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Effect of ZnO loading to activated carbon on Pb(II) adsorption from aqueous

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Article  in  Carbon · February 2006

DOI: 10.1016/j.carbon.2005.07.040

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 Carbon 44 (2006) 195–202
www.elsevier.com/locate/carbon

Effect of ZnO loading to activated carbon on Pb(II) adsorption

from aqueous solution
a,1
Yosuke Kikuchi , Qingrong Qian a, Motoi Machida b,*
, Hideki Tatsumoto b

a
Graduate School of Science and Technology, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
b
Faculty of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan

Received 4 March 2005; accepted 30 July 2005

Available online 13 September 2005

Abstract

The effect of zinc oxide loading to granular activated carbon on Pb(II) adsorption from aqueous solution was studied in com-
parison with zinc oxide particles and oxidized activated carbon. Cu(II), Cd(II) and nitrobenzene were used as reference adsorbates
to investigate the adsorption. The BET surface area and point of zero charge (pHPZC) in the aqueous solution were measured for the
adsorbents. The adsorption isotherms were examined to characterize the adsorption of heavy metals and organic molecules. The
heavy metal adsorption was improved by both the zinc oxide loading and the oxidation of activated carbon. In contrast, the adsorp-
tion of nitrobenzene was considerably reduced by the oxidation, and slightly decreased by the zinc oxide loading. The zinc oxide
loading to the activated carbon was found to be effectively used for the Pb(II) adsorption whereas only a part of surface functional
groups was used for the zinc oxide particles and the oxidized activated carbon. From the experimental results, the surface functional
groups responsible for the Pb(II) adsorption on the zinc oxide loaded activated carbon were considered to be hydroxyl groups that
formed on the oxide, while those on the oxidized activated carbon were considered to be carboxylic groups.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Activated carbon; Impregnation; Adsorption; Adsorption properties

1. Introduction environments and ecosystems by toxic heavy metals

Zinc oxide is widely used in daily life and industry,
for example, additives in cosmetics for reducing UV
penetration, catalysts for synthesis of methanol, vulcani-
zation accelerator for rubber, sensors for oxygen gas [1–
3], antistatic agents in paint, an antibacterial agent in
ion-exchange resin [4], and absorbents for gases such
as NOx, SOx, CH4, CO2, CO, O2, H2 [5,6]. In particular,
zinc oxide is able to dissociate hydrogen in a heteroge-
neous manner [7–10] and water to create hydroxyl
groups [11,12]. On the other hand, the pollution of water
*
Corresponding author. Tel./fax: +81 43 290 3129.
E-mail address: machida@faculty.chiba-u.jp (M. Machida).
1
Present address: Miura Co., Ltd., 864-1 Hojyotsuji, Matsuyama,
Ehime 799-2430, Japan.
such as Hg(II), Cr(VI), Cd(II) and Pb(II) has been
attracting much attention in recent years. Adsorption
of these heavy metals is an attractive option to reduce
their levels in aqueous solution, since in general adsor-
bents are easy to handle, and can be used for various sit-
uations without large apparatus [13]. Carbonaceous
materials such as activated carbon are the most com-
monly used adsorbent for water treatment. Activated
carbon has a large specific surface area and a well-devel-
oped porous structure, resulting in an attractive force
toward organic molecules [14–16]. However, specific
functional groups such as carboxyl, hydroxyl and amine
on the activated carbon are essential for the adsorption
of heavy metals [17,18]. Minerals in ash contained in
charcoal also play an important role in the adsorption
of heavy metals [19]. In the present work, zinc oxide

