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Journal of Colloid and Interface Science 310 (2007) 498–508

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Comparative study for the removal of methylene blue via adsorption and
photocatalytic degradation
E.A. El-Sharkawy a,∗ , Afaf Y. Soliman b , Kawthr M. Al-Amer b
a Chemistry Department, College of Science, King Faisal University, Al-Hofuf 31982, Saudi Arabia
b Chemistry Department, Girls’ College of Education at Al-Hofuf, Agency of Girls’ College, Saudi Arabia

Received 16 November 2006; accepted 3 February 2007


Available online 12 February 2007

Abstract
Physically and chemically activated carbons were prepared from date pits and olive stones. Titania and WOx -TiO2 /MCM-41 were prepared as
photoactive catalysts. Surface characterizations were investigated from ash content, pH, base neutralization capacities and FT-IR techniques. The
textural characteristics, namely specific surface area (SBET ) and pore texture, were determined from low temperature adsorption of N2 at 77 K.
The decolorization of aqueous solution of methylene blue was performed by means of two alternative methods. Steam-activated carbons own
higher surface area compared with ZnCl2 -activated carbons, and the micropore surface area represents the major contribution of the total area.
Steam-activated carbons were the most efficient decolorizing adsorbents owing to its higher surface area, total pore volume and the basic nature
of the surface. The calculated values of G0 , H 0 and S 0 indicate the spontaneous behavior of adsorption. The photocatalytic degradation is
more convenient method in decolorizing of methylene blue compared with the adsorption process onto activated carbons.
© 2007 Elsevier Inc. All rights reserved.

Keywords: Activated carbons; Surface area; Pore texture; Methylene blue; XRD; Photocatalytic

1. Introduction for most pollutants in waste water or at the supplying drinking


water. These higher adsorption capacities were correlated to the
Textile dyes represented the main source for aquatic pollu- porous nature of activated carbons and its high internal surface
tion with colored compounds. Sauer et al. report that approxi- area and therefore favored as excellent adsorbent among the
mate amounts of 1–15% are discharged in waste water during others. The use of different wastes of lignin origin to prepare
the dyeing process and textile industries [1]. The contamina- the activated carbons, e.g. date pits and olive stone, is one of
tion of waste water with these dyes consumes the dissolved the aims of the present investigation. Such selection of younger
fossil materials is based on the potential of obtaining high qual-
oxygen and therefore affects the aquatic life, causing thus envi-
ity activated carbons, the huge volume as agriculture by-product
ronmental problems [2,3]. Methylene blue is cationic dye, used
solid wastes and their uses as cheapest precursor for the active
extensively for dying cotton, wool and silk. The risk of the pres-
carbons.
ence of this dye in waste water may be arisen from the burns
On the other hand, photocatalytic degradation has received a
effect of eye, nausea, vomiting and diarrhea.
great attention as an alternative method in the removal of en-
Adsorption has been reported as an efficient method for the
vironmental pollutants in aqueous as well as gaseous media
removal of different toxic pollutants in waste effluents, among
[4,5]. Anatase-type titania has been proven as environmental
of which heavy metals, dyes, odors, oils and organic pollutants
friendly catalysts because of its capability to decompose the dif-
were. Activated carbons are widely used as powerful adsorbents
ferent organic and inorganic pollutants [6–10]. The efficiency
of photocatalytic degradation could be enhanced by anchoring
* Corresponding author. Address for correspondence: Chemistry Department, of photoactive catalysts on suitable support particularly that of
College of Education at Al-Arish, Suez Canal University, Egypt. large surface area [11]. The adsorption of pollutants on a high
E-mail address: easharkawy@yahoo.com (E.A. El-Sharkawy). surface area supports, e.g. active carbons [12,13], increases its
0021-9797/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.02.013
E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508 499

concentration around supported titania; its diffusion to titania 313–323 K on oil bath to allow the evaporation of titanium
and thereby promotes the photocatalytic process [14–16]. The isopropoxide or its hydrolysis onto the support surface. The
use of MCM-41 as a support for photoactive catalyst has not sample was washed with deionized water to remove the non-
been studied yet. deposited titanium compound and then calcined at 773 K in
Herein, the present study aimed to: prepare powerful adsor- inert atmosphere for 4 h. The calcined sample was impregnated
bents from cheapest agriculture solid wastes, prepare titania and with aqueous solution containing the appropriate amount of am-
WOx -TiO2 /MCM-41 as a photoactive catalyst, characterize ac- monium tungstate to obtain 4 and 8 wt% WO3 . The sample was
tive carbons investigated as well as the home-made catalyst and dried and calcined at 773 K in inert atmosphere.
compare the removal efficiency of methylene blue via adsorp-
tion and photocatalytic degradation. 2.2. Techniques

