Microporous and Mesoporous Materials 119 (2009) 208–216

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Hydrothermal synthesis and characterization of core/shell ALOOH microspheres

Liangmiao Zhang, Wencong Lu *, Liuming Yan, Yongli Feng, Xinhua Bao, Jipeng Ni, Xingfu Shang, Yong Lv
Department of Chemistry, Shanghai University, Shanghai 200444, PR China
State Key Laboratory of Powder metallurgy, Central South University, Changsha 410083, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The AlOOH core/shell microspheres were successfully synthesized via a one-step template-free hydro-
Received 8 July 2008 thermal route. By simply changing the ratio of alcohol to water, core/shell microspheres constructed with
Received in revised form 14 October 2008 nanoplatelets and their curling structures could be selectively synthesized. A series of controlled exper-
Accepted 20 October 2008
iments have also been carried out to better understand the formation mechanism of AlOOH spheres and
Available online 30 October 2008
the function of reactants used in the experiments. The formation of core/shell structures may involve
aggregation of amorphous building clusters into spheres and their subsequent reaction, dissolution,
Keywords:
and re-deposition process. The morphology, structure, and composition of the spheres are investigated
AlOOH
Core/shell microspheres
using field-emission scanning electron microscopy, transmission electron microscopy, and X-ray diffrac-
Hydrothermal method tion analysis. The specific surface area and pore-size distribution of the obtained product as determined
Water treatment by gas-sorption measurements show that the boehmite core–shell microspheres exhibit high Brunauer–
Emmett–Teller (BET) surface area and porosity properties. The as-prepared AlOOH core–shell superstruc-
tures are powerful in the removal of Congo red pollutant from waste water.
Ó 2008 Elsevier Inc. All rights reserved.

1. Introduction one-step solution route for the preparation of inorganic core/shell

and hollow microstructures.
The fabrication of highly ordered micro- and nanostructures has Alumina is one of the most important oxides and has been stud-
attracted much interest in areas of materials science [1]. In partic- ied intensively over a long period of time because of its broad
ular, the fabrication of hierarchical and complex nano- and micro- applications in adsorbents, composite materials, ceramics, cata-
structures assembled using nanoparticles, nanorods, nanoribbons, lysts and catalyst supports [15]. The synthesis of nanostructured
and so forth, as building blocks at different levels, has become re- alumina has received considerable interest due to their promising
cently a hot topic in material research fields [2]. Core/shell and hol- properties, such as high elastic modulus, thermal and chemical sta-
low spheres, as two special kinds of 3D curved microstructures bility, and optical characteristics. The alumina can be obtained
with inner cavities, are of great interest for a large spectrum of through the dehydration of the boehmite, and the original size
applications, such as adsorbents [3], delivery carriers [4], catalysts and the morphology of the boehmite nanostructures can be re-
[5], gas sensors [6], chemical reactors [7], control release of various tained. Up to now, many kinds of interesting and delicate boehmite
substances [8], and protection of environmentally sensitive biolog- nanostructures, such as nanoribbons [16], nanofibers [17,18],
ical molecules [9]. Up to now, various kinds of metal oxide [10], nanobelts [19], nanotubes [20], bundles of aligned boehmite nano-
sulfide [11], and hydrate [12] with core/shell and hollow micro- wires [21], and flower-like 3D nanoarchitectures [22] have been
structures have been successfully synthesized. For the case of prepared. More recently, we have developed a facile hydrothermal
TiO2, the unique core/shell structure shows dramatic activity synthetic strategy for selectively preparing hierarchical canta-
enhancement in photocatalytic phenol degradation [13]. Since loupe-like AlOOH superstructures based on self-assembly of 1D
the utility or property of nano- and microstructure is inextricably nanorods [23]. AlOOH self-encapsulated structures have been syn-
linked to its shape and size [14], it is a meaningful work to design thesized successfully by hydrothermal method in the presence of
and fabricate different kinds of nano and microstructures by using PS-b-PHEA amphiphilic block copolymer as the structure-directing
appropriate nanoscale building blocks and void space. However, it reagent [24a]. Pan et al. reported the preparation of Al2O3 hollow
still remains a major challenge to develop a facile, template-free, shells via the calcinations of Al/AlOOH  nH2O core–shell particles,
although Al coexisted with AlOOH [24b,c]. However, it still remains
a significant challenge to develop facile, mild, template-free and
shape-controllable route for the formation of pure AlOOH core/
* Corresponding author. Address: Department of Chemistry, Shanghai University,
Shanghai 200444, PR China. Tel.: +86 21 66133513; fax: +86 21 66133522.
shell and hollow microstructures. In this paper, we report a tem-
E-mail address: [email protected] (W. Lu). plate-free hydrothermal route to fabricate AlOOH core/shell

