Journal of Colloid and Interface Science 303 (2006) 494–502

www.elsevier.com/locate/jcis

Mesopore control of high surface area NaOH-activated carbon

Ru-Ling Tseng ∗
Department of Safety, Health and Environmental Engineering, National United University, Miao-Li 360, Taiwan
Received 15 June 2006; accepted 10 August 2006
Available online 25 September 2006

Abstract
Activated carbon with BET surface areas in a narrow range from 2318 to 2474 m2 /g was made by soaking the char made from corncob in a
concentrated NaOH solution at NaOH/char ratios from 3 to 6; the mesopore volumes of the activated carbon were significantly changed from 21
to 58%. The relationships between pore properties (Sp , Vpore , Vmicro /Vpore , Dp ) and NaOH dosage were investigated. Comparisons between the
methods of NaOH and KOH activation revealed that NaOH activation can suitably control the mesopore specific volume of the activated carbon.
Elemental analysis revealed that the H/C and O/C values of the activated carbons of NaOH/char ratios from 3 to 6 were significantly lower. SEM
observation of surface hole variation of the activated carbon ascertained that the reaction process was inner pore etching. Based on the above
three measurements and experimental investigations, the assumption made by previous researchers, namely that NaOH and KOH produce similar
results, was challenged. Furthermore, the adsorption kinetics was used to investigate the adsorption rate of an Elovich equation to determine the
relationships between the adsorption behavior on larger molecules (dyes) and smaller molecules (phenols) and the pore structure of the activated
carbon.
© 2006 Elsevier Inc. All rights reserved.

Keywords: Activated carbon; NaOH activation; Adsorption; High surface area; Mesopore

1. Introduction
Activated carbon is already a very important industrial raw
material [1,2]. It can be used as an electrode base material
for supercapacitors [3–5], as a catalyst support for fuel cells
because of its porous features [6], and for storage for large
quantities of CH4 (at the same pressure) and H2 because of its
adsorption capabilities, higher safety features, and energy sav-
ings [7,8]. Furthermore, the demand for high surface porous
activated carbon is increasing for both traditional adsorption
and modern energy storage (electricity and gas). Because of all
these uses, large-scale production is necessary. In the prepara-
tion of activated carbon all of the following should be taken
into consideration: environment, economics, and function. In
2001, Lillo-Rodenas et al. succeeded in preparing high surface
area microporous-activated carbon with a BET specific area of
2746 m2 /g [9]. Later, from 2003 to 2005, some researchers re-
ported that the reaction mechanism of NaOH is similar to that of
KOH and that the same high surface area activated carbon could
be obtained using NaOH activation as KOH activation [10–16].
These activated carbons were successfully employed as cata-
lysts in the direct methanol fuel cell (DMFC) [11], for electric
double-layer capacitance (EDLC) [14,15], and methane stor-
age [13,16]. The above research revealed that using NaOH ac-
tivation in activated carbon preparation is useful. The reasons
can be summarized as follows:
1. The molecular weight of KOH (56.1 g/mol) is larger than
that of NaOH (40.0 g/mol). Thus the dosage (weight mea-
surement) of NaOH-activated carbon is less than that of
KOH-activated carbon.
2. NaOH is cheaper than KOH [9].
3. Based on life cycle assessment, NaOH is more environmen-
tally friendly [13].
4. NaOH is less corrosive than KOH [9]. The equipment for
NaOH activation would last longer.

* Fax: +886 37 333187. Some of the raw material used with high surface area ac-
E-mail address: trl@nuu.edu.tw. tivated carbon with NaOH activation were anthracite, pitch
0021-9797/$ – see front matter © 2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2006.08.024
 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502 495

