Journal of Colloid and Interface Science 367 (2012) 531–536

Contents lists available at SciVerse ScienceDirect

Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Short Communication

Mesoporous hollow spheres from soap bubbling

Xianglin Yu a, Fuxin Liang a, Jiguang Liu a,⇑, Yunfeng Lu b, Zhenzhong Yang a,⇑
a
State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b
Department of Chemical and Biomolecular Engineering, University of California at Los Angeles, Los Angeles, CA 90095, USA

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

Article history: The smaller and more stable bubbles can be generated from the large parent bubbles by rupture. In the pres-
Received 30 December 2010 ence of a bubble blowing agent, hollow spheres can be prepared by bubbling a silica sol. Herein, the trapped
Accepted 28 September 2011 gas inside the bubble acts as a template. When the porogen, i.e., other surfactant, is introduced, a mesostruc-
Available online 10 October 2011
tured shell forms by the co-assembly with the silica sol during sol–gel process. Morphological evolution
emphasizes the prerequisite of an intermediate interior gas flow rate and high exterior gas flow rate for hol-
Keywords: low spheres. The method is valid for many compositions from inorganic, polymer to their composites.
Soap bubble
Ó 2011 Elsevier Inc. All rights reserved.
Hollow spheres
Mesoporous structure

1. Introduction
Mesoporous materials have been extensively template synthe-
sized using supramolecular structures of amphiphilic species with
proper compositions [1–5], and they have shown promising applica-
tions in many areas due to their high specific surface area and tun-
able composition and pore characteristics [6,7]. Aiming at practical
applications, it is important to control their morphology ranging
within thin film [8–10], fiber [11–13], particulate [14,15], and
monolith [16]. Among those morphologies, a hollow sphere with
mesoporous shell is particularly interesting due to their potential
applications in controlled release, nano-container, diagnostic and
ultrasonic imaging, and light weighted material [17–24]. Although
core–shell based approach is mainly used to synthesize such hollow
spheres [25–29], removal of the core template is required and the
shell is usually fractured by the arisen osmotic pressure. Instead of
hard cores, a liquid emulsion droplet can also be employed as tem-
plate to synthesize mesoporous hollow spheres [30,31]. Recently,
dual templates have been used to prepare mesoporous hollow silica
spheres [32,33]. The procedure also involves many steps to remove
the templates and separate from the liquid dispersion. Different
from traditional synthesis in liquid media, the aerosol-assisted syn-
thesis in gas media is a more facile procedure [15]. Macroscopic
phase separation of additional polymers during aerosol-assisted
synthesis of particles has given a core–shell structure, and the corre-
sponding mesoporous hollow spheres are synthesized after the tem-
plates are dissolved [34]. A more economic method is required for
mesoporous hollow spheres with fewer components sacrificed.
Inspired by bubbling soap, we speculate that the procedure can
be employed to synthesize mesoporous hollow spheres just using
⇑ Corresponding authors. Fax: +86 010 62559373.
E-mail addresses: jiguangl@iccas.ac.cn (J. Liu), yangzz@iccas.ac.cn (Z. Yang).
gas bubble as a template. However, large soap bubbles easily break
up so that it is very difficult to obtain hollow spheres just by solidi-
fying these bubbles. In fact, an equilibrium black film of the bubbles
is about 101 nm thick [35]. If a bubble ruptures, the soap surfactant
can rapidly diffuse to the weaker interface due to Marangoni effect
[36] for ensuring the elastic film to recover, which is available for
generating smaller bubbles. A recent report indicates that the curved
membrane during the rupture of large bubbles can spontaneously
fold and entrap air inside forming numerous smaller bubbles [37].
These smaller bubbles usually are more stable than the large parent
bubbles. It is conjectured to synthesize small hollow spheres using
the smaller bubbles as templates when the membrane is material-
ized by proper chemistry.
2. Materials and methods
2.1. Materials
The chemicals used in this study and their sources are as follows:
Phenolic resin and Fe3O4 nanoparticles were, respectively, prepared
by our group according to literature [38,39]. Tetraethyl orthosilicate
(TEOS), hydrochloric acid (HCl), and SDS (sodium dodecyl sulfate,
C12H25SO4Na) were purchased from Beijing Beihua Fine Chemical
Co., Ltd. (China). Pluronic P123 (Mw = 5800, EO20PO70EO20) was
from BASF Company (Germany). All the chemicals were used as re-
ceived without any further purification.
2.2. Methods
2.2.1. Synthesis of precursor sols
The precursor silica sol was prepared by mixing the porogen
surfactant, blowing agent, tetraethoxysilane (TEOS), water and

