Pt-catalyzed formation of Ni nanoshells on carbon nanotubes

Article abstract of DOI:10.1002/anie.200701671

Full metal jacket: Carbon nanotubes (CNTs) are used as templates to form well-defined anisotropic magnetic nanowires with ferromagnetic behavior at room temperature. Uniform assembly of catalytic Pt nanoparticles on the CNTs yields organic-inorganic hybri

Full text of DOI:10.1002/anie.200701671

Communications
DOI: 10.1002/anie.200701671
Magnetic Nanotubes
Pt-Catalyzed Formation of Ni Nanoshells on Carbon Nanotubes**
Marek Grzelczak, Miguel A. Correa-Duarte,* Verónica Salgueiriæo-Maceira, Benito Rodríguez-
Gonzµlez, JosØ Rivas, and Luis M. Liz-Marzµn
[
6]
Apart from their intrinsically interesting one-dimensional
ticle interactions; or c) the assembly of magnetic nano-
particles onto surface-modified CNTs through electrostatic
interactions, which leads to the synthesis of anisotropic CNT-
2
(
1D) morphology, sp -bonded carbon nanotubes (CNTs) have
remarkable, structure-dependent electronic, mechanical,
[
1]
[3]
optical, and magnetic properties that make them promising
components in nanocomposite architectures. CNTs have also
found numerous other, already demonstrated applications in
many different fields, including catalysis, sensors, semicon-
ductor devices, biological environments, data storage/proc-
based magnetic composites.
Whereas the use of pre-formed magnetic nanoparticles
allows the selection of nanoparticles with well characterized
magnetic properties, which can be maintained within the
composite, these systems suffer from the inherently weak
magnetic interaction between the small magnetic core volume
of the nanoparticles involved. The decay of this dipole–dipole
interaction potential between single magnetic particles is such
that polyelectrolyte layers or even a silica shell only a few
[
2]
essing devices, and reinforced nanofiber materials. CNT-
based nanocomposites have been created by the assembly of a
variety of nanoparticles (NPs) onto surface-primed CNTs. In
most of these examples, the assembled NPs display mutual
interactions but their individual nanosized nature is main-
[
6g]
nanometers thickcan minimize these interactions.
An
[
3,4]
tained within the resulting 1D CNT-based nanocomposites.
alternative method involves the growth of a continuous shell
of a pre-selected magnetic material on a suitable anisotropic
template, such as nanowires or nanotubes, so that the
magnetic response is better defined all along the nano-
structure.
Herein we present the synthesis of well-defined, aniso-
tropic magnetic nanotubes, using CNTs as templates, in which
the sp carbon structure is preserved while obtaining a
Among such nanocomposites, the combination of CNTs with
magnetic materials offers an increased interest owing to the
monodimensionality of the final composites, which results in
an increase of the magnetic anisotropy, and the possibility of
alignment under manipulation with external magnetic fields.
Such aligned CNTs are particularly attractive for the design
of, for example, new reinforced nanofiber materials.
2
CNTs can thus be used as unique templates for the
synthesis of 1D magnetic nanomaterials, which have recently
ferromagnetic behavior at room temperature. The magnetic
material is grown directly on the CNT outer surface in a
process that is mediated by an assembled layer of pre-
synthesized, catalytic Pt nanoparticles. This intermediate step
yields organic–inorganic hybrid composites which serve as 1D
substrates for the preparation of magnetic CNT-supported Ni/
[
5]
received considerable attention. In particular, colloidal
dispersions of anisotropic magnetic nanoparticles have been
prepared by different techniques, such as: a) the selective
control of the growth rates of different faces through
[
5]
relatively simple variations in surfactant composition;
b) the assembly of pre-formed magnetic nanoparticles into
chains or necklaces through magnetic dipole–dipole interpar-
[*] M. Grzelczak, Dr. M. A. Correa-Duarte, Dr. B. Rodríguez-Gonzµlez,
Prof. L. M. Liz-Marzµn
Departamento de Química Física
Universidade de Vigo, 36310 Vigo (Spain)
Fax: (+34)986-812-556
E-mail: macorrea@uvigo.es
Dr. V. Salgueiriæo-Maceira, Prof. J. Rivas
Departamento de Química-Física y Física Aplicada
Universidade de Santiago de Compostela
15782 Santiago de Compostela (Spain)
[
**] M.A.C.-D. and V.S.-M. are grateful to the Isidro Parga Pondal
Program (Xunta de Galicia, Spain) for fellowships. This work was
supported by the Spanish Xunta de Galicia (grant no. PGIDIT06P-
XIB314379PR), the Spanish Ministerio de Educación y Ciencia
(
Consolider Ingenio 2010, “Nanobiomed”), and by the European
Commission Marie Curie RTN “SyntOrbMag” (contract no.
