Zeolite like metal–organic frameworks (ZMOFs) (1)

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DOI: 10.1002/adma.200501576

Recent Progress in the Synthesis of Porous
Carbon Materials**
By Jinwoo Lee, Jaeyun Kim,
and Taeghwan Hyeon*
In this review, the progress made in the last ten years concerning the
synthesis of porous carbon materials is summarized. Porous carbon
materials with various pore sizes and pore structures have been synthesized using several different routes. Microporous activated carbons
have been synthesized through the activation process. Ordered microporous carbon materials
have been synthesized using zeolites as templates. Mesoporous carbons with a disordered pore
structure have been synthesized using various methods, including catalytic activation using metal species, carbonization of polymer/polymer blends, carbonization of organic aerogels, and
template synthesis using silica nanoparticles. Ordered mesoporous carbons with various pore
structures have been synthesized using mesoporous silica materials such as MCM-48, HMS,
SBA-15, MCF, and MSU-X as templates. Ordered mesoporous carbons with graphitic pore
walls have been synthesized using soft-carbon sources that can be converted to highly ordered
graphite at high temperature. Hierarchically ordered mesoporous carbon materials have been
synthesized using various designed silica templates. Some of these mesoporous carbon materials
have successfully been used as adsorbents for bulky pollutants, as electrodes for supercapacitors
and fuel cells, and as hosts for enzyme immobilization. Ordered macroporous carbon materials
have been synthesized using colloidal crystals as templates. One-dimensional carbon nanostructured materials have been fabricated using anodic aluminum oxide (AAO) as a template.

1. Introduction
Porous carbon materials have received a great deal of attention due to their many applications.[1] Porous carbon materials
have been applied to gas separation, water purification, cata-

–
[*] Prof. T. Hyeon, Dr. J. Lee, J. Kim
National Creative Research Initiative Center for Oxide

Nanocrystalline Materials
and School of Chemical and Biological Engineering
Seoul National University
Seoul 151–744 (Korea)
E-mail:
[**] We thank the financial support by the Korean Ministry of Science
and Technology through the National Creative Research Initiative
Program.

Adv. Mater. 2006, 18, 2073–2094

lyst supports, and electrodes for electrochemical double layer
capacitors and fuel cells.[2] According to the International Union of Pure and Applied Chemistry (IUPAC) recommendation, porous carbon materials can be classified into three types
based on their pore sizes: microporous < 2 nm, 2 nm < mesoporous < 50 nm, and macroporous > 50 nm. Porous carbon
materials have been synthesized using various methods. The
following are representative traditional methods.
1) Chemical activation, physical activation, and a combination of the physical and chemical activation processes.[3]
2) Catalytic activation of carbon precursors using metal
salts or organometallic compounds.[4]
3) Carbonization of polymer blends composed of a carbonizable polymer and a pyrolyzable polymer.[5]
4) Carbonization of a polymer aerogel synthesized under
supercritical drying conditions.[6]

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Although many porous carbon materials have been developed using the above-mentioned methods, the synthesis of
uniform porous carbon materials has been very challenging.
Over the last ten years, many kinds of rigid and designed inorganic templates have been employed in an attempt to synthesize carbons with uniform pore sizes. Knox and his co-workers
pioneered the template synthesis of porous carbons.[7] Since
then, many porous carbon materials with uniform pore sizes
having micropores, mesopores, or macropores have been
synthesized using various inorganic templates. Figure 1a depicts the overall concept of the template procedure, which is
essentially the same as that used to fabricate a ceramic jar,
but scaled down to the nanometer regime. To make a jar, a
piece of wood with the desired shape is first carved, and then
clay is applied to the surface of the wood. Through heating at

ca. 1000 °C under air, the clay is transformed to ceramic and
the wood is simultaneously burnt to generate the empty space
inside the jar. The general template synthetic procedure for
porous carbons is as follows: 1) preparation of the carbon precursor/inorganic template composite, 2) carbonization, and
3) removal of the inorganic template. Various inorganic materials, including silica nanoparticles (silica sol), zeolites, anodic
alumina membranes, and mesoporous silica materials, have
been used as templates. Figure 1b to 1d describes the synthesis of microporous, mesoporous, and macroporous carbons
using zeolite, mesoporous silica, and synthetic silica opal as
templates, respectively. Figure 1e shows the synthesis of carbon nanotubes (CNTs) using an anodic alumina membrane
template. Broadly speaking, the template approaches can be
classified into two categories. In the first approach, inorganic

Taeghwan Hyeon received his B. S. (1987) and M. S. (1989) in Chemistry from Seoul National
University, Korea. He obtained his Ph.D. from the University of Illinois at Urbana-Champaign
(1996). Since he joined the faculty of the School of Chemical and Biological Engineering of
Seoul National University in September 1997, he has focused on the synthesis of uniform-sized

nanocrystals and new nanoporous carbon materials and published more than 100 papers in
prominent international journals. He is currently a Director of National Creative Research Initiative Center for Oxide Nanocrystalline Materials supported by the Korean Ministry of Science
and Technology. He has received numerous awards, including the Korean Young Scientist Award
from the Korean President and DuPont Science and Technology Award. He is currently serving
as an editorial advisory board member for Advanced Materials, Chemical Communications, and
Small.

Jinwoo Lee was born in Seoul, Korea, in 1974. He received his B.S. (1998), M.S. (2000), and
Ph.D. (2003) from the Chemical and Biological Engineering Department of Seoul National University, Korea. During his graduate research under the direction of Prof. Taeghwan Hyeon, he
worked on the synthesis of mesoporous carbon materials using mesostructured silica templates.
As a postdoctoral researcher he is studying the biological applications of large-pore mesoporous
carbons.

Jaeyun Kim was born in Tongyeong, Korea, in 1978. He received his B.S. (2001) and M.S. (2003)
from the Chemical and Biological Engineering Department of Seoul National University, Korea.
Since then he has worked on his doctoral thesis studying the synthesis and application of
mesoporous carbon and the self-assembly of nanoparticles under the direction of Prof. Taeghwan Hyeon.
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REVIEW

stroms in diameter. These MSCs have been applied
to various areas including the separation of gas
molecules, shape-selective catalysts, and electrodes
for electrochemical double-layer capacitors. MSCs
have advantages over inorganic molecular sieves
(zeolites) in terms of their hydrophobicity and high
corrosion resistance. The most representative synthetic method for the synthesis of MSCs is the pyrolysis of appropriate carbon precursors. Miura
et al. prepared MSCs by pyrolyzing a mixture of
coal and organic additives.[8] The carbon materials
obtained using organic additives have pore structures different from those of the carbons prepared
from coal only. By changing the experimental conditions it was possible to finely tune the pore size
of the MSCs. For example, by changing the carbonization temperature and the mixing ratio of coal,
pitch, phenol, and formaldehyde, MSCs having a
uniform pore size of around 0.35 nm were synthesized. The Miura group also used ion-exchange resins to produce MSCs.[9] Spherical polystyrene
based resins with a sulfonic acid group were ionexchanged with several kinds of cations, and the resulting resins were carbonized at between 500 and
900 °C. In this way resins having various cations including H+, K+, Na+, Ca2+, Zn2+, Cu2+, Fe2+, Ni2+,
and Fe3+ were prepared from the ion-exchange resin. When the ion-exchanged resin was carbonized
at 900 °C under a nitrogen atmosphere, the MSCs
prepared from the resins with di- or trivalent catFigure 1. a) Schematic representation showing the concept of template synthesis.
ions maintained sharp pore distributions, whereas
b) Microporous, c) mesoporous, and d) macroporous carbon materials, and e) carthose prepared from the resins with univalent catbon nanotubes were synthesized using zeolite, mesoporous silica, a synthetic silica
ions lost most of their pores. The main reason for
opal, and an AAO membrane as templates, respectively.
this drastic difference is that di- or trivalent cations

can form ionic crosslinks connecting two or three
functional groups in the resins, and these crosslinks act as piltemplates such as silica nanoparticles are embedded in the
lars to stabilize the pores during the carbonization process.
carbon precursor. Carbonization followed by the removal of
the template generates porous carbon materials with isolated
The wide-angle X-ray diffraction (XRD) pattern of the carpores that were occupied by the template species. In the secbonized samples revealed the presence of metal-sulfide nanoond approach, a carbon precursor is introduced into the pores
particles, which are responsible for the formation of uniformly
of the template. Carbonization and the subsequent removal of
sized micropores. Films of these MSCs were fabricated for
their applications in gas separation.
the templates generate porous carbons with interconnected
Microporous carbon membranes have been prepared using
pore structures. In this review, we summarize the recent develvarious polymeric resins.[10] Carbon membranes have been
opments in the synthesis of porous carbon materials, focusing
on the synthesis of porous carbon materials with uniform pore
prepared in two main configurations, that is, unsupported carsizes via the template approaches. The main part of the review
bon membranes and membranes supported on macroporous
is divided into three sections based on the pore sizes: micropomaterials. A supported carbon membrane was prepared by
rous, mesoporous, and macroporous carbon materials.
casting 13 wt % polyamic acid in N-methylpyrrolydone
(NMP) on a macroporous carbon support.[10a] The resulting
polymer was heat-treated through a two-step process involv2. Microporous Carbon Materials
ing imidization at 380 °C and subsequent carbonization at
550 °C. The gas-permeation experiment showed that the gas
2.1. Disordered Microporous Carbons (Molecular Sieving
transport through the MSC membrane occurs according to
Carbons)
the molecular-sieving mechanism. The membrane had selective permeation for O2/N, He/N, CO2/CH4, and CO2/N. The
Molecular sieving carbons (MSCs) are special forms of actihighest separation factors were achieved at 25 °C. A molecuvated carbons that possess uniform micropores of several ang-