1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2008.10.017
 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216 209

microspheres via a surface reaction-dissolution-recrystallization The UV–vis absorption spectrum of the products was recorded as-
process. Judicious choice of the alcohol amounts and reaction time prepared using a Shimadzu UV-2051PC photospectrometer.
affords the synthesis of spheres with adjustable morphology and
interior structure that is tunable from solid to sphere-in-sphere. 2.3. Water purification experiment

2. Experimental section Both of our product and commercial c-AlOOH nanoparticles

(10 nm) were used to adsorb Congo red from water solution. The
2.1. Preparation commercial c-AlOOH nanoparticles was purchased from Share-
nano Co. and used directly without further treatment. Eighty mil-
AlOOH with core/shell microarchitecture were prepared using ligram nanoparticles were, respectively, added to 100 mL Congo
the hydrothermal method in a mixed ethanol–water solution. In red (C32H22N6O6S2Na2, Amresco Inc.) solution (25 mg L1) under
a typical procedure, 2 mmol of Al(NO3)39H2O was dissolved in stirring continuously at about 25 °C. Analytical samples were taken
20 mL distilled water at room temperature forming a homoge- from the suspension after various adsorption times and centri-
neous solution. And then, another 20 mL absolute ethanol was fuged at 10,000 rpm for 5 min to remove the particles. UV–vis
added slowly. In addition, 0.5 mmol trisodium citrate dehydrate absorption spectra were recorded at different intervals to monitor
(C6H5Na3O72H2O) was added, and the resulting solution was fur- the process.
ther stirred vigorously for 30 min. The resulted clear and colorless
solution was transferred into a Teflon-lined stainless autoclave fill-
ing 80% of the total volume. The autoclave was sealed and main- 3. Results and discussion
tained at 200 °C for 24 h. The autoclave was then cooled to room
temperature naturally. This procedure resulted in a white powder In our experiments, AlOOH microspheres with core/shell struc-
precipitated. Finally, the white powder was filtered and washed for tures were firstly prepared in a 0.5 mmol TSC ethanol–water solu-
several times using distilled water and absolute ethanol, and dried tion by hydrothermal treatment at 200 °C for 24 h. The SEM images
in a vacuum at 60 °C for 12 h. Moreover, the effect of growth con- of the as-prepared microspheres are shown in Fig. 1 (panels a, b).
ditions, such as TSC amounts and reaction durations, on the mor- From Fig. 1a, it is obvious that microsphere agglomerates can be
phology of AlOOH particles was investigated. The detailed obtained. The rarely found broken microsphere presented in
experimental parameters about the solvent, heating temperature, Fig. 1b indicates that the as-prepared microsphere has a uniform
and reaction time for corresponding samples are listed in Table 1. shell, but the ‘‘criminal” (the core) has ‘‘escaped” from the ‘‘micro-
prison” (the shell). The energy-dispersive X-ray spectrum (EDS)
2.2. Characterization analysis (Fig. 1b, inset) confirms that only Al and O elements were
detected, and the atomic ratio of O and Al is 2.1 according to the
The crystal structure and phase purity of the products were EDS semiquantitative analysis, which is close to the ideal value of 2
examined by means of X-ray diffraction (XRD, D/max-RB, Cu Ka considering the instrumental error. The corresponding TEM image
radiation) analysis. The sample morphology was checked by scan- depicted in Fig. 1c also demonstrates that the as-prepared products
ning electron microscopy (SEM, JSM-6700F, JEOL), equipped with are microspheres composed of solid core (dark, inner), shell (dark,
energy-dispersive spectroscopy (EDS) analyzer. A small amount outer) and the inner nanospace (lighter, middle). Some of them are
of products were ultrasonically dispersed in alcohol and deposited partially fused to form larger microsphere aggregates. To further
on copper grids coated with ultra-thin films for transmission elec- describe the surface structure of these microspheres, the high-res-
tron microscopy (TEM, JEM-2010F, JEOL) measurements. The nitro- olution TEM images are shown in Fig. 1d and e. The figures illus-
gen adsorption and desorption isotherms at 77 K were measured trate a porous microsphere shell composed of loosely stacked
using a Micrometrics ASAP 2020 V3.00 H system after the sample nanoplatelets and nanotubes as second order structure. These lam-
was degassed in a vacuum at 120 °C for 400 min. Specific surface ellas tend to curl to form tubular structure with a diameter of sev-
areas were calculated using Brunauer-Emmett-Teller (BET) model. eral nanometers and length of 30–50 nm. It can facilitate the

