Applied Surface Science 252 (2006) 5967–5971

www.elsevier.com/locate/apsusc

Preparation of activated carbon from cherry stones by

chemical activation with ZnCl2
M. Olivares-Marı́n a,*, C. Fernández-González a, A. Macı́as-Garcı́a b,
V. Gómez-Serrano a
a
Departamento de Quı́mica, Inorgánica, Facultad de Ciencias, Universidad de Extremadura, Badajoz, Spain
b
Área de Ciencia de Materiales e Ingenierı́a Metalúrgica, Escuela de Ingenierı́as Industriales,
Universidad de Extremadura, Avda. de Elvas s/n, 06071 Badajoz, Spain

Available online 5 December 2005

Abstract
Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the
preparation of activated carbon by chemical activation with ZnCl2. The influence of process variables such as the carbonisation temperature and the
ZnCl2:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were
characterised texturally by adsorption of N2 at 196 8C, mercury porosimetry and density measurements. Information on the surface functional
groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is
prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m2 g 1. The effect of the
increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature,
whereas the opposite applies to the effect on the surface functional groups and structures.
# 2005 Elsevier B.V. All rights reserved.

PACS: 61.43.Gt; 68.43. h; 81.05.Rm; 82.45. Jn

Keywords: Cherry stones; ZnCl2 activation; Activated carbon; Characterisation

1. Introduction Spanish cherry is produced, a great quantity of cherry stones is

Activated carbon is a porous carbon material which
possesses a high adsorption capacity and that is widely used
as adsorbent in the purification of liquids and gases and also as
catalyst and catalyst support [1]. Its textural and surface
properties depend on the raw material and on the method used
in its preparation. Nowadays, activated carbon can be produced
from a large number of abundant and low-cost materials, which
possess a high carbon content and a low inorganic content [2].
The raw materials in the order of their importance and in terms
of activated carbon production are the following: wood, coal,
lignite, coconut shell, peat and others [2]. In the Comunidad
Autónoma de Extremadura, mostly in the Valle del Jerte
(Cáceres province, Spain), where more than 60 wt.% of the
* Corresponding author. Tel.: +34 924289395; fax: +34 924289395.
E-mail address: maraom@unex.es (M. Olivares-Marı́n).
0169-4332/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2005.11.008
yearly generated as a waste in the industrial production of kirsh
(cherry brandy). Using cherry stones, the pyrolysis [3], surface
modification of resultant pyrolysed and activated products
[4,5], and preparation of activated carbon by the method of
physical activation [6] have been studied previously. Here,
instead, the preparation of activated carbon from the same
starting material by the method of chemical activation, using
ZnCl2 as the activating agent, is investigated. The effects of
process variables such as the carbonisation temperature and the
ZnCl2/cherry stones ratio (impregnation ratio) on textural and
chemical-surface properties of the products thus obtained are
examined. Impregnation with ZnCl2 causes degradation of the
cellulosic material and, on carbonisation, dehydration. These
processes result in charring and aromatisation of the carbon
skeleton and creation of the pore structure [1]. Materials such as
peach stones [7], corn cob [8], paper mill [9], sugar cane [10],
coconut shells and palm seeds [11], and almond shells [12] have
been used previously in activation treatments with ZnCl2.
5968 M. Olivares-Marı́n et al. / Applied Surface Science 252 (2006) 5967–5971
2. Material and experimental methods
Cherry stones (CS, hereafter) were used as the starting
material in the preparation of activated carbon. CS, as received
from the Asociacion de Cooperativas del Valle del Jerte, in
successive steps were first air-dried, crushed and sized, the
fraction of particle sizes between 1 and 2 mm being chosen.
Then, CS were contacted with dilute H2SO4 solution for 24 h
and washed with distilled water until pH 6 was eventually
reached in the residual liquid. In the impregnation of CS,
100 mL of ZnCl2 aqueous solution (i.e., the amount of
activating agent present in such a solution was that
corresponding to a given ZnCl2:CS ratio by weight) were
brought into contact with 25 g of the material and the liquid/
solid phases were maintained in contact, under mechanical
agitation, at 85 8C for 7 h. Evaporation during this time was
avoided using a close-up glass container. Once such a time
elapsed, the supernatant liquid was separated by vacuum
filtration and the remaining solid was oven-dried at 120 8C for
24 h. ZnCl2 was not analysed in the residual liquid in order to
assess the amount of activating agent uptaken by CS.
The heat treatments of ZnCl2–impregnated CS were carried
out in a horizontal cylindrical furnace, Chesa. An amount of
approximately 7 g of impregnated product, once weighed in an
