Colloids and Surfaces A: Physicochem. Eng.

Aspects 299 (2007) 7987

Modication in adsorption characteristics of activated carbon
produced by H
3
PO
4
under owing gases
Badie S. Girgis

, Amina A. Attia, Nady A. Fathy

Surface Chemistry Laboratory, National Research Centre, 12622 Dokki, Giza, Egypt
Received 31 July 2006; received in revised form 12 November 2006; accepted 14 November 2006
Available online 18 November 2006
Abstract
Activated carbons were derived frompeach stone shells by H
3
PO
4
-scheme under standard conditions: 50%H
3
PO
4
and pyrolysis for 2 h at 500

C.
Five carbons were prepared by changing the gas atmosphere during thermal treatment (no external gas, owing of either nitrogen, carbon dioxide,
steam or air). Additional carbon was obtained by extra-heat treatment at 800

C of the standard carbon, for 2 h. Characterization was performed

by adsorption of N
2
at 77 K, and testing of capacity was carried out towards p-nitrophenol, methylene blue and lead ions from aqueous solution.
All carbons were high quality adsorbents with high surface area and essentially microporous structure with low degree of mesoporosity. Running
external gases reduces mostly the carbon porosity, except air and steam which generate higher mesoporosity on expense of microporosity. High
uptake of p-nitrophenol appears, affected to low extent with gaseous atmosphere except steam which raises adsorption considerably. Flowing air is
the most effective in enhancing the adsorption of methylene blue, which was attributed to the formation of O-functionalities with acidic nature, and
to enhancement of wider microporosity. Removal of lead ions from aqueous, non-buffered, solutions was considerable in comparison to previous
studies, and attributed to the acidic nature of carbons in addition to the presence of inorganic and organic phosphate compounds. Lead ions removal
was considerably enhanced by running air during thermal treatment (two-fold increase) due to the formation of acidic oxygen-functionalities
associated with metal exchange by the negatively charged carbon surface.
2006 Elsevier B.V. All rights reserved.
Keywords: Activated carbon; Adsorption; Peach stones; Porosity; H
3
PO
4
-activation; Lead ions
1. Introduction
Activated carbons are manufactured by the pyrolysis of car-
bonaceous materials of vegetable origin, such as wood, coal,
peat, fruit stones and shells, or synthetic polymers such as vis-
cose rayon, PAN, or phenolics, followed by activation of the
chars obtained from them. This route is known as the physical
(or thermal) scheme of activation, as it involves two thermal
treatment stages. An alternative route, also a well-established
and old as well, is denoted by the chemical activation scheme
and involves only one thermal treatment stage comprising both
decomposition and activation steps. For many decades, zinc
chloride has been the chemical in choice as an activant but
was replaced by H
3
PO
4
in the near decades [18]. Activation
with H
3
PO
4
offers many recommending advantages over the
traditional thermal activation scheme as it is performed in

Corresponding author.
E-mail address: girgisbs@hotmail.com (B.S. Girgis).
one pyrolysis step at a much lower temperature (400600

C),
leads to a much higher carbon yield (3550%), and most of the
impregnant can be recovered by multi-stage extraction.
Any carbonaceous material high in carbon content with low
ash, natural or synthetic, can be used as precursor for the prepa-
ration of activated carbon. Several factors are considered when
selecting an appropriate raw material. Industrially, an inexpen-
sive material with high density and sufcient volatiles, available
in high amounts, is usually preferred. Classical examples as
feedstocks for carbon production were: wood, coal and coconut
shells (and are still in use) [9]. However, these materials are
not widely encountered in most countries, which directed atten-
tion to other locally abundant sources of low economic value.
Of these sources, agricultural wastes and by-products, are fas-
cinating as they fulll most of the required properties as they
are endowed with high carbon content, low inorganic, and are
renewable materials generated in huge amounts every year. For
this purpose, an elaborate reviewon the suitability of agricultural
wastes for the production of activated carbon was published by
Heschel and Klose [10]. Accordingly a large number of feed-
0927-7757/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.11.024
80 B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987
stocks of botanical origin have been extensively exploited based
on their prevalence in the considered region of the world (e.g.
bagasse [4], wood trees [11,12], fruit stones [6,8], nutshells
[1315], water hyacinth [16], coffee beans [17], cotton stalks
[18], olive stones [7], and many others).
During pyrolysis of the H
3
PO
4
-impregnated precursor, ow
of external gases was generally avoided lest it results in extended
gasication and affects the produced carbon. Nevertheless, con-
trolled ow of gases was reluctantly applied [1923] and found
not excessively harmful as expected to the obtained adsorbents.
Some gases were, thus, cautiously circulated which are known
to exhibit moderate oxidizing power, such as steam, carbon
dioxide, air, in addition to nitrogen. Several recommending
properties were shown by enhanced widening of porosity, and
increased metal removal.
Previous reports related to H
3
PO
4
-activation of lignocellu-
losic materials, and others, indicated that a temperature range
within 400 and 500

