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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY

Nanotechnology 17 (2006) 3939–3943 doi:10.1088/0957-4484/17/15/055

Synthesis, characterization and catalytic


properties of CuO nanocrystals with
various shapes
Kebin Zhou1,2 , Ruipu Wang1 , Boqing Xu1 and Yadong Li1
1
Department of Chemistry and National Center for Nanoscience and Nanotechnology,
Tsinghua University, Beijing 100084, People’s Republic of China
2
College of Chemistry and Chemical Engineering, Graduate University of the Chinese
Academy of Sciences, Beijing 100049, People’s Republic of China

E-mail: ydli@tsinghua.edu.cn

Received 9 May 2006, in final form 22 June 2006


Published 11 July 2006
Online at stacks.iop.org/Nano/17/3939
Abstract
CuO nanocrystals with different shapes, i.e. irregular nanoparticles, nanobelts
and nanoplatelets, have been synthesized by controlling a few critical
synthesis parameters to explore their catalytic properties. It was found that
the rate of CO oxidation on the nanoplatelets is over six times higher than that
on the nanoparticles and about three times higher than that on the nanobelts
at 110 ◦ C. Based on combined characterizations, such as BET, XRD, TEM,
HRTEM and CO temperature-programmed reduction, the relationship
between the catalytic reactivity and the shape as well as the predominantly
exposed crystal planes of the CuO nanocrystals has been discussed.

1. Introduction Thus, the nature of the metal oxide surface should be


of paramount importance. In recent years, the shape-
Nanostructured materials present great promise and opportu- controlled synthesis of nanostructured CuO has attracted
nities for a new generation of materials with improved and considerable attention [22–26]. In the present work, large
tailorable properties for applications in sensors, optoelectron- scales of CuO nanoplatelets and nanobelts were synthesized
ics, separation and catalysis. Catalysts, for example, are through a facile softer synthetic route, which involved the
mostly nanoscale particles, and catalysis is a nanoscale phe- precipitation of copper salts with concentrated NaOH solutions
nomena [1, 2]. Up to now, significant progress has been made at room temperature. CuO nanoparticles with irregular shape
in controlling the size of nanoscale materials and in under- were also prepared by a traditional precipitation method for
standing their unique size-dependent catalytic properties [3–6]. comparison. The CO catalytic oxidation over these copper
Meanwhile, controlling the shape of nanoparticles is an equally oxides was investigated and the shape and the exposed crystal
important aspect of desired catalyst synthesis [7–11]. It is planes were found to influence the catalyst performance
known that the reactivity depends on the crystal plane of the significantly. The results indicate that shape-controlled
catalyst for structure-sensitive reactions [12–15]. One would synthesis of nanomaterials may present great opportunity for
expect catalysis to be greatly dependent on the nanocrystal- the design of catalysts with desired properties.
lite shape used, since different nanocrystallites with different
shapes expose different crystal planes [16, 17].
2. Experimental details
Copper oxide is one of the most important catalysts,
and is widely used in environmental catalysis. For carbon 2.1. Synthesis of CuO nanocrystals with different shapes
monoxide oxidation, CuO catalysts may even substitute
the noble metal catalysts because of their high catalytic 2.1.1. CuO nanobelts. Cu(NO3 )2 ·3H2 O (3.0 g) was dis-
activity [18, 19]. Previous studies indicate that this reaction solved in distilled water, and appropriate amounts of con-
is an apparent structure sensitive process and the surface centrated NaOH solution were rapidly added under stirring
lattice oxygen of CuO is involved during the reaction [20, 21]. in a Teflon flask at room temperature. The black precipitate

0957-4484/06/153939+05$30.00 © 2006 IOP Publishing Ltd Printed in the UK 3939


K Zhou et al

together with mother liquor at room temperature for 12 h. The


final product was collected by filtration, washed with deionized
water, dried at 60 ◦ C for 24 h, and then calcined at 350 ◦ C
for 4 h.

