General synthesis and gas-sensing properties of multiple-shell metal oxide hollow microspheres

Article abstract of DOI:10.1002/anie.201004900

A sphere of many coats: A facile sequential templating process for the general preparation of metal oxide hollow microspheres with multiple shells (red), such as α-Fe₂O₃, Co₃O₄, NiO, CuO, ZnO, and ZnFe₂

Full text of DOI:10.1002/anie.201004900

Communications
DOI: 10.1002/anie.201004900
Microspheres
General Synthesis and Gas-Sensing Properties of Multiple-Shell Metal
Oxide Hollow Microspheres**
Xiaoyong Lai, Jun Li, Brian A. Korgel, Zhenghong Dong, Zhenmin Li, Fabing Su, Jiang Du,
and Dan Wang*
Hollow spheres with nanometer-to-micrometer dimensions,
controlled internal structure, and shell composition have
attracted tremendous attention because of their potential
application in catalysis, drug delivery, nanoreactors, energy
conversion and storage systems, photonic devices, chemical
sensors, and biotechnology.[1] Single-shell and double-shell
hollow spheres of various compositions have been synthe-
sized by a number of methods, such as vesicles, emulsions,
micelles, gas-bubble, and hard-templating methods.[2] More
recently, efforts have focused on the fabrication of hollow
spheres with multiple shells, as these materials are expected to
have better properties for applications such as drug release
with prolonged release time, heterogeneous catalysis, lithium-
ion batteries, and photocatalysis.[3] For example, multiple-
shell hollow microspheres of Cu2O have been prepared by
vesicle templating and an intermediate-templating phase-
transformation process.[3a,b] Multiple-shell azithromycin
hollow microspheres were fabricated by hierarchical assem-
bly.[3c] Cao and co-workers reported the synthesis of triple-
shelled SnO2 hollow microspheres by chemically induced self-
assembly in the hydrothermal environment which exhibited
enhanced electrochemical performance.[3d] Yao and co-work-
ers reported excellent cycle performance and enhanced
lithium storage capacity of multiple-shell Co3O4 hollow
microspheres synthesized by oriented self-assembly.[4] These
preparative methods, however, are suited for each specific
material and cannot be applied generally to a wide range of
materials. Currently, there is no general synthetic approach
for fabricating multiple-shell hollow nanostructures of any
desired material.
Herein, we present a straightforward and general strategy
to prepare metal oxide hollow microspheres with a controlled
number of shells. Carbonaceous microspheres were used as
sacrificial templates. The microspheres were saturated with a
desired metal salt solution and then heated in air; the
carbonaceous template evaporates and templates the forma-
tion of metal oxide shells. The number of shells is controlled
by the metal ion loading and the process is general for a wide
range of metal oxide materials.
Scheme 1 illustrates the general process of fabricating
multiple-shell hollow metal oxide microspheres. The key to
this process is the use of carbonaceous particles rich with
surface functional groups available for metal ion adsorption.[5]
Scheme 1. Illustration of the sequential templating approach to multi-
ple-shell hollow metal oxide microsphere synthesis.
Multiple shells are generated by supplying enough shell
precursor material to the sacrificial carbonaceous spheres.
Recently, our group reported the synthesis of hollow core–
shell ferrite microspheres,[5b] demonstrating that carbona-
ceous particles can absorb a significant amount of metal ions
within the interior of the particle (Figure S1 in the Supporting
Information). In this work, we extend these methods and
demonstrate the general and facile synthesis of multiple-shell
hollow microspheres of a wide range of different metal oxides.
