Materials Letters 82 (2012) 2628

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Shape-controlled synthesis of zinc phosphate nanostructures by an aqueous solution

route at room temperature
Ning Xie a, b, c,, Decheng Feng a, Hui Li b, Chunwei Gong a, Liang Zhen c
a
b
c

School of Transportation Science and Engineering, Harbin Institute of Technology, Harbin 150090, China
School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

a r t i c l e

i n f o

Article history:
Received 7 January 2012
Accepted 12 May 2012
Available online 19 May 2012
Keywords:
-Zn3(PO4)24H2O
Nanosheets
Nanoplates
Room temperature
Aqueous solution method

a b s t r a c t
-Zn3(PO4)24H2O nanosheets, nanoplates and microspheres constructed by nanosheets have been successfully
synthesized by an aqueous solution method at room temperature without using any surfactants or templates.
X-ray diffraction pattern, scanning electron microscopy, transmission electron microscopy and UVvis diffuse
reectance spectroscopy were used to characterize the samples. The shape evolution of -Zn3(PO4)24H2O is
related to the pH value in the reaction system. This simple method might be useful for the synthesis of nanostructures of other phosphates.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The synthesis and self-organization of micro-/nanostructures with
special shape, size, and hierarchy have been attracted considerable attentions in the past few decades because of their importance in basic
scientic research and potential technological applications [1]. The design of two-dimensional (2D) and three-dimensional (3D) micro-/
nanostructures with well-controlled morphologies and architectures
has given an impetus to the development of nanoscience and nanotechnology as a key factor in tailoring the physical and chemical properties
of micro-/nanostructures [2]. Due to their interesting properties, great
attentions have been devoted to the exploration of various and effective
approaches for the synthesis of 2D and 3D micro-/nanostructures, most
of which involve high-temperature vapor-deposition methods [3,4].
Recently, solution-phase method has been acting as an effective and facile
synthetic route for the synthesis of 2D and 3D micro-/nanostructures
with some signicant advantages, including less-complicated techniques,
cost-effective, large-scale production and relative low-temperature
[57]. However, the scale-up synthesis strategy of 2D and 3D micro-/
nanostructures realized at room temperature in aqueous solutions
without using surfactants and templates still remains a major challenge.
Zinc phosphate (Zn3(PO4)2) is one of the most important multifunctional metal phosphates for various potential applications, including
ion-exchange materials, chelating agents, corrosion-resistant coatings,
glass ceramics, biomedical cements, and high-quality fertilizers [8,9].
Corresponding author at: School of Transportation Science and Engineering,
Harbin Institute of Technology, Harbin 150090, China. Tel./fax: + 86 451 86282191.
E-mail address: xiening@hit.edu.cn (N. Xie).
0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.05.037

The most frequent applications of zinc phosphates were as environmentally friendly anticorrosive pigments for coating products (iron and steel
alloys) and dental cements due to its low solubility in water/biological
environment and biocompatibility [8,9]. Especially, nowadays these
materials have been used in catalyst, electric motors and transformers
and in the automotive industry [8,9]. Various synthetic strategies, including a disodium phosphate-assisted sonochemical route [10], a chemical
method by using cetyltrimethylammonium bromide (CTAB) as capping
reagent [11], chemical precipitation using yeasts as a template [12],
have been investigated for the synthesis of zinc phosphate micro/
nanostructures.
Recently, a general room temperature, surfactant-free aqueous
solution method has been developed for a large-scale synthesis various
ternary metal oxides, including chromate [13], molybdate [14], tungstate
[15], sulfate [16], and carbonate [17]. This solution-phase method at room
temperature is very competitive because of its unique advantages, such
as no heating, no surfactants or polymer-assisted, easy-manipulating,
low-cost, and large-scale productivities. Herein, we further report our
interesting nding that zinc phosphate nanosheets and nanoplates can
be obtained by this simple solution-phase method at room temperature.
Moreover, by simply adjusting the pH value in the reaction system, the
nanosheets can be self-organized to 3D microspheres.
2. Experimental section
All reagents were analytical grade and used as received without further purication. In a typical synthesis process, 5 mmol of NH4H2PO4
and 10 mmol of NaCl were rst dissolved in 25 mL distilled water in a
50 mL glass beaker. 5 mmol of Zn(NO3)2 was dissolved in 25 mL distilled

