1678 Letters to the Editor / Carbon 411 (2002) 1645 – 1687

Preparation of highly mesoporous and high surface area

activated carbons from vinylidene chloride copolymer
containing yttrium acetylacetonate
Hisashi Tamai*, Masayuki Kouzu, Hajime Yasuda
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Kagamiyama 1 -4 -1,
Higashi-Hiroshima 739 -8527, Japan
Received 18 November 2002; accepted 24 March 2003

Keywords: A. Activated carbon; B. Activation; C. BET surface area; D. Porosity

Activated carbons have been widely used as an effective
adsorbent for water purification and gas separation, and as
support materials in catalysis systems. In addition, recent-
ly, applications as energy storage devices, e.g. electrodes
for electric double layer capacitor (EDLC) and methane
storage, have attracted much interest. Activated carbons
are produced from various carbonaceous materials, e.g.
coals, polymer materials, nutshell, pitches, etc., by carboni-
zation followed by activation process. Most activated
carbons produced commercially from these precursors are
microporous (pore size ,2 nm) and have large surface
area.
Activated carbons consisting of larger pores such as
mesopores (2–50 nm) are supposed to be more effective
for the adsorption of large molecules and as electrodes for
EDLC providing high power density because electrolyte
ions can be transported more smoothly into the inside of
mesopores than that of micropores.
Regarding the preparation of mesoporous activated
carbons, Oya et al. suggested the addition of cobalt-
acetylacetonate [Co(acac) 3 ] into phenolic resin prior to the
activation process [1]. We obtained highly mesoporous
activated carbons from pitch containing rare earth metal
complexes by steam activation method [2]. Although the
resulting activated carbon powders showed a mesopore
surface ratio more than 80%, the BET specific surface area
was below 300 m 2 / g. Furthermore, we reported highly
mesoporous activated carbon fibers prepared by steam
activation of pitch fiber containing yttrium acetylacetonate
[Y(acac) 3 ] [3]. The BET specific surface area and the
mesopore surface ratio of the resulting activated carbon
fibers were about 1400 m 2 / g and 80%, respectively.
However, the pore size distribution was wide in the region
of pore sizes of .2 nm. Yamada et al. reported the
preparation of highly mesoporous carbons by dehydro-
*Corresponding author. Tel.: 181-824-247-731; fax: 181-
824-245-494.
E-mail address: tamai@hiroshima-u.ac.jp (H. Tamai).
fluorination of polytetrafluoroethylene with potassium or
sodium [4,5]. The resulting porous carbons exhibited a
mesopore ratio more than 70%. However, the use of
polytetrafluoroethylene and alkali metals is expensive and
it is difficult to treat them safely. Recently, as a simple
preparation method of mesoporous activated carbon, Hu et
al. reported activated carbons from ZnCl 2 -impregnated
coconut shells by CO 2 activation [6,7]. The resulting
2
activated carbons were more than 2200 m / g in BET
2
specific surface area and 1200 m / g in mesopore surface
area. On the other hand, many workers reported the
preparation of mesoporous carbons by the template method
using mesoporous silica and silica-sol, etc. [8–12]. By
applying the template method, excellent mesoporous car-
bons with narrow pore size distribution and in some cases
with high BET surface area and high mesoporosity [9]
were prepared. However, the template method is compli-
cated because of the preparation of templates, the com-
pounding of templates with carbon or carbon precursors,
and the removal of templates. Thus this method is trouble-
some for the preparation of large amounts of carbon.
In addition to pore characteristics, the form and the
morphology of the carbons are important for practical
applications of the porous carbons. Thermoplastic polymer
is one of the useful carbon precursors, because it can be
conveniently melt fabricated to various forms such as fiber
and film. From these points of view, in this work, we
investigated the highly mesoporous and high surface area
activated carbons with narrow pore size distribution using
vinylidene chloride / methyl acrylate random copolymers
[Poly(VDC / MA)]. The resulting activated carbons possess
2
high BET specific surface area (2100 m / g) and high
2
mesopore surface area (1400 m / g). The preparation
method is very simple, i.e. mixing of Poly(VDC / MA) with
Y(acac) 3 and carbonization followed by steam activation.
The activated carbon obtained by this method can be
prepared in various forms such as fiber and film, since
Poly(VDC / MA) is a typical thermoplastic material. The
ratio of Poly(VDC / MA) / Y(acac) 3 can be varied and the
ratio of 100 gave the best result regarding mesopore ratio.