C, proved to be the optimum range

for developing high quality and capacity activated carbons
[1,6,7,12,2430].
In the present investigation, the developed activated carbons
were prepared from peach stone shells by impregnation with
50% H
3
PO
4
followed by thermal treatment at 500

C, under its
own atmosphere and/or owing of different gases. Porosity was
characterized by N
2
adsorption at 77 K. Testing of the adsorp-
tion capacity from solution was carried out by determining the
adsorption isotherms of p-nitrophenol and methylene blue. It
was intended to assess the impact of gaseous atmosphere on
the adsorption characteristics of organic pollutants. One bottle
test for the removal of lead ions was achieved, as well, for the
standard and modied carbons.
2. Materials and techniques
2.1. Activated carbons
The precursor of activated carbons was local peach stones,
discarded from food processing industry. This was rst washed
with hot water, free from dirt, depitted, and the woody shells
crushed and ground in a laboratory mill to a grain size from 0.5
to 3.0 mm. The activant, H
3
PO
4
, was manufactured by Rasayan
(Turkey) with a concentration of 85%. In each experiment 50 g
of the nely ground peach stones were soaked in a 100 ml solu-
tion of 50%H
3
PO
4
, left overnight to achieve good soaking, then
transferred to a stainless steel reactor and admitted to a temper-
ature controlled electric furnace. Dimensions of the S.S. reactor
are 60 cm of length and inner diameter of 40 mm and closed at
one end. The open end reactor was tted with a tight socket of
same material with two S.S. narrowtubing of 8 mminner diame-
ter, one to reach internally before bottomwith 2 cmand the other
connected to the tube socket. The impregnated mass was then
heatedslowlytoreachnal temperature of 500

Cwithin2 h, and
soaked at this temperature for other 2 h, and heating stopped. The
produced carbonized material was thoroughly washed by boil-
ing in 500 ml aliquots of water, decanted, and rewashed several
times until washings ltrate reached pH6.5, nally ltered
and dried overnight at 110

C.
Five samples of activated carbons were prepared in the above
described manner: (1) standard activation in absence of any gas
ow (PS55), (2) activation under ow of nitrogen gas (PS55N),
(3) activation under ow of CO
2
(PS55C), (4) activation under
ow of breathing air (PS55A), and (5) activation under ow
of steam (PS55S). In cases 24, the gas was admitted from an
outside source to pass through the long side arm and within the
particles of impregnated raw material. The product carbon in
each case was weighed to determine its yield, and ash content
estimated by ignition at 900

C for 1 h. An additional sample

was prepared from PS55 by extra-heat treatment at 800

C for
1 h, to assess its effect on the adsorption properties.
2.2. Characterization of porosity parameters
For this purpose, adsorption isotherms of N
2
at 77 K were
determined using a sorptometer type Gemini 2375 V3.03. Sam-
ples were pre-outgassed at 200

