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Effect of OH − on morphology of Cu2O particles prepared through
reduction of Cu(II) by glucose
WANG Yuejun(王岳俊), ZHOU Kanggen(周康根)
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
© Central South University Press and SpringerVerlag Berlin Heidelberg 2012
Abstract: Cu2O particles with different shapes were prepared via reducing Cu(II) in alkaline system by glucose at 50 °C. The
products were characterized by Xray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy
(TEM). It is found that the shape of Cu2O particles changes with the change of concentration of NaOH. The different shapes of Cu2O
particles are due to the absorption of OH − ions on Cu2O particles, which arise the variety of growth mode of Cu2O, and then
influence the morphology of Cu2O particles.
Foundation item: Project(50674100) supported by the National Nature Science Foundation of China
Received date: 2011−05−27; Accepted date: 2012−03−22
Corresponding author: ZHOU Kanggen, Professor, PhD; Tel: +86−731−88836442; Email: zhoukg63@yahoo.com.cn
2126 J. Cent. South Univ. (2012) 19: 2125−2129
flask at room temperature (25 °C). Secondly, the precursor
and glucose solutions were heated up to 50 °C,
respectively. Finally, the glucose solution was dumped
into the reaction vessel rapidly to reduce the precursor at
50 °C. The products were collected by centrifugation,
washed for 5 times with distilled water and 2 times with
ethanol, and then, dried at 65 °C for 24 h. Preparation
processes of precursor and Cu2O paste were both under
stirring (500 r/min). The pH values were measured
timely during the glucose reduction.
In the reaction, the Cu 2+ ions are reduced first to
Cu + by glucose and Cu + can react with OH − to form
Cu2O, which is described as follows:
Cu(OH)2=Cu 2+ +2OH − (or CuO+H2O=Cu 2+ +2OH − ) (1)
Cu 2+ +3OH − +C6 H12 O6=Cu + + C 6 H 11 O - Fig. 1 XRD patterns of Cu2O with different shapes:
7 +2H2 O (2)
(a) Octahedron; (b) Sphere
Cu + +OH − =CuOH (3)
2CuOH=Cu2O+H2O (4) The TEM micrographs and the selected area
electron diffraction (SAED) patterns of Cu2O particles
2.3 Measurement of quantities of OH − absorbed on with different shapes are provided in Fig. 3. Figure 3(a)
Cu2O particles shows the TEM and SAED micrographs of the spherical
Firstly, 4 g Cu2O particles were put into 200 mL Cu2O particles when the NaOH concentration is
NaOH solution. Secondly, the suspension was stirred by 2.50 mol/L. The TEM images clearly indicate that the
ultrasonication for 30 min, and then the suspension was spherical particles are all polycrystals, as indicated by the
filtrated using 0.45 μm polyether sulfone membrane filter. ringlike SAED pattern taken on these spherical particles.
Finally, the concentration of OH − was measured in the Figure 3(b) shows the TEM and SAED micrographs of
filtrate by acidbase titration. the octahedral Cu2O particles when the NaOH
concentration is 6.25 mol/L. The TEM image
2.4 Characterization of Cu2O particles unambiguously reveals that it is a perfect Cu2O single
The XRD of the powder was carried out using a crystal, and the SAED pattern can be identified as the
Rigaku D/Max 2550 Xray diffractometer with Cu Kα á111ñ zone axis projection of the Cu2O reciprocal lattice.
radiation (λ=1.541 8 Å). The morphology and particle Therefore, both single crystal particles and
size of Cu2O particles were investigated by SEM polycrystalline powders can be prepared selectively in
(JSEM6360LV, Japan). TEM images were taken with a similar procedures by simply changing the concentration
Hitachi Model800 transmission electron microscope of NaOH.
using an accelerating voltage of 200 kV.