N. Xie et al. / Materials Letters 82 (2012) 2628

water in the other glass beaker. After both were stirred to form homogeneous aqueous solutions, Zn(NO3)2 aqueous solution was added into
mixed aqueous solution of NH4H2PO4 and NaCl under magnetic stirring
at room temperature. The pH value was adjusted by NaOH aqueous
solutions. After stirring for 10 min, the resulting suspension was
maintained at room temperature for 5 days without stirring or shaking.
Then the white products were collected by centrifugation, washed several times with distilled water and absolute ethanol, and nally dried in air
at 60 C for 60 min.
X-ray diffraction pattern (XRD) was obtained on a Rigaku D/max-rA
X-ray diffractometer with Cu K radiation ( = 1.5406 ). The morphology of the samples was observed by scanning electron microscopy
(SEM), performed on FEI-Quanta 200F scanning electron microscopy.
The transmission electron microscopy (TEM) and selected area electron
diffraction (SAED) pattern were taken out on a Phillips Tecnai 20
microscopy with an accelerating voltage of 200 kV. The as-synthesized
powders were rst dispersed in ethanol by ultrasonic treatment and
then a small drop of the dispersions was transferred to a holey carbon
lm supported on a copper grid for TEM observation. The optical diffuse
reectance spectrum was measured on a UVvis scanning spectrophotometer (SHIMADZU UV 2550).
3. Results and discussion
Fig. 1 shows the SEM images of the as-synthesized -Zn3(PO4)24H2O
samples. The reaction process at relatively low pH value of 3 produces a
uniform population of -Zn3(PO4)24H2O nanosheets with an square
shape, as shown in Fig. 1a. The square nanosheets have an average length
of ~10.6 m and width of ~6.1 m (Fig. 1b). Detailed SEM observation
indicates that the thickness of these nanosheets ranges from 50 nm
to 100 nm (see for example, Fig. 1c). Moreover, some small nanosheets
are stacked on the at surface of big nanosheets. With increasing the
pH value of the reaction system to 4, square shape-like -Zn3(PO4)2
4H2O nanoplates are formed (Fig. 1d). The nanoplates have an average
length of ~20.3 m, width of ~10.4 m and thickness of ~200 to
500 nm (Fig. 1e and f). In addition, some nanoplates tend to grow

27

cross-like nanostructures. The formation of cross-like nanostructures

should be related to the high pH value, and the nanosheets may tend
to be self-assemble in this reaction condition. With increasing pH value
of the reaction system to 6 results in the formation of spherical-like
microstructures with size of ~6 m, as shown in Fig. 1g. Higher
magnication SEM image shown in Fig. 1h reveals that the microsphere
is composed of many layers of nano scale sheet-like structures [1]. The
constructed nanosheets have a uniform thickness of ~50 nm (Fig. 1i).
Apparently, the shape evolution of -Zn3(PO4)24H2O is sensitive to
pH value in the reaction system. With increasing pH value of the reaction
system from 3 to 4 and 6, the -Zn3(PO4)24H2O nanosheets grow largely and thickly to form nanoplates and microspheres. It should be noted
that it is hard to precipitate between Zn2 + and PO42 ions when the
pH value is below 3, while the nal products are irregular shapes when
the pH value is above 6.
Fig. 2 shows the XRD patterns of the as-synthesized -Zn3(PO4)2
4H2O nanosheets, nanoplates, and microspheres with pH values of 3, 4,
and 6 in the reaction system. The sharp diffraction peaks indicate
the well crystallization of -Zn3(PO4)24H2O. All the diffraction peaks
in Fig. 2b and c can be perfectly indexed as the orthorhombic phase of
-Zn3(PO4)24H2O (JCPDC No. 33-1474, cell constants: a=10.611 ,
b=18.312 and c=5.0309 ). No characteristic peaks from other impurities can be detected from the XRD data, which indicates that the assynthesized products have high phase purity. For the nanosheets synthesized with pH value of 3, there is some impurity in the nanosheets, as
shown from Fig. 2a.
Fig. 3a shows a typical TEM image of an individual -Zn3(PO4)2
4H2O nanosheet. Due to the nanosheet being very thin, it shows a
relatively transparent image under the electron beam. Fig. 3b is the
SAED pattern recorded on the selected -Zn3(PO4)24H2O nanosheet,
which reveals its single crystalline in nature. As indexed, the pattern of [1]
zone axes is present for the nanosheets. Numerous SAED pattern analyses
demonstrate that the as-synthesized -Zn3(PO4)24H2O nanosheets are
all of single-crystalline.
Fig. 4 shows a typical diffuse reection spectrum of the Zn3(PO4)24H2O nanosheets. There is an abroad absorption band in

Fig. 1. SEM images of -Zn3(PO4)24H2O nanoplates synthesized at different pH values. (ac) pH value = 3, (df) pH value = 4, and (gi) pH value = 6.

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N. Xie et al. / Materials Letters 82 (2012) 2628

Fig. 2. XRD patterns of -Zn3(PO4)24H2O (a) nanosheets, (b) nanoplates and

(c) microspheres constructed by nanosheets. Mark is from impurity.

Fig. 4. UVvis diffuse reection spectrum of -Zn3(PO4)24H2O nanosheets. Inset is

(Ephoton)2 vs Ephoton curves of -Zn3(PO4)24H2O nanosheets.

Acknowledgments
This work was nancially supported by the Projects of Natural
Scientic Research Innovation Foundation in Harbin Institute of
Technology (HIT.NSRIF. 2009100), Key Laboratory Opening Funding
of Special Materials Lab on Transportation (HIT.KLOF.2009105),
Program of Excellent Team at HIT, and China Postdoctoral Science
Foundation (No. 20110491065).

References
Fig. 3. (a) TEM image and (b) SAED pattern of an individual -Zn3(PO4)24H2O
nanosheet.

the wavelength of 230400 nm. A classical Tauc approach [18] is

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The value estimated from the intercept of the tangents to the plots
of (Ephoto) 2 vs Ephoto was 3.6 eV (inset in Fig. 4).
4. Conclusions
In summary, this paper reports the large-scale synthesis of Zn3(PO4)24H2O nanosheets, nanoplates and microspheres constructed
by nanosheets in aqueous solution at room temperature without using
any surfactants or templates. The nanosheets are of single crystalline
in nature. The shape evolution is related to the pH value in the reaction
system. This facile, room temperature, solution-phase method might be
useful for the synthesizing nanostructures of other phosphates.

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