0021-9797/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.09.077
532 X. Yu et al. / Journal of Colloid and Interface Science 367 (2012) 531–536

Scheme 1. Schematic illustration of preparing hollow spheres by blowing bubbles of a sol containing surfactants. Two surfactants play different roles. While one surfactant is
responsible for the bubble formation as a blowing agent, the other one is responsible for the formation of mesostructures within the shell by the co-assembly with the silica
precursor. A large parent bubble formed from the orifice is blown and ruptured into smaller bubbles at a medium gas flow rate level. In the heating zone, the smaller bubbles
are solidified by a sol–gel process for forming hollow spheres. In order to accelerate the solidification of bubbles, ammonia gas could be introduced through an inlet in the
upper part of the heating tube. The corresponding mesoporous hollow spheres are synthesized after the surfactants are removed either by dissolution or calcination.

2 M HCl under stirring for 2 h forming a homogeneous sol. The Plu-
ronic series block copolymer P123 and SDS were chosen as the
porogen surfactant and blowing agent, respectively. In a typical
experiment, the weight ratio of TEOS, P123, SDS, 2 M HCl in respect
to water was 5 wt.%, 3 wt.%, 1 wt.%, 40 wt.%, respectively.
2.2.2. Preparation of hollow spheres
The synthesis procedure was illustrated in Scheme 1. The single
large parent bubbles with a size of several millimeters to about two
centimeters were generated by a home built apparatus. Nitrogen
(N2) gas was used as interior gas to blow bubbles, and exterior
gas flow is also N2 for blowing down the bubbles and being used
as the carrier gas. The precursor sol was pumped to the apparatus,
blown and ruptured into some representative morphology such as
smaller bubbles, droplets and membranes, which is dependent on
gas flowing rates. The samples were carried by the exterior gas
through a heating tube about one meter in length and 6 cm in
diameter at a high temperature, for example, 200 °C, which expe-
rienced a mean residence time of approximate 6–10 s. In order to
accelerate the solidification of the samples, the ammonia gas at a
flow rate of 20 mL/h was introduced into the heating tube through
an inlet in its upper part. If porogen (e.g. P123) is introduced into
the precursor sol, mesoporous hollow spheres could be obtained
after the surfactant was removed from the solidified hollow
spheres by calcined at high temperature (e.g. 450 °C) or washed
with water. As for the synthesis of phenolic resin/silica or Fe3O4/
silica composite, phenolic resin or the Fe3O4 nanoparticles were
added to the above sol directly, while the other compositions were
kept constant as above. Carbon of the silica/phenolic resin compos-
ite spheres could be selectively removed by heating them at 550 °C
in air, silica of the silica/phenolic resin composite hollow spheres
could be removed by 10% HF solution.
2.3. Characterization
Transmission electron microscopy (TEM) images were taken
with a JEOL 100CX electron microscope with an accelerating voltage
of 100 kV. The samples were prepared by dropping their ethanol dis-
persion solution onto carbon coated copper grids. HR-TEM charac-
terization was performed on HITACHI H-9000 NAR with an
accelerating voltage of 300 kV. Scanning electron microscopy
(SEM) images and EDS analysis were taken with a HITACHI S-4300
apparatus operated at an accelerating voltage of 15 kV. The samples
were dropped onto the silicon slides, ambient dried and vacuum
sputtered with Pt. Nitrogen adsorption/desorption isotherms at
77 K were obtained using a Micromeritics ASAP 2020M Surface Area
and Porosity Analyzer. The samples were degassed at 300 °C for 11 h.
The Brunauer–Emmett–Teller (BET) method was utilized to calcu-
late the specific surface areas. The pore size distributions of the sam-
ples were derived from the adsorption branches of the isotherms
using the Barrett–Joyner–Halenda method. The total pore volumes,
Vp, were estimated from the amount adsorbed at a relative pressure
of P/P0 = 0.98. Infrared spectra of the samples were recorded on a
BRUKER EQUINOX 55 FT-IR spectrometer, where the samples were
pressed with KBr for measurement. X-ray powder diffraction
(XRD) data were acquired on a Rigaku D/max-2500 X-ray diffrac-
tometer equipped with monochromated Cu Ka radiation
(k = 1.5406 Å). Thermogravimetric analysis (TGA) experiments were
performed using the Perkin-Elmer Pyris 1 TGA under nitrogen or air
at a heating rate of 10 °C/min.
3. Results and discussion
As depicted in Scheme 1, a single large parent bubble is gener-
ated by a home built soap bubbling apparatus, which contains two
gas inlets for the interior blowing gas and the exterior carrier gas,
respectively. The size of the parent bubble could be adjusted from
several millimeters to about two centimeters by changing the gas
flow rates, especially interior gas flow rate. The large parent bubble
would rapidly rupture under the pressure of exterior gas flow for
generating numerous smaller bubbles or fragments, which de-
pends on the two gas flow rates. Introducing a silica sol into a soap
solution (e.g., SDS solution), the special smaller ‘‘silica’’ bubbles can
be generated due to the rupture of parent bubbles; and then a sol–
gel process occurs within the bubble membrane when they pass
through a heating zone especially with the aid of catalytic ammo-
nia gas, which was selected to accelerate the solidification since an
increase in pH usually brings about an increase in the hydrolysis
rate [40]. If additional template surfactant, e.g., block copolymers
P123, is also introduced into the sol as a porogen, the co-assembly
of the surfactant with the silica precursor would result in the mes-
oporous structure of silica shell. After the removal of the surfac-
tant, mesoporous hollow spheres are derived.
3.1. Morphological evolvement of the as-prepared particles
In the presence of SDS as a bubble blowing agent, a precursor
solution, i.e., a silica sol containing 5.0 wt.% TEOS and 1.0 wt.%
SDS, was blown into the heating zone by nitrogen gas flow. The
morphology of the as-prepared particles extremely depends on
the double gas flow rates. Only liquid streamed down from the
 X. Yu et al. / Journal of Colloid and Interface Science 367 (2012) 531–536 533

