Materials Chemistry and Physics 144 (2014) 213e225

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Materials Chemistry and Physics

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

Review

Design, preparation, and application of ordered porous polymer

materials
Qingquan Liu*, Zhe Tang, Baoli Ou, Lihua Liu, Zhihua Zhou*, Shaohua Shen, Yinxiang Duan
School of Chemistry and Chemical Engineering, Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education,
Hunan University of Science and Technology, Xiangtan 411201, China

h i g h l i g h t s

Breath gures involve polymer casting under moist ambience.

Hard template employs monodisperse colloidal spheres as a template.

Soft template utilizes the etched block in copolymers as template.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 10 August 2013
Received in revised form
6 January 2014
Accepted 10 January 2014

Ordered porous polymer (OPP) materials have extensively application prospects in the eld of separation
and purication, biomembrane, solid supports for sensors catalysts, scaffolds for tissue engineering,
photonic band gap materials owing to ordered pore arrays, uniform and tunable pore size, high specic
surface area, great adsorption capacity, and light weight. The present paper reviewed the preparation
techniques of OPP materials like breath gures, hard template, and soft template. Finally, the applications
of OPP materials in the eld of separation, sensors, and biomedicine are introduced, respectively.
2014 Elsevier B.V. All rights reserved.

Keywords:
Microporous materials
Polymers
Etching
Adsorption
Microstructure

1. Introduction
Ordered porous materials, which were developed rapidly in
1990s, are a kind of materials with ordered nano-structure. Emergence of ordered porous materials attracted a great deal of attention from the eld of physics, chemistry, and materials, at the same
time, ordered porous materials developed rapidly into one hot
research focus [1]. Generally, ordered porous materials can be
classied into ordered porous inorganic (OPI) materials and ordered porous polymer (OPP) materials. The preparation and
application of OPI materials are becoming mature, whereas OPP
materials still have huge development space in the preparation
techniques and application elds.
OPP materials have a series of advantages like light weight, ordered alignment of pores, high specic surface area, great adsorption capacity, uniform pore size, and tunable pore size, and this

* Corresponding authors. Fax: 86 731 5829 0045.

E-mail addresses: qqliu@hnust.edu.cn (Q. Liu), zhou7381@126.com (Z. Zhou).
0254-0584/$ e see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matchemphys.2014.01.013

type of materials have great application prospects in the eld of

biomedicine [2e4], biological lm [5,6], bioreactor [7], adsorption
[8,9], catalyst supports [10,11], separation [12,13], and growth
templates of nanomaterials with specic shapes [14]. Therefore,
preparation and application of OPP materials have has drawn much
interest of researchers and scientists in the eld of polymer materials. Up to now, OPP materials can be classied into two types:
OPP membrane and OPP monoliths. The term monolith refers to
unibody structures composed of interconnected repeating cells or
channels [15]. Since Nakahama et al. rstly prepared ordered
porous polystyrene (PS) membranes via microphase separation of
polystyrene-b-polyisoprene and ozonolysis, the last two decades
have witnessed the great progress of OPP membrane in the synthetic routes, and in selective separation and photonic application
[16].
The development of etching techniques made the preparation of
OPP monoliths with thickness of a few millimeters possible.
Compared to traditional polymer materials with continuous pore
size distribution, OPP monoliths have uniform pores with large
aspect ratio. Buchmeiser think this type of materials possess

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Fig. 1. Sequence of images depicting the growth and aggregation of water droplets near the surface of an evaporating polymer solution. The time interval between frames 1 and 5 is
50 s [22].

enormous potential as advanced materials for many high-tech

application such as microelectrophoresis, bioseparation, and
bioreactor [17]. Hillmyer et al. suggest that OPP monoliths have two
special advantages in the template synthesis [18]. One is the
preparation of nanomaterials with large aspect ratio (>104); and
the other is that functional groups left on the pore wall during
etching block copolymers can meet special template synthesis.
Moreover, the functional groups can be transferred into the other
groups, which further widen the application eld of OPP monoliths.
The present review attempts to introduce the preparation routes of
OPP membrane and monoliths in the next sections. The application

of OPP membrane and monoliths is also covered in the third section. Finally, a short summary and prospect on the eld of OPP
materials is provided at the end of this review.
2. Preparation techniques
2.1. Breath gures
Breath Figures derived from almost 100 years ago had not drawn
extensive attention until Widawski et al. [19] applied this method
to prepare porous polystyrene-b-polyparaphenylene lm with

Fig. 2. SEM images of ordered PS-b-PDMAEMA membrane with through-pores. (a) Top, (b) bottom, and (c) cross section. (d) The membrane transferred onto a piece of dense
nanober mesh [27].

