VOLUME 2, NUMBER 12, DECEMBER 2002

© Copyright 2002 by the American Chemical Society

CuO Nanowires Can Be Synthesized by

Heating Copper Substrates in Air
Xuchuan Jiang, Thurston Herricks, and Younan Xia*

Department of Chemistry, UniVersity of Washington, Seattle, Washington 98195-1700

Received August 14, 2002; Revised Manuscript Received October 11, 2002

ABSTRACT
This paper describes a vapor-phase approach to the facial synthesis of cupric oxide (CuO) nanowires supported on the surfaces of various
copper substrates that include grids, foils, and wires. A typical procedure simply involved the thermal oxidation of these substrates in air and
within the temperature range from 400 to 700 °C. Electron microscopic studies indicated that these nanowires had a controllable diameter in
the range of 30−100 nm with lengths of up to 15 µm by varying the temperature and growth time. Electron diffraction and high-resolution TEM
studies implied that each CuO nanowire was a bicrystal divided by a (111) twin plane in its middle along the longitudinal axis. A possible
mechanism was also proposed to account for the growth of these CuO nanowires.

Cupric oxide (CuO) has been extensively studied because
of its close connection to high-Tc superconductors.1 The
valence of Cu and its fluctuation are believed to play
important roles in determining the superconductivity of
various types of cupric compounds.2 Cupric oxide has also
been known as a p-type semiconductor that exhibits a narrow
band gap (1.2 eV) and a number of other interesting
properties.3 For example, monoclinic CuO solid belongs to
a particular class of materials known as Mott insulators,
whose electronic structures cannot be simply described using
conventional band theory.4 Recent studies by several groups
indicate that CuO could exist in as many as three different
magnetic phases.5 It was a 3D collinear antiferromagnet at
temperatures below 213 K. When the temperature was raised,
it first became an intermediate noncollinear incommensurate
magnetic phase up to 230 K and then acted like a 1D
quantum antiferromagnetic material. With regard to its
* To whom correspondence should be addressed. E-mail: xia@
chem.washington.edu.
10.1021/nl0257519 CCC: $22.00 © 2002 American Chemical Society
Published on Web 10/24/2002
commercial value, CuO has been widely exploited for use
as a powerful heterogeneous catalyst to convert hydrocarbons
completely into carbon dioxide and water.6 Cupric oxide is
also potentially useful in the fabrication of lithium-copper
oxide electrochemical cells, and the relation between the
microstructure of CuO solid and its potential as a cathode
material has been systematically investigated.7 As it has
already been demonstrated for many other semiconductors
(e.g., Si, CdSe, and ZnO),8 it is reasonable to expect that
the ability to process CuO into nanostructured materials
should enrich our understanding of its fundamental properties
and enhance its performance in currently existing applica-
tions.
Cupric oxide can be prepared as nanoparticles of various
sizes using a number of methods, with notable examples
including mechanical milling of commercial powders,9
activated reactive evaporation of copper,10 and alcohothermal
decomposition of copper acetate.11 None of these methods,
however, seems to be suitable for the preparation of CuO as
Figure 1. SEM images of CuO nanowires prepared by directly heating copper TEM grids in air at 500 °C for (A-C) 4 h and (D) 2 h. (E,
F) SEM images of CuO nanowires that were formed on the surface of a copper wire (0.1 mm in diameter) by heating at 500 °C for 4 h.

nanowires. However, Pfefferkorn et al. (in the 1950s) found
that both CuO and Cu2O whiskers could be formed by
oxidizing copper substrates at elevated temperature.12 The
whiskers were characterized by a relatively short length (<5
µm) and a large diameter (>100 nm), and the surface
coverage of these whiskers was also fairly low. Several
groups recently attempted to synthesize CuO nanowires,
albeit their efforts have been met with limited success. In
1334
one demonstration, Wang et al. proposed that CuO nanowire
might be involved as a byproduct when Cu2O nanowires were
formed by reducing copper sulfate with hydrazine in a basic
solution.13 In another recent study, Yang et al. observed the
formation of polycrystalline nanowires containing both CuO
and Cu2O when Cu2S nanowires were oxidized by O2 at
elevated temperatures.14 Herein we describe a simple pro-
cedure for the synthesis of uniform CuO nanowires with
Nano Lett., Vol. 2, No. 12, 2002
Figure 2. (A) TEM image of CuO nanowires prepared by heating a copper grid at 500 °C for 4 h. (B) Electron diffraction pattern taken
from a random assembly of these CuO nanowires. (C) TEM image of an individual CuO nanowire showing the twin plane in the middle
of this wire (indicated by an arrow). (D) High-resolution TEM image showing the twin boundary of a nanowire. (E) Electron diffraction
pattern recorded from an individual CuO nanowire. Indices without subcript t refer to the upper side of the nanowire shown in (C), and
indices with subscript t refer to the other side. The e beam was parallel to the [110] axis. These results indicated that each CuO nanowire
was a bicrystal: the growth directions were [1h11] and [111], respectively.