0008-6223 / 03 / $ – see front matter  2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016 / S0008-6223(03)00145-3
 Letters to the Editor / Carbon 41 (2002) 1645 – 1687
Poly(VDC / MA) [VDC / MA ratio59 / 1] was purchased
from Aldrich. The average molecular weight determined
by gel permeation chromatography was 6.5310 4 . Poly-
(VDC / MA) containing Y(acac) 3 was prepared by mixing
of P(VDC / MA) with Y(acac) 3 in tetrahydrofuran (THF),
and then THF was removed by flash distillation. Prior to
activation, the precursor was carbonized. The precursor
polymer was heated up to the prescribed temperature at a
rate of 1.67 8C min 21 under Ar atmosphere, kept for 1 h,
and then cooled to room temperature. The activation of the
carbonized samples was carried out by steam. The sample
was directly put into the furnace, in which N 2 containing
H 2 O was flowing at 900 8C, for the prescribed time.
The pore characteristics of the activated carbons were
determined from N 2 adsorption / desorption isotherms using
a Quantachrome NOVA-3200. Mesopore size distributions
and the surface area were determined by BJH method.
Fig. 1 shows N 2 adsorption / desorption isotherms of the
activated carbons derived from Poly(VDC / MA) containing
Y(acac) 3 . The activated carbon obtained from Poly(VDC /
MA) without Y(acac) 3 (AC-Y0) is a type I isotherm
according to the IUPAC classification. The major uptake
on the activated carbon occurs at low relative pressure
(,0.1) and reaches the plateau at high relative pressure.
Fig. 1. Adsorption / desorption isotherms of the activated carbons
obtained from Poly(VDC / MA) containing Y(acac) 3 .
1679
This indicates that the activated carbon is microporous. On
the other hand, the shapes of adsorption / desorption iso-
therms changed dramatically by the addition of Y(acac) 3
into Poly(VDC / MA). They belong to a type IV. The
uptake of N 2 on the present activated carbons increased
even at high relative pressure (.0.5). Among these
activated carbons, the activated carbon obtained from
Poly(VDC / MA) containing 0.3 wt.% of yttrium exhibited
the highest N 2 adsorption. The uptake of N 2 decreased
with increase of yttrium contents in Poly(VDC / MA).
Additionally, the activated carbons derived from Poly-
(VDC / MA) containing Y(acac) 3 show hysteresis loops on
the adsorption / desorption isotherms in the region of 0.5–
0.95 of relative pressure. These isotherms suggest that a
considerable amount of mesopores are present in the
activated carbons.
Table 1 summarizes the pore characteristics, viz. BET
specific surface area (BET-SSA), mesopore specific sur-
face area (MP-SSA), mesopore ratio, and pore volume
determined from the N 2 adsorption / desorption isotherms.
The carbon yields are calculated from the weights before
and after activation. The activated carbon obtained from
Poly(VDC / MA) (AC-Y0) is microporous and exhibited
BET surface area of more than 2600 m 2 / g. On the other
hand, the activated carbons obtained from Poly(VDC / MA)
containing Y(acac) 3 were mesoporous. The mesopore
surface area increased with increase in yttrium content in
0.1–0.3 wt.%, and gradually decreased with further addi-
tion of yttrium compound. Thus the addition of a small
amount of yttrium into Poly(VDC / MA) is effective for the
formation of mesopores. In general in the preparation of
activated carbon by physical methods such as steam
activation, the increase in mesopore ratio resulted in the
decrease in micropore ratio. That is, the improvement of
mesopore formation with increase of activation time causes
the disappearance of micropore structure. Thus BET
specific surface area often decreased with excessive activa-
tion, namely the increase in burn-off of carbon. Regarding
the activated carbons from Poly(VDC / MA) containing
Y(acac) 3 , as shown in Table 1, the activated carbons
exhibited high BET surface area in spite of increase in
mesopore surface area. This indicates that the addition of a
small amount of Y(acac) 3 accelerated the formation of
mesopores without disappearance of micropores by burn-
off of carbon.
Table 2 shows the influence of carbonization tempera-
ture on pore characteristics of the activated carbons
derived from Poly(VDC / MA) containing 0.3 wt.% of
yttrium, which exhibited the highest values in BET and
mesopore surface area. BET surface areas of the activated
carbons carbonized at various temperatures, 400, 600, and
800 8C, are 1900–2000 m 2 / g, and mesopore surface areas
are more than 1250 m 2 / g. The carbon carbonized at
800 8C for 1 h followed by activation at 900 8C for 40 min
exhibited high mesopore surface area (1304 m 2 / g) and
large pore volume (2.06 ml / g). Thus we could prepare an
1680 Letters to the Editor / Carbon 411 (2002) 1645 – 1687