gas inlet and there is no bubbles generated when the interior gas
flow rate is low enough, e.g., below 10 L/h; on the other hand,
the silica sol was atomized and sprayed into the heating zone when
the interior gas flow rate is high enough, e.g., above 60 L/h. These
liquid droplets were solidified into silica particles due to sol–gel
reaction under heated. So, when the interior gas flow rate was be-
low 10 L/h or at a much high level above 60 L/h, silica particles
were obtained.
With the interior gas flow rate rising, the large parent bubbles
would be generated. However, if the exterior gas flow rate is low
enough, these bubbles would be solidified before rupture, and then
the solidified bubbles will fly off to the tube wall, they would rup-
ture into nanosheets because their shells were so thin, which were
verified by Fig. 1a. With the exterior gas flow rate rising, some par-
ent bubbles will rupture into small bubbles before solidification
meanwhile other parent bubbles will still solidify before rupture,
So hollow spheres and nanosheets coexisted (Fig. 1b). When the
exterior gas flow rate further rise, hollow spheres will be predom-
inant because of the rupture of parent bubbles.
At a given constant exterior gas flow rate of 120 L/h, hollow
spheres were predominantly generated when the interior gas flow
rate was controlled within an intermediate level of 10–60 L/h. At a
given interior gas flow rate, e.g., 40 L/h, morphology of the
obtained sample evolved significantly from nanosheets to hollow
spheres with increasing the exterior gas flow rate. Nanosheets
(Fig. 1a) were predominantly synthesized when the exterior gas
flow rate was at a low level of 40 L/h, which thickness can also
be controlled by changing the TEOS content. These nanosheets
resulted from the parent bubbles which have not transformed into
smaller bubbles. Curved edge and thickness of the nanosheets im-
ply that they are indeed generated from the rupture of the solidi-
fied parent bubbles. When the exterior gas flow rate was
increased to a certain extent, the parent bubbles tended to rupture
into numerous smaller bubbles before solidification due to the
increasing pressure difference. For instance, when the exterior
gas flow rate was increased to 70 L/h, hollow spheres appeared
(Fig. 1b) coexisting with the nanosheets. When the exterior gas
flow rate was further increased above 100 L/h, hollow spheres
were predominant (Fig. 1c). By increasing the exterior gas flow rate
from 100 to 300 L/h, size of the hollow spheres becomes smaller
and rather broad in size distribution (Fig. 1d–f). The morphological
evolution dependent on gas flow rates is summarized in Fig. 2.
At an exterior gas flow rate of 120 L/h and an interior gas flow
rate of 40 L/h, the typical silica hollow spheres (Fig. 1c) were