controllable diameters in the range of 30-100 nm and with
lengths of up to 15 µm. Structural analysis by electron
diffraction and high-resolution TEM indicated that each
nanowire was a bicrystal divided by a (111) twin plane in
the direction parallel to the longitudinal axis.
In a typical procedure, the copper substrate was cleaned
in an aqueous 1.0 M HCl solution for ∼20 s, followed by
repeated rinsing with distilled water. After it had been dried
under a N2 gas flow, it was placed in an alumina boat (Al-
23, Alfa Aesar, MA) and immediately heated to the set-point
temperature (at ambient pressure) in a VWR box furnace.
We have tested a number of copper substrates: TEM grids
(cat. no. 01801, Ted Pella, Redding, CA), foils (99.9% purity,
0.05 mm thick, EM Science, Gibbstown, NJ), and conven-
tional electrical wires (99.9% purity, 0.1 mm in diameter,
ARCOR, Northbrook, IL). CuO nanowires of similar quality
could be grown on the surfaces of all of these copper
substrates. SEM images were obtained using a field-emission
microscope (Sirion, FEI, Portland, OR) operated at an
acceleration voltage of 5 kV. TEM images were taken with
a Philips EM-430 microscope operated at 80 kV. The high-
resolution TEM image was recorded on a TOPCON 002B
Nano Lett., Vol. 2, No. 12, 2002
microscope operated at 200 kV. The X-ray diffraction (XRD)
pattern was recorded from a powder sample using a Philips
PW-1710 diffractometer (Cu KR radiation, λ ) 1.5406 Å)
at a scanning rate of 0.02°/s in 2θ ranging from 10 to 70°.
The surfaces of all of the copper substrates were tarnished
(when viewed by the naked eye) after they had been treated
in air at elevated temperatures. Further examination under
an optical or electron microscope indicated the formation of
wirelike nanostructures over the entire surfaces of these
substrates. Figure 1A-C shows the SEM images of a copper
grid after it had been heated in air at 500 °C for 4 h. All
nanowires were mainly grown in the planes parallel to the
surface of this TEM grid. Although the entire surface of this
grid was covered by a high density of nanowires, those
protruding from the edges (Figure 1B) appeared to be
straighter, much longer, and more uniform in diameter as
compared with wires formed on the top surface (Figure 1C).
The length of these nanowires could be conveniently
controlled by changing the growth time. Figure 1D shows
the SEM image of another TEM grid after it had been heated
in the box furnace at 500 °C for 2 h. In comparison with the
nanowires shown in Figure 1B, a growth rate of ∼3 µm/h
1335
Figure 3. TEM images of CuO nanowires prepared by heating copper grids in air for 4 h at various temperatures: (A) 400, (B) 500, and
(C) 600 °C. The corresponding size distributions of these nanowires are shown in graphs D to F. These results suggest that the diameter
of the CuO nanowires could be varied in the range of 30 to 100 nm by controlling the reaction temperature.
could be derived. Figure 1E and F shows the SEM images grid, indicating the uniformity that could be achieved for
of a copper wire (0.1-mm diameter) after it had been heated these nanowires. Some of these wires appeared to be thicker
in air at 500 °C for 4 h. Similar to that of grid samples, the than they should be as a result of overlapping between wires
surface of this microscale wire was also completely covered at different levels. Figure 2B shows the electron microdif-
by a dense array of uniform CuO nanowires. Because of the fraction pattern recorded from a random assembly of
surface curvature of this substrate, each nanowire was grown nanowires. All rings could be indexed to the diffraction peaks
in the direction essentially perpendicular to the support. of monoclinic CuO rather than those of cubic Cu2O,
We further characterized the size, structure, and crystal- indicating the phase purity of these nanowires. The nanowires
linity of these nanowires using TEM and electron diffraction. could also be removed from the original copper grid (or other
The original copper TEM grids could be directly used for substrates) by rinsing with ethanol, redeposited onto a
some of these studies. Figure 2A shows the TEM image of carbon-coated TEM grid, and used for high-resolution TEM
an array of nanowires protruding from the edges of a copper studies. Figure 2C shows the TEM image of an individual
1336 Nano Lett., Vol. 2, No. 12, 2002
nanowire whose middle is clearly divided by a twin plane
along the longitudinal axis. Figure 2D displays a high-
resolution TEM image, further confirming the bicrystallinity
of this nanowire. Each side of this wire was, indeed, a single
crystal with a well-defined fringe space pattern, and a twin
defect could be observed in the middle. The interplanar
spacing for each side was 2.52 and 2.32 Å, respectively.
These two values corresponded well with the spacing
calculated for {1h11} and {111} planes in monoclinic CuO
(cell ) 4.69 Å × 3.43 Å × 5.13 Å, β ) 99.55°).15 Figure
2E shows a diffraction pattern that would be typically
observed when the electron beam was focused on an
individual nanowire along the [110] direction. The mirror-
image relationship between the two sets of diffraction spots
confirmed the formation of a bicrystalline structure within
each nanowire. The growth direction for each side of this