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215

Fig. 3. Ferrocenyl-based oligomer lms prepared from CS2/toluene solution. (a) SEM of the top surface, (b) partial enlargement of pore arrays. AFM images: (c) top view, (d) 3D
image [30].

uniform pore size. This method involves polymer casting from solution under moist ambience. With the solvent evaporation, cooling
of the solution surface enables gaseous water condensation and
growth. Meanwhile, the water droplets spontaneous form hexagonal arrays on the surface and embed into the polymer. After
complete evaporation of both solvent and water, the imprint of
water droplets is left on the polymer matrix and polymer lms with
2D [20] or even 3D [21] ordered pore arrays are produced. This
method appears extremely attractive since it allows the generation
of porous polymer lms with tunable pore size, which have potential application in biology, chemistry and technology.
Size and order of pores depended on the size and order of water
droplets formed by moist air ow. Therefore, many scientists made
efforts to investigate the mechanism and process of water droplet
formation [22e24]. Barrow et al. [22] observed the process of
droplets formation on the surface of polymer solution via high
speed microphotographic apparatus, as shown in Fig. 1. Number
and size of water droplets on the solution surface increased with
increasing exposure time to a humid atmosphere. Finally, vapor
condensation produced near mono-disperse water droplets which
formed a close-packed monolayer. Pitois and Francois [23,24]

observed the formation process of water droplets by lightscattering experiments, and they found that the evolution with
time of the mean droplet radius by a power law with an exponent of
1/3. They thought polymer precipitated at the interface of water
droplets and solution, and water droplets behaved like solid
particles.
Breath-gure strongly depends on the interfacial forces existing
between the water droplets and the polymer solution, and the
forces can be modulated by inserting polar groups in the polymer.
Park et al. [25] reported the fabrication of PS lm with hierarchically ordered porous structure by breath gures. The hierarchical ordering of aqueous droplets on polymer solution is realized by
the imposition of physical connement via various shaped gratings.
The authors found that ordered structure can be tuned by dissolving a bit of surfactant in the polymer solution. Hill group [26]
fabricated poly(1,8-diamino-naphthalene) macroporous lms
with regular pores by breath gures, and the pore diameters could
be controlled from 0.2 to 1 mm. An amphiphilic block copolymer,
polystyrene-b-poly (N,N-dimethylaminoethyl methacrylate) (PS-bPDMAEMA), was synthesized by Wan group [27] via atom-transfer
radical polymerization. Ordered porous membranes with thickness

Fig. 4. SEM images of honeycomb lms. (a) After crosslinking for 30 min. (b) Cross sectional view after heating to 200  C. (c) After heating to 320  C. Scale bars are 5 mm [7].

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Fig. 5. SEM images of macroporous PS lms, formed by SiO2 colloidal crystal template
[46].

of about 2 mm was prepared by casting the copolymer solution at an

air/ice interface, and SEM images of porous membrane were shown
in Fig. 2. They found that the pores were of through structure, and
the pore diameter of the membrane could be easily regulated in the
range of 1e5 mm by changing humid air ow speed and the solution
concentration.
The pore channels derived from droplet imprint could be
decorated by functional group terminated polymer or adding other
functional materials. Amphiphilic ferrocenyl-based oligomer molecules played a crucial role in stabilizing the template of water
droplets, and the surface morphology of the lms could be easily
modulated by changing solvent properties, oligomer concentration,
and evaporation time. Amino-modied pore could be generated by
mixing PS and amino-terminated PS via breath gure route [28].
Due to its hydrophilic property, the amino group was oriented towards the water droplet during the formation of breath gure. In
fact, amino-terminated PS acted as a surfactant and could reduced
the interface tension between water droplets and PS. Consequently,
hydrophilic group terminated polymer could increase the contact
surface of water droplets and polymer matrix, and decrease the size
of water droplets. Wu et al. [29] employed a surfactant-encapsulated polyoxometalate complex (SEC-1) to functionalize the pore
channels of PS lms by doping SEC-1 into PS solution. They found
that during the self-organization of water droplets, amphiphilic
SEC-1 self-assembled at the interface of PS solution and water
droplets. Moreover, SEC-1 could play a role in stabilizing the water
droplets and improving the order of the pore channels. The excellent work reported by Hao et al. [30] described the preparation of
amphiphilic ferrocenyl-based oligomer lms with ordered 2D
porous structures via breath gures, and SEM images of the products are shown in Fig. 3.