analytical balance, was placed in a boat like small size ceramic
container and heated from room temperature to the maximum
heat treatment temperature in N2 atmosphere (flow rate = 100 -
mL min 1). The heating rate was 10 8C min 1. The heating
time at maximum heat treatment temperature was 2 h. Two
series of activated carbons were prepared by maintaining the
ZnCl2:CS ratio fixes (i.e., 3:1 by weight) and by varying the
carbonisation temperature in the 400–800 8C, or vice versa
(ZnCl2:CS ratio, 1:1, 2:1, 3:1 and 4:1; temperature, 500 8C).
The samples are designated as ZT and ZN, where T represents
the carbonisation temperature and N the proportion of ZnCl2 in
the initial ZnCl2/CS mixture. With comparison purposes a
carbonised product was prepared by heating CS at 500 8C for
2 h. This product is noted as C-500.
After their preparation, the samples were characterised
texturally by gas adsorption (N2, 196 8C), mercury porosi-
metry and helium and mercury density measurements.
Information on the surface functional groups and structures
of the carbons was obtained by FT-IR spectroscopy. The
isotherms for N2 at 196 8C were determined using a
semiautomatic adsorption apparatus (Autosorb-1), Quanta-
chrome. About 0.10 g of sample was used in each adsorption
experiment. The carbon adsorbent was outgassed at 250 8C for
12 h, at a pressure lower than 10 3 Torr, prior to effecting
adsorption measurements. A mercury porosimeter (Autoscan-
60), Quantachrome, was used in the experiments of mercury
intrusion. The mercury density (rHg) was measured just before
carrying out the experiment of mercury porosimetry. About
0.5 g of sample was evacuated until the pressure of 13.33 Pa
was reached in the filling apparatus, Quantachrome. The
helium density (rHe) was measured in a Quantachrome
steropycnometer, using around 3 g of sample. The FT-IR
spectra of the samples were recorded between 4000 and
400 cm 1, using a Perkin-Elmer 1720 spectrometer. Fifty scans
were taken at 2 cm 1 resolution. Pellets were prepared by
thoroughly mixing carbon and KBr at the 1:500 carbon/KBr
weight ratio in a small size agate mortar. The resulting mixture
was compacted in a Perkin-Elmer manual hydraulic press at
10 tons for 3 min.
3. Results and discussion
3.1. Effect of carbonisation temperature
Fig. 1(a) shows the N2 adsorption isotherms measured for C-
500 and the ZT samples. The isotherm obtained for C-500 is a
typical type 1 isotherm of the well-known BDDT classification
system, which indicates the carbonised product prepared from
CS is an essentially microporous solid. For C-500 SBET is
330 m2 g 1, Vmi is 0.16 cm3 g 1 and Vme is 0.03 cm3 g 1. From
the shape of the adsorption isotherm it follows that the pore size
distribution of C-500 in the micropore range is mainly made up
of narrow pores.
The shape of the adsorption isotherms for the ZT samples
denotes that the micropore content (also see the values of Vmi
and W0 in Table 1) is high in these samples. Nevertheless, Vmi or
W0 depends on the carbonisation temperature of ZnCl2–
impregnated CS. Thus, the micropore volume first increases
with increasing temperature between 400 and 500 8C and then
decreases at higher temperatures. At 700 and 800 8C is similar
the degree of development of the microporosity. The pore size
distribution in the micropore range is wider for Z400, Z500 and
Z600 than for Z700 and Z800. SBET, as expected, follows the
same trend as Vmi or W0. It also holds for Vme. However, Vme-P
decreases gradually with increasing temperature. As far as the
region of the macropores is concerned, the highest Vma appears
for Z700. The pore size distribution (Fig. 1b) is similar for
Z500, Z700 and Z800. Also notice that the content of narrow
macropores is lower in Z400 and that the content of narrow
mesopores is higher in Z400, Z500 and Z600. The total pore
volume is as high as 1.29 cm3 g 1 for Z700.
In short, from CS by varying the carbonisation temperature it
is possible to prepare activated carbon with a high development
of the porosity, namely, Vmi is 0.69 cm3 g 1 for Z500, Vme is
0.15 cm3 g 1 (and Vme-P is 0.26 cm3 g 1) for Z500 and Vma is
0.53 cm3 g 1 for Z700. For different activated carbons the
micropore volume lies between 0.15 and 0.50 cm3 g 1, the
mesopore volume between 0.02 and 0.10 cm3 g 1, and the
macropore volume between 0.2 and 0.8 cm3 g 1 [13]. In view
of the results obtained in this previous study of the effect of
temperature on the preparation of activated carbon from CS,
500 8C was chosen as optimum temperature.
The FT-IR spectra registered for the series ZT (Fig. 2a)
display a number of stronger bands or shoulders at 3407, 1696,
1585 and 1251–1189 cm 1, which are assigned in turn to
n(O–H) vibrations, n(C O) vibrations, n(C C) vibrations and
n(C–O) vibrations; n, stretching. The spectral changes indicate
that the increase in temperature during the preparation of the
samples causes a reduction of OH groups, CO groups and C C
structures. The CO groups are very sensitive to the increase in
 M. Olivares-Marı́n et al. / Applied Surface Science 252 (2006) 5967–5971 5969