coke [13,14,16], and commercial activated carbon [11]. The Table 1

anthracite was ground and sieved to a fine powder of particu- Characteristic of phenols and dyes
late sizes from 0.1 to 0.2 mm [13,16], the pitch coke was also Phenol 4-CP 2,4-DCP MB BB1 AB74
powdered [14], and the commercially activated carbon was of M.W. 94.1 128.6 163.0 284.3 419.3 466.4
particulate size 120/170 mesh [6]. The method for mixing raw
material and NaOH was mostly physical [9,11,13,14]. The liter-
ature revealed that the BET surface of activated carbon prepared 2.2. Measurements of physicochemical properties
by a physical method is better than that by an impregnation
method [9]. However, during the commercial production of ac- The BET surface area of the carbon (Sp ) was obtained from
tivated carbon, physical mixing needs particulate NaOH, while the N2 adsorption isotherm at 77 K with a sorptiometer (Porous
Materials, BET-202A). The definitions of total pore volume
the impregnation method can use alkali liquor (concentrated
(Vpore ), micropore volume (Vmicro ), and average pore size (Dp )
NaOH solution). Because of more convenient storage, trans-
were detailed in previous reports [19,26]. Elemental analysis of
portation, and lower cost, alkali liquor is preferred for industrial
part of the AC samples was performed by using an elemental
production. Furthermore activated carbon powder of very fine
analyzer (Elementar Co., Model Vario EL III). The microstruc-
particles (0.1–0.2 mm) is of limited application.
ture of the AC samples was evaluated by means of a scanning
In our laboratory, a series of studies were conducted to pre-
electron microscope (JEOL Co., Model JSM 5600).
pare porous carbons from various plant wastes using the KOH
activation method. Carbons prepared in this way have been
2.3. Procedures for adsorption experiments
evaluated for the possibility of applications in industrial pol-
lution control as well as in supercapacitors [17–25]. In this
Six solutes including acid blue74 (AB74), basic brown 1
work, char (0.833–1.65 mm) made from corncob was used as
(BB1), methylene blue (MB), 2,4-dichlorophenol (2,4-DCP),
raw material and the impregnation method was used for soak-
4-chlorophenol (4-CP), and phenol, all from Merck Co., were
ing the char in a NaOH solution at various ratios of NaOH to
used. Table 1 shows some characteristics of the phenols and
char. Comparisons were done of the physicochemical properties dyes. The effects of the molecular weight and pore structures
of the corncob carbons activated by NaOH and KOH and for of activated carbons on their adsorption kinetics will be fur-
different agent/char ratios. The physical properties measured ther discussed later. The adsorption kinetic experiments are the
included the BET surface area, pore-size distribution, total pore same as those detailed in the literature [19,26].
volume, micropore volume ratio, and SEM observation. The
chemical property measured included elemental analysis. The 3. Results and discussion
kinetics of the adsorption of methylene blue, basic brown 1,
acid blue 74, 2,4-dichlorophenol, 4-chlorophenol, and phenol 3.1. Physical and chemical properties of activated carbon
in aqueous media are discussed systematically.
Researchers utilize the adsorption of inert gases for under-
2. Materials and methods standing the activated carbon pore structure in determining the
suitability for various applications. Fig. 1 shows the typical ad-
2.1. Preparation of carbon by NaOH activation sorption/desorption isotherms of N2 at 77 K for all ACs with
different NaOH/char ratios. The curves of NaOH/char ratios
In this study, activated carbon was prepared using a two-step from 0.5 to 3 are of the horizontal type at P /P0 > 0.2. Similar
