Available online at www.sciencedirect.

com

Bioresource Technology 99 (2008) 4803–4808

Preparation and gas storage of high surface area microporous

carbon derived from biomass source cornstalks
Feng Zhang a, Hua Ma b, Jun Chen b, Guo-Dong Li a, Yu Zhang a, Jie-Sheng Chen a,*

a
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China
b
College of Chemistry, Nankai University, Tianjin 300071, PR China

Received 3 August 2007; received in revised form 18 September 2007; accepted 19 September 2007
Available online 29 October 2007

Abstract

Microporous carbon (MC) with a high surface area has been prepared from cornstalks through carbonization and KOH activation.
The surface area of the obtained product varies to some extent but the pore size of the material remains within the micropore region as
the concentration of KOH activating agent is increased. The MC we prepared exhibits H2 adsorption capacities up to 4.4 wt% at 77 K
and this material is also able to adsorb considerable amounts of CH4 and CO2. The high adsorption capacities for gases are attributed to
the relatively narrow pore size and the high surface area of the porous carbon material.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biomass; Cornstalks; Hydrogen storage; Microporous carbon

1. Introduction
Among the conventional carbon materials, diamond
and graphite are two of the most important ones, whereas
the discovery of fullerenes and carbon nanotubes has
brought the carbon materials research into a new era
(Kroto et al., 1985; Iijima, 1991). During the past two dec-
ades, enormous efforts have been focused on fullerenes and
carbon nanotubes (Braun et al., 2000; Ajayan, 1999).
Nevertheless, other forms of carbon materials including
carbon fibers, glassy carbon, carbon black and amorphous
carbon are equally important, both from the industrial and
from the academic viewpoints. Porous carbons represent a
typical type of carbon materials, and in recent years, there
has been increasing interest in novel applications of porous
carbons in the fields of, for example, electrode manufac-
ture, catalysis, and gas storage and separation (Tokumitsu
et al., 1999; Blanco et al., 2006; Aksoylu et al., 2001; Hynek
* plates have been used for the preparation of porous car-
Corresponding author. Tel.: +86 431 85168581; fax: +86 431
85168624.
E-mail address: chemcj@jlu.edu.cn (J.-S. Chen).
et al., 1997; Wang et al., 2007; Nijkamp et al., 2001; Jure-
wicz et al., 2004).
In order to reduce emissions from fossil fuels, renewable
and clean energies have been intensely sought all over the
world. Among a series of energy sources, hydrogen is a
very promising candidate for replacement of conventional
fossil fuels (Dresselhaus and Thomas, 2001; Schlapbach
and Züttel, 2001). However, the bottleneck for the intro-
duction of hydrogen, especially in the fuel cell system of
mobile applications, is the appropriate hydrogen storage
techniques. In this context, activated carbons, especially
microporous activated carbons, are attractive because of
their low density, low cost, richness in raw materials, high
surface area and good chemical stability.
Conventionally, porous carbon materials were prepared
from coal, petroleum coke, pitch, synthetic organic com-
pounds and lignocellulosic materials. However, most of
the porous carbons obtained through conventional tech-
niques have a low surface area (<2500 m2/g), limiting their
applications to a considerable extent. Recently, rigid tem-
bons (Yang et al., 2007; Ma et al., 2001; Che et al., 2003;
Deng et al., 2007; Titirici et al., 2007). Nevertheless, the

