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concentrations in the permeate solution. Single gas permeation ex-
periments were performed at 200 C in a cross-flow gas permeation
setup [3a]. Pervaporation experiments were performed with water/
1,4-dioxane and water/glycol binary liquids at 7580 C in a dead-end
pervaporation unit [4a,5]. The permeate composition was analyzed by
Karl Fischer titration.
Received: November 14, 2003
Final version: May 4, 2004
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1550  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400129
Uniform Metal Nanotube Arrays by
Multistep Template Replication and
Electrodeposition**
By Cheng Mu, Yuxiang Yu, Rongming Wang, Kai Wu,
Dongsheng Xu,* and Guolin Guo
Since the discovery of carbon nanotubes,[1] hollow nano-
tubes have attracted considerable attention due to their fun-
damental significance and potential applications in nanoscale
devices, sensors, and energy storage/conversion.[213] In partic-
ular, metal nanotubes raise special interest because of their
conductivity, catalysis, and the feasibility of chemically modi-
fying their outer/inner surfaces and edges. For example, gold
nanotube membranes have unfolded potential applications in
nanoelectrode ensembles, sensors, chemical and biological
separations, and biocatalysis.[14]
To date, only a few examples of metal nanotubes have been
reported in the literature.[1419] Template-based techniques
have been employed to prepare aligned metal nanotube ar-
rays such as gold,[14] cobalt,[15] iron,[15] and nickel,[16] where
the inner surfaces of the template pores need to be chemically
modified prior to deposition. Xia and co-workers have synthe-
sized noble metal nanotubes such as gold, palladium, and plat-
inum via galvanic displacement reactions between silver or se-
lenium nanowires and appropriate precursors of these metals
in aqueous media.[17] Bismuth and antimony nanotubes have
been obtained by low-temperature solvothermal meth-
ods.[18,19] However, a general approach for fabricating aligned
metal nanotube arrays is still elusive. Precise control of the
nanotube growth process and formation of well-aligned arrays
will be of great help in investigating their physical properties
and their potential use in nanoscale fluidic chemical and bio-
logical separations, sensors, and catalysis. In this work, we de-
sign a well-controlled process for fabricating uniform metal
nanotube arrays via a multistep template replication and elec-
trodeposition approach. The obtained nanotubes are highly
ordered and uniform in wall thickness and diameter along the
entire tubes.
[*] Prof. D. S. Xu, C. Mu, Y. X. Yu, Prof. K. Wu,
Prof. G. L. Guo
State Key Laboratory for Structural Chemistry of Unstable and Stable
Species, College of Chemistry and Molecular Engineering,
Peking University
Beijing 100 871 (P.R. China)
E-mail: dsxu@chem.pku.edu.cn
Prof. R. M. Wang
Electron Microscopy Laboratory and State Key Laboratory for
Mesoscopic Physics, School of Physics
Peking University
Beijing 100 871 (P.R. China)
[**] This work was supported by the Major State Basic Research Devel-
opment Program (Grant No. 2000077503) from the Ministry of
Science and Technology, China and KW is grateful for financial sup-
port from the NSFC (Grant No. 20125309).
Adv. Mater. 2004, 16, No. 17, September 3

The first step of our synthesis involves the deposition of
carbon nanotubes (CNTs) onto the interior walls of anodic
aluminum oxide (AAO) templates by the pyrolytic decompo-
sition of ethyne at 650750 C in an argon atmosphere.[20] A
gold thin film was coated on one side of the CNTs/AAO
membrane by vacuum evaporation, in order to make a con-
ductive contact. Then nickel was electrodeposited into the
pores of the CNTs/AAO membranes in order to form a coax-
ial nanocable structure consisting of a nickel core and CNT
sheath.[21] These Ni/CNT/AAO membranes were put into a
furnace and heated at 400 C for 10 h in air, leading to the oxi-
dation of nickel to nickel oxide. Further heating at 600 C for
2 h in air resulted in the CNTs in the template membranes
burning up. In this way, a highly ordered, annular nanochan-
nel membrane was obtained. Metals such as platinum, gold,
bismuth, indium, and nickel were then electrodeposited into
the annular nanochannel to form a coaxial sandwich nano-
structure consisting of a nickel oxide core, a metal intermedi-
ate layer, and an AAO sheath. In the end, the nickel oxide
core and the AAO membrane were chemically dissolved to
expose the produced metal nanotubes. Details of the whole
procedure are schematically shown in Figure 1.