process. Corncob was first carbonized into char. The char was
soaked in a concentrated NaOH solution, oven-dried, and then
activated. The pretreatment for the corncob and the method for
char preparation were the same as those for previous KOH ac-
tivation [21].
The char was sieved to a uniform size ranging from 0.833 to
1.65 mm as the raw material for the second step of the process.
The preparation method and product treatment in the second
step of the process were the same as those for previous KOH
activation [21]. In the second step the char was dried and acti-
vated at 780 ◦ C for 1 h. In this study, the activation agent KOH
was replaced by NaOH. The samples were classified according
to the NaOH/char ratios and denoted as CobNa05, CobNa10,
CobNa20, CobNa30, CobNa40, CobNa50, and CobNa60. The
first three letters, Cob, represent the raw material, corncob; the Fig. 1. Adsorption/desorption isotherms of N2 at 77 K on activated carbons
forth and fifth letters, Na, represent activation by NaOH; and derived from corncob with NaOH activation. (Carbons are CobNa05 ("),
the last two digits represent the weight NaOH/char ratio (from CobNa20 (a), CobNa30 (e), CobNa40 (2), CobNa50 (5), and CobNa60 (F),
0.5 to 6). respectively.)
496 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502
Fig. 2. Pore-size distribution of the activated carbons derived from corncob with
NaOH activation. (Carbons are CobNa05 ("), CobNa20 (a), CobNa30 (d),
CobNa40 (2), CobNa50 (5), and CobNa60 (F), respectively.)
Langmuir-type curves imply lower mesopores and macropores,
and large numbers of straight cylinder () micropores. The ini-
tially adsorbed volumes (of ACs) of NaOH/char ratios from 4
to 6 were almost the same (335–367 cm3 /g) at P /P0 approach-
ing zero, and the adsorbed volume increased with increased
P /P0 from 0 to 0.5, implying a wide pore-size distribution from
micropore to mesopore, and funnel pores (>). The curve of
CobNa60 shows a wider hysteresis loop. This is mainly due to
Fig. 3. BET surface area (Sp ), total pore volume (Vpore ), micropore volume rate (Vmicro /Vpore ), and mean pore size (Dp ) of NaOH- and KOH-activated carbons at
different agent/char ratios.
factors, among others, such as slit-shaped pores and ink-bottle-
type pores () [27]. The adsorbed volume of ACs increased
with increased NaOH/char ratio at P /P0 above 0.5.
Fig. 2 shows a typical pore-size distribution of all ACs acti-
vated at different NaOH/char ratios. The main pore sizes of the
ACs at NaOH/char ratios from 0.5 to 3 were below 3 nm, but
the pore sizes of the ACs at NaOH/char ratios from 4 to 6 were
below 4.2 nm.
Figs. 3 shows comparisons of Sp , Vpore , Vmicro /Vpore , and
Dp of carbons activated by NaOH and KOH. In Fig. 3a, at
NaOH/char ratios 0 to 1, the Sp values increased little. This is
because of the insufficient NaOH to cover the entire surfaces
of the carbon, resulting in physical pyrolysis on the carbon
surfaces (proved by SEM observation section); the rate of in-
crease of Sp rate of NaOH-activated ACs is higher than that
of KOH-activated ACs at agent/char ratios 1–3. In this range,
NaOH etched the carbon uniformly within pores. Thus, an in-
creased NaOH dosage resulted in an increase of Sp (Fig. 3a
proves it), and the Sp of NaOH-activated ACs was almost con-
stant (2318–2474 m2 /g) at NaOH/char ratios above 3. In this
range the Sp was not increased any further. The reason is that
the high dosage of NaOH kept on etching the carbon and turned
the micropores into mesopores (Figs. 3b and 3c prove it). In
Fig. 3b, the rate of increased Vpore of NaOH-activated ACs is
higher than that of the KOH-activated ACs at agent/char ratios
from 1 to 3; the Vpore values of the NaOH-activated ACs were
 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502 497