0008-6223/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2005.07.040
196 Y. Kikuchi et al. / Carbon 44 (2006) 195–202
was loaded to granular activated carbon to increase its
capacity to absorb heavy metals, principally Pb(II) ions,
by creating hydroxyl groups on zinc oxide in the aque-
ous solutions as mentioned above. Preparation of zinc
oxide particles and oxidation of activated carbon were
also carried out to compare their adsorption capability
with that of the zinc oxide loaded activated carbon.
2. Experimental
2.1. Preparation of adsorbents
The base adsorbent used in the study was commer-
cially available granular activated carbon made from
coconut shell (Calgon Mitsubishi Chemical Corpora-
tion, Diasorb W10-30). The activated carbon was
repeatedly boiled with de-ionized water until the solu-
tion pH no longer changed, then it was dried overnight
at 110 °C followed by calcination at 350 °C in air for
4 h, and allowed to cool in a desiccator; this was referred
to as GAC in the study. The zinc oxide were loaded to
the 110 °C dried granular activated carbon by the equi-
librium adsorption of Zn(II) ions from aqueous solution
followed by calcination in air at 350 °C for 2 h. The
cycle was repeated four times to increase the amount
of zinc oxide loading. The Zn(II) solution was prepared
by dissolving zinc nitrate hexahydrate in de-ionized
water at 15.3 mmol/L. Five-hundred millilitre of Zn(II)
solution including 7.0 g of the dried activated carbon
was agitated at 100 rpm for 7 days to reach the equilib-
rium state. The Zn(II) adsorbed activated carbon was
filtered from the solution, and then dried in oven at
110 °C before calcination at 350 °C. The zinc oxide
loaded activated carbon was referred to as ZnO-GAC.
In order to elucidate the influence of zinc oxide loading
on textual properties of the activated carbon, the ZnO-
GAC was washed with 1 M hydrochloric acid to remove
zinc oxide loading to the activated carbon followed by
repeated washing with de-ionized water until a constant
solution pH was obtained. This was referred to as ZnO-
GAC (HCl aq.). Changes in structure of the activated
carbon by ZnO loading were inspected comparing the
GAC and ZnO-GAC with and without HCl (aq.) wash-
ing. The ZnO particles were prepared by precipitation of
zinc nitrate solution with ammonia solution. The precip-
itated Zn(OH)2 was repeatedly washed with de-ionized
water to remove ammonia, dried in an oven, calcined
in air at 350 °C for 2 h to remove nitrate ions, and
cooled in the desiccator. The oxidized activated carbon
was prepared by oxidation with nitric acid [20–26].
Eight-hundred millilitre of 36% nitric acid solution
including 20 g of the activated carbon was heat treated
for 6 h with the temperature controlled to around
90 °C to avoid boiling the acid. Brown vapor of NO2
was continuously generated during the oxidation exper-
iment. The oxidized activated carbon was cooled down
to room temperature, filtered from nitric acid, washed
with de-ionized water until the pH exhibited a constant
value, dried overnight in the oven at 110 °C, and then
calcined in air at 350 °C for 4 h to completely remove ni-
trate ions [27]. The oxidized granular activated carbon
was referred to as Oxi-GAC.
2.2. Properties of adsorbents
The BET surface area and pore distribution for the
adsorbents were measured using a surface analyzer
(Beckman Coulter Model SA3100). The surface areas
for micropores and mesopores were separately calcu-
lated using the t-plot method based on N2 adsorption
isotherms [28,29]. The point of zero charge (pHPZC)
was measured to investigate the total surface charge
for the adsorbents according to the method of Smičiklas
et al. [30]. The mixture of 100 mg of adsorbent and
50 mL of 0.1 M potassium nitrate solution was agitated
at 25 °C for 24 h to allow it to reach the equilibrium
state. The initial pH of potassium nitrate solution was
changed from 1.5 to 10 using 0.1 M nitric acid and
0.1 M potassium hydroxide. When the equilibrium solu-
tion pH did not change with increasing the initial pH,
the constant pH value was considered to be the point
of zero charge (pHPZC) for the adsorbent. At a solution
pH lower than pHPZC, the total surface charge will be
positive on average, whereas at the higher solution pH
it will be negative [14,31]. The equilibrium solution pH
was measured by a portable pH meter (HORIBA Model
D-21).
Surface functional groups of the adsorbents were
determined by the method of Boehm [32–34]. On the
Boehm titration the following assumptions were made
to distinguish the surface carbon–oxygen complexes
according to their acidity: NaOC2H5 neutralizes carbox-
ylic, lactonic, phenolic, and carbonyl groups; NaOH
neutralizes carboxylic, lactonic, and phenolic groups;
Na2CO3 neutralizes carboxylic and lactonic groups;
NaHCO3 only neutralizes carboxylic groups [24,35,36].
One gram of the adsorbent was separately mixed with
15 mL of the above-mentioned basic solutions, and agi-
tated at 100 rpm for 4 days to complete the neutraliza-
tion. Five millilitre of remaining basic solution was
separated from the adsorbent, and back titration was
carried out by 0.1 M hydrochloric acid using methyl
red as a color change pH indicator. All chemicals used
in the study were of reagent grade.
2.3. Adsorption measurements
The Pb(II) stock solution was prepared by dissolv-
ing lead (II) chloride in de-ionized water at 0.1 wt.% of
Pb(II). The stock solution was diluted with de-ion-
ized water at a desired concentration. The adsorption
 Y. Kikuchi et al. / Carbon 44 (2006) 195–202 197