0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.09.052
4804 F. Zhang et al. / Bioresource Technology 99 (2008) 4803–4808
templating preparation is a multi-step process, and the cost
is usually high. Biomass sources are renewable, in a sense,
because photosynthesis converts CO2 and water into car-
bohydrates contained in biomasses. Utilization of biomass
resources to form more valuable matters is particularly
attractive as the rapid consumption of fossil fuels would
lead to shortage in energy and raw materials on this planet.
It has been reported that hydrocarbons and hydrogen are
able to be obtained from biomasses through a catalytic
pathway (Huber et al., 2005; Cortright et al., 2002). Bio-
masses such as wood and coconut have been used to pre-
pare porous activated carbons. Cornstalks contain rich
carbon species and the major components of cornstalks
are cellulose, hemicellulose and lignin, which can also act
as a suitable precursor for the formation of porous acti-
vated carbons (Youssef et al., 2004; Zhang et al., 2004;
Cao et al., 2006; Fan et al., 2004). However, again the sur-
face area of biomass-derived porous carbons reported so
far is rarely over 2500 m2/g.
Here we report a simple strategy for the preparation of
high surface area (>3000 m2/g) microporous carbon (MC)
with a relatively narrow pore size distribution (PSD) from
an easily accessed biomass – cornstalks. It is of significance
that the MC we obtained exhibits considerable adsorption
capacities for H2, CO2 and CH4.
2. Experimental
2.1. Preparation of MC
A four-step method was used in the preparation of the
MC material. At first, the raw cornstalks (RCs) were
washed, dried at 373 K and chopped into 1.5 cm pieces in
length. The chopped stalks were then heated at 673 K for
3 h in an atmosphere of N2. At this step, carbonized prod-
uct (CP) and tar were formed. About 1.0 g CP was soaked
in a KOH solution with a particular concentration for
about one day. Afterward, the CP was separated from
the solution by filtration, heated at 1023 K in the presence
of N2 for 2 h, washed with distilled water and treated with
dilute HCl solution. Finally, the carbon material was fur-
ther washed with distilled water until the pH value of the
system reached about 7.0, and dried at 373 K. The MCs
activated with various KOH solutions (concentrations
6.0 mol/L, 7.0 mol/L, 9.0 mol/L and 10.0 mol/L) are
denoted as MC1, MC2, MC3, MC4, respectively.
2.2. Characterization and gas storage measurements
The elemental analyses were conducted on a Perkin-
Elmer 2400LS II elemental analyzer. The X-ray photoelec-
tron spectroscopy (XPS) was performed on a Thermo
Electron Corporation ESCALAB 250 XPS spectrometer,
whereas the X-ray diffraction (XRD) patterns were
recorded on a Siemens D5005 diffractometer with Cu Ka
radiation (k = 1.5418 Å). The infrared (IR) spectra were
recorded on an IFS 66V/S FTIR spectrometer using KBr
pellets, and the electron spin resonance (ESR) spectroscopy
was performed on a JES-FE3AX ESR spectrometer. The
Raman spectra were obtained on a Renishaw 1000 Raman
spectrometer with the 514.5 nm excitation line of an Ar+
laser. The N2 adsorption/desorption measurements were
conducted on a Micromeritics TriStar 3000 system. Prior
to each measurement, the sample was evacuated at 473 K
for 12 h to remove the adsorbed guest species such as
water. The surface area data were calculated on the basis
of the Brunauer–Emmett–Teller (BET) model whereas
the PSD was obtained through the Horvath-Kawazoe
approach. The transmission electron microscopic (TEM)
images of the porous carbon samples were taken on a
JEOL JEM 3010 electron microscope operated at 300 kV.
The H2 adsorption isotherms for the porous carbon mate-
rials were measured on an AMC PCT-2000 H2-adsorption
system at 77 K, whereas the CO2 and CH4 adsorption mea-
surements were performed on a CAHN 2000 Quartz
Microbalance at both 195 K and 298 K.
3. Results and discussion
3.1. Formation of MC
Usually, the preparation process of porous carbons con-
