Compressible porous hybrid monoliths: Preparation via a low molecular mass gelators-based gel-emulsion approach and exceptional performances

Article abstract of DOI:10.1039/c5ta08342g

A cholesteryl derivative, BuDphe, which is a low molecular mass gelator (LMMG), was synthesized and used as a stabilizer for the creation of a number of water/oil gel-emulsions, of which the oil could be a mixture of butyl methacrylate (t-BMA) and p-divinylbenzene (DVB), a mixture of t-BMA, DVB and polydimethylsilane (PDMS), or that of t-BMA, DVB, PDMS and trimethoxymethylsilane (MTMS). Polymerization of these mixtures resulted in porous polymeric or hybrid monoliths, M-1, M-2, M-3, M-4 and M-5, respectively, of which the first is a pure poly-t-BMA monolith, the second to the fourth ones contain an increasing amount of PDMS, and the last is a hybrid of poly-t-BMA, PDMS and hydrolyzed MTMS. The hybrid monoliths, in particular M-5, as prepared possess not only hydrophobicity, porosity, and low-density, but also an unprecedented flexibility in the dry state with a maximum shape recovery corresponding to 100% of the original thickness after more than 70% compression strain. Moreover, silylanization also improves the thermo-stability of the porous materials. An absorption test demonstrated that M-5 is an excellent absorbent for a number of organic solvents and oils. The material after absorption can be re-generated and the liquids absorbed can be recovered by simple squeezing. Furthermore, the absorption-separation process with CH₂Cl₂ as an example solvent could be repeated at least 10 times with no significant reduction of its absorption capacity. Combination of the excellent flexibility, great absorptivity, easiness in preparation, and low-energy consumption in drying makes the hybrid monoliths, in particular M-5, possess the potential to find real-life applications.

Full text of DOI:10.1039/c5ta08342g

View Article Online
View Journal
Journal of
Materials Chemistry A
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Chen, L. Liu, K.
Liu, Q. Miao, Y. Lü and Y. Fang, J. Mater. Chem. A, 2015, DOI: 10.1039/C5TA08342G.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/materialsA

Please do not adjust margins
Journal of Materials Chemistry A
Page 1 of 11
View Article Online
DOI: 10.1039/C5TA08342G
Journal of Materials Chemistry A
ARTICLE
Compressible Porous Hybrid Monoliths: Preparation via A Low-
molecular Mass Gelators-based Gel Emulsion Approach and
Exceptional Performances
Received 00th January 20xx,
Accepted 00th January 20xx
Xiangli Chen, Lingling Liu, Kaiqiang Liu, Qing Miao, Yanchao Lü, Yu Fang*
DOI: 10.1039/x0xx00000x
A cholesteryl derivative, BuDphe, which is a low-molecular mass gelator (LMMG), was synthesized and used as a stabilizer
for creation of a number of water/oil gel- emulsions, of which the oil could be a mixture of butyl methacrylate (t-BMA) and
p-divinylbenzene (DVB), a mixture of t-BMA, DVB and polydimethylsilane (PDMS), or that of t-BMA, DVB, PDMS and
trimethoxymethylsilane (MTMS). Polymerization of them resulted in porous polymeric or hybrid monoliths, M-1, M-2, M-3,
M-4 and M-5, respectively, of which the first is a pure poly-t-BMA monolith, the second to the fourth are the ones
containing increasing amount of PDMS, and the last is a hybrid of poly-t-BMA, PDMS and hydrolyzed MTMS. The hybrid
monoliths, in particular M-5, as prepared possess not only hydrophobicity, porosity, and low-density, but also an
unprecedented flexibility in dry state with a maximum shape recovery corresponding to 100% of the original thickness
after more than 70% compression strain. Moreover, silylanization also improves the thermo-stability of the porous
materials. Absorption test demonstrated that M-5 is an excellent absorbent for a number of organic solvents and oils. The
material after absorption can be re-generated and the liquids absorbed can be recovered by simple squeezing.