C for 2 h under vacuum, and

after cooling, the adsorbent was surrounded by liquid N
2
and
adsorption data measured. Texture parameters were determined
by applying the BET-equation (S
BET
), total pore volume from
liquid nitrogen held at P/P
o
=0.95 (V
P
) and average pore radius
from the relationship r
P
=2V
P
/S
BET
.
Additional information was obtained by applying the
s
-
method employing the adsorption data on non-porous carbon
reported by Selles-Perez and Martin-Martinez [31]. From a plot
of V
a
versus
s
(at same relative pressure), it was possible to
evaluate total surface area (S

t
) from slope of the rst linear sec-
tion connecting to the origin, the non-microporous surface area
(S

n
) from slope of the linear section connecting latter points;
micropore volume from intercept of latter line with the V
a
-
axis. An estimate of the mesopore volume was calculated from
V

meso
= V
P
V

o
assuming negligible volume due to macrop-
ores, and S

mic
from S

t
S

n
.
2.3. Adsorption capacity from the liquid phase
Two organic probe solutes were chosen for this purpose,
these are p-nitrophenol (PNP), representing phenolic pollutants,
and methylene blue (MB) representative of colored pollu-
tants. Adsorption isotherms were determined by contacting
100 mg of the respective carbon with 100 ml solution of increas-
ing concentrations of either solute. Residual concentrations of
the tested sorbates were determined spectrophotometrically by
using UV/Vis-Shimadzu (UV-2401 PC) spectrophotometer at
their corresponding wavelengths of 317 nmfor PNP and 664 nm
for MB. The Langmuir model adsorption parameters were deter-
mined from a plot of the linear equation:
C
e
q
e
=
1
q
o
K
L
+
1
q
o
C
e
(2.1)
where C
e
and q
e
are solute in solution and on solid, q
o
is the
monolayer capacity and K
L
is the Langmuir constant, from
which the free energy of adsorption is evaluated from [32]:
G = RT ln K
L
(2.2)
B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987 81
A dimensionless constant (R
L
), a characteristic of the isotherm,
is termed the separation factor was also estimated by [33]:
R
L
=
1
1 +K
L
C
0
(2.3)
where C
0
is the initial highest solute concentration. Its
value ranges between R
L
>1 (unfavorable), R
L
=1 (linear) and
0 <R
L
<1 (favorable) isotherm.
2.4. Adsorption capacity of lead ions
The activated carbons under consideration were tested in sin-
gle bottle experiments using a stock solution of 1000 mg/l Pb
2+
(1.6 g lead nitrate in 1 l distilled water). A weight of 0.1 g
of each dried powdered activated carbon was contacted with
100 ml of PbNO
3
solution in a glass stoppered bottle and
shaken for 24 h to attain equilibrium. The supernatant liquid
was removed and measured by an atomic absorption spectropho-
tometer (ASS), a Perkin-Elmer model 2380 conventional 10 cm
slit for airacetylene burner. Absorbance values for lead were
taken at a wavelength of 383.3 nmafter averaging 1 s integration
time.
3. Results and discussion
3.1. Porosity modication in relation to purging gas
The adsorption isotherms of N
2
in Fig. 1, exhibit Type I fea-
tures of the BDDT classication, with a well-developed sharp
knee at low relative pressures that tend to become almost
parallel to the pressure axis at high pressures. This indicates
an essentially microporous character, micropore lling occurs
signicantly at relatively low partial pressures <0.1P/P
o
, the
adsorption process being complete at 0.5P/P
o
[34]. According
Fig. 1. Adsorption isotherms of N
2
/77 K for modied carbons at 500

C.
82 B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987
Fig. 2.
s
-Plots for the obtained modied carbons with 50% H
3
PO
4
at 500

C.
to the
s
-classication advanced by Selles-Perez and Martin-
Martinez [35], the obtained plots (Fig. 2) exhibit the typical
-1a type. This type is distinguished by having only one linear
straight portion starting at an
s
-value near to 1, and connect-
ing the high pressure points. Carbons with narrow and uniform
microporosity, thus, may be predicted to occur.
Table 1 summarizes the abovementioned textural parameters,
S
BET
, V

P
, r
P
, S

t
, S

n
, V

o
and V

meso
. Bottomlines give the ratios
of microporosity calculated fromsurface area S

mic
/S

t
and from
pore volume V

o
/V
P
; where S

mic
= S

t
S

n
.
Generally, the S
BET
values are equal to or slightly less than
that estimated by the
s
-method (6.5%). All carbons exhibit
high surface areas between 1050 and 1400 m
2
/g, with high total
pore volumes of 0.570.69 ml/g and corresponding average radii
of 9.511.4

