Microporous and Mesoporous Materials 152 (2012) 163–171

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Microporous and Mesoporous Materials

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Chemical versus physical activation of coconut shell: A comparative study

Marcos J. Prauchner a,⇑, Francisco Rodríguez-Reinoso b
a
Inst. de Química, Universidade de Brasília, Brasília-DF, C.P. 4478, CEP: 70904 970, Brazil
b
Dep. de Química Inorgánica, Universidad de Alicante, Alicante, Apartado 99, E-03080, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Granular activated carbons with high porosity were produced from dried endocarp of coconut shell using
Received 5 April 2011 both physical activation with CO2 and chemical activation with H3PO4 or ZnCl2. Efforts were focused on the
Received in revised form 1 September 2011 elucidation of the activation processes and on the establishment of correlations between these and the
Accepted 19 November 2011
properties of the synthesized materials. The results show that the physical process permits to tailor the pore
Available online 30 November 2011
size distribution more accurately. However, the resulting materials present relatively low packing densities
due to the occurrence of empty spaces that originate, at least partially, from the structure of conductor ves-
Keywords:
sels present in the botanical structure of the precursor. On the other hand, chemical activation with H3PO4
Activated carbon
Activation
or ZnCl2 permits to reduce drastically the occurrence of such empty spaces, leading to materials with higher
H3PO4 packing densities, which positively affect the volumetric adsorption capacity. Further, chemical activations
ZnCl2 leads to lower weight losses during the activation processes and permits the synthesis of carbons with
CO2 higher mechanical resistance and elevated proportion of mesopores.
Ó 2011 Elsevier Inc. All rights reserved.

1. Introduction structure available. The main differences are that carbonization

It is well-known that activated carbon is considered to be the
general adsorbent due to the large range of applications. Numerous
works are being continuously published concerning its use as
adsorbent for: treatment of potable water; purification of air;
retention of toxins by respirators; removal of organic and inorganic
pollutants from flue gases and industrial waste gases and water;
recuperation of solvents and hydrocarbons volatilized from petro-
leum derivatives; catalysis; separation of gas mixtures (molecular
sieve activated carbons); storage of natural gas and hydrogen; en-
ergy storage in supercapacitors; recovery of gold, silver and other
noble metals; etc. A good range of activated carbons applications
are depicted in Refs. [1,2].
Activated carbon can be prepared from almost any organic
material rich in carbon and preferably with low content in inor-
ganic matter. The processes more commonly used to prepare the
materials are physical and chemical activation. For physical activa-
tion (also called thermal activation) the char obtained by carbon-
ization of the precursor is partially gasified by an oxidant
atmosphere (usually steam or carbon dioxide) at temperatures in
the range of 700–900 °C. For chemical activation, the precursor is
previously impregnated with a chemical (usually H3PO4, ZnCl2 or
Na or K hydroxides or salts). The impregnated material is then car-
bonized under an inert atmosphere and, finally, the carbonized
material is washed to remove the chemical and to leave a porous
⇑ Corresponding author. Tel.: +55 61 3107 3851; fax: +55 61 3107 3900.
E-mail address: marcosjp@unb.br (M.J. Prauchner).
and activation are usually independent steps during physical acti-
vation, whereas the steps cannot be separated during chemical
activation (the chemical acts on the material being carbonized)
[1,2]. Most activated carbon production employs lignocellulosic
materials [3–24] or degraded and coalified plant matter (peat
and all ranks of coals) as the precursor [25,26]. However, a large
range of materials such as pitch, polymers, resins, rubber, sludge
and leather can be also used [3,27–29].
Taking into account the large volume of activated carbon re-
quired to attend the increasing world demand, biomass derivatives
are very interesting raw materials because they are abundant and
inexpensive (generally agricultural residues) and they are obtained
from renewable sources. Further, they usually exhibit: (i) low con-
tents of inorganic material (usually in the range of 0–1%), which is
desirable since the carbon yield is usually low, especially for phys-
ical activation, and the presence of inorganic matter can affect the
adsorption properties of the resulting materials [4]; (ii) relatively
high volatile contents (above 50%), which permits to generate, dur-
ing carbonization, a rudimentary pore structure that can be easily
developed later by gasification; and (iii) relatively high density,
which positively influences the mechanical properties of the
resulting materials [1,2].
Concerning chemical activation with H3PO4 and ZnCl2, the
interaction of the lignocellulosic chains with the chemical favors
the formation of highly developed porous structures [5–13]. The
preparation of highly microporous carbons by chemical activation
of different ligninocellulosic precursors with KOH and NaOH has
been also reported [5,14–16]. However, it is worthy to highlight