sists of carbonization and activation, in which various
chemical reactions proceed. It is not possible to pinpoint
the exact chemical reactions during the formation of por-
ous carbons, but the likely reaction routes can be inferred
on the basis of IR, Raman and ESR spectroscopies, com-
position analysis and XRD.
IR spectroscopy is a useful technique to identify the var-
iation of functional groups during formation of carbons
from source materials in which dehydration is the most
important reaction. The first step is carbonization treat-
ment. In this process, some C–O and C–C bonds are
cleaved to form small molecules including CO, H2O and
CO2. In our experiment, we observed yellow tar which
appeared at the end of the carbonization tube after carbon-
ization treatment of the cornstalks, and it is believed that
the tar arises from the C–O and C–C bonds cleavage in
the carbonization. The IR spectra indicate that there are
a variety of functional groups (–OH, –COO , C–H and
C–O–C) in the RC, whereas after carbonization the
amounts of these groups decrease to a great extent. When
the CP is socked in a KOH solution, the latter becomes yel-
low rapidly. Obviously, the KOH solution dissolves the tar
species occluded in the CP. The IR spectrum of the MC
shows a broad band at 1089 cm 1 associated with C–O–
C stretching vibrations and bands around 1573 cm 1 and
3410 cm 1 due to C@C bonds and hydroxyl groups and/
or sorbed water molecules, respectively. Table 1 shows
the chemical compositions of the raw material, the carbon-
ized product and the microporous carbons with various
surface areas. It is seen that both carbonization and activa-
tion result in the increase of the carbon content and the
decrease of the H content. Therefore, a considerable
 F. Zhang et al. / Bioresource Technology 99 (2008) 4803–4808
Table 1
Chemical compositions of the raw material, the carbonized product and
the microporous carbon with various surface areas
Raw Carbonized MC1 MC2 MC3
material product
C (wt %) 44.1 70.8 84.0 88.0 90.8
H (wt %) 6.4 3.0 2.8 2.3 0.3
N (wt %) 0.9 0.4 0.4 0.4 0.3
amount of oxygen atoms and hydrogen atoms must have
been driven away from the cornstalk structure upon car-
bonization and activation. The yields of the MCs from
raw material are about 17%. It is worthwhile to note that
in the final MC materials, the content of carbon increases
in the order MC1 < MC2 < MC3 < MC4 whereas that of
hydrogen decreases in the order MC1 > MC2 >
MC3 > MC4. This is because that with increase of the con-
centration of the KOH solution, more hydrocarbon species
are removed through reaction with the activating agent
during the activation process.
Two broad peaks at around 1580 cm 1 and 1360 cm 1
appear in the Raman spectra of both the CP and the
MC. These two peaks are also observed previously for
many carbon materials, such as activated charcoal, acti-
vated carbon fibers and porous carbons (Tuinstra and
Koenig, 1970; Singh et al., 2002; Polarz et al., 2002). The
1580 cm 1 band is associated with the vibration of carbon
atoms with sp2 electronic configuration in graphene sheet
structure, and the 1360 cm 1 band corresponds to the dis-
ordered and imperfect structures of carbon materials
(Kayiran et al., 2004; Pol et al., 2004). In addition, no
Raman signals for the raw material are detected, indicating
that there are nearly no aromatic structures in the texture
of cornstalks. On the basis of the Raman spectra, we can
conclude that some carbon atoms in the cornstalks are
assembled into graphene sheet structures during carboniza-
tion. After activation treatment, more graphene sheets are
formed, but the resulting carbonaceous matter still has a
low graphitization degree since the relatively strong band
at 1360 cm 1 remains (Su et al., 2005; Yang et al., 2005;
Bacsa et al., 2004).
ESR spectroscopy is useful for investigation of carbon
materials with respect to their structure transformation
during heat treatment. The main components of the corn-