A. This supports the previously noticed types of
adsorption isotherms and
s
-plots. Ratios of micropore areas
(S

mic
/S

t
) equal to 0.93 and 0.97, conrm the essential microp-
orous character of all activated carbons derived frompeach stone
shells (PS55-series) under different gaseous atmospheres. Only
treatment under air or steam that leads to some modications
in porosity resulting in small pore widening where mesopores
are enhanced (V

meso
/V
P
to 0.16 and 0.18) and non-microporous
areas raised from around 50 to 100 m
2
/g.
Thus, pyrolysis of H
3
PO
4
-impregnated peach stones at
500

C, under the various gaseous atmospheres, does not

degrade seriously the well-developed texture characteristics of
the microporous carbon. Flowing of an additional stream of N
2
,
CO
2
or steamdoes not affect much the carbon yield (43.846.0%
instead of 41.8%, without external gas). Only in case of air that
additional gasication diminishes the carbon yield to 30.0%.
Under this specic atmosphere the total specic surface area or
pore volume are not affected, but the mesopore parameters (S

n
and V

meso
) are increased, although these still constitute no more
than 7 and 16% of total parameters. Passage of air concurrently
during pyrolysis, thus, enhances pore widening to some limited
extent and modies the porous structure of the activated carbon.
FTIR-spectra of PS55A indicated a considerable reduction
in the broad and strong band between 3500 and 3000 cm
1
,
assigned to free or H-bonded water as well as OH groups
that appeared in the present PS55-carbon. However, a small but
B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987 83
Table 1
Some physico-chemical properties of tested activated carbons and their porous characteristics
Parameters Sample
PS55 PS55N PS55C PS55A PS55S PS55/800

C
% Yield 41.8 43.8 44.7 46.0 30.0 40.0
% Ash content 2.88 4.02 3.7 6.73 7.05 1.52
Slurry pH 4.6 4.0 4.3 5.5 3.4 3.5
S
BET
(m
2
/g) 1393 1153 1227 1404 1053 1184
V
P
(cm
3
/g) 0.6895 0.5716 0.6043 0.6679 0.5995 0.5874
r
P
(

A) 9.9 9.9 9.9 9.5 11.4 9.9

S

t
(m
2
/g) 1407 1159 1294 1436 1373 1249
S

n
(m
2
/g) 55 62 36 101 87 39
V

o
(cm
3
/g) 0.6339 0.4978 0.5627 0.5627 0.4947 0.5380
S

mic
/S

t
0.96 0.95 0.97 0.93 0.94 0.97
V

o
/V
P
0.91 0.87 0.93 0.84 0.82 0.92
distinct absorption, due to carboxylic acid groups, appeared at
1720 cm
1
for the air-treated carbon, in addition to a strong
sharp peak at 1577 cm
1
assigned to OH vibration probably
in the carboxylic group. This might suggest the formation of
abundant CO functionalities upon forcing air during pyrolysis
of the acid-impregnated precursor. Some of these groups impart
an acidic nature to the obtained carbon, as the slurry pHof PS55
(=4.5) is reduced to 3.4 for the PS55A as shown in Table 1.
It is interesting to follow the effect of extra-heat treatment of
the present derived activated carbon PS55 at 800

C. It seems to
be thermally stable such that thermal treatment at 300

C higher
than the temperature of preparation results in a small reduction in
total (especially the microporous) surface area or pore volume.
Heating, here, is associated with a small (15%) shrinkage in
the carbonaceous particles with collapse in some of the ne
micropores which essentially contribute to the high surface area.
Thus, we might anticipate the suitability of the present activated
carbon, derived from peach stone shells, in industrial processes
involving current regeneration processes at high temperatures
(e.g. in case of decolorization of sugar liquor). Such trend is
attributed to the inherited physical hardness of the precursor
that withstand heating conditions preventing the collapse of the
internal porosity.
3.2. Adsorption capacity from the liquid phase
It is well-established that activated carbons are mostly
employed in purication processes carried out in the liquid phase
(ca. 80%) which necessitate their testing in this mediumto assess
their feasibility and suitability. Efuent uids generated in sev-
eral disciplines of life (domestic, industrial, agricultural) contain
a host of pollutant solutes that seriously affect the quality of sur-
face water. In particular, colored bodies (e.g. dyes) and odorous
tasty compounds (e.g. phenolics) constitute a large proportion
of water contaminants. Since a long time ago p-nitrophenol
(PNP) and methylene blue (MB) were recommended as probe
molecules for assessing the adsorption capacity of solids includ-
ing activated carbons [36]. These solutes have been in use since
this date, and still in application to the present time [3743].
Their cross-sectional areas were also established and accepted
since Giles and Trivedi [36] to be 52.2 and 120