Table 1
Detailed experimental parameters for the synthesis of AlOOH samples and their morphologies.

Sample Solvent Molar ratio of Al3+/TSC Temperature (°C) Time (h) Morphology
A1 H2O/ethanol = 1:1 2:0.5 200 3 Aggregates of solid spheres
A2 H2O/ethanol = 1:1 2:0.5 200 6 Aggregates of solid spheres
A3 H2O/ethanol = 1:1 2:0.5 200 21 Microspheres with coarse surface
A4 H2O/ethanol = 1:1 2:0.5 200 22 Microspheres with puffy structure
A5 H2O/ethanol = 1:1 2:0.5 200 24 Core–shell microspheres
A6 H2O/ethanol = 1:1 2:0.5 200 48 Core–shell microspheres
A7 H2O/ethanol = 1:1 2:0 200 24 Nanowires
A8 H2O/ethanol = 1:1 2:0.125 200 24 Bunched nanowires
A9 H2O/ethanol = 1:1 2:0.25 200 24 Mixture of nanowires and hollow nanospheres
A10 H2O/ethanol = 1:1 2:1 200 24 Core–shell microspheres
A11 H2O/ethanol = 1:1 2:1.5 200 24 Core–shell microspheres and microspheres with puffy structure
A12 H2O/ethanol = 1:1 2:2 200 24 Aggregates of solid spheres
A13 H2O/ethanol = 1:3 2:0.5 200 24 Hollow spheres assembled from nanorods
A14 H2O/ethanol = 3:1 2:0.5 200 24 Solid aggregates with irregular morphology
A15 H2O/ethanol = 1:1 2:0.5 180 24 Aggregates of solid spheres
A16 H2O/ethanol = 1:1 2:0.5 220 24 Core–shell microspheres
A17 H2O/methanol = 1:1 2:0.5 200 24 Nanorods stacked flowers
A18 H2O/1-butanol = 1:1 2:0.5 200 24 Hollow spheres with dense shells
A19 H2O/1-hexanol = 1:1 2:0.5 200 24 Microsphere with hollow inner space
A20 H2O/1-octanol = 1:1 2:0.5 200 24 Bunched nanowires
210 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216

Fig. 1. TEM and SEM images of AlOOH core/shell microspheres. (a) SEM images of as-synthesized samples; (b) high-magnification SEM image of the special broken structure
and the corresponding EDS pattern (inset); (c) TEM general view of the corresponding product; (d) and (e) a HRTEM image of the shell.