3.2 Discussion
3 Results and discussion Two completely different mechanisms are usually
used to explain the formation of single crystals and
3.1 Characterization of Cu2O particles polycrystals [20]. A diffusion mechanism is generally
The XRD patterns of products with octahedron and accepted to explain the formation of monodispersed
spherical shapes are shown in Fig. 1. All the peaks can single crystals. According to this mechanism, the crystal
be indexed into the cubic symmetry of Cu2O. No nuclei will make a facet oriented growth via the
impurity peaks are observed, indicating that the products constituent complexes diffusion to these primary particles,
are phasepure Cu2O. and the morphology of monocrystal is determined by the
Cu2O powders obtained from different experiments relatively growth rate of different crystal faces [12,
are characterized by SEM, as shown in Fig. 2. It can be 20−21]. For Cu2O monocrystal, when (111) plane grows
deduced that spherical Cu2O particles are synthesized relative fast, the shape of Cu2O crystal tends to be
when the concentration of NaOH is 2.50 mol/L. As the cube. When (100) plane grows relatively fast, it tends
concentration of NaOH increases, quasispherical Cu2O to be octahedron. On the other hand, an aggregation
particles with angularity appear (Fig. 2(c)). When the mechanism is also employed to explain the formation of
NaOH concentration is 6.25 mol/L, the shape of Cu2O monodispersed polycrystals [10, 20]. This mechanism
particle is octahedron. considers that the aggregations of uniform single
J. Cent. South Univ. (2012) 19: 2125−2129 2127
Fig. 2 SEM images of Cu2O particles prepared in presence of different concentrations of NaOH: (a) 2.50 mol/L; (b) 3.75 mol/L;
(c) 5.00 mol/L; (d) 6.25 mol/L
crystalline subunits lead to nuclei growing into the final different shapes of Cu2O crystal particles were obtained
larger polycrystalline assemblies. via changing the concentration of NaOH. The result
It could be concluded that spherical Cu2O indicates that the competition exists between aggregation
polycrystals were obtained in this work because the growth and (100) facet oriented growth of crystal
growth mode of Cu2O nuclei was aggregation, and nucleus when the concentration of NaOH changes. It
octahedral Cu2O single crystals were owing to the could be attributed to having a large number of OH − on
growth mode of (100) facet oriented growth. In this work, Cu2O particles surface in alkaline systems.
2128 J. Cent. South Univ. (2012) 19: 2125−2129
−
In order to study the effect of OH on growth mode particles. Thus, repulsion between singlenuclei,
of Cu2O crystal nucleus, the pH values were registered molecule clusters, and primary particles is low,
timely during glucose reduction of Cu(II), as shown in aggregation is the leading growth mode, and the crystal
Fig. 4. And the absorption quantities of OH − ions on nucleus grow into spherical particles finally.
Cu2O particles at different pH values (NaOH solution 2) When the concentration level of NaOH is high,
with different concentrations) are listed in Table 2. there are more OH − ions adsorbed on the surface of Cu2O
particles. This brings about stronger repulsion among
primary particles, which restrains the aggregation growth.
Thus, diffusion mechanism is the growth mode of Cu2O
crystal nuclei. As to this work, it is accepted that the OH −
would be selectively adsorbed on (111) facet of Cu2O
crystals, then slow the growth rates of (111) facet [12].
The increase of NaOH concentration will augment the
adsorption of OH − on Cu2O particle, in especial, on (111)
crystal facet. So, the nuclei tend to preferentially grow
along (100) directions and form octahedrons bounded by
(111) facets.
4 Conclusions
Fig. 4 Change of pH values during reaction in presence of
different NaOH concentrations 1) When NaOH concentration is 6.25 mol/L, there
are more OH − ions adsorbed on surface of Cu2O
Table 2 Absorption quantities of OH − on Cu2O in different particles, and the repulsion among primary particles
alkaline systems restrains aggregation growth mode and high density of
NaOH concentration NaOH concentration Absorbed OH − on (111) facet restrains the growth of (111) facet. As
before adsorbed/ after adsorbed/ quantity of OH − / a result, relatively faster growing of (100) facet is
(mol∙L −1 ) (mol∙L −1 ) (mmol∙g −1 ) eliminated, with morphology of Cu2O forming into
0.993 0 0.961 0 1.570 octahedron finally.
0.491 0 0.474 0 0.865 2) When NaOH concentrations are 2.50 mol/L and
3.75 mol/L, the repulsion is lower, aggregation is the
0.089 1 0.084 2 0.245
leading growth mode, and Cu2O nuclei grow into sphere
0.045 1 0.043 5 0.080 finally.
0.014 3 0.013 9 0.020 3) When NaOH concentration is 5.00 mol/L, there
is a balanced competition between aggregation growth
In this work, every reaction finished after 20 min. It and (100) facet growth. As a result, Cu2O nuclei grow
can be seen in Fig. 4 that when NaOH concentration is into quasispherical particles.
2.50, 3.75, 5.00 and 6.25 mol/L, the pH values change
from 12.35 to 11.80, 12.65 to 12.18, 13.2 to 12.8 and References
13.2 to 12.9 in reaction process, respectively. Table 2
shows that there is a strong adsorption between Cu2O [1] SMITH M, GOTOVAC V, ALJNOVIC L J. LUCICLAVCEVIC M.