equilibrium of Pb(II) onto the adsorbents was investi- 100 8

gated with batch systems. Fifty mL of Pb(II) solution
bearing 100 mg of the adsorbents in a 100 mL stoppered 7
conical flask was agitated at 100 rpm in a water bath 80

Equilibrium solution pH
whose temperature was controlled at 25 °C. In our pre-

Pb(II) removal, %
6
liminary study, 3 days was found to be sufficient to at- 60
tain the adsorption equilibrium state [18]. The solution
was separated from the adsorbent with the decantation 5
technique, and diluted with 0.1 M hydrochloric acid to 40
convert all Pb(II) species to Pb2+. The Pb(II) concentra- 4
tion of the solution was determined by atomic absorp-
20
tion spectrometry (AAS, HITACHI Model 180-30). 3
The amount of Pb(II) on the adsorbent at equilibrium
was calculated from the difference between the initial 0 2
and final concentrations of the Pb(II) solution. Adsorp- 0.0 0.1 0.2 0.3 0.4
tion of nitrobenzene as an organic molecule, Cu(II), and Amount of ZnO loading, Zn-mmol/g
Cd(II) was also investigated to compare with the Pb(II)
adsorption. The concentration of nitrobenzene was Fig. 2. Pb(II) removal rate and equilibrium Pb(II) solution pH as a
function of the amount of zinc oxide loaded to the GAC.
determined by UV spectrometry (Shimadzu UV-210).

ally known to be adsorbed to surface C–O complexes

3. Results and discussion
3.1. Amount of ZnO loading
Fig. 1 shows the amount of ZnO loading on activated
carbon as a function of the number of zinc oxide loading
cycles. The amount of Zn(II) gradually increased with
increase in the number of cycles with the equilibrium
solution pH kept constant. As shown in Fig. 2, the
Pb(II) removal was proportionally promoted by intro-
ducing zinc oxide to the activated carbon. No significant
changes in equilibrium solution pH were observed for
the Pb(II) adsorption on the zinc oxide loaded activated
carbon in each loading cycle. Zn(II) cations are gener-
0.4
ZnO on activated carbon,
on activated carbon [37,38] as well as Cu(II), Pb(II)
and Cd(II) [18,39,40]. Therefore, during the first cycle
the zinc loading will also principally take place, binding
with acidic functional groups on the activated carbon
followed by binding with the rest of them and via zinc
oxide from the second through fourth steps.
3.2. Properties of adsorbents
Table 1 shows the pH of the mixture of de-ionized
water and the adsorbents, point of zero charge (pHPZC),
surface area and pore distribution of the adsorbents.
Total surface area was decreased by oxidation [26,41]
with a decrease in micropore surface area and an in-
crease in mesopore surface area. These results indicate
that the micropores were converted to mesopores on
8 oxidation, thus decreasing the total surface area. In con-
trast, the total surface area was increased by zinc oxide
loading, accompanied by an increase in mesopore area
Equilibrium Zn(II) solution pH

0.3 6 and no significant decrease in micropore area. The total

surface area and the pore distribution were preserved
after removing zinc oxide by washing with hydrochloric
Zn-mmol/g

0.2 4

Table 1
Electrostatic properties, surface area and pore distribution of the
0.1 2 adsorbents
Adsorbent GAC Oxi- ZnO ZnO- ZnO-GAC
GAC particles GAC (HCl aq.)