stalks are cellulose, hemicellulose and lignin and no radi-
cals are present in the RC, as demonstrated by the
absence of ESR signals for the raw material. The ESR
spectrum of the carbonized sample consists of a narrow sig-
nal with Lorentzian shape and g = 2.0021. As previously
observed for carbon materials, this signal arises from local-
ized paramagnetic centers, which are most probably associ-
ated with aromatic p-radicals produced during the thermal
treatment of the cornstalks. The presence of aromatic p-
radicals implies that an imperfect carbon structure, such
as the one with carbon atoms containing unpaired elec-
trons on the edges of small graphene sheets (Zhecheva
et al., 2002; Alcántara et al., 1999; Kawamura, 1998), is
4805
formed. In the spectrum of the CP after thermal treatment
at 1023 K for 2 h under N2 atmosphere (without activating
agent), the ESR signal intensity is reduced distinctly, indi-
MC4 cating that recombination of free radicals occur in the CP
during thermal treatment at 1023 K. However, no ESR sig-
92.3 nal has been detected for the MC prepared at 1023 K using
0.2
0.3
KOH as an activating agent. It is therefore concluded that
the activation reaction removes the carbon atoms with
unpaired electrons from the carbon material.
To better understand the structure of the activated prod-
uct, powder XRD has been recorded. The characteristic
peaks of the XRD pattern of the activated product without
washing are in good agreement with those of
K2CO3Æ1.5H2O, suggesting that the KOH used as an acti-
vating agent has been converted into K2CO3 via reactions
with the carbon atoms of the CP during the activation
treatment. A broad peak at around 2h = 23.6o, as observed
previously for most non-graphitized carbon materials,
appears in the XRD pattern of the MC. To investigate
the number of parallel graphene sheets of the ordered
domains in amorphous carbons, the empirical parameter
R, was described by Dahn and co-workers (Liu et al.,
1996; Dhan et al., 1997). R = 1 will be achieved, if the car-
bon material is composed of single graphene sheets only.
Calculation based on the XRD pattern of the MC results
in R = 1.28, indicating that the as-synthesized MC is pri-
marily composed of single graphene sheets and both flat
and curved graphene sheets may exist (Townsend et al.,
1992; Harris et al., 2000). In other words, the carbon mate-
rial we obtained is essentially non-crystalline and nearly no
ordered stacking of graphene sheets is present in the texture
of the material although the material has been treated at a
temperature as high as 1023 K.
The N2 adsorption/desorption isotherms at 77 K for the
MC materials are shown in Fig. 1a. It is of interest that the
isotherms trace type I curves, and no hysteresis loop is
observed for all the curves. Fig. 1b displays the Horvath–
Kawazoe PSDs and it is seen that a large proportion of
the pores have a diameter of 1–2 nm. Although the pore
size distribution curves suggest that pores with a diameter
ranging from 2 to 10 nm are also present in the MC mate-
rials, these wider pores are dispersively populated in the 2–
10 nm size region. On the basis of the N2 adsorption/
desorption isotherms and the PSD data, the carbon mate-
rials we obtained may be considered to be largely
microporous.
On the basis of the results of IR, Raman, ESR spectros-
copies, composition analysis and XRD, it is believed that
the MC formation proceeds as follows. In the carboniza-
tion, most of heteroatom elements such as O and H are dri-
ven off from the structure as volatile species, such as H2O,
CO, CO2 and tar, via pyrolytic decomposition of the raw
material whereas most of the remaining carbon atoms are
assembled into graphene sheets. These graphene sheets
are cross-linked with one another and are arranged in an
irregular manner, leaving plenty of interstices between the
sheets which give rise to micropores. However, most of
4806 F. Zhang et al. / Bioresource Technology 99 (2008) 4803–4808