1387-1811/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2011.11.040
164 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171
that very high amounts of the chemical (up to around four times
the mass of precursor) have to be employed in order to achieve ele-
vated pore volumes and, as already described by Molina-Sabio and
Rodríguez-Reinoso [5], the development of porosities above
0.4 cm3/g by activation with KOH inevitably leads to powdered
carbons. Therefore, this procedure is not adequate to prepare gran-
ular carbons with high adsorption capacity. In turn, a recent report
shows it is possible to prepare binderless monoliths from petro-
leum pitch based mesophase [27].
Within the large range of biomass derivatives used as activated
carbon precursors (woods and components, fruit shells, pulp and
stones, bagasse, etc.), coconut shell is one of the most employed
for industrial purposes, mainly due to its large availability in sev-
eral regions of the world.
This work presents a detailed study about the production of
highly porous granular activated carbons from coconut shell
using either physical activation with CO2 or chemical activation
with H3PO4 or ZnCl2. In spite of the large amount of published
papers dealing with physical and chemical activation of biomass
derivatives [3–24], including coconut shell [4,6,17,18], most of
the works are devoted to just empirically explore the influence
of preparation parameters (mainly temperature and activating
agent proportion) on the surface area and the pore volume by
mass unit of the resulting material. Therefore, a deeper knowl-
edge about the matter is needed in order to make it possible to
tailor the porosity of carbons intended for specific applications
such as gas storage and molecular sieving. In the present paper,
efforts are focused on (i) the elucidation of the process involved
in each kind of activation, and (ii) the establishment of correla-
tions among the different processes and the properties of the
resulting materials, including aspects such as mechanical resis-
tance, pore size distribution and pore volume on a volumetric ba-
sis, which are important parameters for practical application of
the products.
2. Experimental
2.1. Raw-material
The present work was carried out using dried endocarp of coco-
nut (Cocos nucifera) shell originated from Mexico as raw material.
The ground shell was sieved to separate the particles in the range
of 2.00–2.83 mm, which were used as the starting material in all
preparations. Some characteristics of the precursor are described
in Table 1.
Table 1
Characterization of the starting material.
Ash content (%)a
Elemental composition (%) C 52.0
H 6.0
N 0.1
S 0.0
O 40.9
Extractive (%)b
Biopolymeric composition (%) Ligninc
Cellulosed
Hemicellulosee
Carbon yield (%)f
a
Residual mass after thermal treatment at 600 °C under air until constant mass.
b
According to norm TAPPI T 12 os-75, described in Ref. [30].
c
Based on the norm TAPPI T 222 os-74, described in Ref. [30].
d
Based on the procedure described in Ref. [31].
e
Residual mass after extraction of lignin and cellulose.
f
Residual mass after thermal treatment of the dried (100 °C under reduced
pressure overnight) grains up to 850 °C (2 °C/min, 2 h) under N2 flow (100 mL/min).
2.2. Methods
For physical activation with CO2 the precursor was previously
carbonized under a flow of nitrogen (100 mL/min) up to 850 °C
(2 °C/min; 2 h). Then, the carbonized sample was heat treated un-
der a CO2 flow of 100 mL/min at 750 °C (5 °C/min) for different
periods of time.
For chemical activation, the precursor was initially impregnated
with a solution of the chemical (2 mL/g of precursor). The solution
concentration was adjusted to provide the desired mass ratio of
phosphorous or zinc to the precursor; these ratios will be ex-
pressed as XP or XZn, respectively, along the text. Initially, the mix-
ture was stirred at 85 °C for 2 h keeping the solution volume nearly
constant. This period of time was sufficient to permit a complete
diffusion of the chemical through the particles, which was inferred
from the uniform dark aspect of the transversal section of cut
grains. The temperature of the solution was later increased to the
boiling point until complete dryness, which forced the incorpora-
tion of all chemical into the particles; at this stage, the temperature
reached about 150 °C. The impregnated material was then heat
treated in a tubular horizontal furnace up to a final temperature
for 2 h (1 °C/min) under flowing nitrogen (100 mL/min) and subse-
quently washed to remove the chemical. For H3PO4 removal the
washing was carried out with distilled water until the pH of the
rinse remained constant and close to six. In the case of ZnCl2 the
chemical was firstly removed with a boiling dilute solution of
HCl (the acid increases the Zn solubility) and then the grains were
washed with abundant distilled water until a pH  6 for the rinse.
The washed products were dried overnight under reduced pressure
in an oven at around 90 °C.
2.3. Characterization
Adsorption–desorption isotherms of N2 ( 196 °C) and CO2
(0 °C) were obtained in a volumetric automatic system, Omnisorb
610. The micropore volume (Vmic) was determined from the N2 iso-
therms by applying the Dubinin–Radushkevich (DR) equation; the
mesopore volume (Vmes) was calculated by subtracting Vmic from
the volume of N2 adsorbed at a relative pressure (p/p0) of 0.95
(V0.95). In turn, the CO2 isotherms permitted to determine the
narrow micropore volume (Vnmic) by applying the Dubinin-
Radushkevich (DR) equation. Finally, the wide micropore volume
(Vwmic) was calculated by subtracting the Vnmic from Vmic. The basis
for the use of these equations is described in Refs. [32,33].
The analyses of mercury porosimetry were carried out in an Auto-
Pore IV 9500 V1.05 using a pressure range of 0.0036–10.33 MPa.
Using this pressure range, pores with a dimension covering the range
172–62 lm could be analyzed.
The helium density was determined by using an automatic pic-
nometer Accupyc 1330 from Micromeritics. The packing or tap
1.0
density (also called bulk density) was determined by a procedure
based on the ASTM D 2854-89 standards, by weighing a known
volume of gently trapped granules dried overnight at 110 °C.
3. Results and discussion
0.6
49
3.1. Physical activation
43
8
Before being physically activated with CO2, the coconut shell
30.5
was firstly submitted to carbonization under a nitrogen flow. The
graphs in Fig. 1 present the weight loss along carbonization up to
different final temperatures in the absence of chemicals (Fig. 1a)
and in the presence of H3PO4 or ZnCl2 (the effects of the chemicals
concern the discussions about chemical activation, in Section
3.2.1). In addition, they show the bulk density of the resulting
materials. The graphs were purposely built making the density of
 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171 165