inward and outward mass transportation when used in the trans- ing effect was observed for those reacted for 48 h (Fig. 2e and f).
port-related applications. The formation of such spheres may involve aggregation of AlOOH
We have carried out a series of controlled experiments to better building clusters into spheres and their subsequent reaction, disso-
understand the formation mechanism of core/shell AlOOH micro- lution, and re-deposition process.
spheres. Fig. 2 shows the morphological evolution of AlOOH micro- XRD analysis was used to determine the structure and phase of
structures at different time during synthesizing. When the reaction the sample. No diffraction peaks are present after the reaction for
time was less than 1 h, no precipitate was formed. The micro- 6–18 h (Fig. 3a and b), indicating the amorphous nature of these
spheres with a diameter ranging between 0.2  1.5 lm appeared solid microspheres. The EDS analysis (Fig. 2b, inset) confirms that
after the reaction for 3 h (Fig. 2a). Amorphous precipitate frag- only Al and O elements are exist in the microstructures with an
ments rolled to irregular agglomerates and the agglomerates acted O/Al molar ratio of about 2.04, which is close to the ideal value
as the cores for the formation of the solid microspheres. As time of 2 considering the instrumental error. AlOOH diffraction peaks
prolonged, the primary formed disordered particles grew into big- eventually appear with a longer reaction time of 21 h (Fig. 3c).
ger homogeneous solid spheres (entirely dark; Fig. 2b). Fig. 2c is The corresponding XRD patterns of the as-prepared core/shell
the TEM image of the product reacted for 21 h. Small surface nano- structure reacted for 24 h are shown in Fig. 3d. All the detectable
wires were formed and further grew with time, forming an urchin- peaks in this pattern could be assigned by their peak positions to
like prickly surface (Fig. 2d). With increasing reaction time to 1 orthorhombic c-AlOOH (JCPDS card no. 21-1307). No peaks for
day, it was found that the nanowires formed shells on the solid other phases were observed, indicating its high purity and crystal-
cores, creating a core/shell structure as shown in Fig. 1. A hollow- linity. The main peaks of AlOOH in the XRD pattern are broadened,
 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216 211

Fig. 2. TEM and SEM images of the products prepared at 200 °C for (a) 3 h; (b) 6 h, (inset: EDS pattern); (c) 21 h; (d) 22 h; (e) 48 h; (f) typical TEM image of an individual core–
shell sphere.

Fig. 3. XRD patterns of the core/shell microspheres prepared at 200 °C for (a) 6 h; (b) 18 h; (c) 21 h; (d) 24 h.
212 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216

implying that crystalline size of the AlOOH particle is very small. dium citrate dehydrate was added, tightly packed bundles self-
With the reaction time increasing, samples have a tendency to assembled from nanowires were appeared (Fig. 4b). Increasing
gradually crystallize (from XRD patterns of these samples as shown the amount of trisodium citrate dehydrate to 0.25 mmol led to
in Fig. 3). the formation of a mixture of nanowires bundles, nano and micro
Citrtate anion (Cit3 or citrtate3), as a coordination agent and spheres (Fig. 4c). Some of the nanowire bundles had shown the
shape modifier, plays a key role in determining the morphology tendency to curl, and some of them had grown into a spherical
of the final products. First, as a strong ligand, it can coordinate with structure. With an increase in the dosage of trisodium citrate dehy-
Al3+ to form citrate–aluminum complexes [25a], which prevents drate to 0.5 mmol; microspheres with core/shell structure were
AlOOH from precipitating [25b]. Second, citrate anion can selec- obtained (Fig. 1). When the amount of trisodium citrate dehydrate
tively bind to some crystal planes and restrict their growth, whose was further increased to 1 mmol, it was also observed micro-
effect is also applied in the synthesis of ZnO 3D architectures [26], spheres with core/shell structure (Fig. 4d). With an increase in
Ag nanorods [27], and CuO nanorods [28]. To demonstrate the the dosage of trisodium citrate dehydrate to 1.5 mmol, the as-syn-
important role of trisodium citrate dehydrate for the preparation thesized product was developed and underdeveloped core–shell
of solid microspheres and core/shell structures, the trisodium cit- structures (Fig. 4e). And some tiny, regular nanoplatelets existed
rate dehydrate concentration of the precursor solution for the in the surface (Fig. 4f and inset of Fig. 4e), which inspired us to fur-
solvothermal reaction was varied from 0 to 2 mmol. In the absence ther modify the core/shell structure; e.g., to develop the nanoplat-
of trisodium citrate dehydrate, only bunches of side-by-side nano- elet structure in the shell while preserving the core/shell
wires were obtained (shown in Fig. 4a). When 0.125 mmol of triso- characteristic. The change in the morphology clearly revealed that