Table 2
a Total pore volumes, BET surface areas, t-plot micropore areas and
1000
average pore widths of the MCs obtained through KOH activation
Volume Adsorbed (cm3/g)

Sample KOH Pore BET t-Plot Average

800 concentration volume surface micropore pore width
(mol/L) (cm3/g) area area (m2/g) (nm)
600 (m2/g)
MC4 MC1 6 1.16 2140 1120 1.25
400 MC3 MC2 7 1.22 2600 1160 1.34
MC3 9 1.38 3000 1450 1.42
MC2
MC4 10 1.44 3200 1440 1.50
200 MC1

0 general, average pore width and porosity development

0.0 0.2 0.4 0.6 0.8 1.0
increases with the KOH/precursor ratio. A carbonized
p/p0
material has a less developed pore system or its pores are
partially blocked by tar, heteroatoms and so on. During
b 0.010 the activation, the activating agent reacts with the reactive
centers of the carbonized material, such as disorganized
PSD (cm3/(g nm))

0.008 carbons, carbons with heteroatoms and carbons on graph-

0.006
0.004
0.002
0.000
2 4 6 8
Pore width (nm)
Fig. 1. (a) N2 adsorption/desorption isotherms at 77 K for MC1, MC2,
MC3 and MC4, and (b) the pore size distributions of MC1, MC2, MC3
and MC4 obtained from the N2 adsorption isotherms at 77 K.
the micropores formed at this stage are blocked by the tar,
heteroatoms and so on. As a result, the CP does not show
high adsorption capacity for its less developed pore struc-
ture. When the CP is soaked in a KOH solution, some
tar in the carbonaceous matter is dissolved, whereas the
activation treatment makes the micropore structure further
developed. In this process, the CP is converted to a carbon
material that contains a large number of randomly
arranged micropores with different shapes and sizes, and
high specific surface area is achieved for the final MC
product.
The MC we prepared is advantageous over the conven-
tional activated carbon materials because our material pos-
sesses a narrower PSD with a much higher surface area.
However, it should be pointed out that the surface area
of the final product depends on the KOH concentration
for activation treatment.
Table 2 lists the total pore volumes, the BET surface
areas, the t-plot micropore areas and the average pore
widths for MC1, MC2, MC3 and MC4 calculated on the
basis of adsorption isotherms of N2 at 77 K. It is seen that
the higher the concentration of the activating KOH solu-
tion, the higher the surface area of the MC material. In
ene edges, creating new pores and widening the existing
MC4
ones. Therefore, when the concentration of the KOH solu-
tion is increased, the extent to which the activation reaction
MC3
proceeds becomes greater, and the porosity of the material
MC2
becomes richer.
MC1
We found that when the concentration of the KOH
solution is 10 mol/L, the surface area reaches the highest
value, but further increasing the concentration to 13 mol/
10 12
L results in slight decrease of the surface area of the MC.
This is because that the activating agent not only develops
the porosity but also damages the structures of the pores at
too high a concentration. In addition, the activation agent
we used is a KOH solution instead of solid KOH which
was usually used previously. The use of KOH solution ren-
ders it possible for the activating agent to be dispersed in
the carbonized carbon structure more homogeneously,
and consequently, the pores formed in the final product
are more uniform than those obtained through the conven-
tional preparation approaches using solid alkalis for acti-
vation. The incompact texture of the cornstalks favors
the easy diffusion of KOH solution and this may also
account for the high surface area and the narrow pore of
the carbon material. We have tried to prepare porous car-
bons using other biomass sources, for example, rice husk,
pine needle and pinecone hull through similar routes but
the obtained porous carbons all have a low surface area.
3.2. Gas storage properties
The adsorption capacity of MC4 has been tested for H2,
CH4, and CO2 under isothermal conditions. The adsorp-
tion isotherm of hydrogen at 77 K indicates that the
adsorption is not saturated up to 4 MPa and the adsorp-
tion capacity is about 4.4 wt% at this pressure. The pore
size of the carbon material is just a few times that of the
dynamic diameter (0.41 nm) of a H2 molecule. Therefore,
the potential fields of force from surrounding walls of the
micropores overlap so that the interactions between the
 F. Zhang et al. / Bioresource Technology 99 (2008) 4803–4808 4807