40
-20 0.8
(a) without chemicals 35
0.7
0
30

Packing density (g/cm )

0.6
Weight loss:
25
Weight loss (%)

20 94 %
0.5

n (mmol/g)
79 %
20 52 %
40 0.4
25 %
15 0%
0.3
60
10

3
0.2
80 5
0.1
0
100 0.0 0.0 0.2 0.4 0.6 0.8 1.0
0 100 200 300 400 500 600 700
p/p0
0
Heat treatment temperature ( C)
Fig. 2. N2 adsorption–desorption isotherms of carbons produced by physically
activation of coconut shell with CO2 up to different burn-off values. Closed symbols:
-20 0.8
adsorption; open symbols: desorption.
(b) H3PO4
0
Packing density (g/cm )
0.6 exhibits only a rudimentary pore structure, the nitrogen molecules
Weight loss (%)

20 face serious difficulties to diffuse throughout their narrow pores at

196 °C. Therefore, the N2 adsorption equilibrium was not reached
40 0.4
for the sample at normal conditions of analysis, so that a low-pres-
sure hysteresis loop is seen in the corresponding isotherm. Rodrí-
60
0.2
guez-Reinoso and Linares-Solano [20], working with chars with
very narrow microporosity, reported that the N2 adsorption equi-
3

80
librium can take even weeks to be reached at 196 °C.
100 0.0 On the other hand, CO2 adsorption experiments are usually car-
0 100 200 300 400 500 600 700 ried out at 0 °C. Although CO2 has a critical dimension similar to N2
Heat treatment temperature (ºC) (0.33 and 0.364 nm, respectively), the relatively high adsorption
temperature confers an elevated diffusion rate to the CO2 mole-
-20 0.8 cules, so that they are able to access very narrow pores in relatively
(c) ZnCl2 short periods of time. At this point, it is worthy to stress that CO2
adsorption experiments are usually carried out only up to the
Packing density (g/cm )

0
0.6 atmospheric pressure. Since it is only about 3% of the CO2 satura-
Weight loss (%)

20 tion pressure at 0 °C, only very narrow pores are filled during the
experiments. In this way, it is generally assumed that the pore vol-
40 0.4 ume determined from CO2 adsorption isotherms corresponds only
to the pores with width lower than 0.7 nm (narrow micropore vol-
60
ume – Vnmic), as proposed by the group of Rodríguez-Reinoso
3

0.2
[32,33]. Since chars present only a rudimentary porosity, it is fea-
80
sible to consider that their Vnmic nearly corresponds to both Vmic
and V0.95. Therefore, Vmic and V0.95 of the sample corresponding
100 0.0
0 100 200 300 400 500 600 700 to the 0% of burn-off in Fig. 3 was considered as equal to Vnmic.
Heat treatment temperature (ºC) Thermal treatment at 750 °C under a CO2 atmosphere leads to a
slow gasification of the carbonized coconut shell, resulting in a low
Fig. 1. Weight loss during carbonization of the dried (100 °C under reduced
pressure overnight) coconut shell and packing density of the resulting materials;
carbonizations were carried out (a) in the absence of chemicals and in the presence
1.25
of (b) H3PO4 or (c) ZnCl2.
V0.95
Vmes
1.00
Vmic
the dried precursor (0.65 g/cm3) to coincide with the 0% of weight Vwmic
loss. 0.75 Vnmic
V (cm /g)