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lar-sieving carbon film with a nanometer-sized
a)
nickel catalyst was prepared from polyimide-containing nickel nitrate.[11] The combination of the
catalytic function with the molecular-sieving property was also investigated. The molecular-sieving
property of the MSC film with a nickel catalyst was
comparable to that of Zeolite 5A. It was found
that the MSC catalyst carbonized at low temperab)
ture (600 °C or 650 °C) showed a high selectivity in
the competitive hydrogenation reactions of butene
isomers (butene and isobutene). In the narrow
nanospace of the MSC with a nickel catalyst, smaller molecules can be more easily hydrogenated
compared to larger molecules. Considering the relative sizes of butene and isobutene, the hydrogenation of isobutene was much slower than that of butene. However, perfect shape selectivity could not
be achieved, because of the presence of the cataFigure 2. a) Schematic explaining the overall template synthetic procedure for microlyst particles on the outer surface of the MSC carporous carbons using a zeolite Y template. b) High-resolution transmission electron
bon matrix. Consequently, the elimination of the
microscopy (HRTEM) image of the ordered microporous carbon prepared following the
procedure reported. The inset corresponds to a diffraction pattern taken from this image.
nickel catalyst particles formed on the outer surReproduced with permission from [18]. Copyright 2001 American Chemical Society.
face of the MSC film is extremely important to
achieve perfect shape selectivity.
Shiflett and Foley reported the fabrication of a stainlessbon precursor.[14] The chemical vapor deposition (CVD)
steel-supported MSC membrane via the ultrasonic deposition

method was also adopted for the introduction of carbon into
of poly(furfuryl alcohol) on stainless-steel tubes and subsethe channels of USY zeolite. CVD was carried out by exposquent pyrolysis at 723 K.[12] The membrane was successfully
ing the zeolite to propylene gas at 700 or 800 °C. The resulting
applied to gas separation with the following permeances, meamicroporous carbons exhibited high surface areas of over
sured in moles per square meter per Pascal per second: nitro2000 m2 g–1. The similar morphology of the resulting micropo–12
–11
–10
gen, 1.8 × 10 ; oxygen, 5.6 × 10 ; helium, 3.3 × 10 ; and hyrous carbon particles and the original zeolite template partidrogen, 6.1 × 10–10. The ideal separation factors as compared
cles, observed using scanning electron microscopy (SEM),
to that for nitrogen were 30:1, 178:1, and 331:1 for oxygen, hedemonstrated that the carbonization occurred inside the chanlium, and hydrogen, respectively.
nels of the zeolite template. However, the Kyotani group
failed to synthesize ordered microporous carbon arrays and
the carbon material that they fabricated possessed a consider2.2. Ordered Microporous Carbon Materials Synthesized
able amount of mesopores. The generation of mesopores reUsing Zeolite Templates
sulted from the partial collapse of the carbon framework after
the removal of the zeolite template by HF etching. The thin
To make microporous carbon materials not only with uniwall thickness of the carbon, derived from the small pores of
form pores, but also with ordered regular pore arrays, rigid inthe zeolite template (0.74 nm), did not exhibit a sufficiently
organic templates are required. Zeolites are aluminosilicate
high mechanical strength to survive the removal of the temmaterials having ordered and uniform sub-nanometer sized
plate. Rodriguez-Miraso et al. adopted a similar approach to
pores. Zeolites have been widely used as molecular sieves, solproduce microporous carbon using zeolite Y as a template,
id acid catalysts, and catalyst supports, and have also been
and they went on to examine the oxidation behavior of the reused as shape-selective catalysts owing to their uniform mosulting porous carbon.[15]
[13]
lecular-sized pores. Because the walls of zeolites have a uniThe Mallouk group synthesized phenol–formaldehyde (PF)
form thickness of < 1 nm, zeolites have been used as inorganic
polymers by making use of the acidity of the zeolite frametemplates for the synthesis of microporous carbons with uniwork inside various zeolites, for instance, zeolites Y, b, and L,
form pore sizes. USY zeolite was adopted as the template to
and then carbonized the polymer/zeolite composites to obtain

prepare a microporous carbon by the Kyotani group.
porous carbons.[16] Phenol was infiltrated into the narrow
Figure 2a shows the overall template synthetic procedure for
pores of the zeolite by the vapor-phase infiltration method.
microporous carbons using a zeolite Y template. A carbon
These carbons possessed a considerable amount of mesopores,
precursor was incorporated into the pores and channels of the
which was consistent with the results obtained by Kyotani and
zeolite. Carbonization followed by the removal of the zeolite
co-workers. Moreover, the ordered structure of the zeolite
template produced microporous carbon materials. Poly(acrywas not faithfully transferred to the resulting porous carbons.
lonitrile) or poly(furfuryl alcohol) was employed as the carLater, the Kyotani group was able to successfully synthesize

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the structural regularity of the corresponding zeolite template.
The extent of such transferability, however, strongly depended on the kind of zeolite template employed. The
authors concluded that in order to obtain microporous carbons with high structural regularity the pores in the zeolite
template should be sufficiently large (> 0.6–0.7 nm), as well as
being three-dimensionally interconnected. More recently, the
Kyotani group also synthesized a nitrogen-containing microporous carbon with a highly ordered structure by using zeolite Y as a template.[20] The formation of nitrogen-doped carbon in the zeolite channels was achieved by the impregnation

of FA and subsequent CVD of acetonitrile. The nitrogen-incorporated and ordered microporous carbon exhibited a
stronger affinity to H2O adsorption than the nitrogen-free, ordered, microporous carbon materials with similar pore structures, demonstrating the polar and hydrophilic nature of the
nitrogen-doped carbon.
For many industrial applications, such as the selective permeation of gas molecules, the control of the pore size is a critical issue. Consequently, we expect more research on the poresize control of ordered microporous carbon materials to be
conducted in the future.

REVIEW

uniformly sized and ordered microporous carbon materials
using zeolite Y as a template via the two-step carbonization
method.[17] The one-step carbonization method did not enable
the complete filling of the channels and pores of the zeolite
template, and this resulted in the extensive collapse of the carbon framework during the removal of the template. In order
to prevent this partial collapse of the carbon framework, the
additional incorporation of carbon was achieved by a CVD
process using propylene gas after the initial carbonization by
the heat-treatment of the zeolite/furfuryl alcohol (FA) composite at 700 °C. The carbon obtained after the removal of the
zeolite template exhibited an ordered zeolite replica structure, as confirmed by the strong (111) reflection of zeolite Y
at a 2h angle of 6.26° in the XRD pattern. Although ordered
microporous carbon materials with a negative replica structure of zeolite Y were obtained by the two-step method, there
was still an amorphous (002) peak at the 2h angle of 23° in the
XRD pattern, which demonstrated the partial collapse of the
carbon framework in the zeolite channels. Later, the same research group reported the synthesis of ordered microporous
carbon having a rigid framework, but without the amorphous
(002) peak, using heat treatment of the carbon/zeolite composite obtained by the above two-step method at 900 °C.[18]
The carbon inside the channels seemed to be better carbonized and its structure would be expected to be more rigid and
stable as a result. Consequently, the long-range ordering of
the carbon particles replicated from the zeolite template
might be better retained than that of the carbon obtained
without this heat treatment at 900 °C. The carbon so produced

had almost no mesoporosity (its micropore and mesopore volumes were 1.52 cm3 g–1 and 0.05 cm3 g–1, respectively). The
(111) peak of the ordered microporous carbon prepared by
the additional heat treatment at 900 °C was more intense than
that obtained without the additional heat treatment, indicating the presence of a larger amount of highly ordered carbon
structure in the microporous carbon. The surface area of the
ordered microporous carbon was found to be 3600 m2 g–1,
which is much higher than that of the carbon prepared without the additional heat treatment (2200 m2 g–1). Although the
surface area of some KOH activated carbons is over
3000 m2 g–1, these carbons always suffer from the presence of
some mesoporosity and have a broad pore distribution, which
is undesirable for many applications, such as gas storage.
Figure 2b shows the high-resolution transmission electron microscopy (TEM) image of the ordered microporous carbon
obtained from zeolite Y. Its excellent 3D ordering is clearly
demonstrated. The internal structure of this ordered microporous carbon was also characterized using 13C solid-state
NMR, and was found to consist of a condensed aromatic ring
system. In a subsequent paper, the same research group extended the two-step replication process to other zeolite systems, in order to make various ordered microporous carbon
arrays.[19] The optimum conditions to be used to obtain carbon
with the highest long-range ordering varied depending on the
zeolite templates that were used. When using the simple CVD
method, unlike in the case of zeolite Y, the carbons inherited

3. Mesoporous Carbon Materials
Over the last decade, there have been significant advances
in the synthesis of mesoporous carbon materials.[21] Mesoporous carbon materials are very important for applications
involving large molecules, such as adsorbents for dyes, catalyst
supports for biomolecules, and electrodes for biosensors.

3.1. Mesoporous Carbons with Disordered Pore Structures
Catalytic activation using metal ions was employed to
synthesize several types of mesoporous carbon materials.

Yasuda and co-workers synthesized mesoporous activatedcarbon materials by the steam invigoration of pitches mixed
with 1–3 wt % of rare-earth metal complexes, such as
Ln(C5H5)3 and Ln(acac)3 (where Ln = Sm, Y, Yb or Lu).[22]
All of the resulting mesoporous carbons had high mesopore
ratios of up to 80 %, surface areas of ca. 200 m2 g–1, and pore
sizes ranging from 20 nm to 50 nm. These mesoporous activated carbons selectively adsorbed large molecules, such as vitamin B12, blue acid 90 dye, dextran, nystatin, and humic
acid, reflecting their large mesopore volumes. Oya and coworkers synthesized activated-carbon fibers containing a significant fraction of mesopores with sizes of several tens of
nanometers from the catalytic activation of a phenol resin
mixed with cobalt acetylacetonate.[23]
The carbonization of polymer blends composed of two different types of polymers, that is, a carbon precursor polymer
and a decomposable polymer that is pyrolyzed to generate
pores, produced mesoporous carbon materials. Ozaki et al.
synthesized mesoporous carbons with a pore diameter of

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ca. 4 nm from the carbonization of a polymer blend composed of phenolic resin and poly(vinyl butyral).[5b] Later, Oya
and co-workers synthesized carbon fibers from the carbonization of a polymer blend composed of a phenol–formaldehyde
(PF) polymer embedded in a polyethylene (PE) matrix with a

PF/PE weight ratio of 3:7.[5c] A bundle of PF-derived thin
carbon fibers smaller than several hundred nanometers in diameter was produced. The nanofiber bundle so obtained was
easily separated into thin fibers. These polymer-blend carbonization methods have been extensively used to synthesize
many other mesoporous carbon materials.[5]
The carbonization of organic aerogels prepared by the sol–
gel technique, followed by supercritical drying, produced
porous carbon materials.[6] Silica aerogels having high mesoporosity were prepared by the sol–gel polymerization of silica
precursors, followed by supercritical drying.[24] The supercritical drying process relieves the large capillary forces generated
during the drying process, and makes it possible to preserve
the highly crosslinked and porous structure generated during
the sol–gel polymerization. Pekala et al. synthesized carbon
aerogels from the carbonization of organic aerogels based on
a resorcinol–formaldehyde (RF) gel.[6] The resulting mesoporous carbon materials had high porosities (> 80 %) and high
surface areas (> 400 m2 g–1). Subsequent studies on the poresize control of carbon aerogels were conducted by Tamon
et al.[25] The pore radius of the RF aerogels was controlled in
the range of 2.5–6.1 nm by changing the molar ratios of resorcinol to sodium carbonate and resorcinol to water.
Metal species were incorporated into the carbon framework
during the preparation of carbon aerogels in order to modify
their structure, conductivity, and catalytic activity. Titanialoaded carbon aerogels were prepared by adding titanium alkoxide during the sol–gel reaction, and the resulting composite
aerogels were used for the combined adsorption and photocatalytic removal of waste water. Subsequent heat treatment
at high temperature (between 500 and 900 °C) under a He
flow generated a highly crystallized, titanium dioxide loaded
mesoporous carbon.[26] A ruthenium/carbon aerogel composite was prepared via a novel two-step metal-vapor-impregnation method.[27] The resulting composite had highly dispersed
Ru particles attached to the carbon aerogel and was used as
the electrode material for supercapacitors. Capacitances
greater than 250 F g–1 were obtained for the samples with
50 wt % Ru and the capacitance of these composites could be
tailored by varying the Ru loading and/or the density of the
host carbon aerogel.
Carbon aerogels with a partially graphitized structure were

synthesized by catalytic graphitization using Cr, Fe, Co, and
Ni.[28] HRTEM, XRD, and Raman spectroscopy showed the
presence of graphitized areas with a 3D stacking order. The
resulting carbon aerogels had a well-developed mesoporosity
along with a graphitic character, which allow them to be used
as the electrode materials for supercapacitors and fuel cells.
The synthesis of mesoporous carbon foams was achieved by
Lukens and Stucky using RF gels as the carbon precursor and
microemulsion-polymerized polystyrene (PS) microspheres as