A
2
, for PNP and
MB, respectively.
The adsorption isotherms of the carbons under consideration
are presented in Figs. 3 and 4, and the Langmuir-model param-
eters are listed in Table 2. Adopting the above values for the
areas covered by adsorbed PNP and MB, the monolayer capac-
ities (q
o
) were converted into area measured by them (S
PNP
and
S
MB
), and consequently the fraction of accessible surface area
compared to S-BET area (S
PNP
/S
BET
and S
MB
/S
BET
).
Activated carbon PS55 exhibits a high afnity towards PNP
where it uptakes 315 mg/g, however, it seems accessible only to
half of the N
2
-measured surface area (51%). p-Nitrophenol is a
bulkier molecule than N
2
molecules, in addition to the probable
competition of the solvent molecules to the known hydrophilic
nature of the carbon surface. Aconsiderable effect of the gaseous
atmosphere on the uptake of PNP appears, where N
2
reduces it
appreciably (20%), CO
2
and air maintain it almost the same
(5%), but steamenhances it by about 30%attaining an amount
of 435 mg/g. Likewise, the fraction of area covered by PNP is
still around 0.50, except for the steam-treated carbon where it
Table 2
Adsorption capacity of p-nitrophenol (PNP) and methylene blue (MB) by activated carbons
Sample PNP MB
q
o
(mg/g) S
PNP
(m
2
/g) S
PNP
/S
N
2
q
o
(mg/g) S
MB
(m
2
/g) S
MB
/S
N
2
PS55 315 715 0.51 362 820 0.59
PS55N 244 552 0.48 306 692 0.60
PS55C 303 685 0.56 315 713 0.58
PS55A 333 753 0.54 543 1228 0.87
PS55S 435 984 0.93 320 724 0.69
PS55/800

C 294 665 0.56 316 715 0.60

84 B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987
Fig. 3. Adsorption isotherms of PNP onto modied carbons prepared at 500

C.
becomes much nearer to the N
2
-surface area. It is clear that
the wide difference between S
PNP
and S
BET
is governed by the
type of porosity (micro- or meso-) and their distribution within
the various sizes. Nevertheless, all carbons show good afnity
to the phenolics solute as evident from the G and R
L
val-
ues, which are almost similar except the steam treated carbon.
This particular carbon exhibits relatively higher mesoporos-
ity (around 18% of the total pore volume) and higher acidity
(pH 3.4).
Upon considering the uptake of MB (Table 2), it appears that
the H
3
PO
4
-activated carbon PS55 uptakes a high amount of the
dye from aqueous solution. Gas ow of N
2
, CO
2
or steam, here,
decreases the uptake of MB by about 1020%, whereas purg-
ing air during pyrolysis raises the uptake to a great extent by
50%. Although the former appears to be accessible to around
60% of the N
2
-determined surface area, in case of PS55A it
reaches around 90%. Here, the partially oxidized surface of
the carbon becomes more favorable to the water-dissolved dye
molecules.
It was recentlypostulatedbyGoyal et al. [44] that the amounts
adsorbed of methylene blue, as well as adsorption rate, are
related to the surface properties of the carbons such as sur-
face area, pore size and the concentration of surface functional
groups. When an activated carbon is placed in an aqueous
solution, the acidic surface groups, present on the carbon sur-
face, undergo ionization producing H
+
ions which are directed
towards the liquid phase leaving the carbon surface with neg-
atively charged sites. Larger the number of acidic groups on
the carbon surface, greater will be the negative charge on the
carbon surface. This enhances the electrostatic attractive inter-
actions between the negatively charged carbon surface and the
positively charged methylene blue cations, thereby increas-
ing the adsorption. An oxidized carbon surface, the case with
air-treated carbon, will contain a large population of surface
B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987 85
Fig. 4. Adsorption isotherms of MB onto modied carbons prepared at 500