Pyrolysis of coconut shell in the absence of chemicals leads to a

3

pronounced weight loss between 200 and 300 °C due to the release 0.50
of gases and volatiles resulting from pyrolysis reactions. Neverthe-
less, the packing density undergoes only a small reduction in this
0.25
temperature range. Therefore, it is possible to conclude that a pro-
nounced contraction of the particles took place, which restricts the
development of a porous structure. 0.00
0 20 40 60 80 100
Fig. 2 presents the N2 adsorption–desorption isotherms of
Burn-off (%)
carbons produced by physical activation up to different burn-off
values. The material corresponding to the burn-off of 0% is the shell Fig. 3. Pore volumes as a function of the burn-off during physical activation of
just carbonized at 850 °C. Since this material (so-called char) coconut shell.
166 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171
and almost constant weight loss rate of around 1 wt.%/h. This gas-
ification permits to develop the rudimentary pore structure of the
char, rendering it more easily accessible to N2 at 196 °C. The
adsorption isotherms of the resulting materials rise steeply from
the origin (Fig. 2), indicating a pronounced presence of narrow
micropores, which is confirmed by the Vnmic curve in Fig. 3. In these
pores, the vicinity of the neighboring walls causes an overlapping
of adsorption fields so that the enthalpy of adsorption is enhanced
and the pores are filled at very low relative pressures [20]. For the
sample corresponding to a burn-off of 25% the steep initial branch
is followed by a linear portion nearly parallel to the pressure axis,
this indicating the almost absence of wide micropores and mesop-
ores. In fact, Fig. 3 shows that Vwmic and Vmes are very low for this
sample.
As expected, the adsorption capacity increases with increasing
burn-off. At the same time, a ‘‘knee’’ arises between the steep ini-
tial branch and the linear portion of the isotherms, which results
from the development of wide micropores in which the enhance-
ment of the enthalpy of adsorption is not as large, but a coopera-
tive effect between the adsorptive and preadsorbed molecules is
believed to take place [34]. The higher the burn-off, the more
rounded the ‘‘knee’’ becomes due to the continuous widening of
the pore size distribution. In addition, the linear branch of the iso-
therms becomes no longer parallel to the pressure axis and a hys-
teresis loop appears; the changes observed in this region of the
isotherm indicate a gradual development of mesopores, which is
confirmed by the Vmes curve in Fig. 3. These results are in agree-
ment with the mechanism generally accepted for physical activa-
tion with CO2 [1,2]: the gas reacts with the walls of the pores
(CO2 + C ? 2CO), leading to their gradual widening. An interesting
point is that, in spite of the continuous V0.95 increase, Vnmic and
Vwmic reach a maximum, which can be attributed to the increasing
conversion of narrow micropores and wide micropores to wide
micropores and mesopores, respectively.
3.2. Chemical activation
3.2.1. Effect of activation temperature
The effect of activation temperature during chemical activation
with H3PO4 or ZnCl2 was evaluated using XP and XZn values of 0.30
and 0.40, respectively. Whereas most of the weight loss takes place
in the range of 200–300 °C for simple carbonization, as reported in
Section 3.1 (Fig. 1a), the presence of H3PO4 or ZnCl2 reduces it to
below 150 °C (Fig. 1b and c, respectively). This occurs because
the chemicals act as acid catalysts promoting bond cleavage reac-
tions and formation of crosslinks via such processes as dehydration
and condensation (Ref. [7] concerns a very interesting work about
the chemical aspects involved in the H3PO4 assisted carbonization
of biomass derivatives). The global result is that the carbonization
temperature is decreased. In fact, the impregnating solution at
85 °C confers a dark aspect to the shell grains and they become
partially deformable, from which it is possible to infer that this
Fig. 4. Scanning electron microscopy of the carbons generated from carbonization of coconut shell in the (a) absence of chemicals (850 °C) and in the presence of (b) H3PO4
(XP = 0.30; 450 °C) or (c) ZnCl2 (XZn = 0.40; 500 °C).
temperature is sufficiently high to permit the attack of the chemi-
cal to the lignocellulosic structure of the precursor.
Another point that can be observed in Fig. 1 is that, above
around 300 °C, the weight loss for the treatment in the presence
of the chemicals becomes lower than those corresponding to the
simple thermal treatment at similar temperature. The main reason
is that low molecular weight products are easily removed by dev-
olatilization during simple thermal treatments, before they can be
chemically integrated into the solid. On the other hand, since depo-
lymerization and repolymerization occur at lower temperatures in
the presence of the chemicals [7], as proved by the weight loss
curves, a greater fraction of depolymerization products can be
bonded and retained into the solid matrix, leading to a lower
weight loss.
Despite the pronounced weight losses observed in the early
pyrolysis stages, the samples impregnated with H3PO4 or ZnCl2
underwent a substantial increase in packing density up to around
200 °C (Fig. 1b and c). This increase supposedly occurs because
fragments of ligninocellulosic chains generated by the acid attack
of the chemicals have sufficient mobility to give rise to a reorgani-
zation and redistribution of the botanical structure of the precur-
sor. In this way, empty spaces present in the starting material
are filled, leading to a higher compactation degree. Accordingly
to Fig. 4a these empty spaces seem to correspond mainly to hollow
channels that provide the transportation path for water in the liv-
ing plant. On the other hand, Fig. 4b and c show that transportation
channel are not present in the chemically activated samples.
If the thermal treatment of the impregnated precursor is fol-
lowed between 200 and 400 °C, a pronounced reduction of packing
density occurs in spite of the small weight loss that takes place in
this temperature range (Fig. 1b and c). This occurs because the
chemicals separate the organic chains during the development of
the carbon matrix and leave the structure in an expanded state.
Thus, the subsequent removal of the chemical by leaching with
water makes a structure of micro and mesopore accessible as
shown in Fig. 5, in accordance with the proposal of Rodríguez-
Reinoso and Molina-Sabio [8].
The porosity generated by the chemicals passes through a max-
imum at around 400–450 °C and decreases thereafter. In this con-
text, it is valid to highlight that Jagtoyen and Derbyshire [7]
reported the presence of an absorption band in the FTIR spectra
of samples obtained by chemical activation of different woods with
H3PO4, attributed to phosphocarbonaceous esters; the band is first
observed at about 150 °C, its intensity reaches a maximum at
around 450 °C and is reduced thereafter. These findings suggest
that the porosity reduction above 400–450 °C occurs due to the
thermal contraction of the expanded solid matrix, which is made
possible by the breakdown of the interactions of the chemical with
the developing carbon matrix.
The occurrence of a maximum porosity at a given temperature
during chemical activation with H3PO4 or ZnCl2 is a general behav-
ior that has been reported by several authors [7–10], even though
 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171 167