0.0 0 pH 5.6 3.1 6.6 5.9 5.6

1 2 3 4 pHPZC 8.9 3.3 – 6.8 4.7
Surface area, m2/g 1000 878 17 1256 1258
Number of loading cycles Mesopore, m2/g 186 482 11 481 499
Micropore, m2/g 811 395 0 773 757
Fig. 1. Amount of zinc oxide loaded to the activated carbon and
equilibrium pH of Zn(II) solution as a function of the number of pH; measured for 100 mL de-ionized water containing 100 mg of
loading cycles. adsorbents at 25 °C.
198 Y. Kikuchi et al. / Carbon 44 (2006) 195–202

10 bited similar values for GAC, ZnO-GAC and ZnO-

GAC (HCl aq.), the pHPZC of ZnO-GAC (HCl aq.)
was lower than that of ZnO-GAC suggesting that ZnO
8 loading could modify the surface of the activated car-
bon. As a result of the ZnO loadings, not carboxyl
Equilibrium solution pH

groups but hydroxyl groups were increased, because

6 the adsorption of organic compounds was not signifi-
cantly reduced using ZnO-GAC as described in the pre-
vious section, and in addition only some phenolic
4 groups were increased when GAC was prepared by cal-
cination at 350 °C from 110 °C dried activated carbon as
also shown in Table 2. Based on the results, it is consid-
2 ered that calcination at 350 °C makes the Zn(II) ions ad-
sorbed on the carbon bind to the activated carbon via
oxygen atoms upon the formation of zinc oxide, in
0 which the mesopore surface area also may progressively
0 2 4 6 8 10 12 increase.
Initial solution pH

Fig. 3. Relationship of equilibrium solution pH and initial solution
pH for the mixture of 0.1 M potassium nitrate solution and GAC (m),
ZnO-GAC (d), ZnO-GAC (HCl aq.) (s) and Oxi-GAC (j),
respectively.
acid, showing that some activated effects of developing
the pore structure in the activated carbon were occurred
by introducing zinc oxide. As also tabulated in Table 1,
the point of zero charge (pHPZC) was obtained from
Fig. 3 according to the method of Smičiklas et al. [30].
The equilibrium solution pH was plotted against the ini-
tial solution pH for GAC, Oxi-GAC, ZnO-GAC and
ZnO-GAC (HCl aq.); the constant equilibrium solution
pH exhibiting the point of zero charge (pHPZC) was at-
tained by increasing the initial pH as shown in Fig. 3
[42]. Though both the zinc oxide loading and the oxida-
tion of activated carbon decrease pHPZC, the effect was
more pronounced for the oxidation than for the zinc
oxide loading, indicating that the pH range of negative
surface charge is wider for oxidized activated carbon
(Oxi-GAC) than zinc oxide loaded activated carbon
(ZnO-GAC) as described in the next section. The results
are consistent with the changes in surface functional
3.3. Influence of pH on Pb(II) adsorption
It is generally recognized that the solution pH greatly
influences the adsorption of heavy metals from aqueous
solution onto adsorbents [43–45]. Fig. 4 shows changes
in Pb(II) removal as a function of equilibrium solution
pH for GAC, Oxi-GAC and ZnO-GAC. A steep increase
in Pb(II) removal was observed in the order of Oxi-GAC,
ZnO-GAC and GAC as the equilibrium solution pH was
increased, an order consistent with that of pHPZC. The
surface charge of the adsorbents is positive in the pH
range below pHPZC while it is negative above pHPZC.
Since the Pb(II) species are cations, which are mostly
Pb2+, and small amounts of PbðOHÞþ ; Pb4 ðOHÞ4þ 4 ,
Pb3 ðOHÞ2þ 4 in the pH range studied [19,46–48], an
100
80
Pb(II) removal, %

groups for GAC and Oxi-GAC, because the oxidation 60

with nitric acid can selectively increase the carboxylic
groups on the activated carbon surface as shown in
Table 2. While pH measured in de-ionized water exhi- 40