Fig. 1. N2 isotherms at 196 8C for C-500 and the ZT samples (a) and plots of cumulative pore volume against pore radius (mercury porosimetry) for the ZT samples (b).

temperature as they are absent from Z600, Z700 and Z800. In
contrast, the thermal effect on the ether type structures is of
little significance, these structures being then thermally
stable.
The spectra obtained for C-500 and Z500 (Fig. 2b) show a
similar shape, which indicates that the same surface functional
groups and structures are present in the carbonised product and
the activated carbon prepared at the same temperature.
However, important differences concerning the relative inte-
nsity of bands are observed in both spectra. Whereas in the
spectrum of C-500 the band at 1585 cm 1 is stronger than the
band at 1251–1189 cm 1, the opposite applies to the spectrum
of Z500. Therefore, in the activated carbon the ether structures
appear to increase to the detriment of the C C containing
structures.
3.2. Effect of the ZnCl2:CS ratio
The N2 isotherms measured for the ZN samples are shown in
Fig. 3(a). It follows (see data listed in Table 1 as well) that the
ZnCl2:CS ratio has a strong effect on the development of the
porosity. Thus, SBET, Vmi or W0 and Vme undergo a great
increase with increasing ZnCl2:CS ratio. As a guide, the
percentage of increase in SBET ((SZ4 SZ1/SZ1)  100) is 250.

