Materials Letters 167 (2016) 48

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

Facile synthesis of porous ower-like SrCO3 nanostructures by

integrating bottom-up and top-down routes
Lufeng Yang a,b, Deqing Chu a,b,n, Limin Wang b,c,nn, Ge Ge a, Huilou Sun a
a

College of Environment and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China
State Key Laboratory of Hollow-Fiber Membrane Materials and Membrane Processes, Tianjin 300387, PR China
c
College of Material Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 17 September 2015
Received in revised form
14 November 2015
Accepted 27 December 2015
Available online 29 December 2015

This work shows that a chemical bottom-up and successive top-down approach is a good synthetic
strategy for nanoporous materials. The three-dimensional (3D) ower-like SrCO3 nanocrystals have been
prepared via a hydrothermal treatment process with a subsequently selective etching of the certain
crystalline planes of SrCO3. Pores formed on the owers owing to the loss of by-products of H2O and CO2.
Accordingly, the original ower-like morphology of SrCO3 was not preserved upon pore formation and
during continuous stirring in the synthesis. Rearrangement of the SrCO3 particles via a dissolution-recrystallization process occurred under our certain experimental conditions. Consequently, SrCO3 particles
with coarser surfaces and porous structures were obtained.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
SrCO3
Porous materials
Nanoparticles
Bottom-up and top-down
Crystal growth

1. Introduction
Fabrication of ordered porous materials in nano-scale order has
been one of the most important topics in recent years, and much
attention has been focused on 3D ordered porous materials because of their applications in photonic crystals and catalysis [1].
Besides, integration of bottom-up and top-down routes has recently become one of the dominant challenges in the fabrication of
nano-/micro-structures/devices with advanced functional properties [2,3]. As far as SrCO3 is an important raw material in modern
electronic industry [4]. In addition, SrCO3 is also used to produce
paints, dryers, pigments and so on [5]. Furthermore, SrCO3 has
only one crystal-phase, so it has been widely studied as a model
system for bio-crystallization [6]. The preparation of porous 3D
SrCO3 architectures is typically based on a bottom-up approach
[7]. However, it also requires a combination of top-down processes. A physical top-down synthetic approach facilitates the
designed shape fabrication of functional materials [8]. But it often
suffers from size limitation in the preparation of nanomaterials. In
comparison, a so-called chemical top-down approach has shown
various successful examples in the tailored post-modication of
n
Corresponding author at: College of Environment and Chemical Engineering,
Tianjin Polytechnic University, Tianjin 300387, PR China.
nn
Corresponding author at: State Key Laboratory of Hollow-Fiber Membrane
Materials and Membrane Processes, Tianjin 300387, PR China.
E-mail addresses: dqingchu@163.com (D. Chu),
wanglimin@tjpu.edu.cn (L. Wang).

http://dx.doi.org/10.1016/j.matlet.2015.12.131
0167-577X/& 2015 Elsevier B.V. All rights reserved.

nanomaterials [9,10]. For example, the treatment of transition

metal nanomaterials with various acids resulted in the formation
of hollow materials through the selective etching of certain crystalline planes [11,12]. Thus, it can be speculated that designed
inorganic nanomaterials could be rst prepared using a chemical
bottom-up method and the selective etching of certain crystalline
planes could then result in nanoporous materials.
Here we reported a unique method of the synthesis and characterization of 3D porous ower-like SrCO3 crystals. The synthesis
was performed using a hydrothermal treatment process with a
subsequently selective etching of the certain crystalline planes of
SrCO3. Furthermore, a reasonable explanation is provided to demonstrate the formation of the porous ower-like SrCO3
nanostructures.