Honeycomb-structured polymer lms have received increasing

interest for their potential applications in articial membranes and
templates for nanomaterial growth. These lms were usually made
from polymers, organic/inorganic hybrid complexes. At present,
various copolymers were applied to prepare honeycomb-pattern
lms by breath gures [31]. Yan et al. [32] synthesized hyperbranched
poly(3-ethyl-3-oxetanemethanol)-star-polystyrene
(HBPO-star-PS) by reversible addition fragmentation chain transfer,
and they prepared honeycomb-pattern PS lms with the hyperbranched copolymers via breath gure route. They found that the
pore sizes could be controlled easily by changing the casting volume of the solution, the molecular weight and concentration of the
polymer, and so on. By means of atom transfer radical polymerization (ATRP), Wan et al. [33] synthesized well-dened and comblike structures copolymers of poly(styrene-co-2-(2-3-4-6-tetra-Oacetyl-b-d-glucosyloxy) ethyl methacrylate), which were used as
precursors for the fabrication of bioactive honeycomb-patterned
lms by breath gure method. The pore size and regularity of the
bioactive lms were affected by the polymer structure and the
casting solution concentration. Similarly, highly ordered honeycomb microstructured lms were also generated by activating
2,2,6,6-tetramethyl-1-piperidinyloxyl-terminated PS with p-toluenesulfonic acid in the presence of humidity atmosphere, and ptoluenesulfonic acid played a key role in the preparation of honeycomb lms due to its strong polarity by breath gures [34].
However, it should be noted that porous lms derived from linear
polymer have a poor thermal stability due to low glass transition
temperature. Therefore, improving thermal stability of porous
polymer lms is an urgent research project for scientists. For
instance, Kabuto [7] fabricated mesoporous honeycomb-structured
lms with poly(styrene-co-maleic anhydride) by breath gures.
Chemical crosslinking were achieved by immersing the lms into
an ethanol solution with alkyldiamine. SEM images of crosslinked
mesoporous honeycomb lms were shown in Fig. 4. The authors
found that non-crosslinked lms exhibited hydrophobic property,
and crosslinked lms became hydrophilic. Furthermore, in comparison with non-crosslinked lms, the thermal stability of the
crosslinked lms had an increase of 150 K. The evaporation of
solvent during breath gure could be accelerated by lower pressure. For example, Zhang et al. [35] investigated the effect of vacuum degree on the pore size of the lms, and found that the pore
size could be tuned from 5.6 to 17.1 mm by changing the vacuum
level.
When OPP lms are fabricated by breath gures in the humid
environment, water vapor condense and orderly arrange in the
solution surface. Therefore, amphiphilic property of lm-forming
polymer play a key role in stabilizing water droplets, and tuning
pore size and order degree of pore alignment. As for amphiphilic
block copolymer, the molecular weight of hydrophilic and hydrophobic block also have signicant inuence on the pore size and
shape. For block copolymer of polyethylene oxide-b-polyuorooctylmethacrylate (PEO-b-PFOMA), the small molecular
weight of hydrophobic PFOMA block can accelerate the process of
water vapor condensing, consequently, the pore size of PEO-bPFOMA lms can be effectively tuned by changing the molecular
weight of PFOMA block [36].
Solvent type of block copolymer is also important for successful
generation of OPP lms by breath gures [26,35,37]. In general, the
solvent is immiscible with water, and has a low boiling temperature
and high vapor pressure. The size of water droplets depends on the
volatilization rate of solvent. Too high volatilization rate induces
small water droplets and pore size due to a short condensation
time, which maybe result in unstable pore structure. Too slow
volatilization rate may give rise to aggregation of water droplets
and decrease of order degree of pore alignment. Therefore, organic

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217

Fig. 6. SEM images of porous PDMS lms derived from PS sphere template prepared via heat treatment at 90  C for (a) 3 h, (b) 12 h, (c) 24 h, and (d) 36 h [54].

solvents with suitable volatilization rate such as carbon bisulde,

chloroform, and THF are usually employed in breath gures [26,35].
Moisture in environment is benecial to form water droplet and
solvent volatilization. Generally, the relative humidity reported by
various literature is about 50e90%. It is difcult to form OPP lm in
the environment with too low relative humidity, and too high
relative humidity often results in adhesion of water droplets and
disordered porous lms [38,39].
In addition, suitable solution concentration is also a key factor
for the preparation of OPP lms. High solution concentration will
decrease the embedding depth of water droplets on the solution
surface, and low concentration is unfavorable to obtain the lms
with good pore shape [40,41]. Overall, therefore, amphiphilic
property of lm-forming materials, environmental temperature
and humidity, solvent type, and solution concentration have

signicant inuences on the pore size, pore size distribution, pore

shape, and the order degree of pore alignment.

2.2. Hard template

This technique is also named as direct template, which employs
monodisperse particles as sacricial materials to prepare OPP materials. The preparation of OPP materials by hard template includes
three steps. Firstly, the monomer with initiator inltrates into the
voids of monodisperse particles. Secondly, the monomer is initiated
and situ polymerized. Thirdly, OPP materials can be obtained by
removal of the template. Generally, monodisperse silica colloidal
particles or PS particles are used as the sacricial materials [42e
45].