MRTNCT-2004-005567). We thank Dr. C. Senra (CACTI, U. Vigo) for
performing XPS measurements.
Figure 1. Illustration of the synthetic process comprising the polymer
(PAH) wrapping of CNTs, electrostatic self-assembly of pre-synthesized
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Pt nanoparticles, and Ni reduction to form CNT-supported Ni/NiO
nanoshells.
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Angew. Chem. Int. Ed. 2007, 46, 7026 –7030

Angewandte
Chemie
NiO nanotubes (Figure 1). Potential applications for Ni/Pt
[
7]
nanostructures include their use as catalysts, in oxygen-
reduction reactions within polymer electrolyte membrane
[
8]
[9]
fuel cells, or in direct oxidation methanol fuel cells.
Moreover, CNT-supported Ni/NiO nanotubes could be used
as electrodes that display high electrocatalytic activity for
[
10]
hydrogen peroxide detection in biosensing applications.
Suspensions of Ni nanowires have also been proposed as
magneto-optical switches because of their ability to scatter
[
11]
light that is perpendicularly incident to the wire axis. These
nanowires, when ferromagnetic, have large remnant magnet-
ization owing to their large aspect ratios and hence can be
used in low-field environments where superparamagnetic
[
12]
beads do not perform at all.
Additionally, since these
composite structures involve a Ni/NiO antiferromagnetic/
ferromagnetic interface, an exchange bias effect is expected
which could find promising applications in magnetoresistive
Figure 2. TEM images of CNT@Pt nanocomposites prepared by
depositing 5- (a) and 2.5-nm (b) Pt nanoparticles. Inset in (a): size
distribution of the 5-nm Pt nanoparticle dispersion.
[
13]
devices.
Figure 1 summarizes the experimental procedure, which
involves three main steps. First, CNTs are functionalized by
wrapping them with a positively charged polyelectrolyte
CNTs by catalyzing the reduction of the Ni/hydrazine
complex formed in aqueous solution, as described below.
This reaction allows the CNT/Pt nanocomposites to be coated
with a uniform and homogeneous Ni layer (ca. 10 nm thick),
with no need for surfactants or other stabilizers in aqueous
solution. This feature is relevant since the use of surfactants or
other stabilizers usually hinders subsequent manipulation and
implementation in different applications. The CNT/Pt@Ni
composites reported herein are stable in solution (most likely
because of the presence of a negatively charged NiO surface
layer) and their surface is free of surfactants, thus allowing
further functionalization where required.
(
polyallylamine hydrochloride (PAH)), which then acts as a
molecular glue for the attachment of negatively charged Pt
nanoparticles onto the surface of the CNTs. These nano-
particles, in turn, serve as catalytic centers for Ni reduction.
The so-called polymer wrapping technique is a noncovalent
functionalization which, in contrast to defect-side- and
covalent-side-wall functionalization, prevents the disruption
2
of the nanotubesꢀ intrinsic sp conjugation, thereby preserving
[
14]
their electronic structure. This polymer wrapping technique
relies on the thermodynamic preference of CNT–polymer
interactions over CNT–water interactions, whereas the
second stage (attachment of the Pt nanoparticles) is based
on an electrostatic and van der Waals attraction between the
negatively charged nanoparticles and the positively charged
Figure 3 shows representative TEM and HRTEM images
of the CNT/Pt@Ni samples obtained following the process
described above. These images clearly show the homogeneous
[
15]
PAH-functionalized surface of the CNTs.