surface of the MC and H2 molecules are strong, resulting in 4. Conclusions

easier adsorption of H2 gas at low pressures (Zecchina
et al., 2005; Zhao et al., 2005). In addition, the high surface
area of the MC may also contribute to the large hydrogen
adsorption capacity.
The MC also exhibits rather high adsorption capacities
for CO2 and CH4. The adsorption isotherm of CO2 at
195 K on MC4 indicates that at 1 atm the adsorption satu-
ration is not reached, and up to 9.5 wt% CO2 is adsorbed at
this CO2 pressure. Even at room temperature the uptake
value of CO2 is 4.0 wt% (Fig. 2a). Furthermore, a high
CH4 adsorption capacity of about 3 wt% is also observed
at 1 atm and 195 K for the porous carbon we obtained.
This capacity value exceeds the capacities exhibited by por-
ous van der Waals crystals (2.4 wt% 195 K) (Sozzani et al.,
2005). We also measured the CH4 adsorption capacity at
room temperature and 1 atm for the MC material, and
an uptake value of 1 wt% (Fig. 2b), higher than that for
metal complexes (0.6 wt% 298 K) and van der Waals crys-
tals (0.8 wt% at 1 atm, 298 K) (Sozzani et al., 2005; Seki,
2001), has been observed.
MC materials with a high surface area have been suc-
cessfully prepared from cornstalks through simple carbon-
ization and activation. The pore size of the carbon
materials remains in the range of 1–2 nm, whereas the
BET surface area varies from 2140 to 3200 m2/g depending
on the concentration of the activation agent. Our results
show that the MC derived from cornstalks is able to adsorb
considerable amounts of H2, CO2 and CH4. Further
improvement of gas storage performance for the MC mate-
rial is underway. The successful preparation of the high
surface area MC from cornstalks may open new vistas
for utilization of biomass sources to produce highly valu-
able materials.
Acknowledgement
Financial support by the National Natural Science
Foundation of China is gratefully acknowledged.
References

Ajayan, P.M., 1999. Nanotubes from carbon. Chem. Rev. 99 (7), 1787–
a 1800.
10 Aksoylu, A.E., Madalena, M., Freitas, A., Pereira, M.F.R., Figueiredo,
J.L., 2001. The effects of different activated carbon supports and
8 195 K support modifications on the properties of Pt/AC catalysts. Carbon 39
(2), 175–185.
Weight % CO2

Alcántara, R., Madrigal, F.J.F., Lavela, P., Tirado, J.L., Mateos, J.M.J.,
6 Stoyanova, R., Zhecheva, E., 1999. 13C,1H,6Li magic-angle spinning
nuclear magnetic resonance, electron paramagnetic resonance, and
Fourier transform Infrared study of intercalation electrodes based in
4 ultrasoft carbons obtained below 3100 K. Chem. Mater. 11 (1), 52–60.
Bacsa, R., Laurent, C., Morishima, R., Suzuki, H., Le, L.M., 2004.
298 K
Hydrogen storage in high surface area carbon nanotubes produced by
2
catalytic chemical vapor deposition. J. Phys. Chem. B 108 (34), 12718–
12723.
0 Blanco, J., Petre, A.L., Yates, M., Martin, M.P., Suarez, S., Martin, J.A.,
0.00 0.02 0.04 0.06 0.08 0.10 2006. Characterization of photonic colloidal single crystals by micro-
radian X-ray diffraction. Adv. Mater. 18 (13), 1162–1166.
CO2 pressure (MPa)
Braun, T., Schubert, A.P., Kostoff, R.N., 2000. Growth and trends of
fullerene research as reflected in its journal literature. Chem. Rev. 100
b 3.0
(1), 23–38.
Cao, Q., Xie, K.C., Lv, Y.K., Bao, W.R., 2006. Process effects on
activated carbon with large specific surface area from corn cob.
2.5 195 K Bioresour. Technol. 97, 110–115.
Che, S.A., Lund, K., Tatsumi, T., IiJima, S., Joo, S.H., Ryoo, R.,
Weight % CH4