Fig. 7. Schematic illustration for the fabrication of porous polyimide lms with ordered surface using SiO2 particles as template [56].

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Fig. 8. High-resolution SEM of porous PS membrane by using UV degradation of PMMA [71].

Johnson group [42] utilized monodisperse SiO2 particles as a

template to prepare ordered mesoporous materials for the rst
time. They lled the voids between silica particles with divinylbenzene (DVB) and ethylene glycol dimethyl acrylate (EDMA). After
copolymerization, the silica particles were dissolved by HF, and
obtained 3D ordered porous cross-linked PDVB-b-PEDMA materials
with tunable pore size in the range of 15e35 nm [42]. The similar
process was applied by Colvin et al., who prepared ordered macroporous PS, polyurethane, and poly(methyl methacrylate)
(PMMA) membranes with thickness ranging from 0.5 to 50 mm by

using monodisperse silica particles as a templates [46]. The pore

size could be controlled in the range of 200e400 nm by varying the
polymerization temperature. The membranes exhibited striking
optical properties due to the periodic arrangement of pores in the
polymer matrix. Fig. 5 shows the ordered macroporous PS membrane. Moreover, there are many other reports that OPP materials
were also generated with monodisperse silica particles as templates [47e50].
In comparison with silica particles, there are fewer reports about
employing monodisperse PS particles as a template to prepare OPP

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219

Fig. 9. SEM images of ordered porous PS monoliths. (a) View perpendicular to the cylinder axes. (b) View perpendicular to the cylinder axes. (c) View parallel to the cylinder axes
[74].

Fig. 10. Preparation of functional nanoporous monoliths from triblock copolymer precursors [78].

materials. With PS particles as a template, Caruso et al. fabricated

3D ordered porous polyaniline lattice with excellently electrical
properties, magnetic properties and optical properties. The preparation process included four steps. Firstly, monodisperse PS particles with a diameter of 640 nm assembled into a 3D ordered
structure; secondly, solution of aniline and potassium peroxodisulfate inltrated into the voids in PS particles; thirdly, aniline

was situ polymerized; nally, PS particles were decomposed and

removed by tetrahydrofuran to obtain ordered porous polyaniline
lattice [51]. The preparation conditions of ordered porous polyaniline by hard template were furthermore investigated by Martin
group [52] and Jackowska group [53]. The excellent work by Zhang
et al. introduced the preparation of ordered porous poly(dimethylsiloxane) (PDMS) membranes with monodisperse PS

Fig. 11. FESEM micrographs of PS monoliths with ordered helical channels: (a) parallel to the helical axes and (b) perpendicular to the helical axes [79].

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Q. Liu et al. / Materials Chemistry and Physics 144 (2014) 213e225

Fig. 12. Pathway to nanostructured materials: (a) diblock copolymer, (b) polygranular cylindrical morphology, (c) macroscopically aligned cylindrical morphology, (d) nanoporous
template, (e) and (f) preparation of nanowires and nanoparticles within the template, respectively, and (g) and (h) nanostructured materials [87].

template, and SEM images of ordered porous PDMS were shown in

Fig. 6. Interestingly, the pore size can be tuned just by changing the
temperature and the time of heat treatment [54].
Hard template in combination with self-assembly can also be
employed to prepare OPP materials or composites. Wang et al. [55]
rstly blended poly(amic acid) (PAA) and monodisperse silica
particles in DMF solution. Then the solution was dried under vacuum to obtain PAA/silica composite lm with well-ordered surface
structure based on situ self-assembly of PAA. The produced PAA/
silica lms were thermally treated to convert PAA to polyimide.
Finally, porous polyimide lms with ordered porous structure were
obtained by etching silica particles with hydrouoric acid solution,
as shown in Fig. 7. Zhao group [56] prepared hierarchically ordered
macro-/mesoporous carbons with silica particles as a hard template, triblock copolymer PEO-PPO-PEO as a soft template, and
soluble resols as a carbon source. The procedure included packing
and aging of monodisperse silica particles, evaporation-induced

self-assembly of mesostructures in the void of silica particles,

thermosetting and carbonization of phenolic formaldehyde, and
removal of silica scaffolds by HF. The nal products had a highly
ordered face-centered cubic macrostructure with tunable pore diameters of 230e430 nm and interconnected windows with a size of
30e65 nm.
In general, when hard template was used for the preparation of
OPP materials, uniform silica and PS particles can be removed by HF
and THF, respectively. Hard template has some advantages such as
simple process, low cost, and the generation of membranes with
high ordered pore structure. However, hard template has some
shortcomings, which is difcult to be overcome at present. Firstly,
the template particles have to be treated until they have highly
uniform sizes. Secondly, the sizes of template particles are xed,
and this leads to difcultly tune the pore sizes of porous materials.
Finally, the removal of the template particles is not a simple work,
and easily results in some structure defects in the porous materials.