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the template.[29] Upon pyrolysis under an argon atmosphere,
the organic PS microspheres were burnt off generating large
mesopores. The pore size of the mesoporous carbon foams
was roughly two-thirds that of the template.
Silica materials have been extensively used as templates to
synthesize mesoporous carbons. The template silica materials
were easily removed by treating them with HF or NaOH. As
described in the Introduction, Knox et al. reported the synthesis of spherically shaped mesoporous carbon materials
using silica gel and porous glass as templates.[7] The polymerization of the phenol–hexamine mixture within the pores of
the silica gel, followed by the pyrolysis of the resulting resin in
a nitrogen atmosphere at temperatures below 1000 °C, and
subsequent dissolution of the silica template produced the
mesoporous carbon materials. The further graphitized spherical mesoporous carbons were successfully used as high-performance liquid chromatography (HPLC) column materials.
Our group synthesized mesoporous carbons using commercial silica sol nanoparticles as templates.[30] The polymerization of resorcinol and formaldehyde in the presence of a silica
sol solution (Ludox HS-40 silica sol solution, average particle
size ca. 12 nm) generated RF gel/silica nanocomposites. Carbonization followed by HF etching of the silica sol templates
generated porous carbons, designated as silica sol mediated
carbon (SMC1), having pore sizes predominantly in the range

of 10–100 nm. These carbon materials exhibited very high
pore volumes of over 4 cm3 g–1 and high surface areas of
ca. 1000 m2 g–1. Because the aggregated form of the silica
nanoparticles acted as templates, the pore size distribution of
the resulting carbon was broad, ranging from 10 nm to
100 nm. These SMC1 carbon materials exhibited excellent adsorption capacities for bulky dyes[31] and humic acids.[32] In order to prevent the aggregation of the silica nanoparticles during the synthesis, surfactant-stabilized silica nanoparticles
were used as the template (Fig. 3a).[33] The resulting carbon
material, designated as SMC2, exhibited a narrow pore size
distribution centered at 12 nm, which matched very well with
the particle size of the silica nanoparticle template. Figure 3b
compares the pore size distribution curves and the corresponding nitrogen adsorption/desorption isotherms of SMC1
and SMC2 carbons, demonstrating that SMC2 has a more uniform pore size distribution as compared to SMC1. When silica
nanoparticles with a particle size of 8 nm were used as the
template, SMC2 carbon with uniform 8 nm sized pores was
produced, demonstrating the excellent template role of the
surfactant-stabilized silica nanoparticles.
Jaroniec and his co-workers reported a colloidal imprinting
method to synthesize mesoporous carbons using mesophase
pitch as a carbon precursor and silica sol as a template.[34]
Using colloidal silica particles with different sizes and adjusting the imprinting conditions such as imprinting time and temperature, they were able to synthesize carbon materials with
controlled pore size, surface area, and pore volume.[35] One interesting characteristic of the carbon materials synthesized
using mesophase pitch as a carbon precursor was that they
had nearly no micropores. The same group also reported gra-

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b)

Figure 3. a) Synthetic strategy for uniform mesoporous carbons: 1) gelation of RF in the presence of cetyltrimethylammonium bromide (CTAB)stabilized silica particles; 2) carbonization of the RF-gel/silica composite
at 850 °C to obtain a carbon–silica composite; 3) HF etching of the silica
templates to obtain mesoporous carbons. Reproduced with permission
from [33]. Copyright 1999 Royal Society of Chemistry. b) The pore size
distributions calculated from the adsorption branch of the nitrogen isotherm by the Barrett–Joyner–Halenda (BJH) method and the corresponding N2 adsorption and desorption isotherms (inset) of mesoporous carbons synthesized using isolated CTAB-stabilized silica particles (solid
line) and using silica particle aggregates (dashed line) as templates.

phitized mesoporous carbon with a high surface area by the
colloidal imprinting method via carbonization at 900 °C and
subsequent graphitization at 2400 °C.[36] The resulting graphitic mesoporous carbons were successfully used as the stationary phase for reverse-phase liquid chromatography in the separation of alkylbenzenes, such as benzene, ethylbenzene, and
propylbenzene.[37]
Jang and co-workers synthesized carbon nanocapsules and
mesocellular carbon foams by surface-modified colloidal silica-templating methods.[38] Carbon nanocapsules were synthesized using polydivinylbenzene (DVB) as a carbon precursor,
poly(methyl methacrylate) (PMMA) as a barrier for the pre-

Adv. Mater. 2006, 18, 2073–2094

vention of intraparticle crosslinking of DVB, and surfactantcoated colloidal silica particles as a template. Direct polymerization of DVB on the surface of the silica particles without
PMMA, followed by carbonization and dissolution of the silica template, resulted in mesocellular carbon foams. Jang and
his co-workers also reported the synthesis of mesoporous carbons via vapor deposition polymerization of polyacrylonitrile
on the surface of silica particles.[39]
Lu et al. reported an aerogel-based approach to synthesize
spherical mesoporous carbon particles.[40] In the synthesis, an
aqueous solution containing sucrose and various silica templates was passed through an atomizer and dispersed into
aerogel droplets. Solvent evaporation at 400 °C resulted in
spherical silica/sucrose nanocomposite particles and the subsequent carbonization and removal of the silica templates
generated the spherical porous carbon particles.

Kyotani and co-workers reported the synthesis of mesoporous carbon through the co-polymerization of FA and tetraethylorthosilicate (TEOS).[41] A nanocomposite of carbon and
silica was prepared by using a sol–gel process with TEOS in
the presence of FA, followed by the polymerization of FA,
and its subsequent carbonization. In this synthesis, the silica
template and carbon precursor were simultaneously synthesized to produce a silica/carbon precursor nanocomposite.
Using a similar synthetic procedure, Han et al. synthesized
mesoporous carbon using inexpensive sucrose and sodium silicate as the carbon precursor and template, respectively.[42] Lu
and his co-workers synthesized unimodal and bimodal mesoporous carbons from the sucrose/silica nanocomposites prepared by sol–gel process of TEOS with or without colloidal
silica particles in the presence of sucrose.[43] Lu and his coworkers also reported the synthesis of continuous mesoporous
carbon thin films by a rapid sol–gel, spin-coating process using
sucrose as the carbon precursor and TEOS as the silica precursor.[44] Continuous sucrose/silica nanocomposite thin films
were formed by the spin-coating of homogeneous sucrose/silicate/water solutions that were prepared by reacting TEOS in
acidic sucrose solutions. Carbonization converted the sucrose/
silica thin films into carbon/silica nanocomposite thin films.
The mesoporous carbon thin films exhibited a high specific
surface area of 2603 m2 g–1 and a specific pore volume of
0.21 cm3 g–1. This was the first reported synthesis of continuous mesoporous carbon thin films through a direct and rapid
organic/inorganic self-assembly and carbonization process.

REVIEW

a)

3.2. Synthesis of Uniform Mesoporous Carbons Using
Mesoporous Silica Templates
3.2.1. Synthesis of Ordered Mesoporous Carbons with Various
Pore Structures
In 1992, Mobil Corporation researchers reported the synthesis of mesoporous M41S silica materials from the sol–gel
polymerization of silica precursors in the presence of a surfactant self-assembly.[45] The pore structure and dimension of the

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mesoporous silica materials could be controlled by varying
the experimental conditions, such as the ratio of the silica precursor to the surfactant and the chain length of the surfactant.
The development of the M41S family triggered the synthesis
of many mesoporous silica materials having diverse pore
structures using various organic structure-directing agents, including neutral amine surfactants,[46,47] alkyl(PEO) surfactants,[48] and triblock copolymers.[49] These mesoporous silica
materials have uniform pore sizes and high surface areas. Mesoporous silicas with interconnected pore structures have
been successfully used as the templates for the synthesis of
mesoporous carbon materials. Both the Ryoo group[50] and
our own group[51] employed MCM-48 (alumino)silica materials as the templates for the fabrication of mesoporous carbon.
The carbon precursor, sucrose or in situ polymerized phenol
resin, was incorporated into the 3D interconnected pores of
the MCM-48 template, and subsequent carbonization followed by the removal of the silica template resulted in the
generation of mesoporous carbon materials having 3D interconnected pore structures. Figure 4a shows the overall template strategy used for the synthesis of ordered mesoporous
carbon materials using mesoporous silica templates.[50,51] The
phenol-resin/MCM-48 nanocomposite was prepared by the
in situ polymerization of phenol and formaldehyde in the
pores of the MCM-48 aluminosilicate template. The carbonization of the phenol-resin/MCM-48 nanocomposite, followed
by the dissolution of the aluminosilicate template using aqueous hydrofluoric acid produced an ordered mesoporous car-

a)

b)

Figure 4. a) Schematic representation of the formation of an ordered mesoporous carbon SNU-1. b) TEM image of a mesoporous SNU-1 carbon.
Reproduced with permission from [51]. Copyright 1999 Royal Society of
Chemistry.

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bon (SNU-1). The TEM image of SNU-1 carbon showed a
regular array of 2 nm sized pores separated by 2 nm thick carbon walls (Fig. 4b). Judging by the low-angle XRD pattern,
the resulting carbon was not a real negative replica of the
MCM-48 silica template, because the replicated carbon underwent a structural transformation during the removal of the silica template. It was suggested that the cubic MCM-48 with
the Ia3d structure was converted to a new cubic I41/a structure.[52] Using the same template (MCM-48), Ryoo and his coworkers synthesized mesoporous carbon (CMK-1) using
sucrose as a carbon precursor.[50] To improve the thermal stability and ordering of the resulting mesoporous carbon materials, Yu and co-workers used silylated MCM-48 as a template
and poly(divinylbenzene) as a carbon precursor.[53] The mesoporous carbon synthesized using the silylated MCM-48 silica
template showed much better overall structural order compared to that obtained using pure MCM-48 silica, according
to the small-angle XRD patterns and TEM images.
Following the first report on the synthesis of ordered mesoporous carbons using the MCM-48 silica template, various
mesoporous carbon materials with different pore structures
were synthesized using a variety of different mesoporous silica
templates. For example, our group used a hexagonal mesoporous silica (HMS)[47] template to synthesize mesoporous
SNU-2 carbon.[54] Through this template synthesis, we were
able to indirectly elucidate that the HMS silica possesses a
wormholelike pore structure rather than the originally proposed MCM-41-like hexagonal 1D channel structure. The mesoporous carbon materials synthesized using mesoporous silica templates contain not only mesopores generated from the
replica of the templates, but also micropores formed by the
carbonization of the precursor. For example, SNU-2 carbon

exhibited a bimodal pore size distribution curve, with 0.6 nm
size micropores generated from the carbonization of the carbon precursor and the other centered at 2.0 nm from the replica of the template.
Hexagonally ordered mesoporous silica SBA-15 was used
as a template for a mesoporous carbon designated as
CMK-3.[55] In the original study by the Stucky group, SBA-15
was reported to have a hexagonal tubular pore structure similar to that of MCM-41. However by using SBA-15 silica as the
template, Ryoo and his co-workers successfully synthesized
an ordered mesoporous carbon in which parallel carbon fibers
were interconnected through thin carbon spacers. Through
this synthesis and further studies on the pore structure, the
SBA-15 silica turned out to have complementary pores, which
were generated by the penetration of the hydrophilic ethylene
oxide groups into the silica framework.[56–58] The ordered
structure of the CMK-3 carbon was the exact inverse replica of
the SBA-15 silica without the structural transformation during
the removal of the silica template. CMK-3 type ordered mesoporous carbon was also synthesized by the infiltration of the
carbon precursor via adsorption in the vapor phase and using
p-toluene sulfonic acid impregnated SBA-15 as a template.[59]
A nanopipe-type mesoporous carbon, designated as
CMK-5, was also synthesized by Ryoo and co-workers. The