Figure 1. Flow chart of the multistep template replication process for pre-
paring uniform metal nanotube arrays.
Adv. Mater. 2004, 16, No. 17, September 3 http://www.advmat.de
COMMUNICATIONS
Figure 2A is a scanning electron microscopy (SEM) image
of the CNTs embedded in an AAO template membrane,
clearly demonstrating that the CNTs are highly ordered and
well-decorated on the pore walls of the AAO template. The
A
200 nm
B
5m
200nm
Figure 2. SEM images of A) the CNTs grown on AAO; B) the metal nano-
tube arrays after dissolution of the AAO template and the nickel oxide
cores. The inset in (A) is a close-up of the CNTs in AAO, scale bar:
200 nm. C) Top view of the metal nanotube arrays.
average diameter of the CNTs is 50 nm and their wall thick-
ness is 10 nm (see inset, Fig. 2A). After the sequential pro-
cedure of nickel electrodeposition and oxidation, CNT com-
bustion, platinum electrodeposition, and final dissolution of
the AAO template and the nickel oxide cores, a highly dense
platinum nanotube array was produced, as shown in Fig-
ure 2B. The nanotubes, about 30 lm in length, are well
aligned and the morphology of the initial CNTs is duplicated.
Figure 2C is a top view of the platinum nanotube array,
clearly showing the open ends of the nanotubes.
Transmission electron microscopy (TEM) and high-resolu-
tion TEM (HRTEM) images provide further insight into the
structure of the metal nanotubes. Figure 3A is a typical TEM
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1551
COMMUNICATIONS
A A
300nm
Pt
C
Counts
Cu
Cu
Pt
Pt
0 4 8 12
Energy (keV)
Figure 3. A) TEM image of the as-prepared metal nanotubes. B) The
EDS spectrum of the metal nanotubes shown in Figure 3A.
image of the metal nanotubes, indicating that the nanotubes
possess a uniform inner diameter of 60 nm, and that the in-
ner/outer wall surfaces are quite smooth. It is interesting to
note that several pieces of the residual NiO nanowire cores
remain in the platinum nanotubes. Figure 3B gives the X-ray
energy dispersion spectrum (EDS) taken from the sample
shown in Figure 3A, evidencing that the nanotubes are com-
posed only of platinum.
The magnified TEM image shown in Figure 4A reveals that
the wall thickness of the platinum nanotubes is about 5 nm,
smaller than that of the grown CNTs shown in Figure 2A. This
is due to the thermal expansion effect of the nickel cores,
which ultimately reduces the spacing between the AAO pore-
wall and the NiO cores. Since the wall thickness of the CNTs
increases with the pyrolytic decomposition time, the wall
thickness of the nanotubes can be adjusted simply by control-
ling the deposition time of the CNTs. For instance, the plati-
num tubes have a typical thickness of 1012 nm (Fig. 4B) after
a CNT growth time of 20 min, whereas the wall thickness
decreases to about 5 nm with a CNT growth time of 10 min.
A typical HRTEM image of the nanotube wall (Fig. 4C) iden-
tifies a polycrystalline structure. A detailed analysis of the
HRTEM image yields an interplanar spacing of 0.20 nm,
closely corresponding to that of platinum (200) planes.
To summarize, we have developed a multistep template rep-
lication approach for synthesizing highly ordered platinum
nanotube arrays that are tens of micrometers in length and
1552  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
B
20 nm 200 nm
B
C
tube channel
tube wall
0.20 nm
2nm
Figure 4. TEM images of the metal nanotubes with different wall thick-
ness: A) 5 nm; B) 10 nm. C) A typical HRTEM image of the as-pre-
pared metal nanotubes.