2. Experimental
A typical synthesis procedure of the porous SrCO3 ower-like
nanostructures was as follows: 2 mmol of SrCl2 and 2.5 mmol of
urea were dispersed in a 25 mL of H2O, N,N-Dimethylformamide
(DMF), glycerol system (according to the volume ratio H2O/DMF/
glycerol2/2/1) under vigorous stirring at room temperature.
After being stirred vigorously for 10 min, the mixed solution was
put into a 50 mL Teon-lined stainless steel autoclave. The autoclave was maintained at 120 C for 8 h and then cooled to room
temperature naturally. The resulting white products were centrifuged, washed several times with distilled water and absolute

L. Yang et al. / Materials Letters 167 (2016) 48

ethanol, and dried at 80 C in vacuum for 6 h. To synthesize the

SrCO3 porous ower-like nanostructures, the as-obtained SrCO3
ower-like precursors (200 mg) and 0.4% HCl aqueous solution
(5 mL) were added to a 50 mL beaker containing 20 mL of distilled
water. After being sonicated for 10 min, the solution was placed
aside for 24 h without stirring at room temperature. After discarding the supernatant, the remaining white precipitates were
washed with distilled water and absolute ethanol and then dried
at 80 C in vacuum for 6 h.

3. Results and discussion

The phase of products was rstly characterized by XRD analysis. From Fig. 1(A), we can observe that all of the peaks (curves
(a) and (b)) can be precisely indexed to the orthorhombic phase of
SrCO3 crystals (JCPDS 05-0418). No peaks of impurity were detected in the XRD patterns, indicating that pure SrCO3 samples
were prepared under these experimental conditions.
SEM provided insight into the morphology of the SrCO3 crystals. A panoramic morphology of the porous ower-like SrCO3

Fig. 1. XRD patterns of the as-prepared samples: (A) Porous ower-like SrCO3 nanostructures (a) and ower-like SrCO3 precursors (b); (B) Porous SrCO3 samples obtained
after hydrothermal treatment for different time (all of the samples were then etched by 0.4% HCl for 24 h): (a) t 2 h; (b) t 4 h; (c) t 6 h; and (d) t 10 h. N2 adsorption
desorption isotherm and BJH pore size distribution plots of the as-prepared samples: (C and E). Porous ower-like SrCO3 nanostructures; (D and F). Flower-like SrCO3
precursors.

L. Yang et al. / Materials Letters 167 (2016) 48

Fig. 2. SEM images of 3D hierarchical porous ower-like SrCO3 nanostructures (obtained after hydrothermal treatment for 8 h and then etched by 0.4% HCl for 24 h) and
ower-like SrCO3 precursors (obtained after hydrothermal treatment for 8 h): (a and d). Overall product morphology; (b and e). A detailed view of an individual ower; and
(c and f). Magnied surface of an individual ower.

nanostructures is displayed in Fig. 2(a), indicating the high yield

and uniformity. A magnied SEM image showing the close observation of the crystals is given in Fig. 2(b). It reveals that the
detailed morphology of porous SrCO3 products is well-dened 3D
ower-like shape. A close-up view of ower-like nanostructures in
Fig. 2(c) demonstrates that the surface of SrCO3 crystals are made
of numerous nanoparticles and a lot of pores and ravines engendered in the 3D nanostructures, which may improve their
physical and chemical properties. In contrast, the morphology of
the SrCO3 ower-like precursors is presented in Fig. 2(df). As illustrated in Fig. 2(d), there are abundant SrCO3 nanocrystals highly
disperse in the space. From Fig. 2(e) we can see that the petals of
the SrCO3 ower-like precursors are very spinous and they regularly connect with each other into a 3D ower-like structure.
Remarkably, as shown in Fig. 2(f), the surface of the individual
ower-like precursor is highly smooth.
To further conrm the inner and surface structure of the porous
SrCO3 ower-like nanostructures and their corresponding precursors, N2 adsorptiondesorption measurements were performed. Fig. 1(C) shows the N2 adsorptiondesorption isotherms of
the porous SrCO3 ower-like nanostructures and Fig. 1(D) is the
corresponding graphic of the SrCO3 ower-like precursors. As can
be seen from the adsorption curve (Fig. 1(C)), the N2 adsorption
quantity increases monotonically with the increasing pressure and
this phenomenon usually appears in porous and hollow materials
[13]. The specic surface area of porous ower-like SrCO3 nanostructure is calculated to be 14.3 m2 g  1 from the BET results,
which is much higher than that of the ower-like SrCO3 precursors
(7.9 m2 g  1) (calculated from Fig. 1(D)). Besides, the values of the
BET surface area of the porous SrCO3 samples obtained after hydrothermal treatment for 2, 4, 6 and 10 h are 7.2, 8.8, 9.6 and
11.9 m2 g  1, respectively (all of the samples were then etched by
0.4% HCl for 24 h). However, the results are 4.2, 6.1, 6.8 and
7.2 m2 g  1 for the SrCO3 precursors obtained after hydrothermal
treatment for 2, 4, 6 and 10 h, respectively. The pore size distribution of the porous ower-like SrCO3 nanostructure shows that
a narrow peak appeared in the pore size region from 7.1 to
199.6 nm. Using the BJH method and the desorption branch of the
N2 isotherm, the calculated pore size distribution indicates that
the material has an average pore size of 19.6 nm (Fig. 1(E)). Pores