2.2. Material characterization


Powder XRD was performed on a Bruker D8 advance x-
ray diffractometer with monochromatized Cu Kα radiation
(λ = 1.5418 Å). The size and morphology of all
the materials were measured by using a Hitachi H-800
transmission electron microscope and a JEOL JEM-2010F
high-resolution transmission electron microscope. BET-
surface area of catalysts was measured by N2 adsorption
using the single point method. CO temperature-programmed
reduction (CO-TPR) was conducted on a CATLAB reactor
Figure 1. XRD patterns of (a) CuO nanoparticles, (b) CuO nanobelts equipped with a QIS-20 MS detector. Before the TPR analysis,
and (c) CuO nanoplatelets. the sample (100 mg) was treated with pure Ar with a flow rate
of 50 ml min−1 at a ramp rate of 10 ◦ C min−1 to 250 ◦ C, then
was maintained for 0.5 h at the final temperature, and cooled
appeared quickly, indicating the formation of CuO. The final to room temperature. Then TPR was performed by heating
NaOH concentration is about 5 M. The resultant product was the sample at 10 ◦ C min−1 to 500 ◦ C in a 10% CO–N2 mixture
then aged together with mother liquor at room temperature flowing at 30 ml min−1 . All the samples can be reduced to
for 3 days. The final product was collected by filtration, and metal copper after TPR analysis as detected by XRD.
washed with deionized water to remove any possible ionic rem-
nants, and then dried at 60 ◦ C and calcined at 350 ◦ C for 4 h. 2.3. Catalytic activity evaluation
The catalytic activities for CO oxidation were evaluated in a
2.1.2. CuO nanoplatelets. Cu(CH3 COO)2 ·H2 O (3.0 g) fixed-bed quartz tubular reactor. The catalyst particles (0.15 g)
was dissolved in distilled water, and appropriate amounts of were placed in the reactor. The reactant gases (1.0% CO,
concentrated NaOH solution were rapidly added under stirring 16% O2 , balanced with nitrogen) went through the reactor at
in a Teflon flask at room temperature. The black precipitate a flow rate of 100 ml min−1 and a gas hourly space velocity
appeared quickly, indicating the formation of CuO. The final (GHSV) about 12 000 h−1 . The products were analysed by a
NaOH is about 5 M. The resultant product was then aged gas chromatographer equipped with a TDX column.
together with mother liquor at room temperature for 5 h. The
final product was collected by filtration, and washed with
deionized water to remove any possible ionic remnants, and 3. Results and discussion
then dried at 60 ◦ C and calcined at 350 ◦ C for 4 h.
3.1. XRD, BET and TEM analysis

2.1.3. CuO nanoparticles. CuO nanoparticles were prepared The x-ray diffraction patterns show that all the CuO samples
by a traditional precipitated method: Cu(NO3 )2 ·3H2 O was are of monoclinic structure (figure 1). The BET surface areas
dissolved in distilled water, and then the pH value of the are 38.6, 28 and 22 m2 g−1 for the irregular nanoparticles, the
solution was rapidly adjusted to 10 using Na2 CO3 (1 M) nanobelts and the nanoplatelets, respectively. A TEM image
solution with stirring. The resultant product was then aged (figure 2(a)) shows that the shape of the traditional prepared

Figure 2. TEM images of (a) CuO nanoparticles, (b) CuO nanobelts and (c) CuO nanoplatelets.

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Synthesis, characterization and catalytic properties of CuO nanocrystals with various shapes

Figure 3. (a) HRTEM image of CuO nanoparticles; (b) HRTEM image of a typical CuO nanobelt view along [001] (inset: the SAED pattern);
(c) HRTEM image of a typical CuO nanoplatelet view along [011̄] (inset: the SAED pattern).

CuO nanoparticles is irregular and the particle size is in the 3.2. HRTEM analysis
range of 10–25 nm and agglomeration can be observed. For the
samples prepared by the softer synthetic route, the morphology Structure information about these CuO samples is obtained
and dimensions of the product were found to strongly depend using electron diffraction and HRTEM analysis. Figure 3(a)
on the copper salt precursors. When cupric nitrate was shows a HRTEM image of the CuO nanoparticles. In addition
used, CuO nanobelts could be obtained. A TEM image to the expected irregular morphology, surface faceting is
(figure 2(b)) reveals that they are several hundreds nm in length evident. This implies that various crystal planes are exposed.
and about 20–50 nm wide. While cupric acetate was used as The dominant (111) lattice fringes, which are parallel to some
the copper precursor, CuO nanoplatelets could be obtained. of the small facets, are observed, revealing that the CuO
Figure 2(c) shows typical images of these nanoplatelets. It is nanoparticles predominantly expose the close-packed (111)
clear that each of the particles consists of several triangular planes of the monoclinic structure. Figure 3(b) shows a two-
nanoplatelets. Such an anion dependent growth phenomena of dimensional crystal lattice image of one typical CuO nanobelts
nanocrystals has also been observed in the synthesis of other with its growth axis perpendicular to the electron beam. The
nanocrystals and has been explained in terms of anion selective corresponding electron diffraction pattern (inset of figure 3(b))
adsorption on various crystal planes [27]. We think that the along the [001] zone axis demonstrates that the belt is a single
formation of CuO nanobelts and the nanoplatelets may follow crystal with a growth direction of [010] (see arrow). The
the same story in the present work. Besides the choice of the results are consistent with the CuO nanostructures fabricated
copper precursor, the concentrated NaOH solution (5 M) is by Chang and Zeng [26]. Clearly, the predominantly exposed
also necessitated. In general, the CuO nanocrystallites with planes of the CuO nanobelts are the (001). Figure 3(c) shows
different shapes could be synthesized by controlling a few a HRTEM image of a single CuO nanoplatelet. Electron
critical synthesis parameters, especially the copper precursor. diffraction along the [011̄] zone axis (inset of figure 3(c)) gives
The samples were also investigated after several catalytic test spot points, indicating that the nanoplate is a single crystal.
cycles. Based on the TEM images, no evolution of the shapes Therefore, the (011̄) planes are the predominantly exposed
was observed. ones in the case of CuO nanoplatelets. The results reveal