70 nm in outer diameter. These platinum nanotubes are uni-
form both in their morphology and wall thickness. It is worth
pointing out that our approach to preparing metal nanotubes
completely differs from all previous work on template-based
growth of aligned metal nanotube arrays. Previous studies on
template syntheses of metal nanotubes involve electroless de-
position or electrodeposition of metals on the chemically
modified pore-walls of the templates used.[1416] However, for
those one-step replication processes, it is difficult to provide
precise control of the nanotube growth, and the obtained
nanotube wall thickness is not uniform along the entire tube
length. In our approach, highly ordered annular nanochannel
membranes are first prepared. Therefore, a variety of tem-
plate synthesis strategies could be employed to control the
nanotube growth in these annular nanochannels. In general,
this approach could be used to synthesize a wide range of
nanotubes with various chemical compositions. We have suc-
cessfully prepared aligned nanotube arrays of other inorganic
materials, such as gold, bismuth, indium, nickel, CdS, and
CdSe.[22] Such aligned metal nanotube arrays with open ends
might find a broad range of potential applications in nano-
electrochemistry, catalysis, chemical/biological separation,
and sensor developments.
http://www.advmat.de Adv. Mater. 2004, 16, No. 17, September 3

Experimental
Anodic aluminum oxide membranes containing 70 nm diameter
pores were grown by potentiostatic anodization of high-purity alumi-
num plates (0.2 mm thick, 99.99+ % purity) in an aqueous oxalic acid
solution (4 %) in a water bath. After anodization, the remaining alu-
minum was etched by a mixed solution of HCl (20 %) and CuCl2
(0.1 M), and the barrier layer was dissolved by H3PO4 (5 %). For de-
positing the CNTs, the AAO templates were placed in a furnace with
an argon flow of 100 sccm. After the reactor temperature was in-
creased to 650 C, an ethyne flow of 30 sccm was introduced for
10 min, and then the template membrane was annealed at 650 C in
argon for 10 h prior to cooling it to room temperature.
Electrodeposition of metal was performed potentiostatically in a
three-electrode configuration in which a platinum plate, a saturated
calomel electrode (SCE) and a Au/AAO template membrane served
as the counter, reference, and working electrodes, respectively. Nickel
was electrodeposited at a constant voltage of 1.0 V versus SCE in an
electrolyte of nickel sulfate (0.15 M) and boric acid (0.6 M). After the
electrodeposition of nickel, the Ni/AAO membranes were oxidized at
400 C for 10 h and then heated at 600 C for 2 h in air. Using the an-
nular nanochannel template as a working electrode, platinum nano-
tubes were electrodeposited at a constant voltage of 0.8 V versus
SCE in a mixed aqueous solution of H2PtCl6 (1 g L1) and boric acid
(30 g L1).
For electron microscopy measurements, the AAO template and
NiO cores were dissolved by placing in NaOH (1 M) for 30 min and
then in HCl (1 M) at 50 C for 10 h. The morphology and structure of
the fabricated platinum nanotubes were analyzed by a scanning elec-
tron microscope (DB235 focused ion beam (FIB) system, FEI Com-
pany), a transmission electron microscope (JEM-2000FX TEM with
X-ray energy dispersion analysis equipment, JEOL Company), and a
high-resolution electron microscope (HRTEM, Tecnai F30, FEI Com-
pany).
Received: January 28, 2004
Final version: April 16, 2004
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Synthesis of Ordered Mesoporous
Carbon and Nitrogen-Doped Carbon
Materials with Graphitic Pore Walls via
a Simple Chemical Vapor Deposition
Method**
By Yongde Xia and Robert Mokaya*
Porous carbons with well-ordered pore systems are useful
in a wide range of applications which include catalysts (or cat-
alysts support), storage materials, and as components of elec-
trodes.[1] Recent developments have given rise to the prepara-
tion of mesoporous carbons, which possess well-ordered and
uniformly sized mesopores.[2] The mesoporous carbons, which
are prepared using ordered mesoporous silicates (silica or alu-
minosilica) as solid templates are currently the focus of in-
tense research interest.[210]
Preparation of ordered mesoporous carbons involves filling
the pores of the silicate template with a suitable carbon
precursor followed by carbonization (usually via high temper-
ature treatment) and finally removal of the silicate tem-
plate.[210] The (particle) morphology of the silicate is replicat-
ed in the resulting mesoporous carbon, while the mesopore
channel system of the carbon is an inverse replica of the pore
arrangement in the silicate template.[210] However, despite
their excellent structural ordering and well-defined pore size
distribution, mesoporous carbons in general possess pore
[*] Dr. R. Mokaya, Dr. Y. D. Xia
School of Chemistry, University of Nottingham
University Park, Nottingham NG7 2RD (UK)
E-mail: r.mokaya@nottingham.ac.uk
[**] The authors are grateful to the EPSRC for financial support. Sup-
porting Information is available online from Wiley InterScience or
from the author.
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1553