2. Experimental The ash contents of raw materials were determined by burn-


ing a known weight of raw materials (2.0 g) in a crucible at
2.1. Materials 873 K till the disappearance of black color and a constant
weight obtained.
2.1.1. Active carbons The pH values had to be measured to determine the pre-
Zinc chloride (Z)-activated carbons (C) were prepared by dominant nature of the surface, either acidic or basic. This was
soaking the dried raw materials, namely date pits (DP) or olive performed by soaking 1.0 g of the home-made activated car-
stones (OS), in aqueous zinc chloride solution containing the bons in 50 ml CO2 -free distilled water and shaking for 24 h.
appropriate amount of activating agents for 96 h at room tem- The pH of supernatant water was determined using Orion pH
perature. The raw materials, activating agent ratio of 2:1 (I), 1:1 meter.
(II) and 1:2 (III), were prepared. The mixture was then dried at The base neutralization capacities (BNC) were determined
393 K and then carbonized at 873 K for 6 h in the presence of via the adsorption of different bases, namely NaOH, Na2 CO3
N2 atmosphere. The rate of heating was adjusted to 10 ◦ C/min. and NaHCO3 , from their aqueous solutions (0.2 mol/dm3 ),
The carbonization product was lixiviated with dilute HCl, fol- onto prepared activated carbon. Thus, in 100 ml Quick fit Pyrex
lowed by washing with hot distilled water for several times till bottles amount of 0.2 g sample in 50 ml of the respective
free from chloride ions. The samples were dried at 393 K till base was shacked for 24 h. The residual concentration of each
constant weight. Six samples were prepared using zinc chloride solution was determined by titrating the supernatant against
as activator and designated as DP CZI, DP CZII, DP CZIII, OS 0.1 mol/dm3 HCl.
CZI, OS CZII and OS CZIII. The functional carbon–oxygen groups on the surface of ac-
Steam-activated carbons were prepared, where 50 g of non- tive carbons were identified by using FT-IR technique. The
activated sample was placed in a hot zone reactor over a layer of activated carbon was diluted with KBr, compressed into wafer
silica wool and covered with another silica wool layer. A proper and FT-IR spectra were recorded by Mattson 5000 FT-IR spec-
ratio of steam–nitrogen mixture was admitted and the flow rate trophotometer.
was monitored by orifice type flow-meter. Three samples of The textural properties (surface area, total pore volume and
steam-activated carbons were prepared from date pits or olive mean pore radius) were determined from nitrogen adsorption at
stones by gasification at 1173 K with steam. The proper time 77 K using Nova automated sorptometer. Prior to adsorption,
was adjusted to obtain 27, 38 and 56% burn-off: the catalyst sample was degassed at 473 K for 8 h under a re-
  duced pressure of 10−4 Torr.
% burn-off = (W1 − W2 )/W1 × 100, (1) XRD patterns of MCM-41 supported titania catalysts were
where W1 and W2 are the weight of non-activated and activated recorded using Philips PW 1051 X-ray diffractometer with Ni
carbons, respectively. The samples were designated as DP CS filtered CuKα radiation (λ = 1.5405 Å).
27, DP CS 38 and DP CS 56 from date pits precursor, while OS The adsorption of methylene blue was followed in a static
CS 27, OS CS 38 and OS CS 56 from olive stones precursor. batch experiment. Aqueous solution of certain concentration of
methylene blue was shaken in stoppered Pyrex brown bottles
2.1.2. Catalyst of 100 ml capacity with 0.2 g carbon as adsorbent (activated
TiO2 was prepared by sol–gel method, using titanium (IV) and non-activated) for 36 h. The supernatant liquid was filtered,
isopropoxide as titanium precursor. In this preparation, 10 ml of where the equilibrium concentration of dye was determined us-
titanium (IV) isopropoxide was mixed with 40 ml isopropanol ing Schimadzu double UV–visible spectrophotometer. The ad-
under vigorous stirring. Solution containing appropriate ratio of sorbed amount at equilibrium, Qe (mg/g), was calculated by
H2 O, isopropanol and HCl was drop wisely added with stirring.
Qe = (C0 − Ce )V /W, (2)
The supernatant liquids were evaporated with rotatory evapora-
tor, and the gel was dried and then calcined at 773 K. where C0 and Ce are the initial and equilibrium concentration of
MCM-41 support was prepared following the method re- dye solution, respectively; V is the volume of working solution
ported by Hu et al. [17]. To prepare TiO2 -WO3 /MCM-41, 10 ml and W is the weight of activated carbons used.
of titanium (IV) isopropoxide was added to 3 g of MCM-41 Photocatalytic degradation of methylene blue was performed
and stirred vigorously for 10 min. The mixture was heated at as follow: Pyrex reactor with the size 30 mm lengths, 60 mm
500 E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508