Fig. 13. Schematic illustration of generating well-dened helical nanocomposites (left). FESEM micrograph of SiO2 nanohelices after the degradation of the PS template (right) [98].

Q. Liu et al. / Materials Chemistry and Physics 144 (2014) 213e225

2.3. Soft template

Soft template is that after amphiphilic block copolymers form
periodically ordered structure via microphase separation, OPP
materials can be obtained by etching or dissolving a block of the
copolymers [57,58]. Microphase separation of amphiphilic copolymers can form ve types of periodically ordered structures, but
only ordered cylindrical, double gyriod, and helical morphology
have received tremendous interests. At present, UV degradation
[59,60], ozonolysis [61,62], chemical etching [63] and reactive ion
etching (RIE) [64] have been used for removing the etchable block
of copolymers.
In 1988, Nakahama et al. [62] rstly prepared ordered porous PS
membranes via soft template. Firstly, they synthesized block
copolymer of polyisoprene-b-poly[(4-vinylpheny1)dimethyl-propoxysilae] via anionic copolymerization; secondly, the block of poly
[(4-vinylpheny1)dimethyl-propoxysilae] was crosslinked in a HCl
aqueous solution at room temperature; nally, the block of polyisoprene was degraded by ozonolysis, and OPP membranes were
produced. After that, the subsequent 30 years have witnessed the
huge development of the preparation of OPP material prepared by
soft template.
PS-b-PMMA copolymer can also form ordered cylindrical
structure by microphase separation, as shown in the schematic
diagram of Fig. 11. In this copolymer, PMMA is an etchable block and
form dispersed phase with cylindrical shape, and PS form continuous phase. The thin PS lm with cylindrical PMMA was exposed to
the ozone at room temperature. The ozone-treated lms were
annealed at 170  C for 4 h above the glass-transition temperature of
both PS and PMMA, and ordered porous PS membranes were
generated [65]. Moreover, exposure of PS-PMMA lms to UV radiation, which not only decompose cylindrical PMMA and but also
crosslink continuous PS block, can also fabricate PS lms with ordered cylindrical nanopores [18,66e72]. SEM images of ordered
porous PS-PMMA lms made by this method are shown in Fig. 8.
Hillmyer group has made many excellent works in the eld of
OPP monoliths. They synthesized macroinitiator of hydroxylterminated PS (PSOH) via living anionic polymerization of styrene
and ethylene oxide. The macroinitiator of PSOH was then used in
the ring-opening polymerization of D,L-lactide to obtain PS-b-PLA
diblock copolymers with narrow molecular weight distributions.
PS-b-PLA copolymers formed hexagonally packed nano-cylinders
of PLA in PS matrix via self-assembly in combination with reciprocating shear. Ordered nanoporous PS monoliths were obtained by
removal of PLA block. SEM images of ordered nanoporous PS
monoliths were shown in Fig. 9. Furthermore, the pore size and
spacing could be modied through tuning molecular weight of PLA
block or blending PS-b-PLA with PS [73,74]. Following this technical
routes, poly(cyclohexylethylene) (PCHE) [75] and polyisoprene (PI)
[76] monoliths with ordered nanoporous channels were prepared
from PCHE-b-PLA and polyisoprene-b-polydimethylsiloxane
(PDMS) diblock copolymers, respectively. The aligned cylinders of
PLA block in PCHE and PDMS block in PI were removed by basic
solution and tetrabutylammonium uoride, respectively. In comparison with ordered porous PS monoliths, PCHE and crosslinked PI
monoliths with ordered nanoporous channels had a better thermal
stability or higher softening temperature, which widened the
application range of ordered nanoporous polymer monoliths.
Triblock copolymers could be employed for the preparation of
OPP monoliths with more advanced architectures. Hillymer et al.
[77] synthesized PS-b-PDMA-b-PLA (PDMA: polydimethylacrylamide) triblock copolymers by a combination of controlled
ring-opening and free-radical polymerization techniques. A nanoporous PS matrix with a hexagonally packed array of hydrophilic,
PDMA-coated channels was generated by assembling into a coree