Table 2 and KOH-activated ACs were very different; this is related to

Chemical compositions of the raw material and activated carbon the reaction process, and will be discussed in detail in the fol-
Materials Elemental composition (wt%) lowing section.
C H N S Odiff a Elemental compositions of the raw material of the ACs
Corncob 45.23 6.71 2.43 0.240 45.27 were determined. This is helpful in understanding the activation
Cob-char 69.52 4.10 2.12 0.410 23.86 mechanism and the functional appearance of various applica-
Cob00 74.02 2.10 2.09 0.150 21.65 tions (for example, surface functional groups of adsorption and
CobNa05 72.79 2.01 1.34 0.173 23.68 conductivity of supercapacitors). Table 2 shows the chemical
CobNa10 70.72 1.95 0.94 0.147 26.24
CobNa20 68.88 2.93 1.64 0.183 36.37
compositions (C, H, N, S, and Odiff ) of the raw material and
CobNa30 78.83 1.47 0.74 0.168 16.51 activated carbon according to elemental analysis. The carbon
CobNa40 80.16 1.18 2.01 0.145 16.68 content of all raw materials increased after being heat treated,
CobNa50 80.04 1.14 2.04 0.101 24.24 while the oxygen contents decreased [28]. The chemical C con-
CobNa60 73.12 0.86 1.71 0.050 30.09 tent of the raw material was 45.2 wt%; it was then carbonized
CobK05 71.55 2.56 1.40 0.130 24.35
CobK10 65.83 3.30 1.30 0.073 29.49
to char with C content of 69.5 wt% by heating it for 1.5 h.
CobK20 63.99 3.51 0.86 0.073 31.57 Furthermore, under 1 h pyrolysis at 780 ◦ C, the char was con-
CobK30 56.64 4.63 0.99 0.120 37.62 verted to activated carbon (Cob00) with C content of 74.0 wt%.
CobK40 55.33 4.40 1.17 0.052 39.05 The above facts reveal that C content increased with increased
CobK60 47.57 5.38 0.98 0.240 45.27 temperature, while the oxygen content decreased from 45.3 to
a O : the oxygen is assessed by difference.
diff 21.7 wt%, which is in agreement with studies from the litera-
ture [28].
higher than those of the KOH-activated ACs at agent/char ratios Fig. 4a shows the C content of ACs by NaOH activation and
above 3. It should be noted that although the Sp did not increase by KOH activation. C content of KOH-activated ACs decreased
at NaOH/char ratios larger than 3, the Vpore still kept on increas- with increased agent/char ratios, following the reaction mech-
ing. This feature can be utilized to control the mesopore volume anism of the literature [29]. However, C contents of NaOH-
of the high surface AC in the production process. activated ACs increased with increased agent/char ratios from 3
In the literature, the Sp and Vpore of ACs obtained from to 5, with higher C contents at 78.8–80.0 wt%. This means that
NaOH through physically mixing it with anthracite were sig- the reaction mechanism of NaOH-activated carbon is different
nificantly increased from 1017 to 2208 m2 /g and from 0.05 to from that of KOH-activated carbon. This will be discussed in
0.4 cm3 /g with NaOH/char ratios from 1 to 3 [9]. In this work, detail in the following section.
the Sp and Vpore of ACs were significantly increased from 446 Figs. 4b and 4c show comparisons of the H/C and O/C val-
to 2318 m2 /g and from 0.23 to 1.23 cm3 /g at NaOH/char ratios ues of both the NaOH- and the KOH-activated ACs. Fig. 4b
from 1 to 3; the Sp values are similar to those in the literature, shows that the H/C values of the KOH-activated ACs increased
but the Vpore values were much larger than those of the litera- linearly with increased agent/char ratios, very different from
ture. This is related to the characteristics of the raw materials NaOH-activated ACs; the H/C values of the NaOH-activated
and will be discussed in detail in the following section. ACs slightly decreased with increased agent/char ratios (ex-
In Fig. 3c, the Vmicro /Vpore of the NaOH-activated car- cept agent/char equals to 2). Fig. 4c shows that the O/C values
bon shows micropores (0.744–0.837) at agent/char ratios of of the KOH-activated ACs increased linearly with increased
0.5–3; more micropores were produced because of uniform agent/char values, similar to NaOH-activated ACs, which in-
NaOH etching. The Vmicro /Vpore values of the NaOH-activated creased linearly with increased agent/char ratios from 0 to 2;
carbons were significantly decreased from 0.792 to 0.418 but the O/C values of NaOH-activated ACs decreased rapidly
with agent/char ratios from 3 to 6; the micropores becoming at agent/char ratios between 2 and 3; when agent/char ratios in-
mesopores because of excessive NaOH etching. CobNa50 and creased from 3 to 6, the O/C values slightly rose again.
CobNa60 show mesoporous ACs. Besides, the Vmicro /Vpore of Comparing the physical and chemical properties of both
all KOH ACs were almost constant (0.768–0.844). In many NaOH- and KOH-activated ACs prepared from corncob showed
applications (DMFC, EDLC, methane storage, adsorption in a large difference between them. It is doubtful that the NaOH-
aqueous media) activated carbon with suitable Vmicro /Vpore activation mechanism be similar to the KOH-activation mech-
is required. NaOH activation of this work proved to be able anism [10,12,13]. These interesting issues will be discussed in
to provide high surface area activated carbon with various the following section.
Vmicro /Vpore values.
In Fig. 3d, the Dp of NaOH-activated ACs were almost 3.2. SEM observations and activation mechanism
constant (2.1–2.2 nm) at agent/char ratios from 1 to 3, and in-
creased significantly from 2.1 to 2.8 nm with agent/char ratios Figs. 5a–5d are 2000 magnification SEM photos of Cob-
from 3 to 6. Though the Dp of KOH-activated ACs has maxi- Na10, CobNa20, CobNa30, and CobNa60, respectively. Cob-
mal value (2.9 nm) at agent/char ratio equal to 2, its Sp was only Na10 had contracted, twisted, honeycomb-shaped holes, sim-
1221 m2 /g, not in the range of high surface area, and the Dp ilar to CobK10, which was highly porous with honeycomb-
was almost constant (2.1–2.3 nm) with agent/char ratios from shaped, irregular, cottony holes, with contracted and twisted
3 to 6. The Vmicro /Vpore and Dp values of the NaOH-activated walls [21]. This was caused in both cases by insufficient ac-
498 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502