This strategy permits the assembly of pre-synthesized
nanoparticles of varying morphology (size and shape), as
required by each specific final application. Platinum-covered
CNTs (CNT/Pt) with different Pt loadings can be obtained by
controlling both the deposition time and the CNT:Pt nano-
particles concentration ratio during the deposition process.
CNT/Pt nanocomposites were prepared from Pt nanoparti-
cles with different sizes (see representative TEM images in
Figure 2 and the Experimental Section), with homogeneous
coatings of Pt nanoparticles over the complete surface of the
CNTs invariably being obtained. While some small nano-
particle groups are observed (see Figure 2a), the Pt nano-
particles are, in general, uniformly distributed on the nano-
tubes with the same size distribution as in the original
dispersion (see inset in Figure 2a). The size of the Pt
nanoparticles (av. diameter: 5 nm) selected to demonstrate
the homogeneous Ni reduction and CNT coating was chosen
so that they could be identified during the subsequent coating
steps, but smaller particles can also be used.
Figure 3. Representative TEM images a) of the CNT/Pt structures
coated with a uniform outer layer of nickel (ca. 10 nm) and b) a detail
of a CNT@Ni tip (b). c) HRTEM image showing the polycrystalline
nature of the nickel shell deposited on the CNT/Pt nanocomposites.
d) Illustration of Ni reduction on the CNT/Pt side-walls. Step I involves
the decomposition of hydrazine on the surface of Pt nanoparticles,
which results in a charged surface, and step II the reduction of the
hydrazine/Ni complex on the charged Pt surface.
The CNT/Pt nanocomposites were used as templates for
the preparation of Ni nanotubes by taking advantage of the
catalytic behavior of small Pt seeds. Pt nanoparticles play a
crucial role in the formation of metallic Ni on the walls of the
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Communications
coating of individual CNTs and reveal the crystalline nature
ure 4b) shows the relative distribution of the elements, with
of the Ni layer in the final composite. Crystalline planes can
be observed both in the darker areas (corresponding to the
internal Pt nanoparticles) and over the whole surface of the
nanocomposites, thereby reflecting the polycrystalline nature
of the magnetic nanowires synthesized.
red areas corresponding to Pt (Pt M line) and green areas
a
corresponding to Ni (Ni K line). The image clearly shows
a
that Pt is located on the inner side of the metallic shell with Ni
mostly covering the outer part, as expected for the proposed
onionlike structure.
The proposed mechanism for the formation of metallic Ni
on the surface of the Pt nanoparticles is depicted schemati-
cally in Figure 3d. Complexes between transition-metal ions
The analysis was completed with HRTEM images
(Figure 5), where the multi-wall structure of the CNTs used
[
16]
and hydrazine are easily formed in water and that such
complexes can be decomposed in the presence of hydroxy
[
17]
II
groups, in a process where Ni complexes are reduced to
0
Ni . However, the catalytic decomposition of hydrazine in the
presence of platinum nanoparticles can take place on the
surface of these nanoparticles by an electrophilic addition,
that is, by forming electrophilic radicals which can then react
[
18]
with other hydrazine molecules from solution. The pres-
ence of metallic platinum nanoparticles therefore implies the
reduction of nickel complexes without the need for additional
hydroxy groups present in solution. In fact, we observed that
2
+
reduction of Ni did not occur in experiments using PAH-
functionalized CNTs in the absence of Pt nanoparticles. Thus,
the mechanism of Ni nanotube formation can be explained in
the following terms: the excess hydrazine that is not
2
+
complexed with Ni ions can be catalytically decomposed
on the surface of the platinum nanoparticles supported on the
CNTs. This step generates a charged metallic surface (step I,
II
Figure 3d) which promotes the reduction of the Ni complex
0
into Ni (step II, Figure 3d). Subsequent decomposition of
[
19]
hydrazine on the surface of the reduced metal is facilitated,
thus favoring further Ni reduction and growth of a homoge-
II
neous shell. The process terminates when all the Ni has been
reduced. The advantage of this surface-catalyzed reduction of
II
Ni is the formation of a continuous (though polycrystalline)
Ni layer rather than an outer shell composed of nanoparticles,
with an expected improvement of the resulting magnetic
properties.