C.
O-functionalities of acidic nature (some of the carboxylic type).
This situation might explain the 50%enhanced uptake by carbon
PS55A to reach an exceptional capacity of 543 mg/g.
On extra-heating at 800

C, the acidic O-functional groups

are decomposed, although the phosphate acidic-type of com-
pounds are still persistent which lowers the surface pH from 4.6
to 3.4. Here, the uptake of MB becomes attributed to take place
in the microporous structure and governed by the available pore
size. It was observed by Goyal et al. [44] that the uptake of MB
was small below pH 3.0 and enhanced by solution pH to reach
a maximum at pH of 4.0 and to decrease thereafter.
3.3. Removal capacity of Pb
2+
ions from aqueous solution
The uptake of lead ions from aqueous (non-buffered) nitrate
solution is shown in Table 3, and these values were converted
into surface area covered by the hydrated ionic species (SA
Pb
2+)
as suggested by [45]. Apercentage coverage of total surface area
was then estimated from % SA = SA
Pb
2+/SA
N
2
, and given in
the same table.
The hereby-derived carbons exhibit appreciably higher
uptake capacity for lead ions (65115 mg/g) in comparison to
several reported investigations of 1850 mg/g [4550]. Flowing
air during pyrolysis at 500

C promotes considerably the uptake

of lead ions as it reaches the value of 204 mg/g (1 mmol/g).
Table 3
Uptake of Pb
2+
ions from aqueous solutions
Sample Amount adsorbed
(mg/g)
S
Pb
2+ S
Pb
2+/S
N
2
PS55 85 125 9.0
PS55N 71 104 9.0
PS55C 65 95 7.7
PS55A 204 299 21.3
PS55S 115 167 15.8
PS55/800

C 92 135 11.4
86 B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987
This may be associated with the generation of abundant O-
functional groups of acidic nature that take part in the cation
exchange process of the metal ions. Such acidic functionali-
ties dissociate in the aqueous medium releasing H
+
ions and
creating negatively charged sites suitable for sequestering the
metal ions. Thus, an additional synergetic factor is displayed
here, that is the concurrent owing of air during pyrolysis of the
impregnated precursor instead of subsequent HNO
3
oxidation
in solution. This proved effective to enhance considerably the
removal of lead cations from aqueous solutions, and raises the
area covered by the adsorbed species to 21%. The presence of
inorganic and organic phosphate groups were anticipated to take
an additional active part in the metal adsorption as suggested by
Puziy et al. [5153]. Proton afnity distribution curves, calcu-
lated from potentiometric experiments, showed four types of
surface groups on H
3
PO
4
acid-activated carbons, among them
the phosphorous-containing groups are the most important for
the adsorption of heavy metal ions from acid solutions. This
might explain the distinguished uptake of lead ions exhibited
here as compared to other, laboratory or commercial, activated
carbons. It should be noted that the present aqueous/surface
medium is below the pH precipitation edge range of 6.0 for
lead ions [54]. It seems that the uptake is somewhat enhanced
with pH (from around 70 mg/g at pH 4.0 to 115 mg/g at pH
5.5). An exceptional case is noticed for the post-heated car-
bon PS55, at 800

C, where most of the acidic O-functionalities

are depleted. The good uptake here becomes essentially due
to the persistent phosphate species in addition to the cleared
pore openings facilitating free diffusion of the hydrated lead
ions.
4. Conclusions
Peach stone shells were chemically activated with the
well-established conditions of 50 wt% H
3
PO
4
at 500