(a) (b)
1.00 V0.95 1.00 V0.95
Vmes Vmic
Vmic Vmes
0.75 Vwmic 0.75 Vnmic
Vnmic Vwmic

V (cm /g)
V (cm /g)

3
3

0.50 0.50

0.25 0.25

0.00 0.00
100 200 300 400 500 600
100 200 300 400 500 600
T (ºC)
T (ºC)

Fig. 5. Pore volumes of the samples chemically activated with (a) H3PO4 (XP = 0.30) or (b) ZnCl2 (XZn = 0.40) up to different final temperatures. (Since the samples treated at
150 and 200 °C present very poor porosity and the equilibrium of N2 adsorption was not achieved at normal conditions of analysis, Vmic and V0.95 of these samples were
considered as equal to Vnmic in accordance with the previous discussion presented in Section 3.1.)

the exact position of the maximum differs according to the precur-

sor. These differences seem to result mainly from the distinct (a) XP = 0.91
biopolymeric composition of different biomass derivatives, since 50
Guo and Rockstraw [11] demonstrated that cellulose, lignin and
hemicellulose exhibited distinct behaviors in the chemical activa- 40
tion with H3PO4. XP = 0.54

n (mmol/g)
30
3.2.2. Effect of impregnation ratio XP = 0.40
The effect of varying the impregnation ratio on the properties of 20 XP = 0.24
the chemically activated carbons was evaluated when maintaining
XP = 0.15
the activation temperature constant, 450 and 500 °C for activations 10 XP = 0.09
with H3PO4 and ZnCl2, respectively. Fig. 6 shows some N2 adsorp-
tion–desorption isotherms of resulting materials. It can be seen
0
that all chemically activated carbons present high N2 uptake at 0.0 0.2 0.4 0.6 0.8 1.0
very low relative pressures, typical of carbons with narrow micro- p/p0
porosity. For the materials with the lower activation degrees,
which correspond to the lowest XP and XZn values (0.09 and 0.15, (b)
respectively), the steep initial branch is followed by a linear nearly
40 Zn = 0.9
horizontal portion, indicating the absence of wide micropores and
mesopores. Zn = 0.65
As expected, the increase in the proportion of chemical leads to 30
n (mmol/g)

a gradual increase of the adsorption capacity. At the same time, a Zn = 0.50

‘‘knee’’ arises between the steep initial branch and the linear por-
20 Zn = 0.40
tion of the isotherms, thus indicating the development of wide
micropores; the higher the degree of impregnation the more Zn = 0.25

rounded the ‘‘knee’’ becomes because of the widening of the pore 10

size distribution. Furthermore, for samples activated with H3PO4
the linear branch of the isotherms becomes no longer parallel to
the pressure axis and hysteresis appears, thus showing the pres-
ence of mesopores where capillary condensation takes place. The
higher the impregnation ratio, the higher the slope of the linear
branch and the more pronounced the hysteresis loop, which indi-
cates that the mesoporosity is proportional to the H3PO4 content.
In the case of the samples chemically activated with ZnCl2,
although the ‘‘knee’’ is continuously broadened with the increase
of chemical concentration up to around XZn = 0.90, the slope of
the isotherm linear branch is small even for samples corresponding
to the highest XZn values, and hysteresis is almost nil. Further, it is
worthy to highlight that increases in XZn above 0.90 did not give
rise to substantial changes in the adsorption isotherm of the result-
ing material. Therefore, it is possible to conclude that, although
activation with ZnCl2 is able to generate relatively high mesopore
volumes, the size of the pores seem to be restricted.
The evolution of the values for micro and mesopore volumes
and V0.95 as a function of XP and XZn is shown in Fig. 7. In agreement
with the isotherm features discussed above, up to XP and XZn values
of 0.09 and 0.15, respectively, the porosity development occurs
Zn = 0.15
0
0.0 0.2 0.4 0.6 0.8 1.0
p/p0
Fig. 6. N2 adsorption–desorption isotherms for the samples chemically activated
with (a) H3PO4 up to 450 °C and (b) ZnCl2 up to 500 °C using different impregnation
ratios.
almost exclusively due to the increase of Vnmic. However, for higher
chemical proportions Vnmic becomes constant or slightly decreases,
at the same time that development of wide micropores and mesop-
ores becomes pronounced. While Vwmic reaches a maximum at
intermediate values of XP and XZn and slightly decreases thereafter,
Vmes follows increasing. These results can be interpreted as fol-
lows: small amounts of chemical can be distributed uniformly
throughout the interior of the particles to give rise to narrow
micropores; on the other hand, higher amounts lead to the accu-
mulation of chemical and consequent formation of wide microp-
ores and mesopores in detriment to the narrow micropores.
168 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171