Fig. 1. Morphological evolution of the samples dependent on exterior gas flow rate at a fixed interior gas flow rate of 40 L/h. (a) the nanosheets at an exterior gas flow rate of
40 L/h, (b) a mixture of nanosheets and hollow spheres at 70 L/h, (c) hollow spheres at 120 L/h, (d–f) TEM images of the hollow spheres at three different exterior gas flow
rates of 150 L/h, 200 L/h, 300 L/h. All were prepared with 5.0 wt.% TEOS and 1.0 wt.% SDS.
534 X. Yu et al. / Journal of Colloid and Interface Science 367 (2012) 531–536
Fig. 2. The morphology dependence of the as-prepared particles on the interior and
exterior gas flow rates.
synthesized, which diameters are about 100–200 nm and average
shell thickness is about 15 nm. After SDS was removed by either
dissolution or calcination, the mesoporous structure was not found
from the shell of hollow spheres (Fig. 3). The shell thickness can be
controlled by changing the sol (TEOS) concentration. For example,
the thickness can gradually increases from 15 nm (Fig. 3a), 25 nm
(Fig. 3b) to 40 nm (Fig. 3c) when the TEOS concentration increases
from 5.0 wt.%, 10.0 wt.% to 15.0 wt.%. A minimum thickness about
10 nm was achieved when the TEOS concentration was 2.0 wt.%.
Similar to the shell thickness control, the size of the hollow spheres
also slightly increases with TEOS concentration (Fig. 3a–c).
3.2. Mesoporous structure of the as-prepared silica hollow spheres
It is known that surfactants can co-assembly with a silica sol for
preparing mesoporous structure during the sol–gel process [41].
Herein, when additional porogen P123 was introduced, the shell
Fig. 3. TEM images of some representative silica hollow spheres prepared with different TEOS concentration, while the other conditions were fixed as the spheres shown in
Fig. 1c. (a) 5.0 wt.%; (b) 10.0 wt.%; (c) 15.0 wt.%.
became mesostructure, which reveals the formation of supramo-
lecular structures within the shell. A typical sample was prepared
with 3.0 wt.% P123 meanwhile the concentration of TEOS and SDS
was, respectively, fixed at 5.0 wt.% and 1.0 wt.%. No mesopores
were found before the removal of the surfactant. After the surfac-
tant was removed either by dissolution or by calcination at 450 °C
in nitrogen, the disordered worm-like mesopores within the shell
were clearly observed (Fig. 4a, S1c). A little of fragments derived
from the membrane of parent bubbles could be observed; how-
ever, the amount of mesoporous hollow spheres was still predom-
inant. The HR-TEM image exhibited much more clear mesoporous
structure (Fig. S1d), where similar texture both in and outside of
spheres was caused by the little fragments.
Nitrogen adsorption/desorption isotherms indicates that the
typical sample with 3.0 wt.% P123 presented type IV isotherms
with a distinct hysteresis loop of type H3 observed, indicating
the existence of mesopores [42,43]. Calculated by the Barrett–Joy-
ner–Halenda (BJH) and the Brunauer–Emmett–Teller (BET) meth-
od, the pore size distribution is broad and centered at 5.1 nm,
meanwhile the pore volume is 0.61 cm3/g. The specific surface area
is 380 m2/g (Fig. 4c and d). The removal of the surfactants is further
confirmed by TGA (Fig. S2) and FT-IR (Fig. S3). For comparison, the
samples prepared without P123 only possess a poor surface area
(about 15 m2/g). It can be sure the mesoporous structure indeed
comes from the porogen surfactant, P123. When the content of
P123 was decreased to 1.5 wt.%, the average pore diameter is
4.2 nm, the pore volume is also decreased to 0.22 cm3/g, and the
specific surface area is decreased to 190 m2/g (Fig. S4). Its iso-
therms and the hysteresis loop are similar to that of the sample
prepared at 3.0 wt.% P123. The pores are also disordered worm like
(Fig. S1a, S1b). When the content of P123 was increased from
3.0 wt.% to 5.0 wt.%, this measurement also exhibited a type IV iso-
therms, but the hysteresis loop changed to the type H2 (Fig. 4c),
which is difficult to interpret until now and maybe related to the
‘‘ink-bottle’’ pores and the role of network [42]. However, this
isotherms declares the pore size distribution becomes relatively
 X. Yu et al. / Journal of Colloid and Interface Science 367 (2012) 531–536 535