221

shell cylindrical structure, aligning into hexagonally packed nanocylinder structure, and etching PLA nanocylinders. The preparation
route was presented in Fig. 10. The internal surface chemistry could
be easily tailored since PDMA block inside the pores were hydrolyzed in a controlled method to introduce a desired number of
carboxylic acid substituents to pore wall. The tunable surface
chemistry of ordered nanoporous monoliths was very important
for template growth of different nanomaterials with specic size
and shape. Recently, this research group [78] synthesized polylactide-b-poly(styrene-co-2-hydroxyethylmethacrylate) (PLA-b-P(Sco-HEMA))
and
polylactide-b-poly(styrene-co-2hydroxyethylacrylate) (PLA-b-P(S-co-HEA)) by combination of
ring-open polymerization and RAFT polymerization. The copolymers were reacted with 4,40 -methylenebis(phenyl isocyanate)
(MDI) to form the corresponding cross-linked materials. Then,
cross-linked ordered nanoporous monoliths with different morphologies like lamellae, hexagonally packed cylinders, and hexagonally perforated lamellar were obtained from the cross-linked
polymers by removal of PLA phase.
Recently, Ho group has made some interesting works on the
preparation of polymer monolith with ordered helical channels.
Monoliths containing ordered nanoporous channels with specic
shape were also produced in the last decade. Ho et al. [79,80]
synthesized a chiral block copolymer of polystyrene-b-poly(L-lactide) (PS-PLLA) by a two-step living polymerization. Self-assembly
of the block copolymer formed a novel helical phase, which was
attributed to the contribution of chiral entity. PS monoliths with
ordered helical channels could be produced by hydrolysis of PLLA
block, and SEM pictures are given in Fig. 11. The ordered helical
channels were parallel to the helical axes in the PS monoliths.
Polystyrene-b-poly(ethylene oxide) (PS-b-PEO) is also an
excellent materials to prepare OPP materials by soft template.
Zhang et al. [81] introduced a cleavable trityl ether juncture between PS and PEO blocks. The solvent-annealing of PS-b-PEO copolymers led to highly ordered arrays of PEO cylinders oriented
normal to the lm surface. The trityl ether juncture between PS and
PEO was cloven by treatment of ordered thin lms in triuoroacetic
acid vapor, and the cloven PEO block was selective removed by
washing with methanol. They also proposed that the fabricated
ordered porous PS lms could be stabilized by introducing PS homopolymer with high molecular weight into the copolymers or
crosslinking the PS matrix. Mao et al. [82] described the preparation process of PS monoliths with ordered nanoporous channels by
means of microphase separation of PEO-b-PS. After PEO formed
ordered cylindrical structure, the copolymers were immersed in
aqueous HI solution at 60  C for about several days to remove PEO
block, and PS monoliths with ordered nanoporous channels were
generated. The similar works were also completed by Wei group
[83] and Zhu group [84]. In addition, other copolymers such as
polystyrene-b-polydimethylsiloxane (PS-b-PDMS) [85], polystyrene-b-polybutadiene (PS-b-PB) [86], and polystyrene-b-polyisoprene (PS-b-PI) [88] were also reported as precursor copolymers
to prepare ordered nanoporous polymer materials by soft template.
Up to now, a large number of amphiphilic bi- or tri-block copolymers have been successfully synthesized by scientists. Thus it
can be seen that soft template exhibits excellent exibility and
development prospects in the preparation of OPP materials. This
method can not only control the pore size within the range of 5e
100 nm, and but also realize the functionalization of ordered
nanoporous polymer materials. The key of soft template is to
reasonably design the etchable block of the amphiphilic copolymers, precisely regulate the molecular weight of each block,
and select suitable routes to introduce functional groups onto the
pore wall. However, at present, there are still two drawbacks for
soft template. One is the materials derived from soft template has

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Q. Liu et al. / Materials Chemistry and Physics 144 (2014) 213e225

Fig. 14. Schematic diagrams for producing nanoporous gyroid Ni by PS templates. (a) PS-b-PLLA with gyroid morphology; (b)Nanoporous PS template with gyroid morphology; (c)
PS/Ni gyroid nanohybrids; (d) Nanoporous gyroid Ni [102].