Table 2 20
Acidic surface functional groups of the adsorbents (Boehm titration)
110 °C-dried GAC GAC Oxi-GAC
Surface functional groups, meq./g 0
Carboxylic groups 0.03 0.03 1.14 0 2 4 6 8 10
Lactonic groups 0.04 0.04 0.04 Equilibrium solution pH
Phenolic groups 0.15 0.23 0.23
Carbonylic groups 0.01 0.02 0.15 Fig. 4. Changes in Pb(II) removal rate as a function of equilibrium
solution pH for GAC (m), ZnO-GAC (d) and Oxi-GAC (j),
Total acidic groups 0.23 0.32 1.56
respectively.
 Y. Kikuchi et al. / Carbon 44 (2006) 195–202 199

electrostatic attractive force operates between the Pb(II) 1.4

and the surface of the adsorbents in the pH range above
pHPZC, whereas a repulsive force acts for Pb(II) adsorp-
tion below pHPZC. The Pb(II) removal, therefore, is valid
over a relatively wide range of pH for Oxi-GAC, though 1.2
it is narrow for GAC. For ZnO-GAC, the pHPZC value

C e / Q e , mmol/ L
would lie between those of Oxi-GAC and GAC, because
the surface hydroxyl groups on the zinc oxide can form
0.8
on activated carbon by coming into contact with water
[11,12]; the carboxylic groups mostly found on Oxi-
GAC generally exhibit a lower pKa value than the hydro-
xyl groups possibly formed on ZnO-GAC. 0.4

3.4. Adsorption isotherms

The linear form of LangmuirÕs equation was em- 0

0 0.2 0.4 0.6 0.8
ployed to represent the adsorption isotherms for the
C e , mmo l/ L
Pb(II) and nitrobenzene as follows:
Ce 1 Ce Fig. 6. Langmuir isotherms for nitrobenzene adsorption onto GAC
¼ þ ð1Þ (m), ZnO-GAC (d) and Oxi-GAC (j).
Qe X m K e X m
where Ce and Qe are the equilibrium concentrations in
the adsorption isotherms of the Pb(II) onto GAC,
the solution and on the adsorbent, and Xm and Ke are
Oxi-GAC and ZnO-GAC, and the ZnO particles, in
the maximum number of adsorption sites and the
which the solution equilibrium pH was between pHPZC
adsorption affinity onto the adsorption sites, respec-
and 6.0 for Oxi-GAC, and ranged from 5.0 to 6.0 for
tively. Xm and Ke can be calculated from the slope and
the other adsorbents, revealing that adsorption to the
intercept of the approximated straight line when Ce/Qe
adsorbents except GAC progressed on the negatively
is plotted against Ce.
charged surface of the adsorbents. Furthermore, Pb2+
For all adsorption experiments for the zinc oxide
aqua may be the principal Pb(II) species, and a small
loading adsorbents, zinc ions in the aqueous solution
portion of Pb(OH)+ can be present under the condi-
were detected at less than 2 mg/L, mostly below 1 mg/
tions, since the equilibrium solution pH was always less
L, indicating that the influence of zinc ions on Pb(II)
than 6.0 for all adsorbents. Fig. 6 shows the adsorption
adsorption was negligible in this study, and that zinc
isotherms of the nitrobenzene onto GAC, Oxi-GAC and
can bind strongly to activated carbon. Fig. 5 shows
ZnO-GAC. It is obvious that ZnO-GAC and GAC exhi-
bit good performance compared with Oxi-GAC for the
nitrobenzene adsorption, whereas ZnO-GAC and Oxi-
10
GAC are superior to GAC for the Pb(II) adsorption.
The Langmuir parameters calculated from the approxi-
mated lines in the isotherms were as tabulated in Table
8
3. The adsorption capacity, Xm, of 0.37 mmol/g for
ZnO-GAC is the largest among the adsorbents for the
Pb(II) adsorption except the ZnO particles, and it is
C e / Q e , g/ L