Fig. 4. TEM images of samples synthesized at 200 °C for 24 h with different amount of C6H5Na3O7  2H2O: (a) 0 mmol; (b) 0.125 mmol; (c) 0.25 mmol; (d) 1 mmol; (e)
1.5 mmol; (f) 2 mmol.
 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216 213

hollow spheres with a solid core could be realized when a suitable AlðOHÞ3 ! c  AlOOH þ H2 O ð3Þ
TSC amount was added, and the morphology of c-AlOOH micro-
In addition, the reactants are usually mixed together into one
structure could be controlled by the molar ratio of the Al3+ cation
portion. As reactants are consumed, the chemical environment,
to the citrate anion in the solution. Detailed research is still under
including solution components, pH values, and ionic strength,
way.
etc., changes greatly, bringing more variables to the nanomaterial
The formation of the core–shell structure may involve the fol-
formation. It was observed that alcohol had a great influence on
lowing steps. Firstly, reaction (1) will move toward left at high
the morphologies of the synthesized AlOOH in the adopted reac-
temperature and pressure. Once the concentrations of Al3+ cations
tion system. By increasing the ethanol/water volume ratio to 3:1,
and OH anions reach the critical nucleation concentration, a burst
AlOOH hollow spheres assembled by nanoplatelets are formed, as
of homogeneous nucleation of Al(OH)3 occurs as expressed by
shown in Fig. 5a. By decreasing the ethanol/water ratio to 1:3, only
reaction (2), and a large amount of amorphous Al(OH)3 particles
irregular nanoparticles are observed (demonstrated in Fig. 5b). To
with different sizes generate in the solution. The pH value of the
examine the function of ethanol, a comparative experiment with-
solution was decreased from the initial 6 to 3. Secondly, under
out ethanol is also carried out. Bundles composed of highly parallel
hydrothermal conditions at 200 °C, the newly formed active
and closely packed nanorods are obtained without alcohol in the
Al(OH)3 would be converted to c-AlOOH since such a acid condi-
reaction, as shown in our previously work [23]. The evolution trend
tion is favorable for the existence of c-AlOOH [29]. The reaction
of the morphology of the samples with the increasing ethanol/
can be expressed as reaction (3). With the reaction proceeding con-
water ratios indicates that the ethanol should act as dispersant
tinuously, H+ is produced continuously through the hydrolysis
for nanoparticles. These controlled experiments suggest that the
reactions and reacts with the spheres, leading to the dissolution
ethanol/water volume ratio affects the morphologies of the synthe-
and rearrangement of the surface building clusters. As a result
sized particles [30], and a suitable ethanol/water ratio is advanta-
from this process, surface flakes and their curling structure were
geous for synthesis of core/shell microspheres. It was also observed
initially formed and grown into a thin shell layer. The reactions
that temperature had a great influence on the morphologies of the
and equilibriums in the system are shown as follows:
synthesized products. Fused solid spheres were obtained at 180 °C
3þ 3
Al þ citrate () AlðcitrateÞ (Fig. 6a). As the system was heated to 220 °C, the primary formed
3þ þ 3 þ and disordered particles grew into bigger microspheres with
Al þ H þ citrate () AlHðcitrateÞ ð1Þ
homogeneous shells (Fig. 6b). Thus, the increase of temperature
3þ 3 3
Al þ 2citrate () AlðcitrateÞ2 can provide a favorable environment for the growth of core/shell
structures. To examine the function of different alcohols, compar-
3þ ative experiments are also carried out. The result shows that with
Al þ 3H2 O ! AlðOHÞ3 ðamorphousÞ þ 3Hþ ð2Þ
the increase of the carbon chain lengths and the boiling points of

Fig. 5. TEM images of samples synthesized at 200 °C for 24 h with different amount of alcohol. Volume ratio of ethanol to water is (a) 3:1; (b) 1:3.

Fig. 6. TEM images of samples synthesized at different temperature with other conditions kept constant. (a) 180 °C; (b) 220 °C.
214 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216

the alkyl alcohols, the products are tend to form longer bunched Table 2
nanorods which are similar to the ones generated in pure water BET data of different morphologies.