Figure 1a,b shows a transmission electron microscopy
(TEM) image of hollow microspheres of a-Fe2O3 obtained by
soaking carbonaceous microparticles in an 2 molLÀ1 iron
nitrate solution (detailed synthesis procedures are presented
in the Experimental Section). The hollow microspheres have
a double-shell structure of a 0.45 mm diameter shell with an
outer shell of about 1.5–2.0 mm in diameter. Scanning trans-
mission electron microscope (STEM) imaging and energy-
dispersive X-ray microanalysis (EDS) line scans (Figure S2)
confirmed the hollow double-shell structure of the particles
[*] Dr. X. Lai,[+] Dr. J. Li,[+] Z. Dong, Dr. Z. Li, Prof. F. Su, J. Du,
Prof. D. Wang
State Key Laboratory of Multi-phase Complex Systems
Institute of Process Engineering, Chinese Academy of Sciences
Beijing 100190 (P.R. China)
Fax: (+86)10-6263-1141
E-mail: danwang@mail.ipe.ac.cn
Prof. B. A. Korgel
Department of Chemical Engineering, Texas Materials Institute
Center for Nano- and Molecular Science and Technology
University of Texas at Austin
Austin, TX 78712 (USA)
[+] These authors contributed equally to this work.
[**] This work was supported by the National Natural Science
Foundation of China (No. 20971125, 21031005, and 21006116),
Beijing Municipal Natural Science Foundation (No. 2082022), and
the Foundation for State Key Laboratory of Multi-phase Complex
Systems.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201004900.
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rate of 28CminÀ1. The products were characterized after
different times in the heating process. Relative to the
carbonaceous particle at room temperature in Figure 2a,
the TEM image in Figure 2b showed that there is no visible
change when the sample is heated to 2708C except for the
decrease in diameter from 3.4 to 2.4 mm. A reaction temper-
ature of 3508C led to the formation of a shell around a solid
sphere (Figure 2c). The characteristic peaks of resultant
materials in Raman spectra of Figure 2 f suggest the forma-
tion of hematite, which is also evidenced by its XRD data in
Figure 2g, whereas the reduction of Raman signals of carbon
reveals the degradative oxidation of carbonaceous template.
When the temperature reaches 4308C, the outer hematite
shell somewhat shrunk but the inner solid core sharply
contracted and also changed to a core–shell sphere, resulting
in a core–double shell structure (Figure 2d). Increasing the
temperature further to 5008C led to a hollow core, or a triple-
shell hollow structure shown in Figure 2e. Thermogravimetric
analysis (TGA) results suggest carbon template could be
completely removed (Figure S5a).
The studies of the various reaction conditions confirm that
the multiple-shell metal oxide hollow microparticles form by
a sequential templating process. There are two prerequisites
for this method to work: 1) there must be a large penetration
depth of iron ions within the carbonaceous microsphere, and
2) the rate of metal oxide shell formation must match with the
rate of carbonaceous microsphere disintegration. When the
annealing temperature is relatively low, the contraction of the
carbonaceous microspheres by degradative oxidation is slow
(Figure S5b), allowing iron to concentrate within carbona-
ceous template matrix and cross-link to form the iron oxide
shell. At higher temperature, separation occurs between the
iron oxide shell and the shrinking carbonaceous template
owing to their different rates of formation and disintegration.
If the penetration depth of iron ions within the carbonaceous
microspheres is too short, all the iron ions distribute in the
narrow region near the surface and very likely form a single
shell because of the shorter ion diffusion length. Sequentially,
hollow spheres with only a single shell form, as there is not
enough iron to sustain the formation of more shells (Fig-
ure S6). When the penetration depth of iron ions within the
carbonaceous microspheres is large enough, only a fraction of
the iron within the carbonaceous microspheres joins in the
creation of first outer shell of hematite, whereas the others
remain within inner carbonaceous microsphere and supply
iron resource for the creation of inner shells. Larger
penetration depth of iron ions within the carbonaceous
microspheres possibly lead to the formation of more shells.
A large number of methods are available for increasing the
penetration depth of iron ions, such as adjusting the concen-
tration of precursor solution (in this case) or changing the
solvent, absorption temperature, or time.
Figure 1. TEM images of a,b) double-shell a-Fe2O3 hollow micro-
spheres; c,d) triple-shell a-Fe2O3 hollow microspheres; e,f) quadruple-
shell a-Fe2O3 hollow microspheres.
and their homogeneous composition. Increasing the concen-
tration of the iron nitrate solution to 3 molLÀ1 yielded a-
Fe2O3 hollow microspheres with three shells (Figure 1c,d).