6
close to the amounts of zinc oxide loading of
0.35 mmol/g, suggesting the mono-layer spreading of
4
Table 3
Langmuir parameters obtained from Pb(II) and nitrobenzene
2 adsorption
Adsorbent Pb(II) adsorption Nitrobenzene adsorption
Xm, mmol/g Ke, L/mmol Xm, mmol/g Ke, L/mmol
0
0.0 0.2 0.4 0.6 0.8 GAC 0.052 12 2.0 23
Oxi-GAC 0.24 56 0.68 2.8
C e , mmol/ g ZnO 1.3 4.0 – –
particles
Fig. 5. Langmuir isotherms for Pb(II) adsorption onto GAC (m),
ZnO-GAC 0.37 32 1.6 11
ZnO-GAC (d) and Oxi-GAC (j) and ZnO particles (n), respectively.
200 Y. Kikuchi et al. / Carbon 44 (2006) 195–202
zinc oxide onto the GAC surface, while 0.24 mmol/g of
Xm for Oxi-GAC is limited to only 20% of the carboxylic
sites of 1.14 meq./g determined by the Boehm titration.
Though the adsorption affinity to ZnO-GAC was
superior compared to the ZnO particles, the adsorption
capacity of the ZnO particles is 3.5 times larger than that
of ZnO-GAC. However, the total amount of zinc in the
ZnO particles is 36 times as great as that in ZnO-GAC.
The results suggest that zinc oxide loading to activated
carbon can be effectively used for Pb(II) adsorption,
whereas a part of acidic functional groups, probably
those on the external surface, will contribute to binding
the Pb(II) for the ZnO particles and Oxi-GAC. The acti-
vated carbon thanks to its developed porous structure
and high specific surface area which can accommodate
zinc oxide in a spreading manner, probably the zinc
oxide connects to the activated carbon surface via oxy-
gen atoms, for the adsorptive removal of heavy metals.
The adsorption affinities for Pb(II) adsorption decreased
in the order of Oxi-GAC, ZnO-GAC and GAC. This is
caused by the fact that the carboxylic groups, which are
considered to be the strongest binding sites for heavy
metals [49–51], are abundant for Oxi-GAC though the
hydroxyl groups may be abundant in composition of
surface acidic sites for GAC, ZnO-GAC and the ZnO
particles. Tamura et al. examined the adsorption of hea-
vy metals onto MnO2 and Fe2O3, and concluded that
surface hydroxyl groups contributed to the binding of
heavy metals for the metal oxide [52]. In addition, the
adsorption and desorption of Cu(II) and Cd(II) were
examined as well as those of Pb(II) as shown in Table
4. The amount of Pb(II) on the zinc oxide loaded
GAC was more than that of the oxidized activated car-
bon under the conditions, whereas Oxi-GAC was
advantageous for Cu(II) and Cd(II) adsorption. For
the desorption experiment, though a small amount of
the heavy metals was released to the aqueous solution
for the zinc oxide loaded activated carbon, no Pb(II),
Cu(II) and Cd(II) was detected for the oxidized GAC
probably due to strong binding between heavy metal
ions and carboxyl functional groups. The carboxylic
functional groups are mostly responsible for binding
heavy metal ions for Oxi-GAC, and the hydroxyl groups
for the binding for ZnO-GAC.
Table 4
Adsorption and desorption of Pb(II), Cu(II) and Cd(II)
Adsorbent GAC Oxi-GAC ZnO-GAC
Pb(II) ads., mmol/g 0.043 0.184 0.221
Pb(II) des., mmol/g 0.019 n.d. 0.004
Cu(II) ads., mmol/g 0.059 0.235 0.080
Cu(II) des., mmol/g 0.022 n.d. 0.001
Cd(II) ads., mmol/g 0.015 0.124 0.059
Cd(II) des., mmol/g 0.009 n.d. 0.007
Initial metal concentration; 0.48 mmol/L, agitation at 25 °C for 3 days.
While surface carboxylic and hydroxyl groups are
considered to be adsorption sites for heavy metals in
the study, the graphene layer of activated carbon plays