A scanning transmission electron microscopy (STEM)
analysis of the samples was performed to confirm the
formation of the expected core(CNT)/shell(Pt)@shell(Ni)
structure. The dark-field STEM image (Figure 4a) shows a
mass-thickness contrast, with brighter areas in the material
close to the surface of the CNTs corresponding to Pt
nanoparticles. STEM-XEDS (X-ray energy dispersion spec-
troscopy) elemental mapping of the hybrid structures (Fig-
Figure 5. a) HRTEM image of a Ni-coated CNT. b) Fourier transform
spot pattern of the image shown in (a). c) Reconstructed image
obtained by inverse Fourier transformation after filtering out the spots
from Ni and Pt with the mask shown in the inset (top right) to
enhance the position of the CNT.
in this procedure can clearly be seen. This procedure allowed
us to determine a value for the interwall distance in the multi-
walled nanotubes (MWNTs) of about 0.34 nm. This value
agrees well with the interwall spacing of MWNTs reported by
[
20]
Kiang and co-workers, which range from 0.34 to 0.39 nm
depending on the diameter of the outer nanotubes, as well as
[
21]
with the interplanar distance of graphite (0.336 nm). Inter-
wall and interplanar distances were determined by Fourier
transform analysis of the HRTEM image shown in Figure 5b
for MWNTs (0.34 nm), Pt (0.22 nm), and Ni (0.20 and
0
.17 nm), thereby confirming the pre-designed structure of
Figure 4. STEM analysis of the CNT/Pt@Ni nanostructures. a) Dark-
field image where the Pt particles appear brighter. b) Elemental
mapping by XEDS analysis, with Pt (M line) in red and Ni (K line) in
the obtained CNT/Pt@Ni nanocomposites.
Since the CNT/Pt@Ni nanocomposites formed are
exposed to an oxygen-containing environment during depo-
a
a
green.
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Angewandte
Chemie
sition of the magnetic material, a stable NiO outer layer is
expected to form which passivates the Ni shell and prevents
[
22]
full oxidation. However, the presence of nickel oxides on
the outer surface of the nickel nanotube could not be
confirmed by the Fourier transform analysis shown in
Figure 5. To determine whether nickel oxides were formed
on the surface of the CNT/Pt@Ni nanocomposites the
samples were examined by X-ray photoelectron spectroscopy
(
XPS; see the Supporting Information). Analysis of the Ni 2p
peaks revealed a main peak for metallic Ni (852.8 eV) with
contributions from different Ni oxidation states, presumably
corresponding to the binding energies of NiO and Ni(OH)2
(
854.4 and 856.5 eV, respectively). These main lines are
accompanied by satellite lines with binding energies that are
eV higher, which suggests the presence of these Ni oxides at
6
the outer surface of the nickel wires. Apart from passivation,
this surface oxidation process leads to ferromagnetic/anti-
ferromagnetic (FM/AFM) interfaces (Ni/NiO), which give
rise to an exchange bias effect that increases the potential
applications of these nanocomposites.
The DC magnetic properties of these CNT/Pt@Ni/NiO
nanocomposites were recorded in a SQUID magnetometer.
Figure 6a shows the hysteresis curves collected at 5 K (field
cooled (FC), 2 kOe) and at 300 K. The hysteresis loop at 5 K
is shifted along the applied field direction, with an exchange
bias field, H , of 72 Oe and a coercivity, H , of 380 Oe. The
E
C
hysteresis loop at 300 K is open, with a coercivity of 91 Oe
Figure 6a). The exchange bias effect occurs owing to the
(
exchange coupling at FM/AFM interfaces, which leads to a
shift of the hysteresis loop along the applied field axis.
Exchange anisotropy, which was discovered by Meikle-
[
23]
john and Bean,
refers to the properties of exchange-
coupled FM/AFM materials and the effect is most simply
manifested by an offset of the FC hysteresis loop from zero on
the field axis. This exchange bias effect can therefore be
expected to be the result of an exchange interaction between
the uncompensated surface spins of NiO and metallic Ni in
the Ni/NiO-coated CNT/Pt nanocomposites. This shift of the
hysteresis loop can be established either by cooling the FM/
AFM material in a magnetic saturation field below the NØel
temperature of the antiferromagnet (2 kOe in this case) or by
[
13]
depositing both materials under an external magnetic field.