C. An
additional factor was practiced by forcing several gases during
the pyrolysis stage; these are nitrogen, carbon dioxide, steam
and/or air. Accordingly, many aspects are observed:
1. Derived carbons indicate high quality adsorbents with
surface areas of 10001400 m
2
/g and pore volumes of
0.580.69 ml/g, which are essentially microporous. Applica-
tion of the
s
-method yield surface areas and pore volumes
corroborating the general porosity features as well as S-BET
area values.
2. Concurrent owing of nitrogen, carbon dioxide or steam
results in small loss in the extensive porosity parameters,
with slight increase in mesoporosity. Concurrent ow of air
stabilizes the texture with small enhanced mesoporosity and
is associated with generation of some O-functional groups.
3. Adsorption of p-nitrophenol (PNP) and methylene blue
(MB) (representing phenolics and dyes water contaminants)
showed remarkable values (250435 and 310540 mg/g,
respectively). Concurrent ow of N
2
during pyrolysis
decreases PNP uptake whereas steam raises it. A similar
effect appears for N
2
towards MB removal, whereas air pro-
motes it considerably. Both sorbates cover around 5060%
of the total surface area except the steam treated carbon that
covers up to 90% of S-BET.
4. Developed carbons proved to be good adsorbents for Pb
2+
ions from aqueous solutions (65115 mg/g) which seems
higher than reported for many previous carbons. Air-ow
promoted considerably lead uptake as associated with for-
mation of oxygen groups with cation exchange properties.
5. Extra-heat treatment at 800