Furthermore, the absorption-separation process with CH2Cl2 as an example solvent could be repeated at least 10 times
with no significant reduction of its absorption capacity. Combination of the excellent flexibility, great absorptivity, easiness
in preparation, and low-energy consumption in drying makes the hybrid monoliths, in particular M-5.
www.rsc.org/
creation of new absorbents.1-7 In fact, absorbents from natural
materials such as expanded perlite, zeolites and graphite, as
well as activated carbon, sawdust have long been used as
Introduction
With fast industrialization, clean up organic pollutants, in
particular oil leakages, has attracted increasing attention
during the last few decades. This is because the pollutants may
cause irrecoverable damage to eco-systems via contamination
of water and soil. However, treatment of the pollutants in an
efficient and practical way is a burning challenge to scientists
working in the field. Till now, the most efficient way to clean
up the pollutants from water is separation via selective
absorption. Therefore, a lot of effort has been put into
absorbents, but the performance of them is not as good as
expected because of low oil loading density and low oil-water
selectivity.1, 8 It is of the reasons that people has tend their
attention to synthetic porous materials, including silicas,9
carbon
nanotubes,10
organic-inorganic
hybrids,11
functionalized polymers and resins,12,13 etc. For example, Wu
and co-workers10 reported a sponge-like material, which is
composed of self-assembled, interconnected carbon
nanotubes (CNT). The sponge in densified state swell
instantaneously upon contact with organic liquids. Zhou and
coworkers14 prepared porous polystyrene, and the materials as
prepared exhibit idea oil-water separation and gas
permeability properties. Guo and colleagues15 prepared special
xerogels from a dendrimer of poly-propylenimine and a block
co-polymer that is sulfonated polystyrene-block-poly-
Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal
University), Ministry of Education, School of Chemistry and Chemical Engineering,
{ZꢀꢀvÆ] b}Œuꢀo Üv]ÀꢁŒ•]šÇU ó][ꢀv óíì119, P. R. China. Fax: 0086- 29-81530787; Tel:
0086-29-81530788; E-mail: yfang@snnu.edu.cn
• 9oꢁꢂšŒ}v]ꢂ {µpplementary Information (ESI) available: [Figure S1 1H NMR spectra
of BuDphe, Figure S2 FTIR spectra of BuDphe, Figure S3 MS spectra of BuDphe,
Figure S4 Gelation behaviors of BuDphe in various solvents, Figure S5 Phase
behavior of BuDphe/t-BMA (2%, wt%) after 10 minutes standing, Figure S6 Phase
behaviour of BuDphe /water /t-BMA (total volume is 1 mL) with different water
contents: (a) 0%, (b) 20%, (c) 50%, (d) 80%, (e) 100% (v/v), Figure S7 TGA curves of
M-1 (black line), M-4 (red line), M-5 (blue line) under oxygen flow, Figure S8 (a)
Maximum absorption capacities of M-5 to some organic-solvent mixtures*; (b)
Selectivity of the materials to the solvents* under test, results from GC-MS
studies, Table S1 Theoretical values of the porosities of the porous materials, Table
S2 Experimentally determined porosities of the porous polymeric materials, Video
S1 The porous composite monolith is still flexible after treatment in liquid
nitrogen, Video S2 Compression test on weight illustrating spring-back behavior,
Video S3 Selective absorption of gasoline from water by using M-5, Video S4 The
(ethylene-ran-butylene)-block-polystyrene.
The
porous
materials could be used as oil absorbents for the clean-up of
oil spills, and show high oil absorption capacity, ideal
absorption speed, and in addition, the materials are reusable.
The materials or the methods used for the preparation of
them, however, suffered from some drawbacks such as
complicated preparation processes, high costs for reagents
and apparatus, and energy-consuming for drying, which may
prevent their real-life uses. In fact, with exception of some
porous carbon materials and one silylated nanocellulose
sponge which are cost-expensive, 10,16 other porous polymeric
absorptiontsqueezing processes with M-5 as
DOI: 10.1039/x0xx00000x
a sample absorbent]. See
This journal is © The Royal Society of Chemistry 20xx
J.Mater. Chem. A, 2015, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry A
Page 2 of 11
View Article Online
DOI: 10.1039/C5TA08342G
ARTICLE
Journal Name
absorbents reported till now are almost all hard, brittle and solvent are not at all necessary, and furthermore, 2.5% (w/v)
flammable in dry state, which make them very inconvenient in or even less than that of the stabilizer is enough to produce a
real-life uses. Therefore, creation of porous polymeric gel-emulsion with good stability. No doubt, these advantages
materials with low density, high strength, good toughness, must be beneficial for the practical production of gel-
maximum service life and low cost still remains a significant emulsions, and for their template application.42-46
challenge.