Table 1
Pore characteristics of the activated carbons obtained from Poly(VDC / MA) containing yttrium acetylacetonate
Sample Yttrium Carbonization a Activation Carbon BET-SSA MP-SSAb MP-ratio Pore
content temp. (8C) temp.–time yield (m 2 g 21 ) (m 2 g 21 ) (%) volume
(wt.%) (8C–min) (%) (ml g 21 )
AC-Y0 0 600 900–55 21 2668 306 11 1.26
AC-Y1 0.1 800 900–50 24 2120 594 28 1.20
AC-Y2 0.3 800 900–40 21 2013 1304 65 2.60
AC-Y3 1.0 800 900–45 23 1489 1110 75 1.70
AC-Y4 2.0 800 900–35 21 1063 756 71 1.31
AC-Y5 3.0 800 900–35 23 701 517 74 0.95
Y content in Poly(VDC / MA): AC-Y0 (0 wt.%), AC-Y1 (0.1 wt.%), AC-Y2 (0.3 wt.%), AC-Y3 (1.0 wt.%), AC-Y4 (2.0 wt.%), AC-Y5
(3.0 wt.%).
a
Carbonization time, 1 h.
b
MP-SSA, mesopore specific surface area.

activated carbon of more than 1250 m 2 / g of mesopore
surface. In addition, the pore characteristics of the acti-
vated carbon (AC-Y2) treated with 1 N HNO 3 solution for
3 h is summarized in Table 2. Further increases in both
BET surface area and mesopore surface area were
achieved by HNO 3 treatment. The former and the latter
reached 2140 m 2 / g and 1432 m 2 / g, respectively.
Mesopore size distributions of the activated carbons,
determined by BJH method, are shown in Fig. 2. The
activated carbons obtained from Poly(VDC / MA) contain-
ing Y(acac) 3 possess a pore size in the region of 3–8 nm
and these mesopore size distributions are narrow. Especial-
ly the activated carbons from Poly(VDC / MA) containing
0.3 wt.% of yttrium selectively form pores of 4–8 nm. It is
known that the microporous carbons having a high BET
surface area are prepared from poly(vinylidene chloride).
Actually the activated carbon obtained from Y(acac) 3 -free
poly(VDC / MA) in this work (AC-Y0) is highly porous
and has high BET surface area. It is supposed that the
pores are formed throughout the dehydrochlorination of
polymer and degassing process in the course of carboniza-
tion and activation. On the other hand, Y(acac) 3 decom-
poses itself during carbonization and activation to derive
yttrium oxide (Y 2 O 3 ) particles. Therefore, the presence of
Y(acac) 3 in the polymer precursor may accelerate the pore
formation. Additionally the formed Y 2 O 3 particles cata-
lytically promote the exhaustion of carbon by activation.
That is, Y 2 O 3 particles catalytically accelerate the reaction
of carbon with H 2 O to result in the enlargement of pore
size. It is presumed that high BET and mesopore surface
areas are attributed to the combined actions of the dehy-
drochlorination reaction of polymer and the catalytic effect
of Y 2 O 3 . We carried out X-ray powder diffraction (XRD)
analysis for the resulting activated carbons. The peaks
attributed to the crystalline phase of Y 2 O 3 were observed.
On the basis of the peak attributed to Y 2 O 3 , the crystal size
of Y 2 O 3 was estimated using Scherrer’s equation. The
average crystal size of Y 2 O 3 in the activated carbon
(AC-Y2) is about 12.5 nm. This size is larger than the peak
in pore size distribution of the activated carbons. However,
taking into account the difference in estimating procedure
of these sizes, it is supposed that these sizes are nearly
similar. From these results, we presumed that the forma-
tion of large amounts of mesopore is due to large amounts
of micropores formed by the dehydrochlorination from
Poly(VDC / MA) and the decomposition of Y(acac) 3 re-

Table 2
Pore characteristics of the activated carbons obtained from Poly(VDC / MA) containing yttrium acetylacetonate
Sample Yttrium Carbonization a Activation Carbon BET-SSA MP-SSAb MP-ratio Pore
content Temp. (8C) temp.–time yield (m 2 g 21 ) (m 2 g 21 ) (%) volume
(wt.%) (8C–min) (%) (ml g 21 )
AC-Y2(1) 0.3 400 900–20 20 1891 1272 67 1.88
AC-Y2(2) 0.3 600 900–30 23 1898 1253 66 1.85
AC-Y2 0.3 800 900–40 21 2013 1304 65 2.06
AC-Y2(AT)c 0.3 800 900–40 21 2140 1432 67 2.25
a
Carbonization time, 1 h.
b
MP-SSA, mesopore specific surface area.
c
Treatment of AC-Y2 with 1 M HNO 3 , 4 h.
 Letters to the Editor / Carbon 41 (2002) 1645 – 1687
Fig. 2. Pore size distributions of the activated carbons obtained from Poly(VDC / MA) containing Y(acac) 3 .
sulting in the generation of Y 2 O 3 particles and additionally
the catalytic effect of Y 2 O 3 particles for burn-off of
carbon.
Acknowledgements
This work is supported by a grant-in-aid for ‘Research
for the Future Program’, Nano-carbon, from the Japan
Society for the Promotion of Science.
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