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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J. Lee et al./Porous Carbon Materials

Figure 5. TEM image viewed along the direction of the ordered nanopipe-type carbon and corresponding Fourier diffractogram (inset). Reproduced with permission from [60]. Copyright 2001 Nature Publishing
Group.

condition by pyrolyzing poly(furfuryl alcohol) under a vacuum atmosphere, resulting in the formation of high-quality
CMK-5 carbon.[61] Several other research groups synthesized
similar nanopipe-type ordered mesoporous carbon materials.
The Schüth group synthesized ordered mesoporous carbon,
denoted as NCC-1, whose structure was similar to that of
CMK-5, using hydrothermally treated SBA-15 silica as the
template.[62] Previously, the Zhao group showed that hydrothermal treatment at 140 °C of the silica template induced the
formation of mesotunnels between the main mesopores of
SBA-15.[63] FA was wetted on the inner pore surface of the hydrothermally treated SBA-15 aluminosilicate, and subsequent
polymerization using the acidic Al sites on the template generated poly(furfuryl alcohol), which was used as the carbon
precursor. The Schüth group also synthesized ordered nitrogen-doped mesoporous carbons using SBA-15 as the template
and poly(acrylonitrile) as the carbon/nitrogen source.[64] The
same group also used a conducting polymer, polypyrrole, as
the carbon source to synthesize CMK-3 type mesoporous carbon.[65] The SBA-15 silica template was first impregnated with
ferric chloride, which served as the oxidant for the vaporphase oxidative polymerization of pyrrole vapor at room temperature. The resulting materials had an ordered structure,
high surface area, and large pore volume. Nanopipe-type hexagonally ordered mesoporous carbons were also prepared
through the catalytic chemical vapor deposition (CCVD)

Adv. Mater. 2006, 18, 2073–2094

method using cobalt metal incorporated SBA-15 as the templates.[66] The cobalt/SBA-15 silica was prepared by dispersing
ethylenediamine-functionalized SBA-15 silica in water containing cobalt ions, followed by thermal treatment. Increasing
the deposition time resulted in the generation of highly hexagonally ordered nanopipe-type mesoporous carbon.[66]
Ordered mesoporous carbon CMK-3 with a hollow spherical particle shape was synthesized by CVD.[67] SBA-15 silica
was employed as the template and styrene as the carbon
source. In most templating processes, the morphology of the
mesoporous carbon materials is very similar to that of the
template. However, during this high-temperature CVD process, the carbon precursor that was initially deposited in the
outer pores of the template seemed to block the internal

pores. The subsequent carbonization and removal of the template generated hollow, spherical carbon with a mesoporous
shell structure.
Following the first report on MCM-48 silica, much effort
has been made to synthesize cubic Ia3d mesoporous silica
with large pores for use as a catalyst for large-sized molecules.
However, ordered mesoporous carbon with an Ia3d structure
could not be obtained using a cubic Ia3d structured MCM-48
silica template, because of the disconnectivity between the enantiomerically paired channels.[50,51] Later, three research
groups independently reported the synthesis of cubic Ia3d
structured mesoporous silica with very large pores using a
P123 triblock copolymer ((EO)20(PO)70(EO)20) as the template,[68–70] and the successful replication to highly ordered
mesoporous carbons.[69–71] The Zhao group synthesized largepore 3D bicontinuous cubic Ia3d mesoporous silica by a solvent-evaporation method using P123 triblock copolymer as
the template and a small amount of 3-mercaptopropyltrimethoxysilane (MPTS) and trimethylbenzene as additives.[68] A
mesoporous silica material with a monolithic form was used
as the template for the synthesis of Ia3d cubic structured mesoporous carbon.[69] The Ryoo group synthesized Ia3d cubic
mesoporous silica by hydrothermal treatment using butanol
as a structure modifier.[70] Using the cubic mesoporous silica
as a template, they were able to synthesize not only unimodal
mesoporous carbon, but also tubular bimodal Ia3d ordered
mesoporous carbon, by the controlled polymerization of FA
inside the pores. In contrast to the mesoporous carbon synthesized using the MCM-48 silica template, the mesoporous carbons obtained using the cubic mesoporous silica template retained the bicontinuous Ia3d structures of the template. The
authors claimed that the bridges between the channel-like enantiomeric pore systems of the cubic mesoporous silica template connected the carbon rods in the channels.[69]
The control of the pore size of the mesoporous carbons was
not easy to accomplish through the template approach, because it was difficult to control the thickness of the wall during the synthesis of the mesoporous silicas. Ryoo and coworkers were the first to report the successful control of the
pore size of ordered mesoporous carbons. They employed
mixed surfactants (cetyltrimethylammonium bromide
(C16TAB) and polyoxyethylene hexadecylether-type surfac-

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REVIEW

hexagonally ordered arrays of carbon nanotubules were obtained from the partial wetting of poly(furfuryl alcohol) onto
the SBA-15 silica channels and subsequent carbonization.[60]
The ordered nanoporous carbon was rigidly interconnected
by the carbon spacers that were formed inside the complementary pores between the adjacent cylinders, forming a
highly ordered hexagonal array. The pore size distribution
curve exhibited bimodal pores, corresponding to the inside diameter of the carbon cylinders (5.9 nm) and the pores formed
between the adjacent cylinders (4.2 nm), respectively. The
TEM image, shown in Figure 5, shows an ordered array of
carbon tubules with diameters of ca. 6 nm. In a subsequent
paper, the Ryoo and Jaroniec groups optimized the synthetic

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tants (C16EO8)) in the acidic synthesis of hexagonal mesoporous silica. By decreasing the C16TAB/C16EO8 ratio, the wall
thickness in the mesoporous silica was increased systematically from 1.4 nm to 2.2 nm.[72] The resulting hexagonal mesoporous sieves were used as templates for the synthesis of ordered
mesoporous carbons, which allowed the size of the pores in
the carbon products to be controlled in the range of 2.2 to
3.3 nm. By adjusting the thickness of the silica wall, the pore
diameters of the resulting carbon materials were able to be
successfully controlled.[72]

a)

3.2.2. Mesoporous Carbons with Ultralarge Mesopores
For applications involving large-sized molecules, such as
biosensors using protein-incorporated carbons, mesoporous
carbons having well-interconnected pores with a diameter of
ca. 10 nm are necessary. Although many mesoporous carbons can be synthesized using different mesoporous silica
templates, as described above, the resulting pore sizes are
generally less than 10 nm, because the pore size of the replicated mesoporous carbon is generally determined by the
wall thickness of the silica template. Even in the case of the
nanopipe-type mesoporous carbons, the inner pore diameter
is smaller than 5 nm. To synthesize mesoporous carbon materials with uniform pore sizes of > 10 nm, our group employed mesocellular silica foam,[73] synthesized by the Stucky
group, as the template.[74] The synthetic scheme used for the
mesocellular carbon foam is shown in Figure 6a. Phenol was
incorporated into the complementary pores of the mesocellular aluminosilicate foam (AlMCF). The subsequent polymerization with formaldehyde generated a phenol-resin/
AlMCF nanocomposite. Carbonization followed by the removal of the template produced mesocellular carbon foam.
The key to the success of the synthesis was that the phenol
was only incorporated partially, since it could only fill the
complementary pores of the MCF template. Phenol vapor
could be incorporated into the complementary pores at low
vapor pressure, whereas it could not infiltrate into the main
cells of the AlMCF template, because a very high vapor
pressure was required for it to be incorporated into the large
mesocellular pores. When we used MCF aluminosilicate with
a main cell diameter of 27 nm and window size of 11 nm as
the template, we obtained a mesocellular carbon foam with
a main cell diameter of 27 nm and window size of 14 nm.
Small mesopores with a pore size of 3.5 nm were also generated from the replication of the wall of the silica template.
Spherical cells with a diameter of ca. 27 nm are evident in
the TEM image of the carbon material (Fig. 6b). Subsequently, the Tatsumi group synthesized a mesocellular carbon foam with a main cell size of 24 nm and window size of

18 nm using two successive impregnations of sucrose and
subsequent carbonization.[75] The mesoporous carbon obtained had closed hollow spherical pores, while the carbon
obtained by the single-step impregnation of sucrose had
open mesocellular pores.

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b)

Figure 6. a) Schematic illustration for the synthesis of a mesocellular carbon foam. Reproduced with permission from [74]. Copyright 2001 American Chemical Society. b) TEM image of a mesocellular carbon foam.

3.2.3. Mesoporous Carbons with Graphitic Pore Walls
Given their good electrical conductivity and uniform and
large pores, mesoporous carbon materials with good graphitic
characteristics could find many important applications, including electrodes for electrochemical double-layer capacitors,
fuel cells, and biosensors. It is well known that it is extremely
difficult to synthesize carbon materials with both a high surface area and good graphitic crystallinity. To achieve such a
goal, the Ryoo group synthesized ordered mesoporous carbons with graphitic pore walls (CMK-3G) through the in situ
conversion of aromatic compounds to a mesophase pitch inside the SBA-15 silica template by carbonization under high
pressure using an autoclave.[76] The carbon frameworks were
composed of discoid graphene sheets, which self-aligned perpendicularly to the template walls during the synthesis.
CMK-3G carbon exhibited much better mechanical strength
than the CMK-3 synthesized using sucrose or FA as the carbon precursor. The discoid alignment of the graphitic frame-

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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J. Lee et al./Porous Carbon Materials

3.2.4. Cost-Effective and Direct Synthesis of Mesoporous
Carbons
The cost of synthesizing templated mesoporous carbons is
largely dependent on the production cost of the mesoporous
silica templates, because they are sacrificed in the final step of