Table 1
Textural parameters of the activated carbons
Sample N2 adsorption Mercury porosimetry Density measurements
2 1 3 1 3 1 3 1 3 1 3 1
SBET (m g ) Vmi (cm g ) W0 (cm g ) Vme (cm g ) Vme-P (cm g ) Vma (cm g ) rHg (g cm 3) rHe (g cm 3) VT (cm3 g 1)
Samples ZT
Z400 1472 0.67 0.64 0.13 0.30 0.31 0.67 1.51 0.83
Z500 1566 0.69 0.65 0.15 0.26 0.51 0.55 1.62 1.20
Z600 1345 0.61 0.57 0.11 0.24 0.39 0.60 1.70 1.08
Z700 1004 0.50 0.49 0.04 0.18 0.53 0.54 1.79 1.29
Z800 992 0.49 0.47 0.04 0.11 0.47 0.60 1.87 1.13
Samples ZN
Z1 567 0.28 0.28 0.02 0.02 0.37 0.67 1.58 0.86
Z2 1086 0.54 0.55 0.05 0.15 0.74 0.52 1.64 1.31
Z3 1566 0.69 0.65 0.15 0.26 0.51 0.55 1.62 1.20
Z4 1971 0.74 0.68 0.38 0.45 0.34 0.57 1.67 1.15
The data were obtained from the N2 adsorption isotherms at 196 8C: SBET ( p/p0 = 0.05–0.30, am = 16.2 Å2), Vmi (volume adsorbed, Vad, at p/p0 = 0.10), Vme (Vad at
p/p0 = 0.95 Vad at p/p0 = 0.10) and W0 (Dubinin–Radushkevich equation); mercury intrusion curves: Vme-P and Vma and helium and mercury density values (rHe and
rHg): VT = 1/rHg 1/rHe. Vmi, Vme and W0 are expressed as liquid volumes.
5970 M. Olivares-Marı́n et al. / Applied Surface Science 252 (2006) 5967–5971

Fig. 2. FT-IR spectra of the ZT samples (a) and of C-500 and Z500 (b).

For Z4 SBET is 1971 m2 g 1, Vmi being equal to 0.74 cm3 g 1. and 1340 m2 g 1 (hulls) [6] and 920 m2 g 1 [14]. Vme is
This SBET is much higher than the values reported previously 0.38 cm3 g 1 and Vme-P is 0.45 cm3 g 1 for Z4, which are much
for activated carbons prepared from CS by the method of higher pore volumes than for the ZT samples. For Z4, however,
physical activation with steam, i.e., 930 m2 g 1 (entire stones) the degree of development of the macroporosity is worse than

Fig. 3. N2 isotherms at 196 8C (a) and plots of cumulative pore volume against pore radius (mercury porosimetry) (b) for the ZN samples.
 M. Olivares-Marı́n et al. / Applied Surface Science 252 (2006) 5967–5971
Fig. 4. FT-IR spectra of the ZN samples.
for Z1–Z3. Vma is as high as 0.74 cm3 g 1 for Z2. VT, at most, is
1.31 cm3 g 1 for Z2.
As inferred from the N2 adsorption isotherms, the pore size
distribution in the micropore and mesopore ranges is markedly
affected by the increase in the impregnation ratio. Z1 is
practically a microporous carbon, which further only contains
narrow micropores. The presence of a low content of mesopores
in Z1 is reflected as well by the curve of the cumulative pore
volume versus pore radius (mercury porosimetry, Fig. 3b).
However, Z4 possesses a very wide pore size distribution in the
entire range of micropores and in the range of the narrow
mesopores. This is also clearly shown by the great slope of the
curve of mercury intrusion at pore radii below 200 Å for Z4
(Fig. 3b).
The FT-IR spectra (Fig. 4) are similarly shaped for the ZN
samples. This indicates that the method of preparation of
5971
activated carbon from CS by varying the ZnCl2:CS ratio is not
an effective method to modified the surface functional groups
and structures in the resultant products.
4. Conclusions
From the above results it may be concluded that, using
cherry stones, the ZnCl2-based method of chemical activation is
very effective to prepare activated carbon ranging widely in its
textural and surface properties. As for the textural properties,
the effect associated with the increase in the impregnation ratio
is stronger than that with the rise in the carbonisation
temperature. In contrast, the effect due to the increase in
carbonisation temperature on the surface functional groups and
structures is the more important one.
Acknowledgement
Financial support from MCYT (project BQU2002-03600) is
gratefully acknowledged by the authors.
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