C, for standard carbon, reduced

slightly its porosity and removal capacity for organic solutes,
with no effect on lead ions removal. This proves the stability
of derived carbon due to its inherited hardness that prevent
shrinkage or collapse under thermal effect.
References
[1] J. Laine, S. Yunes, Carbon 30 (1992) 601.
[2] F. Rodriguez-Reinoso, M. Molina-Sabio, Adv. ColloidInterf. Sci. 76(1998)
271.
[3] M. Jagtoyen, M. Thwaites, J. Stencel, B. McEnaney, F. Derbyshire, Carbon
30 (1992) 1089.
[4] B.S. Girgis, L.B. Khalil, T.A.M. Tawk, J. Chem. Technol. Biotechnol. 61
(1994) 87.
[5] M. Molina-Sabio, F. Rodriguez-Reinoso, F. Caturla, M.J. Selles, Carbon
33 (1995) 1105.
[6] C.A. Philip, B.S. Girgis, J. Chem. Technol. Biotechnol. 63 (1996) 48.
[7] L.B. Khalil, B.S. Girgis, T.A.M. Tawk, Adsorp. Sci. Technol. 18 (2000)
373.
[8] B.S. Girgis, A.N.A. El-Hendawy, Micropor. Mater. 52 (2002) 105.
[9] R.C. Bansal, J.B. Donnet, F. Stoeckli, Active Carbon, Marcel Dekker, Inc.,
New York and Basal, 1988.
[10] W. Heschel, E. Klose, Fuel 74 (1995) 1786.
[11] J.M. Blasco, J.P. Gomez-Martin, F. Delgado, J. Rodriguez-Mirasol, J.J.
Rodriguez, Anal. Quim. 85 (1989) 406.
[12] M. Jagtoyen, F. Derbyshire, Carbon 36 (1998) 1085.
[13] B.S. Girgis, S.S. Yunis, A.M. Soliman, Mater. Lett. 57 (2002) 164.
[14] M.M. Johns, W.E. Marshall, C.A. Toles, J. Chem. Technol. Biotechnol. 71
(1998) 131.
[15] A.A. Attia, B.S. Girgis, S.A. Khedr, J. Chem. Technol. Biotechnol. 78
(2003) 611.
[16] W.E. Rashwan, B.S. Girgis, Adsorpt. Sci. Technol. 22 (2004) 181.
[17] H.F. Stoeckli, Carbon 28 (1990) 1.
[18] B.S. Girgis, M.F. Ishak, Mater. Lett. 39 (1999) 107.
[19] H. Teng, T.-S. Yeh, L.-Y. Hsu, Carbon 36 (1998) 1387.
[20] M.M. Johns, W.E. Marshall, C.A. Toles, J. Chem. Technol. Biotechnol. 74
(1999) 1037.
[21] C.A. Toles, W.E. Marshall, M.M. Johns, Carbon 37 (1999) 1207.
[22] L.H. Wartelle, W.E. Marshall, J. Chem. Technol. Biotechnol. 76 (2001)
451.
[23] C. Moreno-Castilla, F. Carrasco-Marn, M.V. L opez-Ram on, M.A.
Alvarez-Merino, Carbon 39 (2001) 1415.
[24] J. Laine, A. Calafat, M. Labady, Carbon 27 (1989) 191.
[25] C.A. Toles, W.E. Marshall, M.M. Johns, Carbon 35 (1997) 1407.
[26] L.B. Khalil, B.S. Girgis, Fuel Sci. Technol. 13 (1994) 131.
[27] B.S. Girgis, Bull. NRC (Egypt) 22 (1997) 89.
[28] Introduction to Activated Carbon, Sales Brochure, Amersfoort Norit,
2001.
[29] A.A. El-Hendawy, S.E. Samra, B.S. Girgis, Colloid Surf. A: Physicochem.
Eng. Aspects 180 (2001) 209.
[30] F. Suarez-Gracia, A. Martinez-Alonso, M.J.D. Tascon, J. Anal. Appl. Pyrol.
63 (2002) 283.
[31] M.J. Selles-Perez, J.M. Martin-Martinez, J. Chem. Soc., Faraday Trans. 87
(1991) 1237.
[32] D. Mohan, P.S. Kumar, S. Singh, D. Gosh, Carbon 42 (2004) 2409.
[33] D. Mohan, K.P. Singh, K. Kumar, G. Singh, Ind. Eng. Chem. Res. (ACS)
41 (2002) 3688.
B.S. Girgis et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 299 (2007) 7987 87
[34] J.F. Byrne, H. Marsh, in: J.W. Patrick (Ed.), Porosity in Carbons: Charac-
terization and Applications, Edward Arnold, Inc., London, 1995 (Chapter
1).
[35] M.J. Selles-Perez, J.M. Martin-Martinez, Fuel 70 (1991) 877.
[36] C.H. Giles, V.S. Trivedi, Chem. Ind. (1969) 1427.
[37] R. Leboda, B. Charmas, Colloid Surf. 135A (1998) 267.
[38] S. Nouri, F. Haghseresht, Adsorption 10 (2004) 79.
[39] A.B. Laszlo, L. Nagy, L. Cabasso, Colloid Surf. 151A (1999) 311.
[40] L. Pikkov, J. Kallas, T. Runtmann, E. Rikmann, Environ. Technol. 22(2001)
229.
[41] B.S. Inbaraji, K. Selvarsani, N. Sulochana, J. Sci. Ind. Res. 61 (2002) 971.
[42] R.-L. Tseng, F.-C. Wu, R.-S. Juang, Carbon 41 (2003) 487.
[43] I.A. Rahman, B. Saad, Malys. J. Chem. 5 (2003) 8.
[44] M. Goyal, S. Singh, R.C. Bansal, Carbon Sci. 5 (2004) 170.
[45] M.A. Ferro-Garcia, J. Rivera-Utrilla, I. Bautista-Toledo, M.D. Mingorance,
Carbon 28 (1990) 545.
[46] C.P. Chen, X. Wang, Separ. Purif. Technol. 19 (2000) 157.
[47] M. Machida, Y. Kikuchi, M. Aikawa, H. Tatsumato, Colloid Surf. 240A
(2004) 179.
[48] S. Akhtar, R. Qadeer, Adsorp. Sci. Technol. 15 (1997) 815.
[49] P. Shekinah, K. Kadirvelu, P. Kanmani, P. Senthikumar, V. Subburam, J.
Chem. Technol. Biotechnol. 77 (2002) 458.
[50] M. Machida, K. Yamazaki, M. Aikawa, H. Tatsumato, TANSO 216 (2005)
13.
[51] A.M. Puziy, O.I. Poddubnaya, V.N. Zaitser, O.P. Konoplitska, Appl. Surf.
Sci. 221 (2004) 421.
[52] A.M. Puziy, O.I. Poddubnaya, A. Martinez-Alonso, F. Suarez-Garcia,
J.M.D. Tascon, Carbon 40 (2002) 1493.
[53] A.M. Puziy, O.I. Poddubnaya, J.A. Ritter, A.D. Ebner, C.E. Holland, Car-
bon 39 (2001) 2313.
[54] C. Faur-Brasquet, Z. Reddad, K. Kadirvelu, P.L. Cloirec, Appl. Surf. Sci.
196 (2002) 356.