a decisive role in the adsorption of organic molecules,
especially those containing aromatic rings; the adsorp-
tion can take place via interactions between p electrons
of the graphene layer and those of the aromatic rings
[14,21]. Both the adsorption capacity, Xm, and the
adsorption affinity, Ke, for the nitrobenzene adsorption
were slightly reduced by loading zinc oxide onto the
activated carbon but significantly reduced by the oxida-
tion as clearly shown in Fig. 6 and Table 3, because the
p electrons of the graphene layer were more strongly
withdrawn by the carboxyl groups generated by oxida-
tion than by the hydroxyl groups probably created on
the zinc oxide. From the results, therefore, it can be
concluded that the adsorption of the Pb(II) from the
aqueous solutions onto the activated carbon will be
improved by loading zinc oxide without a significant
decrease in adsorption capacity or affinity of the
organic molecules as observed in the oxidized activated
carbon.
4. Conclusions
Based on the experimental results for zinc oxide load-
ing to granular activated carbon compared with ZnO
particles and oxidation of activated carbon, the follow-
ing conclusions can be deduced for the effect of zinc
oxide loading on the Pb(II) adsorption to the activated
carbon.
(1) Loading zinc oxide on the activated carbon exhib-
ited some activated effects of enlarging the specific
surface area due to the increase in mesopore sur-
face area, while a detrimental effect was observed
for the oxidation of activated carbon.
(2) Most of the zinc oxide loading to the activated car-
bon can be effectively used for the Pb(II) adsorp-
tion compared with the ZnO particles and the
oxidized activated carbon, because the number of
Pb(II) adsorption sites calculated from the iso-
therms was close to the measured number of zinc
oxide loading, but it was far less than the number
of hydroxyl groups possibly formed on the ZnO
particles and carboxyl groups introduced by the
oxidation of activated carbon.
(3) The zinc oxide loading and the oxidation of acti-
vated carbon reduce the point of zero charge
(pHPZC); the increasing order of the oxidized acti-
vated carbon (Oxi-GAC), the zinc oxide loaded
activated carbon (ZnO-GAC) and GAC in the
pHPZC observation are consistent with the order
of the steep increase in the Pb(II) removal when
the equilibrium solution pH is increased.
 Y. Kikuchi et al. / Carbon 44 (2006) 195–202
(4) The hydroxyl groups created on the zinc oxide are
likely to be responsible for the Pb(II) adsorption
for the zinc oxide loaded activated carbon (ZnO-
GAC) whereas the carboxyl groups are adsorption
sites for the oxidized activated carbon (Oxi-GAC),
because the point of zero charge (pHPZC) for the
zinc oxide loaded activated carbon was between
GAC and Oxi-GAC, and some desorption of
Pb(II), Cu(II) and Cd(II) was observed for ZnO-
GAC but no desorption was detected for Oxi-
GAC, and the adsorption of nitrobenzene was
slightly reduced for ZnO-GAC but it was signifi-
cant for Oxi-GAC.
Acknowledgements
The authors thank Calgon Mitsubishi Chemical Cor-
poration for providing the granular activated carbon.
They are also grateful to Dr. Keiichi Nagao of the
Safety and Health Organization of Chiba University,
and Dr. Masanori Fujinami and Dr. Koichi Oguma of
the Faculty of Engineering of Chiba University, for their
experimental support in the study.
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