Herein, we report on the preparation of some new LMMGs-
For the preparation of the porous materials, various template based gel-emulsions, and their utilization in the template
methods have been employed, but among them the colloidal preparation of porous poly-t-BMA and relevant hybrid
template is almost the most widely adopted one.17-20 In a monoliths, which exhibit good mechanical property, ideal oil
typical preparation, a biphasic system is generated and then absorptivity, and excellent reusability. In addition, the
the continuous phase is polymerized. The colloidal entities preparation is easy, the energy consumption is low, and their
serve to create porosity in the final polymeric materials and internal structure is highly adjustable. This paper reports the
are removed after polymerization. The colloidal systems could details.
be emulsions,21 micro-emulsions,22,23 solid particles,18,24,25
breath figure droplets,26,27 and gel emulsions,28-30 and the pore
sizes can range from a few nanometres to hundreds of micros.
Among the colloidal templates, gel emulsions are more unique
due to the fact that their internal structures could be easily
adjusted by varying their composition.
Experimental
Materials
Tertiary butyl methacrylate (t-BMA, 99%, Sigma-Aldrich),
acrylonitrile (AN, 99%, Sigma-Aldrich), styrene (St, 99%, Sigma-
Aldrich), methyl methacrylate (MMA, 99%, Sigma-Aldrich) and
p-divinylbenzene (DVB, Aldrich) were purified before use by
passing through a neutral aluminum oxide column to eliminate
the pre-added inhibitor in the reactants. After purification, the
monomer and the cross-linker were stored in a freezer if they
were not used directly. 2,2;-Azobis(isobutyronitrile) (AIBN, 97%)
was purchased from Sigma-Aldrich, and was purified by
recrystallization using ethanol before use. Sylgard 184 silicone
Gel emulsions were discovered earlier but only till 1966 a clear
definition was given by Lissant and co-workers.31 In the
definition, gel-emulsions are recognized as two-phase systems,
of which one is the continuous phase and the other the
dispersed phase. In particular, the volume fraction of the
second one is greater than 0.74, which is a critical value in
geometry for a container to be fully filled by non-deformed
balls. In other words, the continuous phase must be
networked thin films with porous structures, which are the
bases for them to be used as templates.32-34 Accordingly, gel
emulsion is also named as high internal phase emulsion (HIPE) elastomer base and curing agent were purchased from Dow
and the porous polymeric monoliths obtained from them are
vꢀuꢁꢃ ꢀ• ^‰}oÇILt9_X35
Corning (Midland, USA), and Boc-phenylalanine was purchased
from Chengdu enlai biological technology Co., LTD. Water used
throughout was doubly distilled. Other reagents were of, at
least, analytical grade, and used without further purification.
Syntheses of the cholesteryl derivative (BuDphe)
It is not difficult to understand that the structure and property
of the porous materials created in the template way are
determined by the structure and the chemical nature of the
gel-emulsions, of which they are produced from. By this token,
development of gel-emulsions with distinctive structure and
property is the priority in the creation of porous polymeric
monoliths with predetermined structure and property.
Practically, surfactants and micro-/nano-particles are
commonly used as stabilizers, which are the third, but may be
most variable component of gel-emulsions with the exception
of water and water immiscible liquid.36-39 Even though
surfactants are easily found, available and most commonly
used stabilizers, yet they are not very efficient since a large
ꢀu}µvšU ñ>ñì9 ~ÁlÀ• }( šZꢁ ꢂ}vš]vµ}µ• ‰Zꢀ•ꢁ, is required. As
for gel emulsions stabilized by micro-/nano-particles, the so
called Pickering emulsions, they may suffer from phase
inversion when the volume fraction of the dispersed phase
ŒꢁꢀꢂZꢁ• ìXòñ>ìXóìX Üvo]lꢁ šZꢁ•ꢁ Pꢁo ꢁuµo•]}v•U ꢀ vꢁÁ l]vꢃ }(
gel emulsions was reported by us recently, of which low-
Scheme 1 The synthesis route of BuDphe
molecular mass gelators (LMMGs) were used as stabilizers.28-
30,40,41
The most distinct difference between the two kinds of The methods used for the preparation of BuDphe, which is a
gel emulsions is that both the continuous phase and the
dispersed phase are liquids, but for the ones reported by us,
the continuous phase is gelled due to presence of the LMMGs.