(see Fig. 7). Sample SBET (m2 g1) Pore volume (cm3 g1) Dmeso (Å)
The nitrogen adsorption–desorption isotherms and porosity of A1 0.15 0 –
the microspheres with different morphologies were further inves- A4 52.7 0.05 36
tigated. BET data of different morphologies are summarized in Ta- A5 443.0 0.60 56
ble 2. It shows the BET surface area of the core–shell microspheres A8 298.8 0.49 66
A9 285.9 0.53 73
is the largest. As it is shown in Fig. 8, the nitrogen adsorption and
desorption isotherms of the core–shell spheres are characteristic of
a type IV isotherm with a type H3 hysteresis loop [31], indicating
the presence of mesopores in the size range of 0–10 nm. This
pore-size distribution is further confirmed by its corresponding
pore-size distribution (inset of Fig. 8). It indicates that the core/
shell microspheres contain mesopores (peak pore ca. 5.6 nm).
These results demonstrate the existence of hierarchically mesopor-
ous structures in the prepared samples, which contributes to a rel-
atively high BET surface area of 443 m2/g (the total pore volume is
about 0.6 cm3 g1). The mesopores and its high surface area will
endow the as-prepared hierarchical microspheres with novel
application potentials.
In recent years, considerable attention has been paid to the
environmental problems involving water treatment. The hollow
and porous structure of the as-obtained products can be expected
useful in the water treatments. Congo red, a common azo-dye in
the textile industry, was chosen as a model organic waste. When
the initial concentration of Congo red in water solution is
25 mg L1, the as-obtained AlOOH can remove about 100% of the
Congo red without any additives at room temperature, as shown
by the UV–vis absorption curves at different times in Fig. 9a. The
characteristic absorption of Congo red at 497.5 nm was chosen as Fig. 8. Typical pore-size distribution of AlOOH microspheres. The inset corresponds
the monitored parameter for the adsorption process. It is estimated to N2 gas adsorption–desorption isotherm.

Fig. 7. Morphologies of the products generated in different alkyl alcohols. Volume ratio of alcohol to water is 1:1. (a) methanol–water; (b) n-butanol–water; (c) n-hexanol–
water; (d) n-octanol–water.
 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216 215

Fig. 9. (a) Absorption spectra of a solution of Congo red (25 mg L1, 100 mL) in the presence of AlOOH microspheres (0.08 g) at time intervals of (1) 0, (2) 5, (3) 15 min,
respectively; (b) adsorption rates of the azo-dye Congo red on (1) new as-prepared AlOOH core/shell microspheres, (2) secondary regenerated particles, (3) commercial
AlOOH, respectively.