(a) 1.75 V0.95

(b) 1.75
V0.95
1.50 Vmes 1.50 Vmes
Vmic
Vmic
1.25 Vwmic 1.25 Vwmic
Vnmic
Vnmic
V (cm3/g)
1.00 1.00

V (cm3/g)
0.75 0.75

0.50 0.50

0.25 0.25

0.00 0.00
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
XP X Zn

Fig. 7. Pore volumes of the samples chemically activated with (a) H3PO4 up to 450 °C or (b) ZnCl2 up to 500 °C using different proportions of the chemicals (Vmic and V0.95 of
the chars, corresponding to XP and XZn values = 0, were considered as equal to Vnmic in accordance with the previous discussion presented in Section 3.1).

For activation with ZnCl2, Vmes and V0.95 tend to stabilize above
a XZn value of around 0.8. In fact, it is logical to think that there is a
limit to the amount of chemical that can be incorporated into the
interior of the precursor particles during impregnation, which
would imply a limit for the developing porosity. However, Vmes
and, consequently, V0.95, continuously increases with the increase
of XP. Such behavior can be related to the plots of micro and mes-
opore volumes as a function of the carbon yield presented in Fig. 8.
As it can be seen, most of the pore development during activation
with ZnCl2 occurs without significant weight loss, but it is followed
by pronounced weight loss during activation with H3PO4. This
weight loss is caused by the acid attack of the H3PO4 during the
impregnation and carbonization steps, which leads to the degrada-
tion of the solid matrix. Such degradation seems to be responsible
for the occurrence of an additional mesoporosity (in addition to
that caused by the non-uniform distribution of the chemical parti-
cles) and, since the extent of degradation is proportional to the
proportion of H3PO4 employed, the mesopore volume continuously
increases with increasing XP. On the other hand, the degradation
induced by the attack of ZnCl2 is less pronounced because it is a
weaker acid, so that the development of mesopores can be attrib-
uted almost exclusively to the non-uniform accumulation of ZnCl2
throughout the particles (a non-degradative mechanism). There-
fore, Vmes tends to a maximum because the amount of ZnCl2 being
incorporated has a limit. At this point it is valid to stress that a
much larger amount of tar is formed around the particles during
impregnation/activation with H3PO4, which corroborates the idea
that H3PO4 induces a more pronounced sample degradation.
3.3. Chemical activation versus physical activation
The results presented in Sections 3.1 and 3.2 demonstrate that
both physical activation with CO2 and chemical activation with
H3PO4 or ZnCl2 are able to generate carbons with high adsorption
capacities. Comparison of Figs. 2, 6a and b evidences pronounced
differences in the isotherm profiles of carbons obtained by the dif-
ferent activation processes: physical activation with CO2 and
chemical activation with H3PO4 or ZnCl2. Outstandingly, the iso-
therms of the physically activated carbons exhibit sharper ‘‘knees’’,
from which it is possible to infer that this procedure gives rise to
carbons with narrower pore size distributions than chemical acti-
vation with H3PO4 or ZnCl2. This finding is corroborated by the
pore size distribution curves presented in Fig. 9. Consequently, it
can be concluded that physical activation with CO2 is more ade-
quate than chemical activation with H3PO4 or ZnCl2 for preparing
activated carbons intended for applications that require an accu-
rate control of pore size distribution, such as the storage of gases
[12,13,21,25,26,35–37] and the separation of gas mixtures by
molecular sieves [22,29]. For example, adsorbents with narrow
pore width distributions centered around 0.8 nm (about twice
the dimension of the methane molecule) permit to optimize the
methane adsorption capacity in fuel cells [13,25]. In turn, separa-
tion of gas mixtures by molecular sieves is based on the differences
1.2 micropores mesopores

1.0
Pore size distribution (cm .g .nm )
-1

Vmic = open symbols

CO2
-1

1.0 Vmes = closed symbols 0.8

3

square: CO2 ZnCl2

circle: H3PO4 H3PO4
0.8
down triangle: ZnCl2 0.6
V (cm /g)