It is the difference that makes the volume fraction of the
dispersed phase need not to be greater than 0.74 because it is
physically trapped within the continuous phase. Moreover,
preparation of gel-emulsions by using LMMGs as stabilizers is
so simple that only agitation at room temperature is required,
and procedures like heating, cooling, and addition of co-
succinic acid derivative of cholesteryl D-phenylalanine, are
schematically shown in Scheme 1. Specifically, cholesteryl L-
phenylalanine with a primary amine group in its end was
synthesized according to a previous report.47 The compound
(5.34 g, 0.01 mol) was dissolved in 100 mL THF and stirred at
room temperature to make sure its full dissolution. To the
system, 100 mL THF solution of succinic anhydride (1.00 g, 0.01
mol) was added drop-wise. After the addition, the mixture was
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 11
JouPrnleaalsoefdMo antoetraiadljsusCt hmeamrgiisntsry A
View Article Online
DOI: 10.1039/C5TA08342G
Journal Name
ARTICLE
heated and refluxed for 24 h. The reaction was monitored by Characterization of the gel-emulsion
TLC. Then, the mixture was filtered, and the filtrate was
SEM observation of xerogel
evaporated to dryness. The solid as obtained was re-
SEM images of the xerogel were taken on a Quanta 200
scanning electron microscope (Philips-FEI). The accelerating
voltage was 20 kV and the emission current was 10.0 mA. The
xerogel for the measurement was prepared by freezing the gel
formed in the concerned liquid at a measured concentration in
liquid nitrogen, and evaporated by a vacuum pump for 24 h.
Before the examination, the sample was attached to a copper
holder by conductive adhesive tape, and then it was coated
with a thin layer of gold.
crystallized from methanol for two times, and then dried in
vacuum to give a desired product (BuDphe) in 70% yield as
1
white powders. H NMR (CDCl3/Me4Si
È400 MHz, Figure S1) :
√
(ppm) 5.37 (t, alkenyl, 1H), 4.55-4.69 (m, CHCOO, 1H), 3.70-
3.73 (m, oxycyclohexyl, 1H), 2.78-3.12 (m, C6H5CH2, 2H), 0.68-
1.99 (m, cholesteryl protons, 41H). FTIR (Figure S2): 3337 (NH),
2944 (CH), 1730 (C=O.-O), 1540 (NH, bending), 1209 (-C-O).
HRMS (Figure S3): m/z calcd for [M - H+]: 632.4393, found:
632.4331. Elemental analysis, Calc. for (found) C42H65NO5: C
74.80 (75.79); H 9.27 (9.38); N 2.15 (2.21).