2.0 Terasaki, O., 2003. Direct observation of 3D mesoporous structure by

scanning electron microscopy (SEM): SBA-15 silica and CMK-5
1.5 carbon. Angew. Chem. Int. Ed. 42 (19), 2182–2185.
Cortright, R.D., Davda, R.R., Dumesic, J.A., 2002. Hydrogen from
1.0 catalytic reforming of biomass-derived hydrocarbons in liquid water.
Nature 418, 964–967.
298 K Deng, Y.H., Yu, T., Wan, Y., Shi, Y.F., Meng, Y., Gu, D., Zhang, L.,
0.5
Huang, Y., Liu, C., Wu, X., Zhao, D., 2007. Ordered mesoporous
silicas and carbons with large accessible pores templated from
0.0 amphiphilic diblock copolymer poly(ethylene oxide)-b-polystyrene. J.
0.00 0.02 0.04 0.06 0.08 0.10 Am. Chem. Soc. 129 (6), 1690–1697.
CH4 pressure (MPa) Dhan, J.R., Xing, W., Gao, Y., 1997. The ‘‘falling cards model’’ for the
structure of microporous carbons. Carbon 35 (6), 825–830.
Fig. 2. Adsorption isotherms of (a) CO2 and (b) CH4 at 195 K and room Dresselhaus, M.S., Thomas, I.L., 2001. Alternative energy technologies.
temperature on MC4. Nature 414, 332–337.
4808 F. Zhang et al. / Bioresource Technology 99 (2008) 4803–4808
Fan, M., Marshall, W., Daugaard, D., Brown, R.C., 2004. Steam
activation of chars produced from oat hulls and corn stover.
Bioresour. Technol. 93, 103–107.
Harris, P.J.F., Burian, A., Duber, S., 2000. High-resolution electron
microscopy of a microporous carbon. Philos. Mag. Lett. 80 (6), 381–
386.
Huber, G.W., Chheda, J.N., Barrett, C.J., Dumesic, J.A., 2005. Produc-
tion of liquid alkanes by aqueous-phase processing of biomass-derived
carbohydrates. Science 308, 1446–1450.
Hynek, S., Fuller, W., Bentley, J., 1997. Hydrogen storage by carbon
sorption. Int. J. Hydrogen Energy 22 (6), 601–610.
Iijima, S., 1991. Helical microtubules of graphitic carbon. Nature 354, 56–
58.
Jurewicz, K., Frackowiak, E., Béguin, F., 2004. Towards the mechanism
of electrochemical hydrogen storage in nanostructured carbon mate-
rials. Appl. Phys. A: Mater. Sci. Process 78 (7), 981–987.
Kawamura, K., 1998. Electron spin resonance behavior of pitch-based
carbons in the heat treatment temperature range of 1100–2000 °C.
Carbon 36 (7-8), 1227–1230.
Kayiran, S.B., Lamari, F.D., Levesque, D., 2004. Adsorption properties
and structural characterization of activated carbons and nanocarbons.
J. Phys. Chem. B 108 (39), 15211–15215.
Kroto, H.W., Heath, J.R., O’Brien, S.C., Curl, R.F., Smalley, R.E., 1985.
C60: Buckminsterfullerene. Nature 318, 162–163.
Liu, Y.H., Xue, X.J., Zheng, T., Dhan, J.R., 1996. Mechanism of lithium
insertion in hard carbons prepared by pyrolysis of epoxy resins.
Carbon 34 (2), 193–200.
Ma, Z.X., Kyotani, T., Liu, Z., Terasaki, O., Tomita, A., 2001. Very high
surface area microporous carbon with a three-dimensional nano-array
structure: synthesis and its molecular structure. Chem. Mater. 13 (12),
4413–4415.
Nijkamp, M.G., Raaymakers, J.E.M.J., van Dillen, A.J., de Jong, K.P.,
2001. Hydrogen storage using physisorption – materials demands.
Appl. Phys. A: Mater. Sci. Process 72 (5), 619–623.
Pol, V.G., Motiei, M., Gedanken, A., Calderon-Moreno, J., Yoshimura,
M., 2004. Carbon spherules: synthesis, properties and mechanistic
elucidation. Carbon 42 (1), 111–116.
Polarz, S., Smarsly, B., Schattka, J.H., 2002. Hierachical porous carbon