that 1 g hollow microsphere AlOOH product as-prepared can re- hai Leading Academic Discipline Project (Project Number: J50101)
move about 300 mg Congo red. The removal of Congo red may be are gratefully acknowledged. The authors thank Prof. Weijun Yu,
associated with the electrostatic attraction between the surface Yuliang Chu and Bo Lu from the Instrumental Analysis Research
of AlOOH nanostructured hollow spheres and Congo red molecules Center of Shanghai University for their Technical Assistance on
[32]. For comparison, we selected the commercial AlOOH nanopar- TEM, SEM and XRD measurements.
ticles to detect the removal capacity of Congo red species. We took
80 mg of the commercial product and the same amount of AlOOH References
core/shell microspheres, respectively, to treat 100 mL Congo red
water solution (25 mg L1) at pH 7. The results in Fig. 9 indicate [1] (a) V.F. Puntes et al., Science 291 (2001) 2115;
(b) X.G. Peng, L. Manna, W.D. Yang, J. Wickham, E. Scher, A. Kadavanich, A.P.
that the core/shell microspheres exhibits superior adsorption abil- Alivisatos, Nature 404 (2000) 59;
ities compared with commercial AlOOH nanoparticles, which (c) Y.W. Jun, J.S. Choi, J.W. Cheon, Angew. Chem. Int. Ed. 45 (2006) 3414;
might be ascribed to the hollow microstructure and high specific (d) G.R. Patzke, F. Krumeich, R. Nesper, Angew. Chem. Int. Ed. 41 (2002) 2446;
(e) C. Burda, X.B. Chen, R. Narayanan, M.A. El-Sayed, Chem. Rev. 105 (2005)
surface area of as-obtained AlOOH. Furthermore, the AlOOH micro- 1025–1102.
spheres adsorbed with Congo red could be renewed by a simple [2] (a) C. Pacholski, A. Kornowski, H. Weller, Angew. Chem. Int. Ed. 41 (2002)
thermal treatment in air at 400 °C for 2 h, and the renewed AlOOH 1188;
(b) M. Adachi, Y. Murata, J. Takao, J.T. Jiu, M. Sakamoto, F.M. Wang, J. Am.
material kept almost the same adsorption performance as shown Chem. Soc. 126 (2004) 14943;
by the line in Fig. 9b. The slight decrease in the removal capacity (c) K.S. Cho, D.V. Talapin, W. Gaschler, C.B. Murray, J. Am. Chem. Soc. 127
of the AlOOH hollow nanostructures for recycling and the facile (2005) 7140;
(d) L. Vayssieres, M. Graetzel, Angew. Chem. Int. Ed. 43 (2004) 3666;
method of regeneration suggest that the product may be applicable
(e) S. Park, J.H. Lim, S.W. Chung, C.A. Mirkin, Science 303 (2004) 348;
in water treatment. It provides a new and more efficient material (f) B. Liu, H.C. Zeng, J. Am. Chem. Soc. 126 (2004) 8124.
for the application in organic waster water treatment. Further- [3] J.B. Fei, Y. Cui, X.H. Yan, W. Qi, Y, Yang, K.W. Wang, Q. He, J.B. Li, Adv. Mater., in
press.
more, as the size of the boehmite structures as-prepared was sev-
[4] Y. Cai, H. Pan, X. Xu, Q. Hu, L. Li, R. Tang, Chem. Mater. 19 (2007) 3081.
eral micrometers, the solid/liquid separation would be fairly easy, [5] H.G. Yu, J.G. Yu, S.W. Liu, S. Mann, Chem. Mater. 19 (2007) 4327.
which is very useful for real application to cut separation cost. [6] X.L. Li, T.J. Lou, X.M. Sun, Y.D. Li, Inorg. Chem. 43 (2004) 5442.
[7] Y. Liu, X. Tan, K. Li, Ind. Eng. Chem. Res. 45 (2006) 3782.
[8] S.W. Cao, Y.J. Zhu, M.Y. Ma, L. Li, L. Zhang, J. Phys. Chem. C 112 (2008)
4. Conclusion 1851.
[9] (a) T. Nakashima, N. Kimizuka, J. Am. Chem. Soc. 125 (2003) 6386;
(b) F. Caruso, R.A. Caruso, H. Mohwald, Science 282 (1998) 1111;
In summary, we have demonstrated a facile hydrothermal meth- (c) Y.D. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, A.P.
od to synthesize core/shell and hollow boehmite microspheres with Alivisatos, Science 304 (2004) 711.
unique urchin-like shell morphology. As-created sphere-in-sphere [10] Y.G. Zhang, Y.C. Chen, T. Wang, J.H. Zhou, Y.G. Zhao, Micropor. Mesopor. Mater.
114 (2008) 257.
structure endows the spheres with greatly enhanced ability to re-
[11] Y.X. Qi, K.B. Tang, S.Y. Zeng, W.W. Zhou, Micropor. Mesopor. Mater. 114 (2008)
move organic pollutants from waste water. Taking into account 395.
the high BET surface area and excellent porous properties, this no- [12] G.T. Duan, W.P. Cai, Y.Y. Luo, F.Q. Sun, Adv. Funct. Mater. 17 (2007) 644.
vel structure is expected to be useful in many other applications, [13] H.X. Li, Z.F. Bian, J. Zhu, D.Q. Zhang, G.S. Li, Y.N. Huo, H. Li, Y.F. Lu, J. Am. Chem.
Soc. 129 (2007) 8406.
such as catalysts, sorbents, ceramics, and optical nanodevices. [14] (a) Y.D. Yin, P.A. Alivisatos, Nature 437 (2005) 664;
And this work may provide new insights into preparing other inor- (b) X.G. Peng, L. Manna, W.D. Yang, J.T. Wickham, E. Scher, A. Kadavanich, A.P.
ganic core/shell spheres with complicated structure. Alivisators, Nature 404 (2000) 59;
(c) J. Park, K. An, Y. Hwang, J. Park, H. Noh, J. Kim, J. Park, N. Hwang, T. Hyeon,
Nat. Mater. 3 (2004) 891;
Acknowledgments (d) M.P. Pileni, Nat. Mater. 2 (2003) 145;
(e) S. Kan, T. Mokari, E. Rothenberg, U. Banin, Nat. Mater. 2 (2003) 155;
(f) M.A. El-sayed, Acc. Chem. Res. 37 (2004) 326;
Financial support to this work from the National Natural Sci- (g) C. Burda, X.B. Chen, R. Narayanan, M.A. El-sayed, Chem. Rev. 105 (2005)
ence Foundation of China under Grant 20503015 and from Shang- 1025.
216 L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 208–216