Adv. Mater. 2006, 18, 2073–2094

the synthesis. The Pinnavaia group developed a very economical route to synthesize mesoporous MSU silica materials via
the sol–gel reaction of sodium silicate under near-neutral conditions.[81,84] The cost of synthesizing MSU-H silica is much
lower than that of the similarly structured SBA-15 silica, given
that a very small amount of acid and inexpensive sodium silicate are used. By adding trimethylbenzene (TMB) to the synthesis solution, mesocellular silica foams, which were denoted
as MSU-F and had a similar pore structure to that of MCF silica, could also be synthesized.[81] The Pinnavaia group used
MSU-H silica as the template to synthesize hexagonally ordered mesoporous carbons, denoted as C-MSU-H.[85] The
pore structure of C-MSU-H was very similar to that of the
CMK-3 carbon synthesized using an SBA-15 silica template.
Our group reported the synthesis of mesocellular carbon
foams using inexpensive MSU-F silica as the inorganic template.[86] The cellular pore structure of C-nano-MSU-F was
very similar to that of mesocellular carbon foams synthesized
using the MCF-silica template. However, the C-nano-MSU-F
was composed of individual particles with sizes of a few hundred nanometers, in contrast to several micrometer-sized particles of the MCF-carbon. This small individual particle size is
highly desirable for the facile access of molecules into the
framework pores.
The procedure employed to synthesize mesoporous carbons using mesostructured silica templates is rather complex
and time consuming. The general synthetic procedure for ordered mesoporous carbons using a mesostructured silica template is as follows: 1) the preparation of the mesostructured
silica/surfactant composite, which often takes about 2–3 days;
2) the removal of the surfactant by calcination or solvent extraction; 3) the generation of the catalytic sites inside the

walls of the mesostructure for the polymerization and, if necessary, the re-calcination; 4) the incorporation of the polymeric carbon precursor, for example, phenol, FA, or sucrose,
into the pores of the mesoporous silica template; 5) the polymerization of the polymeric carbon precursor; 6) carbonization; and, finally, 7) the removal of the silica template with
HF or NaOH solution. This long and complicated multistep
template synthesis limits the application of mesoporous carbons, despite their many desirable and unique characteristics.
A short and facile synthetic procedure needs to be developed
in order for the extensive applications of these mesoporous
carbons.
Recently, much effort has been made to find a way of directly synthesizing uniform pore-sized mesoporous carbon
materials. Sayari and co-workers reported a simple and direct
preparation route to synthesize uniform microporous carbon
materials by the direct carbonization of cyclodextrin-templated silica mesophase materials.[87] During the preparation
of the cyclodextrin/silica mesophase materials, sulfuric acid
was used instead of hydrochloric acid, because it catalyzes the
carbonization of cyclodextrin. The pore size of the resulting
carbon was less than 2 nm, i.e., it was microporous. Moriguchi
and co-workers reported the direct synthesis of a mesoporous
carbon material by the in situ polymerization of divinylben-

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REVIEW

works was consistent with the general tendency of the edgeon anchoring of polycyclic aromatic hydrocarbons in a mesophase pitch on the silica surface.
Mokaya and co-workers synthesized nitrogen-doped mesoporous carbons with graphitic pore walls via CVD of acetonitrile.[77] Pyrolysis/carbonization in the temperature range of
950–1100 °C was found to be suitable for the fabrication of
well-ordered mesoporous carbon. These nitrogen-doped, ordered mesoporous carbon materials had a macroscopic spherical morphology, which was similar to that of the other mesoporous carbons synthesized via CVD methods. Later the
Mokaya group generalized the CVD method and synthesized
many mesoporous nitrogen-doped carbon materials using various mesoporous silica templates including SBA-12, SBA-15,

MCM-48, HMS, and MCM-41.[78] The carbon materials prepared at high CVD temperatures of > 1000 °C exhibited high
graphitic properties.
Fuertes and co-workers synthesized graphitic mesoporous
carbons by the simple impregnation of poly(vinyl chloride)
and subsequent carbonization.[79] These carbons had a good
electrical conductivity of 0.3 S cm–1, which is two orders of
magnitude higher that that of non-graphitized carbon. By
heating them at a high temperature of > 2600 °C, the graphite
crystallite size (Lc) of the mesoporous carbons was increased
to 19.4 nm, while preserving the high Brunauer–Emmett–Teller (BET) surface area of 260 m2 g–1. The Fuertes group also
fabricated an ordered mesoporous graphitic carbon material
using iron-impregnated polypyrrole as a carbon source and
SBA-15 as a template.[80] FeCl3 was used not only as an oxidant
for the polymerization but also as a catalyst which promotes
the formation of a graphitic structure during the carbonization
step. When used as electrode materials for electrochemical
double-layer capacitors (EDLCs), graphitic carbon showed a
superior performance to other non-graphitic mesoporous carbons at high current densities. This superior electrode performance seemed to be derived from highly accessible pores and
the high conductivity of the graphitic framework.
The Pinnavaia group synthesized ordered graphitic mesoporous carbon materials with high electrical conductivity using
MSU-H silica[81] as the template and aromatic precursors,
such as naphthalene, anthracene, and pyrene, as the carbon
sources.[82]
Zhao and co-workers used a melt-impregnation method
using a cheap mesophase pitch to synthesize mesostructured
graphitic carbon materials.[83] The pore walls are composed of
domains with the (002) crystallographic plane perpendicular
to the long axis of the carbon nanorods. They also used Fe2O3
nanoparticle-loaded mesoporous silica to obtain graphite carbon nanofiber bundles.

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2084

zene (DVB) in the hydrophobic phase of a hexagonally
arrayed micelle/silicate nanocomposite and its subsequent carbonization and HF treatment.[88] However, the ordered structure of the DVB/surfactant/silicate composite was not transferred to the resulting carbon materials after the removal of
the silica. The carbon structure achieved had wormholelike
mesopores with diameters of ca. 2 nm. The Inagaki group[89a]
and later the Ozin[89b] and Stein groups[89c] synthesized organic-group-incorporated mesoporous silica materials from the
sol–gel reactions of organosilane precursors in the presence of
surfactant self-assembly templates. The Lu group reported the
direct synthesis of mesoporous carbon from the carbonization
of a phenylene-incorporated mesostructured silica/surfactant
nanocomposite followed by the removal of the silica.[90] The
synthesis of the organosilica/surfactant was achieved by co-assembling octadecyltrimethylammonium bromide (OTAB)
with 1,4-bis(triethoxysilyl)benzene (BTE). After its carbonization at 900 °C, the molecular ordering present in the mesoporous walls disappeared, but an ordered mesoporous silica/
carbon composite was nevertheless obtained. The benzene
molecules present in the walls of the ordered mesostructured
materials were converted to carbonaceous materials. After
the HF etching, a mesoporous carbon with a high surface area
of 850 m2 g–1, a pore volume of 0.5 cm3 g–1, and an average
pore size of 2.5 nm was produced. The hydrogen-adsorption
capacity of the mesoporous carbon was comparable to those
of activated charcoal and activated carbon fiber. Our group
synthesized uniform mesoporous carbons with various pore

structures by the carbonization of P123 triblock copolymer/
phenol-resin/silica nanocomposites.[91] The composites were
simply prepared from the sol–gel polymerization of silica in
the presence of a Pluronic P123 triblock copolymer and phenol. The pore size of the mesoporous carbons was controlled
by varying the ratio of phenol to the P123 triblock copolymer.
Yu and his co-workers reported the direct preparation of mesoporous carbons using as-synthesized MCM-48.[92] The mechanical strength and thermal stability were improved compared to the mesoporous carbons prepared using calcined
mesostructured silica as a template. However, in this process,
an additional carbon precursor, poly(divinylbenzene) was
synthesized inside the empty space of the silica/surfactant
composite after the preparation of the mesostructured
MCM-48. Our group successfully synthesized ordered mesoporous carbon and mesocellular carbon foam with large pores
via the carbonization of mesostructured silica/surfactant
nanocomposites using the surfactant as the carbon precursor.[93] The synthesis was achieved by treating the as-synthesized silica (MCF, SBA-15)/triblock copolymer nanocomposite with sulfuric acid to crosslink the triblock copolymers.
Carbonization followed by the removal of the silica resulted
in the generation of ordered mesoporous carbons. Without
the treatment with H2SO4, ordered mesoporous carbon could
not be synthesized. Pinnavaia and co-workers reported the
synthesis of carbon nanotubes using P123 surfactant inside
mesoporous silica, but they could not obtain ordered arrays of
carbon nanotubes.[94]

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Dai and co-workers reported the preparation of highly ordered and well-oriented mesoporous carbon thin films
through the carbonization of a nanostructured resorcinol-formaldehyde resin and self-assembled block copolymer nanocomposite.[95] The resorcinol monomers were pre-organized
into a well-ordered polystyrene-block-poly(4-vinylpyridine)
(PS-P4VP) self assembled nanostructured film through spincoating followed by solvent annealing. Resorcinol and formaldehyde were in situ polymerized by exposing the film to
formaldehyde gas. Through the carbonization under an N2 atmosphere, a hexagonal carbon channel array was synthesized
by sacrificing the block-copolymer template. The self-assembly of the PS-P4VP/resorcinol mixture was essentially driven
by the hydrogen bonding interaction between resorcinol and

the P4VP block. The mesopores were oriented perpendicular
to the film surface. The pore diameter was ca. 34 nm and the
wall thickness was ca. 9.0 nm.
Very recently, Nishiyama and co-workers reported the fabrication of mesoporous carbon thin films, designated as COU,
with an ordered channel structure via the direct carbonization
of an organic–organic nanocomposite.[96] The synthetic procedure is described in Figure 7a. The key to the success of their
synthetic procedure was the formation of a periodically ordered organic–organic nanocomposite composed of thermosetting polymeric carbon precursors, RF and triethyl orthoacetate (EOA), and the use of a thermally decomposable
surfactant, triblock copolymer Pluronic F127. The reaction
mixture containing the organic–organic nanocomposite was
spin-cast on a silicon substrate, and the resulting film was heat

a)

b)

Figure 7. a) Schematic illustration of the direct synthetic route for an ordered mesoporous carbon (COU): 1) self-assembly of a carbon precursor
and a surfactant and 2) the removal of the surfactant by direct carbonization to obtain COU. Reproduced with permission from [96]. Copyright
2005 Royal Society of Chemistry. b) SEM image of mesoporous COU carbons prepared at the carbonization temperatures of 600 °C.

treated stepwise, first at 90 °C for 5 h in air for the polymerization of resorcinol with formaldehyde, then under a nitrogen
atmosphere at 400 °C for 5 h, and finally at 600 and 800 °C for

© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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J. Lee et al./Porous Carbon Materials

Figure 8. a) TEM and b) HRTEM image of C-FDU-15 calcined at 1400 °C.

c) TEM and d) HRTEM image of C-FDU-16 calcined at 1400 °C. Reproduced from [98].