width and 10 mm thickness contained 200 ml of aqueous so- ing their acidic–basic nature. The presence of such functional
lution of MB, 300 ppm, and 0.5 g catalyst. The reactor was groups as well as the textural parameters strongly affects the
illuminated with UV-irradiation (8 W) of dominant wave length adsorption of ionic dyes. Fig. 1 shows FT-IR spectra of some
254 nm. The degradation was monitored by sampling 2 ml at activated carbons prepared from date pits and olive stones. The
various time intervals, while the absorbance was measured on chemical analysis approved that date pits and olive stones solid
UV–visible double beam spectrophotometer. wastes precursors of activated carbons composed of three main
components, namely cellulose, hemicelluloses and lignin; in
3. Results and discussion addition to minor constituents including oil, protein, fiber, in-
organic and moisture. Depending on the chemical structure of
3.1. Ash content, pH and base neutralization capacities this agriculture, various functional groups were exhibited in FT-
IR spectra [18–24], Table 2.
Table 1 lists the estimated ash content, pH of aqueous sus-
pended carbons and the base neutralization capacities. Inspec-
tion of Table 1 reveals that: (i) for date pits and olive stones, 3.3. Surface area and porosity
the ash content of steam-activated carbons is higher than those
of ZnCl2 -activated carbons. The ash content of steam-activated The adsorption isotherms of N2 at 77 K onto investigated ad-
carbons increases with the increase of % burn-off, leading to sorbents in Fig. 2 were used to determine the surface area and
a decrease of carbon content. (ii) The ash content of ZnCl2 -
pore textures, i.e. SBET , and pore texture. For all carbon prepa-
activated carbons is generally low compared with the non-
rations, the adsorption isotherms are either of type I of Lang-
activated ones. This may be referred to the decrease of % in-
muirian type [25] or a mixture of type I and type II. The initial
organic/% carbon upon carbonization of precursors. Moreover,
part of isotherm indicates a micropore filling, while the slight
the carbonization in the presence of ZnCl2 produces HCl which
curvature of the plateau is referred to the multilayer adsorption
dissolves a fraction of inorganic matters. (iii) ZnCl2 -activated
on the external surface. The adsorption/desorption isotherms of
carbons are acidic carbons (pH ≈ 4.1) while steam-activated
carbons are basic (pH ≈ 9.1), agreeing thus with the determined DP CZ and OS CZ completely overlapped with some excep-
base neutralization capacities. (iv) Base neutralization capaci- tion as figured out for DP CZ sample. In other words, most of
ties of olive stones-activated carbons are more basic compared isotherms for ZnCl2 -activated carbons do not exhibit hysteresis
with date pits-activated carbons. Generally, the acid types on loop which is characteristic for slight shaped and/or inkbottle
surface of ZnCl2 -activated carbons follow the order: phenols > type of pores [26]. The isotherms of DP CZ 1:2 and OS CZ
lactones > carboxylic and increases with the increase of the 2:1 show small hysteresis loops, given from slight pore widen-
amount of ZnCl2 activator. Moreover, the surface basicity in- ing [27]. On the other hand, the olive stones-chemically or
creases with increasing the extent of activation with steam, i.e. physically carbons show hysteresis loops overlapped with the
it is clear as listed that the surface of steam-activated has ill- adsorption branch at relative pressure of P /P 0 = 0.4. The area
defined carboxylic groups. of hysteresis loops increases with the increase of burn-off. This
may be attributed to the creation of larger pores upon activating
3.2. FT-IR investigation with steam [28].
The linear BET plots enabled to determine the specific sur-
FT-IR is a convenient technique used to identify the func- face area of the different adsorbers (SBET , m2 /g) and therefore
tional groups on the carbon surfaces and therefore explor- to calculate the mean pore diameter (d, nm) according to the