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K Zhou et al

Figure 4. Specific rate of CO conversion over CuO nanoparticles, Figure 5. CO temperature-programmed reduction profiles of the
nanobelts and nanoplatelets at 110 ◦ C, the predominantly exposed samples.
crystal planes of each nanostructure are indexed in the figures.
(This figure is in colour only in the electronic version)
temperature in figure 5. The CuO nanoparticles exhibit a broad
CO2 peak around 194 ◦ C. The CuO nanobelts show a sharp
that different methods for CuO sample preparation result in peak at 90 ◦ C, and a direct transformation to metallic Cu was
surfaces with different orientations. detected by XRD analysis. In the case of CuO nanoplatelets,
two main peaks at 77 and 134 ◦ C can be discerned, showing a
3.3. Catalytic activity evaluation relatively complex reduction process. According to Wang et al
[29], the whole reduction process of CuO nanoplatelets may
The catalytic performance of these CuO samples for the follow a sequential step reduction mechanism
oxidation of CO was evaluated. The resulting CuO
nanoparticles gave 100% conversion of CO at 200 ◦ C, while CuO + CO → CuO1−x + CO2 (1)
over the CuO nanobelts and nanoplatelets, the complete
conversion of CO could be obtained as low as about 150 ◦ C. CuO1−x + CO → Cu + CO2 . (2)
No catalyst deactivation was observed during several activity In general, the CuO nanoplatelets are more reducible than the
test cycles. To elucidate the remarkable effects of the catalysts CuO nanobelts under CO atmosphere and the reducibility of
shapes, the specific reaction rates were calculated and are the nanoparticles was the lowest among the samples.
given in figure 4. At 110 ◦ C, the specific reaction rates were CuO is a semiconducting oxide, which crystallizes in the
−2 −1
1.0, 2.0 and 6.4 × 10−8 molCO mcat s on the nanoparticles, complex monoclinic tenorite structure with Cu–O planes along
nanobelts and nanoplatelets, respectively; then the rate on the [11̄0] and [110] directions [30]. The arrangements of atoms
the nanoplatelets is over six times higher than that on the vary with the crystal planes. This means that the free energies
nanoparticles and roughly three times higher than that on and sites for reactant adsorption are different for different
nanobelts. crystal planes. Therefore, the ability to abstract oxygen from
Heterogeneous oxidation catalysis on copper oxide the surface and creation of the oxygen vacancy should also
surfaces is one class of reactions that has received significant vary with the crystal planes. According to the HRTEM
attention. Previous studies suggest that such a reaction analysis results, the irregular nanoparticles predominantly
is an apparent structure-sensitive process and the surface expose the close-packed (111) planes, while the nanobelts and
lattice oxygen of CuO is involved during the catalytic the nanoplatelets predominantly expose the more open (001)
process [18–21]. It is well known that the activation and (011̄) planes, respectively. Generally speaking, the close-
barrier of the catalysed CO oxidation reaction over transition- packed planes of the oxides have lower free energies than the
metal surfaces is determined by the metal–oxygen bond more open planes and the stability of the former are higher than
breaking [28]. Thereby the surface properties of the CuO the later [31, 32]. Thereby the CuO nanoparticles exhibit the
catalysts are strongly related to the nature of the surfaces used lowest reducibility.
in the experiments. And the ability to abstract oxygen from The present results reveal that the shape and the exposed
the surface lattice oxygen of CuO is a key factor to determine crystal planes of the samples play an important role during the
its reactivity. This was characterized by CO-temperature reduction. Combining with the catalytic activity results it is
programmed reduction (TPR). clear that: the higher the reducibility, the better the reactivity
for CO oxidation. The CuO nanoplatelets exposing the (011̄)
3.4. CO-TPR analysis planes more easily release oxygen from the surface lattice,
followed by the nanobelts with (001) planes, in turn they are
During the CO-TPR process, CO was oxidized to CO2 , and the more active than the nanoparticles with the close-packed (111)
QMS traces of CO2 (m/e = 44) are plotted as a function of planes.

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Synthesis, characterization and catalytic properties of CuO nanocrystals with various shapes

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