotherms of the as-received and etched
nanotubes. The arrow indicates the closure of the hysteresis loop.
beyond the mobility radius of the iron particles was not af-
fected by the etching. The hemispherical carving patterns are
more clearly visible after the removal of the iron oxide parti-
cles by washing with acid (Fig. 1b). Small pores are selectively
created in the initially smooth surface of the as-received nano-
tubes. In case of impregnation, the resulting iron particles are
larger compared to CVD (Fig. 1c). Etching for 1 h led to the
partial destruction of the walls of the nanotubes. In contrast
to the CVD samples, the etching patterns are frequently ob-
served in the form of steps, although etching pits and holes
can also be observed (Fig. 1d). Obviously, etching catalyzed
by larger iron particles results in large-area etching patterns,
other than tiny pits.
tended etching. As indicated by the SEM images, small pores
are generated by the etching. This observation is also con-
firmed by the hysteresis observed between the desorption and
adsorption branches of the N2 physisorption isotherms
(Fig. 2). These small pores are completely absent in the walls
of the as-received nanotubes, which expose smooth surfaces.
As a result, the specific surface area of the nanotubes in-
creased from 20–40 m2 g–1 up to 90–110 m2 g–1, corresponding
to an increase of pore volume from 0.16 cm3 g–1 to 0.36 (CVD
iron catalyst) and 0.41 (impregnated iron catalyst) cm3 g–1
0.8 1.0 ended (see Supporting Information Experimental), the in-
crease can be attributed mainly to the catalytic etching.
The TEM image shown in Figure 3a reveals the embedding
of the iron oxide nanoparticles prepared by CVD due to the
etching. High resolution TEM investigations indicate that the
iron oxide nanoparticles are crystalline, with a lattice spacing
of exactly 0.25 nm typical for Fe2O3. The surface roughness
was significantly increased by etching as shown by the TEM
images after removal of iron nanoparticles (Fig. 3b). The high
resolution TEM image shown in Figure 3c clearly demon-
strates the destruction of the wall of the nanotube. The graph-
ene sheets of the nanotube wall were obviously destructed
one after another and finally a hemispherical cave was creat-
ed, roughly as an imprint of an iron oxide particle. In case of
impregnation, the iron particle size amounting to roughly
10–20 nm is significantly larger resulting in a higher contact
area with carbon (Fig. 3d). After removal of the iron particles,
the etching patterns can be distinguished by the diffraction
contrast on the wall of the nanotubes (Fig. 3e). Figure 3f dis-

Figure 3. TEM images of the carbon nanotubes after etching with water through iron catalysts prepared by CVD (a–c) and by impregnation (d–f):
a) and d) after etching; b), c), and e), f) after removal of the iron nanoparticles by dissolution in acid.

3650 www.advmat.de © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2007, 19, 3648–3652

closes the partial destruction of the wall. As a result of the
etching, new edge planes were created. The newly exposed
surfaces are obviously very rich in defects such as steps, kinks,
vacancies, and adatoms.
The increase of the number of surface defects is also
detected by Raman spectroscopy. It is known that highly
ordered pyrolytic graphite is characterized by the so-called
G-band at ∼ 1580 cm–1, whereas microcrystalline graphite
shows additional bands around 1350 and 1620 cm–1, called D
and D′ bands respectively, due to the presence of lattice de-
fects and the loss of the long range in-plane symmetry.[14]
There is strong evidence that the loss of hexagonal symmetry
due to the formation of edge planes is associated with the D
lines.[15] It can be seen in Figure 4 that the intensity ratio of
the D band to the G band increased significantly due to etch-
G steam gasification of carbon was developed to modify carbon
D'
D ring only at the interface between the iron nanoparticles and
Intensity / a. u.
impregnation
etching
CVD
etching
as-received
1000 1200 1400 1600
-1
Raman shift / cm
Figure 4. Raman spectra of as-received and etched carbon nanotubes
using a 514.5 nm laser. The iron catalysts were prepared by CVD or by
impregnation.
ing, for both the CVD and the impregnated samples, indicat-
ing a considerable increase in the areal density of surface
defects.[16] In addition, the contribution of the D′ band appear-
ing as shoulder of the G band to higher wavenumbers was
increased by etching, which is an additional clear indication
for more surface defects.[17]
Correspondingly, after etching more oxygen- and nitrogen-
containing functional groups can be introduced to the surface
of the nanotubes by a treatment with nitric acid, as demon-
strated by X-ray photoelectron spectroscopy (XPS). The
quantitative results are summarized in Table 1. Furthermore,
the functional groups created on etched nanotubes are ther-
Adv. Mater. 2007, 19, 3648–3652
COMMUNICATION
Table 1. XPS oxygen and nitrogen surface atomic concentration of as-re-
ceived and of etched carbon nanotubes treated with nitric acid. The ther-
mal stability of the surface functional groups was determined by XPS
subsequent to heating at 727 °C for 120 min in UHV.