twined nanowire could be derived from the diffraction spots
as [1h11] and [111], respectively.
We also investigated the influence of temperature on the
growth of CuO nanowires. In these studies, copper foils
(∼0.25 cm2 in area) were placed in the furnace and heated
for 4 h at different temperatures in the range of 300 to 800
°C. We found that CuO nanowires were formed only in a
temperature window between 400 and 700 °C. When the
temperature was lower than 400 °C, very few short whiskers
were formed, and the surface was essentially coated by small
particles. As the substrate temperature was increased beyond
700 °C, the surface was covered by a dense film of
micrometer-sized particles. Some of these particles were
characterized by well-defined facets, indicating their high
crystallinity. For samples prepared between 400 and 700 °C,
CuO nanowires were obtained as the major product. It was
also found that the diameter of these nanowires had a strong
dependence on the temperature. Figure 3 shows the TEM
images of three samples that were heated at 400, 500, and
600 °C for 4 h, respectively. These images clearly indicated
that the lateral dimension of these nanowires could be
reduced from ∼100 to ∼50 and ∼30 nm when the reaction
temperature was increased from 400 to 500 and 600 °C,
respectively.
Two mechanismssvapor-liquid-solid (VLS)16 and vapor-
solid (VS)17shave been most commonly used to account for
the growth of nanowires in the gas phase. On the basis of
our SEM and TEM observations, the VLS mechanism could
be excluded because none of our CuO nanowires was
terminated in particles. As a result, the VS mechanism seems
to be responsible for the growth of CuO nanowires observed
in the present study. We note that this mechanism has
recently been applied to explain the formation of nanowires
from a variety of metal oxides.18 The present procedure for
forming cupric oxide nanowires differs from other systems
in that a precursor (rather than the direct oxidation of copper)
is involved. When copper is oxidized in air, the major product
is Cu2O, and CuO is formed slowly only through a second
step of oxidation. In this case, Cu2O served as a precursor
to CuO. The reactions involved in the entire synthesis can
be summarized as the following, with the second one
Nano Lett., Vol. 2, No. 12, 2002
Figure 4. XRD pattern of a copper foil (∼0.25 cm2 in area) after
it had been heated in air at 500 °C for 4 h. The majority of this
copper foil had been converted into Cu2O, with only a small amount
of CuO on the surface (in the form of nanowires).
functioning as the rate-determining step for the formation
of CuO vapor:19
4Cu + O2 f 2Cu2O (1)
2Cu2O + O2 f 4CuO (2)
The slow rate for the formation of CuO ensures a relatively
low vapor pressure for this material in the reaction chamber
and thus a continuous growth mode and uniform diameter
for the CuO nanowires. On the basis of these arguments,
the surface of the copper grid shown in Figure 1A should
be mainly covered by a dense film of Cu2O, with only a
very small amount of CuO in the form of nanowires. This
speculation was confirmed by the XRD pattern shown in
Figure 4, which was taken from a copper foil (∼0.25 cm2 in
area) after it had been heated in air at 500 °C for 4 h. The
temperature effect could also be understood by taking into
account the dependence of the Gibbs free energy of reaction
2 on temperature. Since the change in entropy (∆S) for
reaction 2 has a negative sign, the change in free energy
(∆G) for this reaction will change sign (from negative to
positive) when the temperature is sufficiently high. At this
point, the formation of CuO will be terminated, and thus no
nanowires will be observed. On the basis of the standard
thermodynamic data from the Handbook,20 this transition
temperature was estimated to be around 964 °C. This number
agreed reasonably well with the temperature (800 °C)
observed in the present study. As the temperature dropped
below 400 °C, the formation of CuO became too slow to
maintain a sufficiently high vapor pressure for CuO, and thus
no nanowire growth would occur on the copper substrate.
In summary, we have demonstrated a simple and conve-
nient route to the facial synthesis of uniform CuO nanowires
(30-100 nm in diameter) supported on solid substrates. Both
TEM and electron diffraction studies indicated that these
nanowires were bicrystals, with a (111) twin plane sitting in
the middle of each nanowire along the longitudinal axis.
These nanowires could be grown up to tens of micrometers
in length without branching or entanglement. In addition to
their direct use as a heterogeneous catalyst and as a class of
1337
semiconducting nanostructures for device fabrication, these
nanowires can also serve as templates from which to prepare
nanowires made of other materials (Cu2O, Cu, and Cu2S)
by reacting with gases such as H2 and H2S.21
Acknowledgment. This work has been supported in part
by a Career Award from the NSF (DMR-9983893), an
AFOSR-DURINT subcontract from SUNY-Buffalo, and a
Fellowship from the David and Lucile Packard Foundation.
Y.X. is an Alfred P. Sloan Research Fellow (2000-2002)
and a Camille Dreyfus Teacher Scholar (2002-2007).
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