Adv. Mater. 2006, 18, 2073–2094

rials by heating at temperatures > 700 °C. Notably, the carbon
materials were stable even up to 1400 °C under a nitrogen atmosphere, demonstrating the ultrahigh thermal stability. The
thermal stability might be derived from the synthesis of nanoparticulate polymer precursors before the assembly with
triblock copolymers. The mesostructured metal oxides assembled with preformed nanoparticles were known to be
more thermally stable than those prepared from molecular inorganic precursors.[99]

REVIEW

3 h each for the purpose of carbonization. The X-ray diffraction pattern revealed a sharp reflection peak at a 2h angle of
0.9–1.3°, demonstrating the periodically ordered structure of
the carbon film. The field-emission (FE)SEM image in
Figure 7b clearly shows the hexagonally arranged pores with
a lattice spacing and pore diameter of 7.5 nm and 6.2 nm, prepared at the carbonization temperatures of 400 and 600 °C, respectively.
Zhao and co-workers synthesized an ordered mesoporous
polymer and carbon denoted FDU-14 and C-FDU-14 in powder form through the direct assembly of a Pluronic triblock
copolymer and resol (phenol/formaldehyde).[97] Cooperative
assembly between resols and hydrophilic PEO blocks of P123
resulted in a resol-block-copolymer mesophase in the dilute
basic solution. The method was very similar to that of ordered
mesoporous silica (SBA-15, MCM-48, etc.) and the pore
structure of the resulting polymer and carbon was of Ia3d
symmetry. The carbonization of an FDU-14 polymer material
was conducted at 700 °C under nitrogen. The pore size of the
resulting carbon, C-FDU-14 was 2.7 nm, similar to that of
CMK-3 synthesized using SBA-15 as the template. In a subsequent paper, the Zhao group synthesized ordered mesoporous
polymer and carbon materials with 2D hexagonal (p6m), 3D

caged cubic (Im3m), and lamellar frameworks by simply adjusting the mass ratio of the polymer precursors and amphiphilic surfactants.[98] Figure 8 shows TEM and HRTEM images of C-FDU-15 and C-FDU-16 carbons with hexagonal
(p6m) and cubic (Im3m) structures, respectively. They first
synthesized a soluble low-molecular-weight polymer of resol
and mixed the resol with a Pluronic surfactant to make highly
ordered mesostructured materials. The surfactant was removed by heating at 350 °C. The ordered mesoporous polymers could be converted to ordered mesoporous carbon mate-

3.2.5. Synthesis of Hierarchically Ordered Mesoporous Carbon
Materials
Recently, various mesoporous carbons having hierarchical
structures were synthesized using hierarchically ordered mesoporous silica materials as templates. Bimodal mesoporous
silicas, denoted as Meso-nano-S, were developed by our research group through a simple and low-cost synthetic procedure.[100] Compared to the previous synthesis of bimodal mesoporous silica materials, our synthetic procedure is much
simpler and more cost effective, because sodium silicate is
polymerized under neutral conditions, followed by hydrothermal treatment. The hydrothermal treatment is critical to produce bimodal mesoporous silica materials. Bimodal mesoporous silica is comprised of 30–50 nm sized particles and 3D
wormholelike 4 nm sized pores. The large ca. 20 nm sized mesopores were derived from interparticle voids. The 3D interconnected wormholelike pore structure of Meso-nano-S silica
made it possible for it to be used as the template for producing porous carbon. To make hierarchical mesoporous carbon
using Meso-nano-S as the template, it was found to be important to control the amount of carbon precursor, so that it
would be selectively incorporated into the framework pores
of the Meso-nano-S silica template. The carbon precursor,
phenol, was first adsorbed into the small pores, because capillary condensation into small pores occurs at low pressure. The
Meso-nano-C carbon so produced was composed of 30–50 nm
sized particles having 3D wormholelike pores, and was the exact negative replica of the Meso-nano-S silica template.[100]
Fuertes synthesized spherical-shaped mesoporous carbon
materials with controlled particle diameters ranging from
10 nm to 10 lm by using corresponding mesoporous silica
spheres synthesized at various synthetic conditions.[101]
A modified pitch-based colloidal imprinting method was
used to synthesize bimodal mesoporous carbons.[102] Co-imprinting of hexagonally ordered SBA-15 particles and 13 nm
sized colloidal silica particles in pitch followed by carbonization and removal of the silica templates generated bimodal
mesoporous carbons. Two different sizes of mesopores (i.e.,
3–4 nm and ca. 13 nm) were derived from the wall thickness

of the SBA-15 silica and the colloidal silica particles, respectively. When the carbon synthesis was performed without
using colloidal silica particles, unimodal mesoporous carbon
particles with 3–4 nm sized mesopores were produced.[103]
Very recently, our research group reported a simple and
cost-effective synthesis of a mesocellular silica foam with

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ordered SBA-15-type mesoporous walls, designated as hierarchical mesocellular mesoporous silica (HMMS), using a
Pluronic triblock copolymer as a single structure-directing
agent.[104] Using the HMMS as the silica template and in situ
generated phenol–formaldehyde gel as a carbon precursor, we
were able to synthesize a hierarchical mesocellular mesoporous carbon (HMMC).[104] The TEM image of the HMMC
(Fig. 9a) showed that the ca. 40 nm sized cellular pores of
HMMS were well preserved and that small mesopores were
also present. These small mesopores were generated by the
replication of the 13 nm sized mesopores of the HMMS silica.

a)

directing agent. Using FA as a carbon source, hierarchical

porous monolithic carbon containing wormholelike mesopores and macropores was successfully replicated.[105] It is
possible to fabricate the carbon materials in the monolithic
form by using monolith-shaped mesoporous silica as the template. The macroporosity of the silica template was preserved
in the carbon materials, which indicates that the carbon
source, FA, only infiltrated into the mesopores.
Yoon et al. synthesized hollow core/mesoporous shell
(HCMS) carbon using solid core/mesoporous shell (SCMS)
structured silica as a template.[106] The SCMS template was
synthesized by a two-step process involving the synthesis of a
nonporous solid silica core by the Stöber method and the formation of the mesoporous silica shell by the sol–gel reaction
of TEOS with octadecyltrimethoxysilane (C18TMS) on the
surface of the solid silica spheres. The synthetic scheme for
HCMS is presented in Figure 10a. The selective deposition of
phenol into the mesopores of SCMS is important to preserve
the spherical morphology of the template silica. The diameter
of the hollow core and the thickness of the mesoporous shell
could be controlled by using appropriate SCMS silica templates. The HCMS carbon had very uniform hollow cores and

b)

Intensity (arbi. units)

a)

--1

q[nm ]
Figure 9. a) TEM image of an HMMC carbon. b) Small-angle X-ray scattering pattern of an HMMC carbon showing the regularity of the large
cells and small ordered pores. Reproduced from [104].

The N2 isotherms of HMMC exhibited two major capillary
condensation steps, resulting from the large ca. 40 nm sized
cellular pores (P/P0 ≈ 0.9) and small ordered 4.74 nm sized
mesopores (P/P0 ≈ 0.6) derived from the dissolution of the silicate walls. The BET surface area and single point total pore
volume of HMMC were 853 m2 g–1 and 1.54 cm3 g–1, respectively. The SAXS pattern of HMMC showed two sets of scattering peaks, revealing that the regularity of both the large
cellular pores and small mesopores of HMMS was preserved
during the replication (Fig. 9b).
Linden and co-workers prepared a hierarchical silica monolith possessing fully interconnected uniform mesopores and
macropores, by using a mixture of poly(ethylene glycol) and
alkyltrimethylammonium bromide (CnTAB) as the structure-

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b)

Figure 10. a) Schematic illustration for the synthesis of hollow core/mesoporous shell (HCMS) carbon capsules. b) TEM and SEM images of
HCMS carbon capsules. Reproduced from [106].

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3.2.6. Synthesis of Ordered Mesoporous Materials Using
Ordered Mesoporous Carbons as Templates
Ordered mesoporous carbon (OMC) materials generated

from ordered mesoporous silica templates were used as second-generation templates to synthesize ordered mesoporous
metal oxides.[21d] The rigidity of OMC made it possible to use
it as the template for mesoporous metal oxides. In addition,
the OMC could be easily removed by simple calcination.
The Schüth and Kim groups independently reported the
synthesis of SBA-15-like mesoporous silica using CMK-3 carbon as the template.[110,111] The mesopores of CMK-3 were
filled with the silica precursor, which was either TEOS or sodium silicate, and subsequent sol–gel polymerization was performed using HCl as a catalyst. Further aging and heat treatment designed to remove the CMK-3 carbon-generated
hexagonal mesoporous silica, which was similar to SBA-15 silica. This approach was then extended to the synthesis of other
mesoporous metal oxide materials. The conventional synthetic approach to the production of mesoporous silica using
surfactant self-assembly templates could not be easily extended to the synthesis of non-siliceous metal oxides. Therefore, to overcome this drawback, a two-step template synthetic route to monodisperse mesoporous inorganic spheres
with various compositions and a controllable crystalline phase
was developed.[112] Using spherical-shaped mesoporous carbons as templates, various kinds of mesoporous metal oxides
and phosphides, including TiO2, ZrO2, Al2O3, Ti2Si3Oy,

Adv. Mater. 2006, 18, 2073–2094

Ti2ZrOy, ZrP, and AlP, were synthesized. The resulting mesoporous metal oxides and phosphides had a high surface area
and large pore volume. Highly ordered mesoporous magnesium oxide (MgO) with a high surface area was successfully
synthesized using CMK-3 as a template.[113] This was achieved
by repetitive impregnation of magnesium nitrate and its subsequent thermal conversion to MgO. The resulting materials
preserved their structural order upon heating at 800 °C, as
confirmed by the XRD pattern, which is essential for the basic
property of MgO to be activated. The desorption of chemisorbed CO2 showed that the degree of basicity was comparable to that of MgO supported on SBA-15 silica. Xia and
Mokaya synthesized hollow spheres and shells of metal oxides
using hollow mesoporous carbon spheres as templates.[114] Ordered mesoporous carbon CMK-3 with a hollow spherical
particle shape was synthesized by CVD.[67] Metal alkoxide
was infiltrated into the pores of hollow spherical carbons, and
subsequent removal of the carbon template by calcining at
500–600 °C generated metal oxides with predominantly hollow spherical morphology. The synthesized metal oxides include alumina (c-Al2O3; surface area of 212 m2 g–1), titania
(anatase; 100 m2 g–1), mixed MgO–Al2O3, (322 m2 g–1), and binary MgTiO3 (154 m2 g–1).

The Yu group synthesized a new ordered mesostructured
silica material using MCM-48-templated carbon as a sacrificial template.[115] The MCM-48-templated carbon was not a
negative replica of MCM-48, rather it possessed a new ordered structure with I41/a symmetry.[52] The regenerated
ordered mesoporous silica was distinctly different from
MCM-48 silica materials and was a previously unreported
new structured mesoporous silica.
Boron nitride has good thermal conductivity and chemical
durability. Ordered mesoporous boron nitride was prepared
using tri(methylamino)borazine as a boron nitride source and
CMK-3 carbon as a template.[116] The CMK-3 template was
successfully removed by heating at 1000 °C under ammonia
atmosphere. The ordered structure of CMK-3 was successfully
transferred to the boron nitride structures after the removal
of the CMK-3 carbon template.

REVIEW

mesoporous shells, as shown in Figure 10b. The Yu group
synthesized silicalite-1 zeolite core/mesoporous silica shell
(ZCMC) structures from the sol–gel reaction of TEOS with
C18TMS on the surface of solid pseudohexagonal prismaticshaped silicalite-1 zeolite particles.[107] The ZCMS particles
with their bimodal microporous core/mesoporous shell structure were utilized as the template to fabricate a carbon replica
structure. Interestingly, the pore-replication process took
place only through the mesopores in the shell, and not
through the micropores, due to the smallness of the micropores in the zeolite core, resulting in the production of hollow
core/mesoporous shell (HCMS) carbon with a pseudohexagonal prismatic shape.
Using a similar synthetic procedure, our group synthesized
nanorattles, each composed of a gold nanoparticle encapsulated in a hollow mesoporous carbon sphere, using a silica
template with solid silica cores each containing a gold nanoparticle and mesoporous shell.[108] When the carbonization
step was skipped, nanorattles with a mesoporous poly(divinylbenzene) shell were also fabricated.

Zhao and co-workers synthesized mesoporous carbon rods
using rod-shaped SBA-15 silica as the template.[109] SBA-15
silica rods with lengths of 1–2 lm were synthesized by adding
KCl salt to the hydrothermal synthesis mixture for SBA-15 silica. These SBA-15 silica rods were used as the template for
the synthesis of rod-shaped mesoporous carbon with a
CMK-3 type structure.