Figure 6b shows the 1-kOe field-cooled (FC) and zero-field-
cooled (ZFC) magnetization curves as a function of temper-
ature. The maximum in the ZFC curve at 40 K is usually
ascribed to the average blocking temperature of the magnetic
moment.
The ZFC and FC curves diverge at a maximum blocking
temperature of 186 K, which corresponds to the largest
nanotubes present in the sample. More detailed investigations
of this magnetic behavior will be reported elsewhere. The
magnetic nature of the nanocomposites was also shown by
drying a drop of the dispersion on a Si wafer at 300 K under an
applied magnetic field of 0.2 T, which resulted (Figure 6c) in
their alignment into long chain structures through a magneto-
phoretic deposition process.
Figure 6. a) Hysteresis loops measured at 5 K (field-cooled, 2 kOe)
and 300 K. b) Temperature dependence of the ZFC (close symbols)
and FC (open symbols) magnetization measured at 1 kOe for the Ni/
NiO-coated CNT/Pt nanocomposites. c) SEM image of the nanocom-
posites deposited on a Si substrate and aligned under an external
magnetic field (arrow indicates direction) of 0.1 T. Inset: Higher
magnification TEM image.
structure. The catalytic activity of the CNT-supported Pt
nanoparticles has been used to control the reduction of
metallic Ni onto their surface, along with a passivating NiO
surface layer. The resulting anisotropic and magnetic Ni/NiO
nanotube colloids are excellent candidates for use as building
blocks for the fabrication of novel composite materials with a
magnetic-field-driven preferential orientation. An additional
advantage of this system stems from the fact that the magnetic
CNT structures are stable in the absence of additional
In summary, Ni hollow nanotubes have been grown using
CNTs wrapped with charged polyelectrolytes and coated with
Pt nanoparticles as templates while preserving the CNT
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Communications
stabilizers or surfactants and their magnetic properties permit
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2
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[
Experimental Section
CNT polyelectrolyte functionalization: CNTs were dispersed in ultra
[
3,4]
pure water (18 MWcm) following a published procedure.
Briefly,
CNTs were dispersed in a 1 wt.% aqueous solution of polyallylamine
À1
hydrochloride (PAH) to a concentration of 150 mgL . A combina-
tion of rapid stirring and sonication was used to ensure the presence
of well dispersed, individual nanotubes. Excess PAH was removed by
several centrifugation and redispersion cycles.
Platinum seeds: The Pt nanoparticles to be deposited onto CNTs
were synthesized as follows. Sodium borohydride (2.9 mL, 0.06m) was
added as a reducing agent to a solution of sodium citrate (2.5 mL,
0
.1m) and K PtCl (0.5 mL, 0.05m) in ultrapure water (44 mL) and the
2 4
resulting solution stirred for 10 min.
Pt deposition on the CNT surface: CNT@PAH (0.6 mL,
À1
0
.5 mgmL ) was added to a solution of Pt seeds (50 mL, 0.5 mm).
After allowing to stand for 30 min, the solution was centrifuged
10 min, 8000 rpm) and redispersed in pure water (20 mL) to remove
(
nondeposited nanoparticles.
Ni growth: The CNT/Pt dispersion (20 mL) was added to an
aqueous solution (30 mL) containing an NiCl2 stocksolution
[7] K. Ahrenstorf, O. Albrecht, H. Heller, A. Kornowski, D. Gꢄrlitz,
H. Weller, Small 2007, 3, 271.
(
0.06 mL, 0.25m) and hydrazine (0.12 mL, 2.5m). The mixture was
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magnet and washed with water and ethanol (twice for each solvent).
2002, 106, 1869; b) K.-W. Park, J.-H. Choi, Y.-E. Sun, J. Phys.
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Received: April 16, 2007
[
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Keywords: magnetic properties · materials science · nanotubes ·
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nickel · platinum
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