Characterization of the monoliths
SEM observation
Gelation test
The diameters of the pores and pore throats of the porous
A weighted amount (0.025 g) of BuDphe and a measured polymeric or hybrid monoliths as prepared were semi-
volume (1 mL) of a chosen liquid were placed into a sealed test quantitatively calculated by using the images taken on a
tube (diameter: 1.2 cm, height: 6 cm ) and the mixture was Quanta 200 Scanning Electron Microscopy spectrometer
oscillated at room temperature for 5 min, then the test tube (Philips-FEI, 15 kV and 10 mA). Prior to observation,
was inversed to observe if a gel had been formed or not. Gels approximately 1 cm3 of each sample was mounted on a sample
obtained after oscillation at room temperature were denoted holder and sputtered with gold for 80 s to ensure sufficient
ꢀ• ^D_ ~Pꢁo•X Lv •}uꢁ ꢂꢀ•ꢁ•U •}oµš]}v ꢀvꢃ •}o]ꢃ-like gel may conductivity. The pore size was also measured through the
coexist within a system. This kind of system was referred to as SEM images using software of Image J. The pore sizes of the
^‰ꢀŒš]ꢀo Pꢁo_ ~tD•X C}Œ •Ç•šꢁu• ]v ÁZ]ꢂZ }voÇ •}oµš]}v Áꢀ• porous materials as created were measured in a literature
Œꢁuꢀ]vꢁꢃU šZꢁÇ ÁꢁŒꢁ ꢃꢁv}šꢁꢃ ꢀ• ^{_ ~•}oµš]}v•X I}ÁꢁÀꢁŒU (}Œ method, that is for each measurement, more than 100 pores
systems in which the gelator could not be dissolved even at were taken into account.48
šZꢁ ꢄ}]o]vP ‰}]vš }( ꢀ o]‹µ]ꢃU šZꢁÇ ÁꢁŒꢁ ꢃꢁ(]vꢁꢃ ꢀ• ^L_ TGA measurements
(insoluble). Similar test was also conducted for mixture
Thermo-gravimetric analysis (TGA) was conducted on a
solvents of water and water immiscible organic liquids. At this
thermal analyser (Q1000 DSC+LNCS+FACS Q600SDT). All the
ꢂꢀ•ꢁU Pꢁo• ÁꢁŒꢁ ꢃꢁv}šꢁꢃ ꢀ• ^D9_U ꢀvꢃ •}oµš]}v• ^9_X
measurements were run at a heating rate of 10
to 800 in oxygen atmosphere.
ꢀ/min from 15
Gel-emulsion preparation
ꢀ
The gel emulsions used in the present studies could be Mechanical measurements
prepared in the way as described below. For a typical system,
Mechanical testing under compression with a CTM 2500
universal testing machine frame, following the testing
procedures specified in ASTM D1621-04a (Standard Test
Method for Compressive Properties of Rigid Cellular Plastics).
The length and diameter of the specimen used for the test are
2.0 cm and 1.0 cm, respectively.
its internal phase or dispersed phase is water, which accounts
80% of the total volume of the gel emulsion to be prepared,
and the remaining is the continuous phase, which contains
nearly 72% of monomer liquids (t-BMA, St or MMA), 25% of
DVB, 2% of the gelator, BuDphe, and 1% of AIBN. To make a
gel emulsion, a given amount of water was added, in a drop-
wise manner, into the organic phase under stirring, and then
the system (a homogeneous emulsion) becomes a gel after a
while at room temperature. For the introduction of silanes,
two different ways were adopted. One is dissolved into the
continuous phase, the oil phase, directly, and the other is
physically dispersed into the dispersed phase, water, since
they are water insoluble.
Hydrophilic and lipophilic tests
The contact angle of the monolith was measured in a routine
way on a Dataphysics OCA20 contact-angle system at ambient
temperature.
Density and total porosity determination
ÇZꢁ ꢄµol ꢃꢁv•]šÇ ~Œ• Áꢀ• ꢃꢁšꢁŒu]vꢁꢃ ꢄÇ ꢂµšš]vP the samples to
an cylindrical shape and subsequently measuring the diameter
(d), thickness(h) and weight (m).
Template preparation of porous polymeric monoliths
k
The gel emulsion as prepared was heated to 40 ºC and
maintained at the temperature for 4 h in an oil bath to start
pre-polymerization, and then the temperature of the bath was
O L
(1)
Ï
.
ꢀ: ; Û
.
The total porosity was calculated using following equation.
raised to 85 ºC and reacted at the temperature for another 12
I FI
t
s
h to complete the polymerization. After polymerization, the
monolith was removed from the reaction vessel, and then
washed with ethanol (50 mL) four times. Finally, the polymeric
monolith was naturally dried at ambient temperature until its
weight became constant.
é
s
F
L
(2)
t
@
è: ; D
t
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Journal of Materials Chemistry A
Page 4 of 11
View Article Online
DOI: 10.1039/C5TA08342G

Page 5 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C5TA08342G

Journal of Materials Chemistry A
Page 6 of 11
View Article Online
DOI: 10.1039/C5TA08342G

Page 7 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C5TA08342G

Journal of Materials Chemistry A
Page 8 of 11
View Article Online
DOI: 10.1039/C5TA08342G

Page 9 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C5TA08342G

Please do not adjust margins
Journal of Materials Chemistry A
Page 10 of 11
View Article Online
DOI: 10.1039/C5TA08342G
ARTICLE
Journal Name
32 Lissant, K. J.; Peace, B. W.; Wu, S. H.; Mayhan, K. G. J.
Colloid Interface Sci. 1974, 47, 416.