(a)

(b)

(c)
Fig. 4. (a) C, (b) H/C, and (c) O/C of NaOH- and KOH-activated carbons at
different agent/char ratios.

tivation agents to cover char surfaces, pyrolysis causing sur-

face damage (physical activation phenomenon). CobNa20,
CobNa30, and CobNa60 all had honeycomb, regular hole
mouths with clear angle lines of thick walls. The outer ap-
pearance of these three ACs was slightly different; however,
their pore properties were very different and are individually
described as follows:

1. The micropore volumes of both CobNa20 and CobNa30

were similar (the Vmicro /Vpore value of CobNa20 was 0.78 (d)
and that of CobNa30, 0.79), but the surface areas of both
were very different (the Sp value of CobNa20 is 1352 m2 /g Fig. 5. SEM photos, (a) CobNa10, (b) CobNa20, (c) CobNa30, and (d)
and that of CobNa30, 2318 m2 /g); this means that there CobNa60.
 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502 499

were more micropores in CobNa30 than in CobNa20, and

thus more surface area (about 1.7 times).
2. The surface areas of both CobNa30 and CobNa60 were
similar (the Sp value of CobNa30 was 2318 m2 /g and that
of CobNa60 2362 m2 /g), but the pore structures of both
were very different (the mesopore volume of CobNa30
was 0.256 cm3 /g and that of CobNa60 0.949 cm3 /g).
This means more mesopore volume in CobNa60 than in
CobNa30 (about 3.71 times).
3. The development from CobNa20 to CobNa30 was a
micropore-developing step; during this step, NaOH etch-
ing produced more microporous straight channels ().
But the development from CobNa30 to CobNa60 was a
pore-volume-expanding stage; additional NaOH etching
widened the micropores into funnel-like ink-bottle meso-
pores (>) or ().