poor heat-resistance. The ordered nanoporous channels deform or

disappear when the temperature exceeds Tg of the materials [74].
The other is poor solvent-resistance of the materials, which is easy
to be dissolved or swollen in organic solvent [88].
Ordered porous carbon is a promising material in the eld of
membrane ltration technologies like nanoltration and ultraltration. Ordered porous carbon is often derived from porous
phenolic resin, which is also generated by soft template. For
example, triblock copolymer PEOePPOePEO [89] and diblock
copolymer PS-P4VP [90] are widely used as soft templates to prepare ordered porous phenolic resins. Recently, our research group
has synthesized the copolymer of poly(vinylbenzyl chloride)-bpolylactide (PVBC-b-PLA) via TEMPO living radical and open-ring
polymerization [91].
3. Application
OPP materials have high specic surface area and more than 100
million of ordered nanoporous channels in a square centimeter.
Thus this type of materials has nd extensive application elds
such as growth template for nanomaterials with large aspect ratio
or special shapes, selective adsorption and separation, and biological applications [13].
3.1. Template for nanomaterials growth
Template synthesis is a powerful method for the preparation of
nanoscale materials with specic size and shape. OPP monoliths
have uniform nanopores with large aspect ratio. Therefore, this
type of materials has particular advantage in the preparation of
nanomaterials with specic size and shape. Hillmyer research
group [87] has successfully employed ordered nanoporous PCHE
monoliths as templates for the preparation of polypyrrole nanowires and CdS nanoparticles. The nanowires and nanoparticles
were shown to have dimensions that corresponded to the size of
the nanoporous structure in PCHE monoliths (Fig. 12). Moreover,
the size of the nanowires and nanoparticles could be tunable by
using PCHE monoliths with different pore dimensions. The research

group also investigated crystal growth manipulation of organic

compound in monoliths with ordered nanoporous channels [92].
For example, they used ordered nanoporous PCHE monoliths as
templates for polymorph selectivity growth of anthranilic acid (AA)
and 5-methyl-2-[(2-nitrophyenyl)amino]-3-thiophenecarbonitrile
(ROY), and found that crystal nucleation and polymorph selectivity were inuenced by connement in nanometer scale pores,
most likely due to critical size constraints [93].
Inorganic helical nanostructures have drawn intense attention because of their application in photonic crystals [94],
alignment lms for liquid crystal displays [95]. Helical nanostructures have successfully prepared via a variety of routes like
chemical vapor deposition [96], self-assembly of inorganic precursors in combination with achiral surfactant under nanoconnement [97], and so on. OPP monoliths could be also used
for the preparation of helical inorganic structures. Ho et al. [98]
rstly produced PS with helical nano-channels from the selfassembly of PS-PLLA after removal of PLLA, and then used as
template for the preparation of three-dimensional ordered helical PS/SiO2 nanocomposites via solegel process, as illustrated in
Fig. 13 (left). Moreover, well-dened SiO2 nanohelices (Fig. 13
right) could be generated after the degradation of the PS template, which was carried out under atmosphere condition with a
UV source. The domain size of SiO2 nano-helices suggested that
the nanohelical texture from PS.
The gyroid is one of the most appealing morphologies for
practical application because of its unique structure with two
continuous networks in 3D space [99]. Polymer monoliths with
ordered gyroid channels could be obtained from self-assembly of
block copolymers and removal of degradable minor phase. The
gyroid channels in polymer monoliths could be used as a nanoreactor for electrochemical deposition [100] and solegel processes [101]. Therefore, polymer monoliths with ordered gyroid
channels have potential application in the eld of growth template of nanomaterials with gyroid structure. Recently, wellordered nanoporous gyroid nickel was prepared from PS template with gyroid channels via electroless plating [102], as illustrated in Fig. 14. Firstly, PS template with gyroid channels

Q. Liu et al. / Materials Chemistry and Physics 144 (2014) 213e225

223

Fig. 15. Schematic illustration of gyroid network replication from block copolymer templates and assembly of hybrid solar cells: (a) PFS-b-PLA with gyroid morphology; (b) PFS
template with gyroid morphology; (c) Freestanding gyroid network array; (d) bicontinuous bulk heterojunction solar cell architecture [103].

(Fig. 14(b)) was derived from self-assembly of PS-PLLA block copolymers and selective degradation of PLLA phase. Secondly,
gyroid-forming nanohybrids with bicontinuous nickel networks
(Fig. 14(c)) were generated by electroless plating of Ni via autocatalytic reduction process. Finally, free-standing, nanoporous
gyroid nickel (Fig. 14(d)) was successfully produced by dissolving
PS matrix in tetrahydrofuran.
Steiner et al. [103] utilized microphase separation of poly(4uorostyrene)-b-poly(D,L-lactide) (PFS-b-PLA) to form gyroid
structure (Fig. 15(a)), and selectively etched PLA phase to obtain
PFS gyroid template (Fig. 15(b)). The replication of anatase TiO2
in the gyroid network was conducted by anodic oxidative hydrolysis of aqueous TiCl3 in a standard three-electrode electrochemical cell. The TiO2/PFS nanocomposites were annealed at
500  C for 2 h under argon followed by 1 h under oxygen, which
resulted in complete degradation of PFS template and the
simultaneous crystallization of anatase TiO2 (Fig. 15(c)). Freestanding TiO2 gyroid array was back-lled with a solid state
hole transporting materials and capped with a suitable counter
electrode (Fig. 15(d)). The prepared bicontinuous double gyroid
hybrid solar cell exhibited up to 1.7% power conversion
efciency.