3.2.7. Applications and Functionalization of Ordered
Mesoporous Carbons
Ordered mesoporous carbons denoted as SNU-1 and
SNU-2 were successfully employed as the electrodes for
EDLCs.[51,54,117] EDLCs are considered as promising highpower energy sources for digital communication devices and
electric vehicles, due to their high power density and good cyclability. EDLCs utilize electric double layers formed at the
interface of the electrode/electrolyte, where electric charges
are accumulated on the electrode surface and ions of opposite
charge are arranged on the electrolyte side of the interface.
EDLC electrode materials should have a large surface area
for effective charge accumulation and an appropriate pore
structure for good electrolyte wetting and rapid ionic motion.
To satisfy these requirements, it is desirable to synthesize me-

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soporous carbons with 3D interconnected pore structures.
Consequently, the above-mentioned mesoporous carbons having 3D interconnected pores, SNU-1 and SNU-2, were successfully employed as the electrode materials for EDLCs. The
EDLC performance of SNU-1 and SNU-2 was compared to
that of the most popularly applied activated carbon, MSC-25.
The cyclic voltammograms (CVs) obtained in an organic electrolyte (1 M NEt4BF4 in propylene carbonate) showed that
SNU-1 exhibited a more ideal capacitor behavior than
MSC-25, with a steep current change at the switching potentials (0.0 and 3.0 V), resulting in a more rectangular-shaped
I–V (current–potential) curve. The slow changes at the switching potentials in the cyclic voltammograms of the MSC-25
electrode seemed to stem from the slow reorganization of the
double-layer, owing to the slow ionic motions in the micropores. The steep change in the CV of the SNU-1 electrode in
turn reflected the dominance of the regular interconnected
mesopores among the electrochemically usable pores. The capacitance properties of CMK-3 carbon have also been investigated. In this case, a rectangular-shaped CV was observed
even when the scan rate was increased to 50 mV s–1, which
was similar to the results obtained for SNU-1 and SNU-2.
After the 100th cycle, the capacity decreased to 20 % of that
of the first scan.[118]
CMK-5 with its nanopipe-type hexagonal structure supports
the high dispersion of platinum nanoparticles, exceeding that
of other common microporous carbon materials (such as carbon black, charcoal, and activated carbon fibers). The diameter of the platinum clusters was able to be kept below 3 nm
and the high dispersion of these metal clusters enabled them
to have promising electrocatalytic activity for oxygen reduction, which could prove to be practically relevant for low-temperature fuel cells.[60] A high specific-energy capacity of about
1100 mAh g–1 (Li3C6) for lithium storage in the hexagonally
ordered mesoporous carbon CMK-3 was reported.[119] After
the first cycle, the discharge and charge remained at a reversible capacity level (LixC6, x = 2.3 to 3.0) with good cycle performance. The average loss per cycle (v) was smaller than that
of other mesoporous carbons. The authors concluded that
CMK-3 had the potential to be used in lithium rechargeable

batteries, considering the large absolute value of the reversible capacity and the small loss per cycle. The adsorption of
methane gas into CMK-3 was also investigated.[120] The
amount of adsorbed methane gas was 81.35 mg g–1
(= 117.33 mL(STP) g–1) at the high pressure of 35 kg cm–2 at
298 K. This result was much higher than that of zeolite, but
much lower than that of microporous coordination polymers
with an open framework.
CMK-3 carbons supporting palladium and platinum were
used as the catalyst for the hydrogenation of nitrobenzene
and ethylanthraquinone.[121] The hydrogenation activity of Pd/
CMK-1 and Pt/CMK-1 was superior to that of Pd/activated
carbon and Pt/activated carbon, because of the high dispersion of the palladium species inside the ordered mesopores
having a high surface area. Ordered mesoporous carbons at
various loading levels have larger hydrogen uptakes than Pd-

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or Pt-loaded activated carbons. MnO2 nanoparticles were incorporated into the pores of ordered mesoporous CMK-3 carbon via a sonochemical method.[122] In the analysis of these
MnO2/CMK-3 materials, CMK-3 with a 20 wt % loading of
MnO2 demonstrated improved discharge performance, owing
to the nanometer-sized MnO2 formed within the CMK-3.
Metal nanoparticles could be directly inserted into carbon
rods by the pyrolysis of the metal and carbon precursors in
the ordered mesoporous silica.[123] The growth and aggregation of the metal nanoparticles were hindered inside the confined mesoporous channels, resulting in the formation of
highly dispersed nanoparticles. Pt nanoclusters studded in the
microporous carbon nanorods were synthesized using direct
conversion methods. The size of the Pt nanoclusters was
smaller than the channel size of the SBA-15 silica, while the
size of Pt synthesized by conventional impregnation on
CMK-3 was larger than the channel size of SBA-15. The Pt

nanoclusters were accessible to CO, which indicated that they
were exposed to the gas via the micropores in the carbon rods.
The directly synthesized Pt/C nanocomposite showed an excellent performance in direct methanol fuel cells. Mesoporous
carbons with embedded cobalt nanoparticles were also
synthesized using a similar approach.[124] An ordered nanostructured, tin-based oxide/carbon composite (ONTC) was
prepared for use as the negative electrode material for lithium-ion batteries. ONTC was prepared by filling tin-based oxides into the mesopores of hexagonally ordered mesoporous
CMK-3. Nitrogen-adsorption experiments indicated that tinbased oxide materials were fully deposited into the internal
pores of CMK-3 carbon. The presence of interconnected carbon frameworks prevented aggregation of the tin species,
which resulted in a much better cycle performance for the use
as negative electrodes for lithium-ion batteries than those of
nanometer-sized tin-based oxides.[125]
Ordered mesoporous carbons were used as adsorbents for
biomolecules. Hartmann and co-workers studied the adsorption of cytochrome c on the hexagonally ordered mesoporous
CMK-3 carbon.[126] The adsorbed amount increased near the
isoelectric point of cytochrome c because there is no repulsive
interaction between CMK-3 and cytochrome c. A high adsorption capacity of 18.5 lmol was observed for CMK-3,
which was significantly higher than the reported value using
mesoporous silica materials. The Hartmann group also studied adsorption of vitamin E on the ordered mesoporous carbons using various concentrations of a vitamin E solution in
different solvents, such as n-heptane (nonpolar) and n-butanol.[127] The nonpolar solvent was more suitable for high loadings of vitamin E, which is because of the weak interaction
between the solvent and vitamin E.
A highly sensitive and fast glucose biosensor was fabricated
by simply immobilizing glucose oxidase (GOx) in a mesocellular carbon foam, MSU-F-C.[128] GOx with molecular
dimensions of 5.2 nm × 6.0 nm × 7.7 nm was immobilized in
MSU-F-C by a simple adsorption method and the loading
amount was 40 wt %. Even though the total pore volume of
MSU-F-C is only 1.5-fold higher than that of CMK-3 (4 nm

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particles were pulled away from the electrode there was no
current. Thus, the Mag-MCF-C/CLEA-GOx particles could
be switched alternately in the on and off states by positioning
the magnetic field.

REVIEW

sized pores with hexagonal symmetry), MSU-F-C showed as
much as a 50 times higher GOx loading than CMK-3,
which was because of the large uniform pores (> 20 nm) of
MSU-F-C. The glucose biosensor fabricated with MSU-F-C/
GOx showed a much higher sensitivity (order of magnitude)
and faster response than those using polymer matrices.
Fluorination has been used to modify the properties of
graphite, activated carbons, and carbon nanotubes, and these
fluorinated carbons have found applications as lubricants or
as cathode materials in lithium batteries. Dai and co-workers
synthesized ordered fluorinated mesoporous carbons by fluorination of the corresponding mesoporous carbons using
diluted fluorine gas.[129] The high-temperature fluorination induced the collapse of the ordered structure of the mesoporous
carbon. In contrast, the fluorinated carbon prepared at room
temperature preserved the ordered structure of the pristine
ordered mesoporous carbon. Ordered mesoporous carbon
nitride (CN) was synthesized using a mixture of ethylene diamine and carbon tetrachloride.[130] The physical characteristics of ordered mesoporous CN were very similar to those of
CMK-3 carbon synthesized using a SBA-15 silica template.

The atomic environment of C and N in the walls was similar
to other nonporous carbon nitride materials.
The Schüth group synthesized a magnetically separable, ordered mesoporous carbon, denoted Co-OMC, by the deposition of superparamagnetic nanoparticles on the surface of mesoporous carbon, followed by capping with a carbon
material.[131] Co-OMC on which rhodamine 6G (Rh6G,
C28H31N2O3Cl) was adsorbed was successfully separated
using a magnet. Palladium-loaded Co-OMC was used as a
magnetically separable catalyst for hydrogenation. This catalyst could be recycled after the magnetic separation. The synthetic procedure for Co-OMC was rather complex. A short
and simple synthetic procedure for magnetically separable, ordered mesoporous carbon was developed by our group.[132]
Poly(pyrrole) and the residual Fe2+ ions, which remained after
their use as the polymerization catalyst and were located in
the mesoporous channels, were converted to carbon materials
containing superparamagnetic nanoparticles in the carbon
rods. Our group developed a magnetic mesocellular carbon
foam, denoted Mag-MCF-C, with large interconnected cellular pores of > 20 nm.[133] Magnetic nanoparticles were simply
generated from impregnated iron salts during the carbonization at high temperature. Mag-MCF-C had many desirable
characteristics for the preparation of immobilized magneto–
bio–electrocatalysis.[134] GOx (6.0 nm × 5.2 nm × 7.7 nm) molecules were incorporated into the large cellular pores and
crosslinked by treating with glutaraldehyde, which resulted in
the generation of stable crosslinked enzyme aggregates
(CLEA). As a result of crosslinking, Mag-MCF-C/CLEAGOx maintained more than 90 % of its initial activity after
12 washings as well as after continuous incubation with vigorous shaking for 22 days. When Mag-CLEA/CLEA-GOx particles were brought into contact with the electrode by an
applied magnetic field, an increased anodic current was observed. On the contrary, when the Mag-MCF-C/CLEA-GOx

4. Synthesis of Macroporous Carbon Materials
4.1. Synthesis of Macroporous Carbon Materials Using Silica
Particles as Templates
Spherical submicrometer-sized silica particles have been
used as templates for the synthesis of macroporous carbon
materials with core/shell and hollow structures. The pore size
of the resulting macroporous carbon materials could be easily

controlled by varying the particle size of the silica spheres.
Zakhidov et al. synthesized various macroporous carbon materials using synthetic silica opals, which were made by the
self-assembly of uniform-sized silica spheres, known as colloidal crystals, as templates.[135] Macroporous carbon materials
with glassy carbon, graphitic carbon, and diamond were
synthesized by the infiltration of a phenol resin, the CVD of
propylene gas, and plasma-enhanced CVD, respectively, followed by the carbonization. The removal of the silica template by HF etching generated macroporous carbons with inverse opal structures (Fig. 11). In some cases, before the
infiltration of the carbon precursors, sintering was performed
to create necks between the silica spheres, which provided interconnections between the spherical pores in the resulting
carbons. Since the first report on the synthesis of macroporous carbon using colloidal templating, similar macroporous
carbon materials have been synthesized using simple and

Figure 11. SEM image of a graphitic macroporous carbon synthesized
using 200 nm sized silica opal templates. Reproduced with permission
from [135]. Copyright 1998 American Association for the Advancement of
Science.

cost-effective methods involving the carbonization of an
aqueous solution of sucrose or phenol resin.[136] These macroporous carbons exhibited large pore volumes and high surface areas. For example, macroporous carbon synthesized
using phenol resin as the carbon precursor showed closepacked uniform spherical pores with a diameter of 62 nm, a
total pore volume of 1.68 cm3 g–1, and a BET surface area of
750 m2 g–1.