The residue ratio of a chemical composition of AC is defined

as the chemical composition of AC multiplied by yield of AC
(Yp ) and divided by the chemical composition of the raw ma-
terial (char) activated. Oxygen residue ratio (O) is expressed
as
O = O × Y p /Ochar .
And hydrogen residue ratio (H) is expressed as
H = H × Y p /Hchar .
If C is the only element, with no other chemical composi-
tions (O, H, N, S), in the char that undergoes chemical reaction
during activation, the residue ratios of the other chemical com-
positions should all be 1.
Figs. 6a and 6b show that the oxygen and hydrogen residue
ratios of NaOH- and KOH-ACs in Fig. 6a were similar to those
in Fig. 6b. At higher agent/char ratios (3–6), activation was
under complete chemical reaction; at agent/char ratio equal to
zero, complete physical reaction; and at agent/char ratios from
0.5 to 3, mixed physical and chemical reactions. Figs. 6a and 6b
show very different O and H of NaOH- and KOH-ACs.
The O and H of KOH-ACs at higher agent/char ratios were
above 0.83 and 0.54, respectively, and those of NaOH-ACs be-
low 0.125 and 0.041, respectively.
In the literature, discussions on the reaction mechanism of
the KOH-activated carbon neglected the reactions of oxygen
and hydrogen [29]; Figs. 6a and 6b show higher O and H
for KOH-activated ACs, i.e., less oxygen and hydrogen losses
from char with KOH-activated ACs. On the other hand, with
NaOH activation neither the oxygen nor the hydrogen can be
neglected, because a significant amount of both oxygen and
hydrogen is lost in the process. These reaction mechanisms
are discussed below. Equation (1) is the reaction mechanism
proposed in the literature [10] for explaining the activation of
carbonaceous materials by sodium hydroxide:
6NaOH + 2C ↔ 2Na + 2Na2 CO3 + 3H2 . (1)
On the walls and cover of a container in our laboratory a
white soluble product was found after NaOH activation. The
white soluble product sparked with crack when in contact with
Fig. 6. (a) O and (b) H of NaOH- and KOH-activated carbons at different
agent/char ratios.
humid air or water, which is the same as that described in the
literature [13]; this proved the existence of Na after the reaction.
Reaction products (not containing white soluble product)
were soaked in 600 ml H2 O and dripped with concentrated HCl
solution of equal NaOH equivalents; the CO2 bubble kept being
produced; however, CO2 bubbles ceased when the amount of
the dripped concentrated HCl solution exceeded NaOH equiva-
lents.
The former experiment proved the production of Na and the
latter proved the production of Na2 CO3 . But the product mole-
cular ratio of Na to Na2 CO3 was not 1:1 as is shown in Eq. (1),
because titration proved that the product sodium mostly existed
as Na2 CO3 . The reason might be that the product Na reacted
with O and H back to NaOH. The reaction is described as fol-
lows:
oxidation hydration
2Na −−−−−→ Na2 O −−−−−→ NaOH. (2)
NaOH in Eq. (2) reacts with C again according to Eq. (1). Equa-
tion (2) explains the reason for the large losses of O and H of
the raw material during reaction.
3.3. Adsorption kinetics
The physical and chemical properties of activated carbon are
complicated. Though they can be determined by surface mea-
surement, pore-size distribution analysis, SEM observation, el-
emental analysis, and functional group identification, these are
500 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502

Fig. 7. Fitting of the Elovich equation for the adsorption of dyes and phenols on the NaOH-activated carbons: (a) AB74, (b) BB1, (c) MB, (d) 2,4-DCP, (e) 4-CP,
and (f) phenol. (Carbons are CobNa10 (!), CobNa20 (e), CobNa30 (1), CobNa40 (E), and CobNa50 (P), respectively.)

not enough to express the specific uniqueness of the activated
carbon in various application fields. Our lab has investigated the
relationships between physical properties of activated carbon,
its adsorption behavior, and electric capacitors [30]. Adsorption
on various adsorbates can give more insight into the character-
istics of activated carbon helpful to determine its feasibility for
various applications. Three kinds of dyes and three kinds of
phenols with molecular weights ranging from 94 to 466 g/mol
were studied in this work. Based on previous studies in adsorp-
tion kinetics [20,24,26], the behavior of plant-activated carbon
fits well the Elovich equation. Detailed discussions on Elovich
equation refer to the previous studies [20,24,26]. Fig. 7 shows
the relationships between the adsorption quantity and the con-
tact time. Curves in the figures were obtained from the fitted
Elovich equation; the fittings were good. The adsorption on
AB74 is shown in Fig. 7a. Because the BET surface areas of
CobNa10 and CobNa20 were, respectively, 446 and 1352 m2 /g,
much lower than those of CobNa30, CobNa40, and CobNa50
(2318–2474 m2 /g), the contact time adsorption was also lower.
The Vmicro /Vpore of CobNa30, CobNa40, and CobNa50 were,
respectively, 0.79, 0.63, and 0.54, indicating increased adsorp-
tion with decreased Vmicro /Vpore of AB74. Figs. 7b and 7c
show, respectively, the adsorption on BB1 and MB. The adsorp-
tion behavior of different contact times at various NaOH/char
ratios was similar to that in Fig. 7a. The superiority of ad-
sorption on large molecules of mesopore-activated carbon was
 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502 501