MWCNTs Without thermal treatment After thermal treatment
O N O N
[%] [%] [%] [%]
Without etching 9.72 2.19 4.34 0.78
After etching 9.92 2.42 5.57 1.61
mally more stable, which is of high relevance, because many
applications of nanotubes involve high-temperature processes
such as heterogeneous catalysis. The residual oxygen and
nitrogen groups after treatment at 727 °C for 120 min in UHV
are assumed to be basic sites, which are very active in base
catalysis.
In summary, a localized etching method based on catalytic
nanotubes in a pre-determined manner. The etching, occur-
the nanotubes, created different etching patterns depending
on the iron catalyst by means of an eco-friendly, low-cost pro-
cess using water vapor. Both the surface roughness and the
number of surface defects such as edge planes were signifi-
cantly enhanced. The controlled etching is expected to extend
the applicability of multi-walled carbon nanotubes, because it
was found to be beneficial for the creation of functional
groups. Furthermore, fiber-matrix interactions in composites
are expected to be enhanced for etched MWCNTs, and sinter-
ing of supported metal particles anchored in etching pits
should be less severe.
Experimental
The MWCNTs with inner diameters of 20–50 nm and outer diame-
ters of 50–200 nm were obtained from Applied Sciences Inc. (Ohio,
1800
USA). The following gases were used in this study: helium
(99.9999 %), hydrogen (99.9999 %), and synthetic air (20.5 % oxygen
in nitrogen). The flow of gases was adjusted by mass flow controllers
and referred to standard conditions (STP). The functionalization of
the nanotubes was carried out by refluxing in concentrated nitric acid
for 2 h at 110 °C. Iron was subsequently deposited by impregnation
with an aqueous solution of ammonium ferric citrate (AFC) or by
chemical vapor deposition (CVD) from ferrocene. In case of impreg-
nation, the AFC-loaded nanotubes is calcined in synthetic air at
350 °C for 1 h before the etching process. The CVD of iron and post-
deposition treatment of the iron nanoparticles, including annealing
and sintering, were described elsewhere in detail [5]. A typical etching
process involved the following steps:
The iron-loaded nanotubes (4–6 wt %) were reduced and annealed
at 500 °C in hydrogen and helium (1:1, 100 mL min–1) for 1 h.
Hydrogen (10 mL min–1, or 10 vol %), helium (89 mL min–1, or
89 vol %) and water vapor (1 mL min–1, or 1 vol %) were introduced
to the reactor at a total flow rate of 100 mL min–1. The water vapor
was introduced by flowing helium through a saturator filled with
water at room temperature.
All the gas species were monitored by online mass spectroscopy.
When the water signal (m/e = 18) reached its maximum in about
30 min, the reactor was heated from 500 °C to 670 °C at a rate of
© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de 3651
COMMUNICATION
20 K min–1. The reaction started at about 600 °C, as indicated by the
buildup of CO (m/e = 28) and the consumption of H2O (m/e = 18).
After reaction, the reactor was cooled down to 450 °C in helium
(100 mL min–1).
When the residual hydrogen (m/e = 2) reached its minimum in
about 30 min, synthetic air and helium (1:1, 100 mL min–1) were intro-
duced to remove the coke by oxidation. The decoking process finished
within roughly 5 min, as indicated by the oxygen signal (m/e = 32) of
the MS. The reactor was then cooled down to room temperature.
Finally, the etched sample (FeOx/MWNT) was washed under stir-
ring by 1 M HNO3 at room temperature for 2 h, and then filtered and
dried for further characterization.
The iron loadings were determined with a Pye Unicam 7000 ICP-
OES spectrometer. The morphology and detailed structure of the
nanotubes were studied by scanning electron microscopy (LEO Ge-
mini 1530) and transmission electron microscopy (Philips CM 200
FEG). Raman spectroscopy measurements were performed with a
modular system (Dilor LabRAM) with a laser source of 514.5 nm.
The physisorption measurements were carried out with a Quanta-
chrome Autosorb-1-MP system. The BET surface area was deter-
mined by static nitrogen physisorption at 77 K subsequent to out-gas-
sing at 573 K until the pressure was lower than 5 mbar.
X-ray photoelectron spectroscopy (XPS) measurements were car-
ried out in an ultra-high vacuum (UHV) set-up equipped with a Gam-
madata-Scienta SES 2002 analyser. The base pressure in the measure-
ment chamber was 2 × 10–10 mbar. Monochromatic Al Ka (1486.6 eV;
14 kV; 55 mA) was used as incident radiation, and a pass energy of
200 eV was chosen resulting in an energy resolution better than
0.5 eV. Charging effects were compensated by the usage of a flood
gun. Binding energies were calibrated based on positioning the main
C 1s peak at 284.5 eV. The thermal treatment of the HNO3-treated
nanotubes was performed in UHV (8 × 10–9 mbar) for 120 min in the
preparation chamber of the XPS set-up, followed by transfer in UHV
to the measurement chamber.
Received: March 29, 2007
Revised: May 4, 2007
Published online: October 16, 2007
– Fuel Process. Technol. 1993, 36, 235.