structures from cellulose acetate fibers. Chem. Mater. 14 (7), 2940–
2945.
Schlapbach, L., Züttel, A., 2001. Hydrogen-storage materials for mobile
applications. Nature 414, 353–358.
Seki, K., 2001. Design of an adsorbent with an ideal pore structure for
methane adsorption using metal complexes. Chem. Commun. (16),
1496–1497.
Singh, C., Quested, T., Boothroyd, C.B., Thomas, P., Kinloch, I.A.,
Abou-Kandil, A.I., Windle, A.H., 2002. Synthesis and characterization
of carbon nanofibers produced by the floating catalyst method. J.
Phys. Chem. B 106 (42), 10915–10922.
Sozzani, P., Bracco, S., Comotti, A., Ferretti, L., Simonutti, R., 2005.
Methane and carbon dioxide storage in a porous van der Waals
Crystal. Angew. Chem. Int. Ed. 44 (12), 1816–1820.
Su, F.B., Zhao, X.S., Wang, Y., Zeng, J.H., Zhou, Z.C., Lee, J.Y., 2005.
Synthesis of graphitic ordered macroporous carbon with a three-
dimensional interconnected pore structure for electrochemical appli-
cations. J. Phys. Chem. B. 109 (43), 20200–20206.
Titirici, M.M., Thomas, A., Antonietti, M., 2007. Replication and coating
of silica templates by hydrothermal carbonization. Adv. Funct. Mater.
17 (6), 1010–1018.
Tokumitsu, K., Fujimoto, H., Mabuchi, A., Kasuh, T., 1999. High
capacity carbon anode for Li-ion battery: a theoretical explanation.
Carbon 37 (10), 1599–1605.
Townsend, S.J., Lenosky, T.J., Muller, D.A., Nichols, C.S., Elser, V.,
1992. Negatively curved graphitic sheet model of amorphous carbon.
Phys. Rev. Lett. 69 (6), 921–924.
Tuinstra, F., Koenig, J.L., 1970. Raman spectrum of graphite. J. Chem.
Phys. 53 (3), 1126–1130.
Wang, J.N., Zhang, L., Niu, J.J., Yu, F., Sheng, Z.M., Zhao, Y.Z., Chang,
H., Pak, C., 2007. Synthesis of high surface area, water-dispersible
graphitic carbon nanocages by an in situ template approach. Chem.
Mater. 19 (3), 453–459.
Yang, Q.H., Xu, W.H., Tomita, A., Kyotani, T., 2005. Double coaxial
structure and dual physicochemical properties of carbon nanotubes
composed of stacked nitrogen-doped and undoped multiwalls. Chem.
Mater. 17 (11), 2940–2945.
Yang, Z.X., Xia, Y.D., Mokaya, R., 2007. Enhanced hydrogen storage
capacity of high surface area zeolite-like carbon materials. J. Am.
Chem. Soc. 129 (6), 1673–1679.
Youssef, A.M., El-Nabarawy, Th., Samra, S.E., 2004. Sorption properties
of chemically-activated carbons 1. Sorption of cadmium(II) ions.
Colloids and Surfaces A: Physicochem. Eng. Aspects 235, 153–163.
Zecchina, A., Bordiga, S., Vitillo, J.G., Ricchiardi, G., Lamberti, C.,
Spoto, G., Bjorgen, M., Lillerud, K.P., 2005. Liquid hydrogen in
protonic chabazite. J. Am. Chem. Soc. 127 (17), 6361–6366.
Zhang, T.Y., Walawender, W.P., Fan, L.T., Fan, M., Daugaard, D., Brown,
R.C., 2004. Preparation of activated carbon from forest and agricultural
residues through CO2 activation. Chem. Eng. J. 105, 53–59.
Zhao, X.B., Xiao, B., Fletcher, A.J., Thomas, K.M., 2005. Hydrogen
adsorption on functionalized nanoporous activated carbons. J. Phys.
Chem. B 109 (18), 8880–8888.
Zhecheva, E., Stoyanova, R., Jiménez-Mateos, J.M., Alcántara, R.,
Lavela, P., Tirado, J.L., 2002. EPR study on petroleum cokes annealed
at different temperatures and used in lithium and sodium batteries.
Carbon 40 (13), 2301–2306.