0.6
3

0.4
0.4

0.2 0.2

0.0
100 90 80 70 60 50 0.0
Weight loss (%) 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Pore width (nm)
Fig. 8. Plots of Vmic and Vmes as a function of the weight loss during physical
activation and chemical activation with H3PO4 up to 450 °C or ZnCl2 up to 500 °C Fig. 9. DFT pore size distribution [38] from N2 adsorption isotherms of carbons
(for physical activation, the weight loss includes both the carbonization and obtained by: physical activation with CO2; chemical activation with H3PO4
activation steps). (XP = 0.30; 450 °C); chemical activation with ZnCl2 (XZn = 0.50; 500 °C).
 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171 169

of the diffusion coefficients of the molecules throughout the pores,
so that the control of the pore size distribution is determinant for
the process efficiency.
An additional interesting feature that arises from the compari-
son of the carbons produced by physical and chemical activation
is that if carbons with similar values of V0.95 are compared, those
produced by chemical activation with H3PO4 or ZnCl2 present high-
er packing densities than those produced by physical activation
with CO2 (Fig. 10). Exception must be made to the samples with
low activation degree, which can be justified by the very small
amounts of chemical employed for these samples. It is also worthy
to note that the packing density for both series of chemically acti-
vated carbons fit a single line in the plot.
Fig. 11 presents a graph with the helium densities (so-called
skeleton density) as a function of V0.95 for the same carbons plotted
in Fig. 10. The data show that chemically activated carbons present
lower helium density than physically activated carbons, what can
be attributed to the lower carbonization temperature to which
the formers were subjected. These results seem to be in disagree-
ment with those described in Fig. 10, where the chemically acti-
vated carbons exhibited higher packing densities. What happens
is that, as already discussed in Section 3.2.1, the action of the
H3PO4 and ZnCl2 during chemical activation promotes a redistribu-
tion and reorganization of the lignocellulosic material, leading to
the filling of relatively large empty spaces present in the botanical
structure of the precursor. On the other hand, these empty spaces
are retained during carbonization in the absence of chemicals
(Fig. 4a) and subsequent physical activation, giving rise to very
large macropores that substantially reduce the packing density of
the resulting materials and do not contribute for N2 adsorption
at p/p0 = 0.95. In this way, in spite of their higher skeleton densi-
ties, physically activated carbons present lower packing density
than carbons with similar V0.95 produced by chemical activation
with H3PO4 or ZnCl2. This conclusion is corroborated by the data
obtained from mercury intrusion porosimetry, since they show
that the sample carbonized in the absence of chemicals, which
was the starting material for physical activation, has a much higher
porosity than the samples carbonized in the presence of chemicals,
mainly in the pore radius range above 10 lm (Fig. 12).
At this point it is important to highlight that, since large pores
do not substantially contribute to adsorption and reduce the
apparent density, the suppression of them during chemical activa-
tion has a positive effect on the volumetric adsorption capacity of
the resulting materials. In turn, a high volumetric adsorption
capacity is a very important requirement for activated carbons in-
tended for application in a fixed bed of a given volume, such as in
gas storage systems, where the important property is the capacity
per unit volume.
Besides rendering materials with relatively high packing densi-
ties, chemical activation with H3PO4 or ZnCl2 has other potential
advantages, if compared to the physical process, as it follows:

– Chemical activation with H3PO4 and ZnCl2 usually renders car-

0.60
bon grains with better mechanical properties. During physical
0.55
ZnCl2 activation, a gradual deterioration of the carbon matrix takes
H3PO4 place due to the internal burn-off process, which reduces sub-
0.50 CO2 stantially the stiffness of the grains. In addition, the presence
packing density (g/cm )
3

of empty spaces in the physically activated samples seems to

0.45
contribute to reduce the mechanical resistance of the grains.
0.40 – The weight loss for chemical activation is much lower than for
the process of carbonization/physical activation. Fig. 8 shows
0.35 that for during the carbonization/physical activation processes
0.30
the weight loss can be as high as 98%, depending on the targeted
porosity; in turn, chemical activation with H3PO4 or ZnCl2 leads
0.25 to weight losses around 60%, even if high porosities are
generated.
0.20
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 – The physically activated carbon with a burn-off of 94%, which
3 corresponds to a weight loss around 98% during the global car-
V0.95 (cm /g)
bonization/physical activation process, presents a very low
Fig. 10. Plot of the packing density of activated carbons prepared by physical
mechanical resistance and it is not a practical carbon. This sam-
activation with CO2 and chemical activation with H3PO4 or ZnCl2 versus V0.95. ple has a V0.95 value of 1.22 cm3/g, only 0.41 cm3/g of which cor-
responding to mesopores. On the other hand, mesopore
volumes higher than 0.8 and 1.0 cm3/g can be easily obtained
2.50