Fig. 4. Mesoporous hollow spheres. (a) TEM image of the hollow silica spheres prepared with 3.0 wt.% P123 after surfactants were removed; (b) TEM image of the silica
spheres prepared with 5.0 wt.% P123 after surfactants were removed; (c) nitrogen adsorption/desorption isotherms, and (d) the corresponding pore size distribution plot of
the mesoporous silica spheres prepared with varied P123 content level (s: 3.0 wt.%; 5: 5.0 wt.%). All the spheres were prepared with 5.0 wt.% TEOS and 1.0 wt.% SDS at an
exterior gas flow rate of 120 L/h and an interior gas flow rate of 40 L/h. The surfactants were removed by calcinations at 450 °C.

Fig. 5. Composite hollow spheres. (a) SEM image of the as-prepared phenolic resin/silica hollow spheres with 5.0 wt.% phenolic resin, the inset is its TEM image; (b) TEM
image of the mesoporous phenolic resin/silica hollow spheres, the inset is its magnified TEM image; (c and d) SEM image of the Fe3O4/silica composite hollow spheres with
2.0 wt.% and 5.0 wt.% Fe3O4 nanoparticle in respect to TEOS, the insets are their TEM images. For all the samples, the concentration of TEOS and P123 was fixed at 5.0 wt.% and
3.0 wt.%, respectively. All the spheres were prepared at an exterior gas flow rate of 120 L/h and an interior gas flow rate of 40 L/h. The spheres of sample b, c, and d were
calcined at 450 °C in nitrogen.