33 Chen, Y.; Ballard, N.; Gayet, F.; Bon, S. A. F. Chem.
Commun. 2012, 48, 1117.
Program for Changjiang Scholars and Innovative Research
Team in University (IRT1070).
34 He, H.; Li, W.; Lamson, M.; Zhong, M.; Konkolewicz, D.;
Hui, C. M.; Yaccato, K.; Rappold, T.; Sugar, G.; David, N.
E.; Damodaran, K.; Natesakhawat, S.; Nulwala, H.;
Matyjaszewski, K. Polymer 2014, 55, 385.
35 Cameron, N. R. Polymer 2005, 46, 1439.
36 Esquena, J.; Nestor, J.; Vílchez, A.; Aramaki, K.; Solans,
C. Langmuir 2012, 28, 12334.
37 Nikiforidis, C. V.; Scholten, E. Food Hydrocolloid. 2015,
43, 283.
38 Princen, H. M. J. Colloid Interface Sci. 1983, 91, 160.
39 Dunstan, T. S.; Fletcher, P. D. I.; Mashinchi, S. Langmuir
2011, 28, 339.
40 Chen, X.; Liu, K.; He, P.; Zhang, H.; Fang, Y. Langmuir
2012, 28, 9275.
41 Peng, J.; Xia, H.; Liu, K.; Gao, D.; Yang, M.; Yan, N.; Fang,
Y. J. Colloid Interface Sci. 2009, 336, 780.
42 Mamak, M.; Coombs, N.; Ozin, G. Adv.Mater. 2000, 12,
198.
43 Leventis, N.; Sotiriou-Leventis, C.; Mohite, D. P.;
Larimore, Z. J.; Mang, J. T.; Churu, G.; Lu, H. Chem.
Mater. 2011, 23, 2250.
Notes and references
1
2
Silverstein, M. S. Prog. Polym. Sci. 2014, 39, 199.
Wu, D.; Xu, F.; Sun, B.; Fu, R.; He, H.; Matyjaszewski, K.
Chem. Rev. 2012, 112, 3959.
3
4
5
6
7
8
9
Xing, Y.; Deng, W.; Wang, H.; Gong, C.; Zhang, X.; Jie, J.
J. Nanosci. Nanotechno. 2015, 15, 4450.
aX Yµꢄ_vU tX ~X ꢀX wX /X /}ooꢁct. Czech. Chem. Commun.
1967, 32, 3881.
Peng, J.; Liu, Q.; Xu, Z.; Masliyah, J. Adv. Funct. Mater.
2012, 22, 1732.
Alagha, L.; Wang, S.; Xu, Z.; Masliyah, J. J. Phys. Chem.
C 2011, 115, 15390.
Long, J.; Li, H.; Xu, Z.; Masliyah, J. H. Energ. Fuel. 2011,
25, 701.
Zhu, Q.; Pan, Q.; Liu, F. J. Phys. Chem. C 2011, 115,
17464.
Sayari, A.; Hamoudi, S.; Yang, Y. Chem. Mater. 2005, 17,
212.
10 Gui, X.; Wei, J.; Wang, K.; Cao, A.; Zhu, H.; Jia, Y.; Shu,
Q.; Wu, D. Adv. Mater. 2010, 22, 617.
44 Sadekar, A. G.; Mahadik, S. S.; Bang, A. N.; Larimore, Z.
J.; Wisner, C. A.; Bertino, M. F.; Kalkan, A. K.; Mang, J.
T.; Sotiriou-Leventis, C.; Leventis, N. Chem. Mater.
2011, 24, 26.
45 Brun, N.; Babeau-Garcia, A.; Achard, M.-F.; Sanchez, C.;
Durand, F.; Laurent, G.; Birot, M.; Deleuze, H.; Backov,
R. Energ. Environ. Sci. 2011, 4, 2840.
46 Chen, X.; Wang, X.; Fu, X. Energ. Environ. Sci. 2009, 2,
872.