Further by increasing the concentration of the iron nitrate
solution to 5 molLÀ1, hollow microspheres with four shells
were also obtained (Figure 1e,f). Powder X-ray diffraction
(XRD) confirmed that the all the multiple-shell hollow
microspheres were composed of crystalline a-Fe2O3 (JCPDS
33-0664) without any other phases present.
The shell formation process was studied in more detail by
carrying out the reactions at various temperatures (Figure 2
and Figures S3 and S4). Carbonaceous microspheres were
soaked in the iron nitrate solution and heated to 5008C at the
Moreover, TGA provided another estimate of the rate of
size decrease of the carbonaceous microsphere during heating
(Figure S5b), which was consistent with that observed by
TEM images of intermediate products (Figure 2). We also
note that the size of second shells in double-shell, triple-shell,
and quadruple-shell structures is different from each other,
possibly deriving from shell formation in different stages of
Figure 2. TEM images of carbonaceous microspheres after soaking in
a 3 molLÀ1 solution of iron nitrate: a) before heating, and after heating
at b) 2708C, c) 3508C, d) 4308C, and e) 5008C. f,g) Corresponding
Raman spectra (f) and XRD patterns (g).
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Communications
carbonaceous microsphere contraction (i.e. the different
template sizes). The rate of carbonaceous microsphere
shrinkage could be slowed by heating in an N2 atmosphere,
instead of air. As a result, microspheres soaked in iron nitrate
solution (3 molLÀ1) gave only single-shell hollow micro-
spheres (Figure S7). These results suggest the possibility of
adjusting the textural parameter of multiple-shell hollow
structure through controllable contraction of carbonaceous
microsphere by various techniques, such as heating rate and
atmosphere type., which may be favorable for their practical
application.
The hollow structure morphology of hematite can be
expected to dramatically benefit surface-related applications,
such as gas sensing. Hollow iron oxide microspheres were
tested as an ethanol-sensing material. The gas sensitivity is
defined as the resistance ratio Rair/Rgas, in which Rair and Rgas
are the electrical resistances for sensors in air and in ethanol
gas, respectively. Figure 3 shows the gas-sensing behavior of
Figure 4. a) TEM image of quadruple-shell NiO hollow microspheres;
b) STEM image and c) EDS line scanning of triple-shell NiO hollow
microspheres; TEM images of other multiple-shell hollow microsphere
of d) Co3O4, e) CuO, f) ZnO, g) ZnFe2O4, and h) ZnO@ZnO/
ZnFe2O4@ZnO/ZnFe2O4.
Figure 3. Sensor response in the presence of ethanol from a-Fe2O3
hollow spheres with different numbers of shells: a) single-shell,
b) double-shell, c) triple-shell, and d) bulk a-Fe2O3 particles.
a-Fe2O3 hollow microspheres with different numbers of shells
in the presence of ethanol. Solid a-Fe2O3 particles used as a
reference sample were found to be nearly insensitive to the
presence of ethanol. In contrast, the resistance of the hollow
shells was very sensitive to ethanol. This sensitivity may be
attributed to the larger specific surface areas of the latter (85,
80, and 48 m2 gÀ1 for single-shell, double-shell, and triple-shell
hollow microspheres respectively; Figure S8) than that of the
former (4 m2 gÀ1), which allows them to absorb more gas
molecules. The sensitivity of the electrical resistance to
ethanol is also increased significantly when the particles had
an increasing number of shells. A number of factors in
addition to specific surface area (such as grain size, and
porosity) can affect the gas sensitivity of a semiconductor[6]
and the underlying reasons for the observed behavior still
need further study. Nevertheless, these results exhibit the
considerable advantages of multiple-shell hollow micro-
spheres, which could be potentially useful in gas detection.