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Yu and co-workers reported the synthesis of 3D ordered
macroporous carbon materials with different morphologies.[137] The process of controlling the morphology of the carbon materials was achieved by altering the acid catalyst sites
used for the polymerization of the carbon precursor, i.e., a
mixture of phenol and formaldehyde. The complete filling of
the interstitial pores of sintered colloidal silica crystals was
achieved by the infiltration of a phenol–formaldehyde mixture, and the subsequent infiltration of sulfuric acid, followed
by polymerization. The carbonization and removal of the silica template generated ordered macroporous carbon materials
with solid carbon walls. Using Al-impregnated silica particles
as the template, the polymerization of a phenol resin occurred
selectively on the surface of the silica particles, resulting in
surface-templated macroporous carbon. The resulting macroporous carbons showed a high loading of the Pt–Ru catalyst
nanoparticles. The specific activity of the Pt–Ru alloy catalyst
supported on the macroporous carbon for methanol oxidation
was much higher than those of the commercial E-TEK and
Vulcan XC-72 supported Pt–Ru catalysts generally used for
methanol oxidation. This improved catalytic activity seemed
to be due to the high surface area of the ordered macroporous
carbon, which provided for the high catalyst dispersion, and
the 3D interconnected uniform macropores, which allowed
for the efficient diffusion of the fuel and product. The same
group further controlled the pore size of the macroporous carbon materials in the range of 10–100 nm by using silica
spheres with various particle sizes, and conducted detailed
studies on their use as the electrodes in fuel cells.[138]
The Yu and Jaroniec groups reported the preparation of
highly graphitized ordered mesoporous carbons using commercial mesophase pitch as a carbon precursor and silica colloidal crystals as templates.[139] The synthesis of the graphitized ordered nanoporous carbon was carried out by the

incorporation of mesophase pitch dissolved in quinoline in
the interstitial space of the silica templates under a static vacuum. After carbonization and the removal of the silica template, the resulting carbon was further heated at the high temperature of 2500 °C for 30 min under an argon atmosphere to
generate highly graphitized carbon. Interconnected, ordered
spherical pores and relatively large graphite crystallites (interlayer spacing of ca. 0.33 nm) in the carbon pore walls were
clearly observed in the TEM image. The XRD patterns of the
carbon sample after the graphitization at 2500 °C showed a
sharp (002) peak and other reflections characteristic of a graphitic structure. The Raman spectra of the graphitized carbon
showed a strong G-band signal at 1588 cm–1 and a weak
D-band at 1356 cm–1, which was consistent with the XRD
data showing the highly graphitic characteristics of the macroporous carbon materials.
The Baumann group reported the synthesis of ordered macroporous carbons incorporating various metal nanoparticles
(Co, Ni, and Cu) using polystyrene (PS) microspheres as a
template and a metal-doped hydrogel, which was derived
from the base-catalyzed polymerization of formaldehyde with
the potassium salt of 2,4-dihydroxybenzoic acid, as a carbon

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precursor.[140] Metal ions, such as Co2+, Ni2+, and Cu2+, were
exchanged with the K+ ion in the K+-doped hydrogel. These
metal ions were reduced to metal nanoparticles during the
carbonization step.

4.2. Synthesis of 1D Carbon Nanostructures Using Anodic
Aluminum Oxide (AAO) Templates
Anodic aluminum oxide (AAO) films were prepared by the
electrochemical anodization of aluminum metal in electrolyte
cells.[141] AAO films generally have hexagonally arranged
honeycomb structures with a uniform pore size and a regular
pore-to-pore distance. The lengths and diameters of the channels in the AAO film could be easily controlled by changing

the oxidation time and current density. These AAO films have
been used as the templates for the fabrication of various tubular materials. Using AAO films as templates and various carbon precursors, carbon nanotubes have been successfully
synthesized. The general synthetic scheme for the preparation
of carbon nanotubes using AAO templates is shown in Figure 12. The Martin group reported the synthesis of carbon
nanotubes by depositing polyacrylonitrile in the channels of
the AAO template, followed by carbonization.[142] The Kyotani group achieved similar results using propylene as the carbon precursor.[143] The thermal decomposition of propylene in
the uniform straight channels of the anodic oxide films results

Figure 12. Synthetic scheme for the preparation of carbon nanotubes
using AAO templates. Reproduced with permission from [143b]. Copyright 1996 American Chemical Society.

in carbon deposition on the channel walls. The diameters of
the carbon nanotubes could be easily controlled by changing
the diameters of the AAO templates. Figure 13 shows representative SEM images of the carbon nanotubes synthesized
using AAO templates with different diameters of 30 nm
(Fig. 13a and b) and 230 nm (Fig. 13c and d). Furthermore, it
was also possible to control the wall thickness of the carbon
nanotubes by varying the carbon deposition time.
In the case of the AAO template method, however, the resulting carbon nanotubes had a lower crystallinity than those
grown via the CVD method. To synthesize highly crystalline
carbon nanotubes, the Martin group performed the CVD process using an AAO template incorporating a metal catalyst.[144] A Ni catalyst was deposited in the form of a film by

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immersing the AAO template in an organometallic nickel

solution, followed by the evaporation of the solvent and subsequent heat treatment at 400 °C under an argon atmosphere.
The decomposition of ethylene or pyrene at 545 °C and subsequent removal of the AAO template in a NaOH solution generated 1D carbon structures. Increasing the decomposition
time of the carbon precursors resulted in the generation of
carbon nanofibers instead of carbon nanotubes. Additional
heat treatment of the carbon nanofiber/AAO composite at
500 °C for 36 h converted the carbon nanofibers into highly
ordered graphite nanofibers. The Haslett[145] and Xu
groups[146] reported the synthesis of arrays of aligned multiwalled carbon nanotubes by pyrolyzing acetylene in an AAO
template containing catalytic cobalt nanoparticles at the bottom. The resulting carbon nanotubes had a slightly larger
d-spacing (d002) than that of graphite. The AAO template successfully oriented the growth of the carbon nanotubes. The
carbon nanotubes synthesized using the above method had
the potential to be used for electron field emission, since they
showed a turn-on field of 1.9–2.1 V lm–1 and a field enhancement factor of 3360–5200.[147]
The Martin group reported the fabrication of hierarchical
tube-in-tube carbon nanotubes using an AAO template, by
employing a combination of conventional CVD and the catalytic CVD method involving metal nanoparticles.[148] Firstly,
they used the CVD method to deposit carbon nanotubes inside an AAO membrane. A CNT/AAO composite was then
impregnated with an ethanol solution containing Fe(NO3)3
and reduced under H2 flow at 550 °C to produce Fe nanoparticles inside the as-synthesized carbon tubules. After exposing
the Fe nanoparticle deposited carbon tubule/alumina membranes to ethylene gas for 30 min, highly graphitic carbon
nanotubes with a smaller diameter were generated inside the

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REVIEW

Figure 13. SEM images of carbon nanotubes synthesized using AAO
templates with diameters of 30 nm (a,b) and 230 nm (c,d), respectively.
Reproduced with permission from [143b]. Copyright 1996 American
Chemical Society.

initially synthesized larger carbon nanotubes, forming a hierarchical tube-in-tube nanostructured carbon material. The
hierarchical tube-in-tube membrane was used as an electrode
for Li-ion intercalation. The cyclic voltammograms indicate
that the carbon tubule membrane was reversibly intercalated
with Li+ ions, and exhibited twice the intercalation capacity of
the carbon nanotubes synthesized using a single CVD process.
Both the outer and the inner tubules were electrochemically
active for the intercalation of lithium ions, suggesting the
possible use of this membrane in lithium-ion batteries. The
membranes could also be filled with nanoparticles of electrocatalytic metals and alloys, and these catalyst-loaded carbon
nanostructured materials could be used to electrocatalyze the
reduction of O2 and the oxidation of methanol, which are very
important processes for low-temperature fuel cells.
The Xu group reported the controlled growth of Y-junction
carbon nanotubes using a specially designed Y-branched
AAO template.[149] The channel diameter of the AAO template was proportional to the anodizing voltage. By reducing
the anodizing voltage from 50 V to 35 V in the conventional
process of preparing the AAO template, a Y-branched AAO
template was synthesized. The diameters of the stems and
branches were 40 nm and 28 nm, respectively. Cobalt catalyst
nanoparticles were electrochemically deposited at the bottom
of the AAO template. The catalytic pyrolysis of acetylene at
650 °C and the subsequent removal of the template generated
Y-junction carbon nanotubes. Using a similar method, the Sui
group synthesized multibranched carbon nanotubes by the

catalytic pyrolysis of acetylene using a multi-branched AAO
template.[150] The multibranched AAO template was synthesized under the conditions of an abrupt increase in the anodizing voltage from 30 V to 60 V and subsequent slow decrease
to 30 V.
It is known that the doping of group III or group V elements imparts semiconductor characteristics to carbon nanotubes.[151] Very recently, the Kyotani group reported the
synthesis of double coaxial carbon nanotubes with an
N-doped inner wall and B-doped outer wall using a two-step
template method.[152] First, the CVD of acetonitrile
(CH3CN) on the AAO template at 800 °C for 2 h generated
an N-doped CNT/AAO composite. After annealing under
an N2 atmosphere at 950 °C for 1 h, a second CVD process
was conducted on the N-doped CNT/AAO composite, using
benzene and BCl3 as the carbon and boron sources, respectively. Removing the AAO template with HF etching resulted in the formation of double coaxial carbon nanotubes
with an N-doped inner wall and B-doped outer wall. Using
a similar method, carbon nanotubes with an undoped inner
wall/N-doped outer wall structure or an undoped inner wall/
B-doped outer wall structure were synthesized. Although
the crystallinity of the N-doped carbon nanotubes was lower
than that of the undoped ones, the conductivity of the former was higher than that of the latter, due to the doping effect.

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5. Conclusions and Outlook
The recent progress made in the synthesis of various porous
carbon materials was reviewed in this article. By using appropriate synthetic procedures, porous carbon materials with various pore dimensions and pore structures were synthesized.
These synthetic methods can be divided into two categories:

activation processes and template methods. Although activation processes have frequently been employed for the synthesis of porous carbon materials because of their simplicity and
scalability, in general, porous carbon materials with non-uniform pore sizes and isolated non-interconnected pores are
produced. Many porous carbon materials having a variety of
pore sizes and pore structures were synthesized using various
kinds of designed templates. These porous carbon materials
exhibit uniform pore sizes, high surface areas, and large pore
volumes. These desirable characteristics have led these porous
carbon materials to be extensively applied in various technological areas, including electrodes for batteries, fuel cells, and
supercapacitors, and as hosts for the immobilization of biomolecules for biosensors. For many biotechnological applications, mesoporous carbon materials having large interconnected pores with diameters of > 10 nm need to be
synthesized. For the electrodes of electrochemical devices
such as fuel cells, porous carbon materials with highly graphitic structures are needed, and accomplishing this has been very
challenging. The synthesis and application of various porous
carbon materials having hierarchical structures is expected in
the future. Simple and economical template synthetic procedures should be developed for the broad application of these
synthesized porous carbons.
Received: July 29, 2005
Final version: January 19, 2006
Published online: August 1, 2006

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