47 Li, Y.; Liu, K.; Liu, J.; Peng, J.; Feng, X.; Fang, Y. Langmuir
2006, 22, 7016.
48 Wang, J.; Zhang, C.; Du, Z.; Xiang, A.; Li, H. J. Colloid
Interface Sci. 2008, 325, 453.
49 Rajamanickam, R.; Kumari, S.; Kumar, D.; Ghosh, S.;
Kim, J. C.; Tae, G.; Sen Gupta, S.; Kumaraswamy, G.
Chem. Mater. 2014, 26, 5161.
50 Luo, Y.; Wang, A.; Gao, X. Soft Matter 2012, 8, 1824.
51 Zhang, T.; Wu, Y.; Xu, Z.; Guo, Q. Chem. Commun. 2014,
50, 13821.
52 Han, J.; Xie, K.; Du, Z.; Zou, W.; Zhang, C. Carbohydr.
Polym. 2015, 120, 85.
11 Zhao, H.; Nagy, K. L. J. Colloid Interface Sci. 2004, 274,
613.
12 Janout, V.; Myers, S. B.; Register, R. A.; Regen, S. L. J.
Am. Chem. Soc. 2007, 129, 5756.
13 Ono, T.; Sugimoto, T.; Shinkai, S.; Sada, K. Adv. Funct.
Mater. 2008, 18, 3936.
14 Yu, S.; Tan, H.; Wang, J.; Liu, X.; Zhou, K. ACS Appl.
Mater. Inter. 2015, 7, 6745.
15 Wu, Y.; Zhang, T.; Xu, Z.; Guo, Q. J. Mater. Chem. A
2015, 3, 1906.
16 Zhang, Z.; Sèbe, G.; Rentsch, D.; Zimmermann, T.;
Tingaut, P. Chem. Mater. 2014, 26, 2659.
17 Bian, S.; Zheng, J.; Tang, X.; Yi, D.; Wang, Y.; Yang, W.
Chem. Mater. 2015, 27, 1262.
18 Scholz, S.; Lercher, J. A. Chem. Mater. 2011, 23, 2091.
19 Fu, G.D.; Li, G. L.; Neoh, K. G.; Kang, E. T. Prog. Polym.
Sci. 2011, 36, 127.
20 Zhang, X.; Blanchard, G. J. ACS Appl. Mater. Inter. 2015,
7, 6054.
21 Sugihara, Y.; Yamago, S.; Zetterlund, P. B.
Macromolecules
10.1021/acs.macromol.5b00995.
2015,
DOI:
22 Schmidt-Winkel, P.; Glinka, C. J.; Stucky, G. D. Langmuir
2000, 16, 356.
23 Ma, Y.; Liang, J.; Sun, H.; Wu, L.; Dang, Y.; Wu, Y. Chem.
- Eur. J. 2012, 18, 526.
24 Binks, B. P. Adv. Mater. 2002, 14, 1824.
25 Binks, B. P.; Clint, J. H.; Whitby, C. P. Langmuir 2005, 21,
5307.
26 Boker, A.; Lin, Y.; Chiapperini, K.; Horowitz, R.;
Thompson, M.; Carreon, V.; Xu, T.; Abetz, C.; Skaff, H.;
Dinsmore, A. D.; Emrick, T.; Russell, T. P. Nat. Mater.
2004, 3, 302.
27 Stenzel, M. H.; Barner-Kowollik, C.; Davis, T. P. J. Polym.
Sci., Part A: Polym. Chem. 2006, 44, 2363.
28 Chen, X.; Liu, L.; Liu, K.; Miao, Q.; Fang, Y. J. Mater.
Chem. A 2014, 2, 10081.
29 Jing, P.; Fang, X.; Yan, J.; Guo, J.; Fang, Y. J. Mater.
Chem. A 2013, 1, 10135.
30 Miao, Q.; Chen, X.; Liu, L.; Peng, J.; Fang, Y. Langmuir
2014, 30, 13680.
31 Lissant, K. J. J. Colloid Interface Sci. 1966, 22, 409.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C5TA08342G