2.25
Helium density (g/cm )
3

2.00

1.75

1.50
CO2
H3PO4
1.25 ZnCl2

1.00
0.2 0.4 0.6 0.8 1.0 1.2 1.4
3
V0.95 (cm /g)
Fig. 12. Mercury intrusion porosimetry of the samples carbonized without the
Fig. 11. Plot of the helium density of activated carbons prepared by physical presence of chemicals (850 °C) and in the presence of H3PO4 (XP = 0.30; 450 °C) or
activation with CO2 and chemical activation with H3PO4 or ZnCl2 versus V0.95. ZnCl2 (XZn = 0.32; 500 °C).
170 M.J. Prauchner, F. Rodríguez-Reinoso / Microporous and Mesoporous Materials 152 (2012) 163–171
Fig. 13. Scanning electron microscopy of the grains generated from carbonization in the presence of ZnCl2 (XZn = 0.40; 500 °C) or H3PO4 (XP = 0.30; 400 °C).
by chemical activation with ZnCl2 or H3PO4, respectively. There-
fore, these are important procedures to prepare mesoporous
carbons with applications such as in the adsorption of large
molecules (pesticides, dyes, humic acids, etc.) [24,28,39], for
supporting catalysts [40], drug delivery and bone tissue regen-
eration [41].
– Finally, chemical activation requires shorter soaking times and
lower temperatures than physical activation, thus saving
energy, even though chemical activation requires the treatment
of residual waters resulting from washing.
The above quoted apparent advantageous will be of greater or
smaller importance depending on the application to which the
material is intended for, so that in many cases physically activated
carbons can be required, especially if a controlled micropore size
distribution is needed.
3.4. Chemical activation with ZnCl2 versus chemical activation with
H3PO4
It was showed in Section 3.2.2 that chemical activation with
high proportions of H3PO4 renders carbons with high mesopore
volumes, including large mesopores. In turn, most of the mesop-
ores generated by chemical activation with ZnCl2 are narrow mes-
opores, independent of the activation degree. Nevertheless, the
differences between the pore morphology of carbons activated
with H3PO4 and ZnCl2 are not limited to materials with high acti-
vation degrees: in a general way, activation with H3PO4 renders
carbons with larger mean pore width than activation with ZnCl2.
Although it is difficult to detect the shallow differences in the iso-
therms of carbons with medium or low activation degrees, Fig. 9
makes it clear: note that the pore size distribution curve of
H3PO4 activated carbons is below the curve of the ZnCl2 activated
carbon up to around a pore width of 1.6 nm and above thereafter.
The probable reasons for this difference may be: (i) during carbon-
ization, products of ZnCl2 polymerization have smaller dimensions
than polyphosphate species acting as a template for porosity devel-
opment; (ii) H3PO4 is a stronger acid, so that it leads to a more pro-
nounced degradation of the solid matrix, with consequent pore
widening.
Chemical activation with ZnCl2 generates carbons with nar-
rower pore size distributions, but it produces cracks, as illustrated
in Fig. 13a, that can easily lead to the rupture of the grains. For the
sake of comparison, Fig. 13b presents a micrograph of a grain pro-
duced by chemical activation with H3PO4, where it can be noted
the absence of cracks. The higher the proportion of ZnCl2 em-
ployed, the higher the presence of cracks and the grain breakabil-
ity. Nevertheless, parallel studies have shown that this problem
can be minimized if smaller particle sizes are used, which leads
us to suppose that the cracks are formed due to the difficulties
found by volatile matter to leave the interior of the grains during
the formation of the rigid carbon structure during ZnCl2 assisted
carbonization.
Finally, it is also important to stress that H3PO4 is more easily
removed by washing than ZnCl2 and, at the same time, it is less
problematic from the point of view of the environment; for this
reason, H3PO4 is the chemical activation process more commonly
used in practice.
4. Conclusions
The present work shows that coconut shell based granular acti-
vated carbons with highly developed porosity can be prepared
using both physical activation with CO2 and chemical activation
with H3PO4 or ZnCl2. Nevertheless, each process leads to materials
with specific properties, so that the procedure to be employed has
always to be chosen according to the final application the carbon is
intended for. The physical process permits to tailor the pore size
distribution more accurately, making it possible to obtain carbons
with narrower pore size distributions. However, the resulting
materials present relatively low packing densities due to the occur-
rence of empty spaces that originate from the conductor vessels
present in the botanical structure of the precursor and few contrib-
ute to adsorption. On the other hand, chemical activation with
H3PO4 or ZnCl2 permits to suppress the occurrence of such empty
spaces, leading to materials with higher packing density and bring-
ing about a positive effect on the volumetric adsorption capacity.
Further, chemical activations lead to lower weight losses during
the activation processes and permit to obtain carbons with higher
mechanical resistance and elevated proportion of mesopores. Com-
paratively, activation with H3PO4 renders carbons with higher
mean pore radius than activation with ZnCl2.
Acknowledgement
The present research work was supported by the Brazilian Oil
Company (PETROBRAS).
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