Different types of multiple-shell hollow microspheres,
such as Co3O4, NiO, CuO, and ZnO, could also be fabricated
by soaking the carbonaceous microspheres in solutions with
the corresponding metal ion species (Figure 4a–f and Figur-
es S9 and S10). Furthermore, binary metal oxide (ZnFe2O4)
and heterogeneous metal oxide (ZnO@ZnO/ZnFe2O4@ZnO/
ZnFe2O4) multiple-shell hollow microspheres were also
prepared by the simultaneous or successive use of different
metal ions (Figure 4g,h and Figures S11–S17). Moreover, we
noted that only a minority of metal oxides in which the
diameter of outer shell and inner hollow cores are relatively
close could have their cores in the center of the core–shell
configuration (for example, those in Figure 1 f and Fig-
ure 4a,f), but the position of cores in others is random. This
result may suggest that these inner hollow cores are not fixed
on the outer shell but are movable. Those cores in the former
have very limited movable region (since its diameter is close
to that of outer shell) and thus tend to stay at the center,
whereas those cores in the latter possess relatively broad
movable region and have not fixed position. Nevertheless, all
these results suggest the generality of the present synthesis
method. In particular, the formation of all shells and the
removal of template were completed by a simple one-step
heating treatment, which is highly desirable for large-scale
production.
In summary, a general and facile method for the synthesis
of multiple-shell metal oxide hollow microspheres by using
carbonaceous microsphere as a template was demonstrated.
All of the shells were created by a one-step thermal treat-
ment. The number and composition of shells could be
rationally designed by adjusting the heating conditions and
the concentration and type of metal salt species used. The
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multiple-shell hollow structures with different shapes, sizes,
and compositions by choosing appropriate template and
precursor material. The research may open up new oppor-
tunities for preparing advanced materials based on various
complex multiple-shell hollow structures for multipurpose
applications.
Experimental Section
All reagents were analytical grade and purchased from Beijing
Chemical Co. Ltd., and used without further purification. Hydrated
metal nitrates (Fe(NO3)3·9H2O, Co(NO3)2·6H2O, Ni(NO3)2·6H2O,
Cu(NO3)2·3H2O, and Zn(NO3)2·6H2O) were used as metal precur-
sors. Taking a-Fe2O3 triple-shell hollow microsphere as an example, a
typical synthesis process is described as follows: Carbonaceous
microspheres were synthesized through the emulsion polymerization
reaction of sugar under hydrothermal conditions as described else-
where.[5b] Newly prepared carbonaceous microspheres (0.4 g) were
dispersed in iron nitrate solution (20 mL; 3 molLÀ1) with the aid of
ultrasonication. After ultrasonic dispersion for 15 min, the resulting
suspension was aged for 6 h at room temperature, filtered, washed,
and dried at 808C for 12 h. The resultant composite microspheres
were heated in air at 28CminÀ1 up to 5008C, kept at this temperature
for 4 h, and cooled naturally to room temperature. As-formed
products, a-Fe2O3 triple-shell hollow microspheres, were accumu-
lated. Other metal oxide multiple-shell hollow microspheres, such as
Co3O4, NiO, CuO, and ZnO, were also synthesized by following a
similar procedure.
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Powder X-ray diffraction (XRD) patterns were recorded with an
XꢀPert PRO MPD [CuKa radiation (l, 1.5405 ꢁ)], operating at 40 kV
voltage and 30 mA current. Scanning electron microscopy (SEM)
images were obtained using a JSM-6700 microscope operating at
5.0 kV voltage. Transmission electron microscopy (TEM) images
were taken on a FEI Tecnai F20 instrument at an acceleration voltage
of 200 kV. Raman spectra were performed on LabRAM HR800
spectrometer manufactured by Horiba Jobin Yvon company, France.
The laser excitation wavelength was 514 nm. The thermal analysis was
carried out up to 8008C on a Labsys Evo apparatus (SETARAM,
Caluire, France) at a heating rate of 28CminÀ1 in air. The nitrogen
adsorption–desorption isotherms at the temperature of liquid nitro-
gen (À1968C) were measured on a Quantochrome Autosorb-1
sorption analyzer with prior degassing under vacuum at 2008C
overnight. The gas sensors were fabricated by coating an ethanol
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Received: August 6, 2010
Published online: February 22, 2011
Keywords: transition metals · microspheres · oxides · sensors ·
.
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