[15] (a) M. Uguina, J. Delgado, A. Rodriguez, J. Carretero, D. Gomez-Diaz, J. Molec. [24] (a) X.Y. Wu, D.B. Wang, Z.S. Hu, G.G. Hua, Mater. Chem. Phys. 109 (2008) 560;
Catal. A Chem. 256 (2006) 208; (b) H.M. Kou, Y.B. Pan, J.K. Guo, Ceram. Int. 33 (2007) 305;
(b) A. Khanna, D. Bhat, Surf. Coat. Technol. 201 (2006) 168. (c) H.M. Kou, J. Wang, Y.B. Pan, J.K. Guo, J. Am. Ceram. Soc. 88 (2005) 1615.
[16] S.C. Shen, W.K. Ng, Q. Chen, X.T. Zeng, R.B.H. Tan, Mater. Lett. 61 (2007) [25] (a) W.H. Kuan, M.K. Wang, P.M. Huang, C.W. Wu, C.M. Chang, S.L. Wang, Water
4280. Res. 39 (2005) 3457;
[17] M. Zhang, R. Zhang, G.C. Xi, Y. Liu, Y.T. Qian, J. Nanosci. Nanotechnol. 6 (2006) (b) D.M. Dabbs, U. Ramachandran, S. Lu, J. Liu, L.Q. Wang, I.A. Aksay, Langmuir
1437. 21 (2005) 11690.
[18] Y.Y. Li, J.P. Liu, Z.J. Jia, Mater. Lett. 60 (2006) 3586. [26] Y.F. Zhu, D.H. Fan, W.Z. Shen, J. Phys. Chem. C 111 (2007) 18629.
[19] P. Gao, Y. Xie, Y. Chen, L.N. Ye, Q.X. Guo, J. Cryst. Growth 285 (2005) 555. [27] B.F. Pan, D.X. Cui, C. Ozkan, P. Xu, T. Huang, Q. Li, H. Chen, F.T. Liu, F. Gao, R. He,
[20] (a) D.B. Kuang, Y.P. Fang, H.Q. Liu, C. Frommen, D. Fenske, J. Mater. Chem. 13 J. Phys. Chem. C 111 (2007) 12572.
(2003) 660; [28] H.M. Xiao, L.P. Zhu, X.M. Liu, S.Y. Fu, Solid State Commun. 141 (2007) 431.
(b) H.W. Hou, Y. Xie, Q. Yang, Q.X. Guo, C.R. Tan, Nanotechnology 16 (2005) [29] P. Benezeth, D.A. Palmer, D.J. Wesolowski, Geothermic 26 (1997) 65.
741. [30] J.H. Huang, L. Gao, Cryst. Growth Des. 6 (2006) 1528.
[21] J. Zhang, S.Y. Wei, J. Lin, J.J. Luo, S.J. Liu, H.S. Song, E. Elawad, X.X. Ding, J.M. Gao, [31] (a) D.V. Bavykin, V.N. Parmon, A.A. Lapkin, F.C. Walsh, J. Mater. Chem. 14
S.R. Qi, C.C. Tang, J. Phys. Chem. B 110 (2006) 21680. (2004) 3370;
[22] J. Zhang, S.J. Liu, J. Lin, H.S. Song, J.J. Luo, E.M. Elssfah, E. Ammar, Y. (b) K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol,
Huang, X.X. Ding, J.M. Gao, S.R. Qi, C.C. Tang, J. Phys. Chem. B 110 T. Siemieniewska, Pure Appl. Chem. 57 (1985) 603;
(2006) 14249. (c) J. Yu, H. Yu, B. Cheng, C. Traplis, J. Mol. Catal. A 249 (2006) 135.
[23] Y.L. Feng, W.C. Lu, L.M. Zhang, X.H. Bao, B.H. Yue, Cryst. Growth Des. 8 (2008) [32] L.S. Zhong, J.S. Hu, H.P. Liang, A.M. Cao, W.G. Song, L.J. Wan, Adv. Mater. 18
1426. (2006) 2426.