narrower. The average pore diameter is about 6.6 nm, the pore increased to 450 m2/g (Fig. 4d). TEM image reveals a multiple
volume is increased to 0.89 cm3/g, and the specific surface area is lamellar structure (Fig. 4b) with a regular porous arrangement.
536 X. Yu et al. / Journal of Colloid and Interface Science 367 (2012) 531–536
When the precursor sol was diluted (1/2 and 1/5 of the original so-
lid content) with water, shell thickness could decrease (Fig. S5a
and S5b) but with the hollow spherical contour well retained,
which structure could be observed from the magnified image
(Fig. S5c).
3.3. Composite hollow spheres
The method can be extended to more general systems, for
example, phenolic resin/silica, Fe3O4/silica mesostructured com-
posites. As an example, the phenolic resin was chosen as a repre-
sentative organic component since it is commonly used to derive
carbon [38]. Accordingly, the mesoporous phenolic resin/silica
composite hollow spheres (Fig. 5b) were obtained after the as-pre-
pared hollow spheres (Fig. 5a) were calcined at 450 °C in nitrogen
to remove the surfactants. The worm-like mesopores were con-
firmed by TEM (Fig. 5b) and nitrogen adsorption/desorption analy-
sis (Fig. S6). The spherical contour (Figs. S7a and S7b) was well
preserved after each component was selectively removed, indicat-
ing both the components are continuous within the shell. The
selective removal of the phenolic resin and silica was ,respectively,
confirmed by FT-IR (Fig. S8) and EDS analysis (Fig. S9). It is clear the
characteristic absorption peaks at 1435, 2839, 2927 cm1 corre-
sponding to the organic component are almost completely disap-
pear after the hollow spheres were calcined in air, on the other
hand, there was few silica element retained after these hollow
spheres were treated by HF solution. As another example, a
Fe3O4/silica nanoparticle composite hollow sphere (Fig. 5c) was
synthesized starting from the sol containing the nanoparticle. By
XRD analysis, it is clear the main peaks of cubic crystalline phase
of Fe3O4 nanoparticles still exist and are intensive, which indicates
these nanoparticles retain Fe3O4 crystalline after being incorpo-
rated within the silica shell (Fig. S10). The peak at 32.5° indicates
there is a little of FeO(OH) generated since Fe3O4 nanoparticles
were used in an acid circumstance (the sol is prepared with TEOS
and acid). Calculated by the Scherrer equation [44], the size of
the Fe3O4 nanoparticles is about 11.1 nm. With the increase in
Fe3O4 nanoparticle content from 2.0 wt.% to 5.0 wt.%, the shell
surface became coarser due to the aggregation of nanoparticles
(Fig. 5d). The mesoporous hollow composite spheres are paramag-
netic, which are easy to be separated magnetically.
4. Conclusions
In summary, a soap bubbling assisted synthesis of mesostruc-
tured materials has been proposed starting from a sol. By simply
adjusting gas flow rates, their morphology can be adjusted from
nanosheets to hollow spheres. Especially, at a heating ammonia
atmosphere, morphology of the bubble can be fixated by solidify-
ing during sol–gel process. When additional porogen was intro-
duced, mesostructured materials especially mesoporous hollow
spheres were synthesized. The method is general for a variety of
composition from inorganic, polymer and their composites.
Acknowledgments
This work was supported by the NSF of China (50733004,
20720102041, and 50973121), CAS, and MOST (KJCX2-YW-H20).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jcis.2011.09.077.
References
[1] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710–712.
[2] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W.
Chu, D.H. Olson, E.W. Sheppard, J. Am. Chem. Soc. 114 (1992) 10834–10843.
[3] B. Hatton, K. Landskron, W. Whitnall, D. Perovic, G.A. Ozin, Acc. Chem. Res. 38
(2005) 305–312.