Table 3
Kinetic parameters of the adsorption of phenols and dyes at 30 ◦ C
Solute Carbon 1/b (mol/kg) (1/b) ln ab (mol/kg) r 2 (–)
Phenol CobNa10 0.158 0.261 0.987
CobNa20 0.495 0.790 0.999
CobNa30 0.448 1.289 0.997
CobNa40 0.363 1.456 0.995
CobNa50 0.294 1.579 0.980
4-CP CobNa10 0.237 0.225 0.987
CobNa20 0.756 1.073 0.992
CobNa30 0.778 1.481 0.996
CobNa40 0.763 1.697 0.993
CobNa50 0.716 1.880 0.996
2,4-DCP CobNa10 0.099 1.667 0.983
CobNa20 0.583 2.157 0.999
CobNa30 0.655 2.545 0.996
CobNa40 0.709 2.717 0.998
CobNa50 0.702 2.946 0.998
MB CobNa10 0.044 0.044 0.981
CobNa20 0.207 0.109 0.996
CobNa30 0.299 0.217 0.995
CobNa40 0.328 0.288 0.994
CobNa50 0.341 0.419 0.999
BB1 CobNa10 0.035 0.035 0.981
CobNa20 0.114 0.114 0.991
CobNa30 0.188 0.188 0.988
CobNa40 0.240 0.240 0.991
CobNa50 0.304 0.304 0.996
AB74 CobNa10 0.010 0.019 0.990
CobNa20 0.074 0.028 0.989
CobNa30 0.111 0.057 0.986 Fig. 8. Adsorption kinetic parameters of (1/b) ln(ab) and (1/b) of AB74, BB1,
CobNa40 0.124 0.078 0.986 MB, 2,4-DCP, 4-CP, and phenol at 30 ◦ C on NaOH-activated carbons at differ-
CobNa50 0.133 0.115 0.999 ent agent/char ratios.