of various sizes were previously observed in SEM images, in accordance with these stochastic calculation results. The pore value
of the SrCO3 precursor is so small (Fig. 1(F)). The result was in
conformity with the observation from Fig. 2(F).
Fig. 3 illustrates the morphology evolution of porous SrCO3
ower-like nanostructures at different stages. Initially, Sr2 reacted with CO23 (obtained by the decomposition of urea [14,15]) to
generate SrCO3 particles (Fig. 3(a) and (b)), and then SrCO3 nanospheres (Fig. 3(c) and (d)) were grown by self-assembly of small
primary nanoparticles through an oriented-attachment mechanism after reaction for 4 h. Seed particles continuously adsorb onto
these nanospheres to allow further growth through a ripening
process. Then the intermediate structures develop into initial 3D
ower-like SrCO3 nanostructures (Fig. 3(e) and (f)) via a surface
reconstruction process in 6 h. Further prolonging the reaction time
to 8 h, we got perfect 3D porous ower-like SrCO3 nanostructures
(Fig. 2(a)). Due to the preferential growth of SrCO3 in a certain
direction, the ower-like products were obtained. Further observation (Fig. 2(b) and (c)) revealed that a large amount of irregular nanoparticles of tens of nanometers was randomly distributed in the nanocrystals, as a result of the dissolution-recrystallization process. Surprisingly, with the extension of the reaction time to 10 h, broken ower-like SrCO3 products can be
discerned from Fig. 3(g) and (h), which is the result of further
aggregation of SrCO3 crystals, probably. HCl plays a critical role in
the formation process of porous SrCO3 ower-like nanostructures.
Due to the etching of the certain crystalline planes of SrCO3, porous ower-like nanostructures could appear eventually. Although
the reduction in weight of the ower-like SrCO3 is around 4.2%
after it being etched by HCl, it does not affect the economical
process of the fabrication procedure. Because the mass loss of the
SrCO3 architecture is so low, it can be ignored completely.
The phase of porous SrCO3 nanostructures was characterized by
XRD analysis. As illustrated in Fig. 1(B), the XRD patterns indicated
that all the products were of pure phase of strontianite SrCO3
(JCPDS 05-0418). Meanwhile, with the aging time prolonging from
2 to 10 h, the crystallinity of the as-obtained SrCO3 porous nanostructures became higher to some extent (Fig. 1(B)).
Besides, compared with literature results, the present owerlike SrCO3 containing porous structure is distinctly different with

L. Yang et al. / Materials Letters 167 (2016) 48

Fig. 3. SEM images of the porous SrCO3 samples obtained after hydrothermal treatment for different time (all of the samples were then etched by 0.4% HCl for 24 h): (a and
b) t 2 h; (c and d) t 4 h; (e and f) t 6 h; and (g and h) t 10 h.

the previously reported smooth-surface ower-like SrCO3 [16,17]

and also those SrCO3 architectures of other morphologies [18,19],
thus suggested new potential applications of SrCO3 in the elds
such as catalysts, composites, adsorbents, and devices.

nanostructures featured coarse surfaces and porous structures

following etching treatment.

References
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In this article, porous ower-like SrCO3 was prepared using a
combined bottom-up and top-down route. HCl was introduced as
an etchant to speed up the formation of porous ower-like SrCO3
nanostructure from its corresponding precursor. Differences in the
morphology of the products obtained before and after the etching
treatment were observed. The porous ower-like SrCO3

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