[1] a) R. H. Baughman, A. A. Zakhidov, W. A. de Heer, Science 2002,
297, 787. b) K. P. de Jong, J. W. Geus, Catal. Rev. Sci. Eng. 2000, 42,
481. c) P. Serp, M. Corrias, P. Kalck, Appl. Catal. A 2003, 253, 337.
d) J. M. Nhut, L. Pesant, J. P. Tessonnier, G. Wine, J. Guille, P. H.
Cuong, M. J. Ledoux, Appl. Catal. A 2003, 254, 345. e) O. Zhou,
H. Shimoda, B. Gao, S. Oh, L. Fleming, G. Yue, Acc. Chem. Res.
2002, 35, 1045. f) Y. P. Sun, K. Fu, Y. Lin, W. Huang, Acc. Chem.
Res. 2002, 35, 1096.
______________________
3652 www.advmat.de © 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[2] Bayer MaterialScience AG, Carbon Nanotubes in the Future,
www.baytubes.de (2006).
[3] P. Calvert, Nature 1999, 399, 210.
[4] H. Dai, Acc. Chem. Res. 2002, 35, 1035.
[5] W. Xia, D. Su, A. Birkner, L. Ruppel, Y. Wang, C. Woell, J. Qian,
C. Liang, G. Marginean, W. Brandl, M. Muhler, Chem. Mater. 2005,
17, 5737.
[6] a) S. Maldonado, K. J. Stevenson, J. Phys. Chem. B 2004, 108, 11 375.
b) S. Maldonado, K. J. Stevenson, J. Phys. Chem. B 2005, 109, 4707.
c) M. F. R. Pereira, J. J. M. Orfao, J. L. Figueiredo, Appl. Catal. A
1999, 184, 153. d) G. Mestl, N. I. Maksimova, N. Keller, V. V. Rodda-
tis, R. Schloegl, Angew. Chem. Int. Ed. 2001, 40, 2066. e) J. J. Delga-
do, R. Vieira, G. Rebmann, D. S. Su, N. Keller, M. J. Ledoux,
R. Schlögl, Carbon 2006, 44, 809.
[7] a) P. H. Matter, U. S. Ozkan, Catal. Lett. 2006, 109, 115. b) N. Keller,
N. I. Maksimova, V. V. Roddatis, M. Schur, G. Mestl, Y. V. Butenko,
V. L. Kuznetsov, R. Schloegl, Angew. Chem. Int. Ed. 2002, 41, 1885.
[8] a) P. V. Lakshminarayanan, H. Toghiani, C. U. Pittman, Jr., Carbon
2004, 42, 2433. b) S. Banerjee, T. Hemraj-Benny, S. S. Wong, Adv.
Mater. 2005, 17, 17. c) P. M. Ajayan, T. W. Ebbesen, T. Ichihashi,
S. Iijima, K. Tanigaki, H. Hiura, Nature 1993, 362, 522. d) O. Byl,
J. Liu, J. T. Yates, Jr., Langmuir 2005, 21, 4200. e) S. C. Tsang,
P. H. F. Harris, M. L. H. Green, Nature 1993, 362, 520. f) S. E. Kooi,
U. Schlecht, M. Burghard, K. Kern, Angew. Chem. Int. Ed. 2002, 41,
1353.
[9] T. W. Ebbesen, P. M. Ajayan, H. Hiura, K. Tanigaki, Nature 1994,
367, 519.
[10] H. Darmstadt, C. Roy, S. Kaliaguine, J. Ting, R. L. Alig, Carbon
1998, 36, 1183.
[11] a) J. Liu, A. G. Rinzler, H. Dai, J. H. Hafner, R. K. Bradley, P. J.
Boul, A. Lu, T. Iverson, K. Shelimov, C. B. Huffman, F. Rodriguez-
Macias, Y. S. Shon, T. R. Lee, D. T. Colbert, R. E. Smalley, Science
1998, 280, 1253. b) K. J. Ziegler, Z. Gu, H. Peng, E. L. Flor, R. H.
Hauge, R. E. Smalley, J. Am. Chem. Soc. 2005, 127, 1541.
[12] M. Muhler, W. Xia, DE Patent 102 006 007 208, 2007.
[13] a) J. Yu, F. J. Tian, M. C. Chow, L. J. McKenzie, C. Z. Li, Fuel 2006,
85, 127. b) M. Weeda, H. H. Abcouwer, F. Kapteijn, J. A. Moulijn,
[14] A. C. Ferrari, J. Robertson, Phys. Rev. B 2000, 61, 14 095.
[15] a) T. Hagio, M. Nakamizo, K. Kobayashi, Carbon 1989, 27, 259. b) G.
Compagnini, O. Puglisi, G. Foti, Carbon 1997, 35, 1793.
[16] a) S. Osswald, E. Flahaut, H. Ye, Y. Gogotsi, Chem. Phys. Lett. 2005,
402, 422. b) J. Heremans, I. Rahim, M. S. Dresselhaus, Phys. Rev. B
1985, 32, 6742.
[17] C. Vix-Guterl, M. Couzi, J. Dentzer, M. Trinquecoste, P. Delhaes, J.
Phys. Chem. B 2004, 108, 19 361.
Adv. Mater. 2007, 19, 3648–3652