[4] D.Y. Zhao, J.L. Feng, Q.S. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D.
Stucky, Science 279 (1998) 548–552.
[5] E. Prouzet, T.J. Pinnavaia, Angew. Chem. Int. Ed. 36 (1997) 516–518.
[6] Y.D. Meng, D.R. Chen, X.L. Jiao, J. Phys. Chem. B 110 (2006) 15212–15217.
[7] J.Y. Ying, C.P. Mehnert, M.S. Wong, Angew. Chem. Int. Ed. 38 (1999) 56–77.
[8] Y.F. Lu, B.F. McCaughey, D.H. Wang, J.E. Hampsey, N. Doke, Z.Z. Yang, C.J.
Brinker, Adv. Mater. 15 (2003) 1733–1736.
[9] D.Y. Zhao, P.D. Yang, D.I. Margolese, B.F. Chmelka, G.D. Stucky, Chem. Commun.
22 (1998) 2499–2500.
[10] H. Miyata, T. Suzuki, A. Fukuoka, T. Sawada, M. Watanabe, T. Noma, K. Takada,
T. Mukaide, K. Kuroda, Nat. Mater. 3 (2004) 651–656.
[11] Z.L. Yang, Z.W. Niu, X.Y. Cao, Z.Z. Yang, Y.F. Lu, Z.B. Hu, C.C. Han, Angew. Chem.
Int. Ed. 42 (2003) 4201–4203.
[12] Y.Y. Wu, G.S. Cheng, K. Katsov, S.W. Sides, J.F. Wang, J. Tang, G.H. Fredrickson,
M. Moskovits, G.D. Stucky, Nat. Mater. 3 (2004) 816–822.
[13] J.T. Mccann, D. Li, Y.N. Xia, J. Mater. Chem. 15 (2005) 735–738.
[14] S. Schacht, Q. Huo, I.G. Voigtmartin, G.D. Stucky, F. Schuth, Science 273 (1996)
768–771.
[15] Y.F. Lu, H.Y. Fan, A. Stump, T.L. Ward, T. Rieker, C.J. Brinker, Nature 398 (1999)
223–226.
[16] C.G. Goltner, M. Antonietti, Adv. Mater. 9 (1997) 431–436.
[17] H. Huang, E.E. Remsen, J. Am. Chem. Soc. 121 (1999) 3805–3806.
[18] C.E. Fowler, D. Khushalani, S. Mann, Chem. Commun. 19 (2001) 2028–2029.
[19] G. Fornasieri, S. Badaire, R. Backov, Adv. Mater. 16 (2004) 1094–1097.
[20] J.J. Storhoff, R. Elghanion, R. Mucic, C.A. Mirkin, R.L. Letsinger, J. Am. Chem. Soc.
120 (1998) 1959–1964.
[21] O. Andersen, U. Waag, L. Schneider, G. Stephani, B. Kieback, Adv. Eng. Mater. 2
(2000) 192–195.
[22] S.W. Kim, M. Kim, W.Y. Lee, T. Hyeon, J. Am. Chem. Soc. 124 (2002) 7642–7643.
[23] Y. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, A.P. Alivisatos,
Science 304 (2004) 711–714.
[24] J. Yang, L. Qi, C. Lu, J. Ma, H. Cheng, Angew. Chem. Int. Ed. 44 (2005) 598–603.
[25] G. Zhu, S. Qiu, O. Terasaki, Y. Wei, J. Am. Chem. Soc. 123 (2001) 7723–7724.
[26] Y. Le, J.F. Chen, J.X. Wang, L. Shao, W.C.A. Wang, Mater. Lett. 58 (2004) 2105–
2108.
[27] J. Chen, J. Wang, R. Liu, L. Shao, L. Wen, Inorg. Chem. Commun. 7 (2004) 447–
449.
[28] H.P. Lin, Y.R. Cheng, C.Y. Mou, Chem. Mater. 10 (1998) 3772–3776.
[29] F.J. Suárez, M. Sevilla, S. Álvarez, T. Valdés-Solís, A.B. Fuertes, Chem. Mater. 19
(2007) 3096–3098.
[30] J.A. Zasadzinski, E. Kisak, C. Evans, Curr. Opin. Colloid Interface Sci. 6 (2001)
85–90.
[31] C. Yu, B. Tian, J. Fan, G.D. Stucky, D.Y. Zhao, Chem. Lett. 31 (2002) 62–63.
[32] Y.S. Li, J.L. Shi, Z.L. Hua, H.R. Chen, M.L. Ruan, D.S. Yan, Nano Lett. 3 (2003) 609–
612.
[33] Y.F. Zhu, J.L. Shi, H.R. Chen, W.H. Shen, X.P. Dong, Micropor. Mesopor. Mater. 84
(2005) 218–222.
[34] S.B. Rathod, T.L. Ward, J. Mater. Chem. 17 (2007) 2329–2335.
[35] J.J. Bikerman, J.M. Perri, R.B. Booth, C.C. Currie, Foams: Theory and Industrial
Applications, New York, 1953.
[36] D. Exerowa, P.M. Kruglyakov, Foam and Foam Films Theory, Experiment,
Application, Elsevier, New York, 1998.
[37] J.C. Bird, R. de Ruiter, L. Courbin, H.A. Stone, Nature 465 (2010) 759–762.
[38] Y. Meng, D. Gu, F.Q. Zhang, Y.F. Shi, H.F. Yang, Z. Li, C.Z. Yu, B. Tu, D.Y. Zhao,
Angew. Chem. Int. Ed. 44 (2005) 7053–7059.
[39] B. Liu, W. Wei, X.Z. Qu, Z.Z. Yang, Angew. Chem. Int. Ed. 47 (2008) 3973–3975.
[40] S.L. Chen, P. Dong, G.H. Yang, J.J. Yang, Ind. Eng. Chem. Res. 35 (1996) 4487–
4493.
[41] Y. Wan, D.Y. Zhao, Chem. Rev. 107 (2007) 2821–2860.
[42] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol, T.
Siemieniewska, Pure Appl. Chem. 57 (1985) 603–619.
[43] H.Q. Wang, Z.B. Wu, Y. Liu, J. Phys. Chem. C 113 (2009) 13317–13324.
[44] H. Borchert, E.V. Shevchenko, A. Robert, I. Mekis, A. Kornowski, G. Grübel, H.
Weller, Langmuir 21 (2005) 1931–1936.