3.2. Separation
Xu et al. [27,33] demonstrated that ordered porous PS-bPDMAEMA membrane exhibited high preciseness in the separation
of PS microspheres with close size. Furthermore, the membranes
only required ultralow operation pressure, enabling an energysaving separation process. The magnetic OPP materials can be
considered as magnetic separation materials. Magnetic polymer
lms can be produced by combining lm-forming polymers and
paramagnetic nanomaterials [104]. Fuertes et al. [105] fabricated
OPP polymers with superparamagnetic nanoparticles dispersed in
the matrix, and they demonstrated that this type of materials could
be successfully used as magnetically separable adsorbents. OPP
membranes prepared by Wang et al. [106] exhibited tunable ux
and retention within a relatively wide window. Moreover, the OPP
membranes were able to completely remove 10 nm gold nanoparticles from a mixture containing 2 nm gold particles, which
indicated the membranes having sharp size-discriminating property. Fustin et al. [107] prepared ordered nanoporous polymer
membranes via blending a block copolymer of PS-b-PEO with homopolymer of PAA. The permeability of the membranes could be
readily tuned by removal of PAA from the blending polymer, and

224

Q. Liu et al. / Materials Chemistry and Physics 144 (2014) 213e225

this process provided very interesting opportunities with respect to

ltrations. With increasing the removal amount of PAA, the methanol uxes of the membranes signicantly increased, and this fact
offered a simply way to generate OPP membranes with tunable
permeation properties, enabling an increase of the permeability
while have no obvious effect on its selectivity.
3.3. Sensor
Due to excellent adsorption capacity, OPP materials also can be
applied as a sensor like wet sensors [108]. Sitti et al. [109] designed
a complaint and low-cost nanosensor by means of OPP membranes.
The nanosensor contains a pair of interdigitated electrodes, which
were deposited on the surface of OPP membranes. The resistance
and capacitance between these electrodes varied at different humidity levels, and had a very high sensitivity due to the water
adsorption inside the nano-pores. This sensor can nd application
elds such as in-situ water leakage detection. Alexander et al. [110]
investigated the optical chemistry sensor properties of OPP materials, and demonstrated that OPP materials can construct an
effective platform for optical chemistry sensor. Cartwright et al.
[111,112] prepared multi-functional holographical OPP gratings
with high reection efciency coupled with a tunable wide
reection bandwidth. They employed the OPP gratings as a general
template for the encapsulation of recognition elements, and
developed an O2 sensor by encapsulating the uorophore ruthenium(II) within these nanostructured materials. The O2 sensors
displayed a full detection range from 0 to 100% oxygen concentration, and exhibited stable, repeatable and reversible performance with a fast response time.
4. Summary and perspective
In the present review, we have attempted to give a comprehensive overview about the preparation methods and application
elds of OPP materials. Among the three preparation methods,
breath gures have exhibited excellent adaptability and diversity in
the preparation of polymer membranes with ordered nonporous
channels. Hard template has good convenience and manipulation
in the generation of 2D and 3D OPP materials. Soft template is
suitable to prepare functional polymer membranes or monoliths
with ordered nanoporous channels, and displays excellent exibility and huge development prospects. However, these methods
also have their own drawbacks, which limit the application range of
the materials derived from these methods. Therefore, it is signicantly important to design block copolymers and the sacricial
material, and adopt suitable preparation process according the
need of practical applications.
In comparison to inorganic or metal materials with ordered
nanoporous channels, OPP materials have exhibited many special
functions and superiorities like light weight and simple preparation
process, etc. Although huge development in the preparation and
application of the materials has been made in recently years, there
are still some synthetic routes that need to be further explored. The
following two research areas maybe will attract the interest of
scientists. The rst is that more triblock copolymers will be
explored to produce OPP materials. Amphiphilic triblock copolymers will generate more interesting and complicated ordered
structure by microphase separation. In the triblock copolymers, the
rst block can serve as a matrix of OPP materials, and the second
block can be etched to form nanopores. The third block can be
designed to a source providing functionality. Therefore, triblock
copolymers can provide a potential and feasible route to endow
OPP materials with various functional groups. The second is that
OPP materials with better heat and solvent resistance and

mechanism properties will be targeted. In order to widen the

application elds of OPP materials, excellent heat and solvent
resistance are the key requirement for OPP materials. At present,
the strategy of crosslinking matrix seems to be a good choice to
improve these properties. However, crosslinking will increase the
fragility and the insolubility of the matrix, and solubility is a crucial
factor for the application of OPP materials in the eld of template
materials. Therefore, overall, it is necessary to design block copolymers according to the specic application eld of OPP
materials.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China under Grant 51373051 and The Hunan Provincial Natural Science Foundation of China under Grant 14JJ2095.
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