proven. Figs. 7d–7f show, respectively, the adsorption on 2,4-
DCP, 4-CP, and phenol. When the molecular weights of phe-
nols became lower, the adsorption of mesopore CobNa50 de-
creased. The adsorption contact times of CobNa30, CobNa40,
and CobNa50 of the three carbons in Figs. 7a and 7b were dif-
ferent.
After arrangement, the Elovich equation can be expressed
as [26]
qt = (1/b) ln(ab) + (1/b) ln t.
Equation (3) is the straight line of variables qt and ln t with the
slope of (1/b) and intercept of (1/b) ln(ab). Slopes (1/b), inter-
cepts (1/b) ln(ab), and correlation coefficients (r 2 ) are listed in
Table 3. The r 2 s of the adsorption on phenols and dyes were
more than 0.983 and 0.981, respectively, fitting the Elovich
equation well. In Eq. (3), (1/b) ln(ab) is the adsorption quan-
tity when ln t is equal to zero; i.e., the adsorption quantity when
t is 1 min. This value is helpful in understanding the adsorption
behavior of the first step.
Figs. 8a and 8b separately show and compare the relation-
ships between (1/b) and (1/b) ln(ab) and NaOH/char ratios.
For dyes, the adsorption was less when ln t equal to zero, and
increased linearly with increased NaOH/char. In the case of
phenols, the adsorption at ln t was zero and increased signif-
icantly with increased NaOH/char ratios at the beginning and
then slowed down later. The adsorption at ln t equal to zero
mainly reveals the exterior surface area (Sext ) adsorption stage.
The Sext (surface area sum of macropores and mesopores) of
CobNa10 to CobNa50 was, respectively, 45, 110, 220, 482, and
598 m2 /g. The adsorption quantities of lower molecular phenol
and 4-CP at ln t equal to zero were in accord with the increased
Sext tendency; however, those of larger molecules showed lit-
tle gain. Based on variations in the adsorption quantities at ln t
equal to zero, it was inferred that at ln t equal to zero, adsorbate
of small molecules (phenols) might have entered into voids of
macropores and mesopores besides being adsorbed on the sur-
(3) faces of the activated carbon, while larger molecules did not
enter into the voids of the mesopores; adsorption happened only
in the macropores and on surfaces of activated carbon.
Fig. 8b shows the variation of rate parameter (1/b). The
adsorption rates on AB74 and BB1 linearly increased with in-
creased NaOH/char ratios. The Vmeso of activated carbons with
NaOH/char ratios of 1, 2, 3, 4, and 5 were, respectively, 0.05,
0.12, 0.26, 0.50, and 0.68 cm3 /g according to the t plot, approx-
imately in accord with the increased tendencies of AB74 and
BB1. However, adsorption on the small molecular adsorbate did
not follow this tendency. In the case of adsorption on phenol
and 4-CP, the adsorption rates rapidly increased at NaOH/char
ratios between 1 and 2. The adsorption rates decreased gradu-
ally at NaOH/char ratios between 2 and 5, which was in accord
with the decreasing tendency of Vmicro /Vpore at NaOH/char ra-
tios between 2 and 5 shown in Fig. 3c; i.e., large amounts of
phenol and 4-CP were adsorbed and occupied mesopores at ln t
equal to zero. Thus at ln t > 0, adsorption only happened in
502 R.-L. Tseng / Journal of Colloid and Interface Science 303 (2006) 494–502
the micropores, so the adsorption rate declined. The molecu-
lar weights of MB and 2,4-DCP were between those above two
groups of (four) adsorbates. The variations in the adsorption
rates were also between those of the two groups. These results
reveal that an increased mesopore ratio can cause an increase
in the adsorption rate of the larger molecular adsorbates (dyes:
MB, BB1, and AB74).
4. Conclusions
In this study char from carbonization of corncob was used as
raw material for activated carbon. In the range of agent/char ra-
tios 1 to 3 the BET surface area of NaOH-activated ACs rapidly
increased from 446 to 2318 m2 /g, which is a feature of high
surface area activated carbon. The part of the process in which
micropores kept increasing in this range of agent/char ratios is
called the micropore development stage. The micropore ratios
(Vmicro /Vpore ) of NaOH-activated ACs rapidly decreased from
0.79 to 0.42 with agent/char ratios from 3 to 6; the mean pore
diameters increased from 2.1 to 2.8 nm, but the BET surface
area remained nearly constant (from 2318 to 2474 m2 /g). At
this stage, the micropores were widened into mesopores. This
stage is called the pore-volume-expanding stage. The C con-
tents of NaOH-activated ACs were 78.8–80.0 wt% in the range
of agent/char ratios from 3 to 5. The reaction mechanisms in
previous literature could not explain the activation phenom-
enon. The residue ratios of O and H of the activated carbons
were obtained by elemental analysis. It was found that the re-
action mechanism must be modified into Eqs. (1) and (2); i.e.,
product Na of reaction NaOH with C kept undergoing oxida-
tion and hydration with O and H in the char and forming NaOH
again and reacting with C in the char, yet another reaction in the
activation process. The NaOH reactions in the carbon pores at
the micropore-development and mesopore-volume-expanding
stages were observed with SEM. Furthermore, adsorption ki-
netics were used to prove the phenomenon that the adsorption
rates on a larger molecular adsorbate (dye: MB, BB1, AB74)
would increase with decreased micropore ratios (Vmicro /Vpore
from 0.79 to 0.42).
Acknowledgment
Financial support of this work by the National Science
Council of the Republic of China under Contract No. NSC 94-
2211-E-239-005 is gratefully acknowledged.
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