Table 1
Ash content, pH and base neutralization capacities of investigated carbons prepared from DP and OS solid wastes
Samples Ash pH Carboxylic Lactones Phenolic Total acidic Total basic
wt% (meqv./g) (meqv./g) (meqv./g) (meqv./g) (meqv./g)
DP 2.48 7.96 – – – – –
DP CZ 2:1 3.42 4.30 1.8 2.0 2.2 6.0 0.2
DP CZ 1:1 2.39 4.12 2.10 2.35 2.60 7.11 0.12
DP CZ 1:2 1.89 4.02 2.50 2.75 2.93 8.18 0.08
DP CS 27 4.28 8.98 0.40 0.80 0.55 1.75 1.81
DP CS 38 5.06 9.35 0.24 0.62 0.38 1.24 1.98
DP CS 56 7.98 9.51 0.18 0.43 0.21 0.82 2.4

OS 3.95 8.18 – – – – –
OS CZ 2:1 4.50 4.20 1.20 1.50 1.70 4.40 0.18
OS CZ 1:1 3.23 4.05 1.60 1.75 2.00 5.35 0.10
OS CZ 1:2 2.43 4.00 2.0 1.9 2.4 6.3 0.05
OS CS 27 5.27 8.91 0.14 0.40 0.19 0.73 1.1
OS CS 38 8.18 9.12 0.07 0.28 0.11 0.46 1.5
OS CS 56 9.79 9.40 0.04 0.16 0.06 0.26 1.8
E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508 501

Fig. 1. FT-IR of some investigated samples.

equation: ical activation led to a tremendous increase of SBET , VT and


Smicro , compared with that of non-activated carbons. This
4VT (cc/g)
d (nm) = × 103 , (3) means that the activation process leads to a creation of addi-
SBET (m2 /g) tional pores of more or less dimensions. The effect of activation
where VT is the adsorbed volume near saturation, i.e. at is much more pronounced for date pits than olive stones. This
P /P 0 ≈ 1, multiplied by the factor 15.47 × 10−5 . may be attributed to the different botanical structure of date pits
Listed in Table 3 are the values of textural parameters, and olive stones, where the yield of carbon prepared from date
namely SBET , VT , C (constant), Vmicro (micropore volumes), pits are relatively higher than olive stones.
Smicro /SBET and Vmicro /VT . According to the classification of IUPAC-pore dimensions,
It is evident that the surface area of ZnCl2 -activated and the pores of adsorbers can be grouped into micropores (d <
steam-activated carbons are comparable. The physical or chem- 2 nm), mesopore (d = 2–50 nm) and macropore (d > 50 nm).
502 E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508

Table 2
Main FT-IR spectrum bands assignments
DP CZ DP CS OS CZ OS CS Assignments Refs.
594 581 577 574 ν O–H in OH groups, lower 650
shift due to hydrogen bonds
751 750, 890 716, 898 741, 872 C–H aromatics or NO2 726–890
bending in aromatic nitro
groups
1431 (b) 1470 1402, 1450 1418 Inorganic ester 1435
Overlapped broad 1244 820 (sh), 1207 Broad band Ester (CH3 –CO–O–), 815, 1240
band 800–1250 (broad) 950–1350 cyclic C–O–C groups
conjugate with C=C–O–C
in olefinic or aromatic
structures
Overlapped broad Overlapped bands 906, 975 Broad band OH bending vibrations 1374
band 800–1250 within 1300–1400 950–1350
1431 1442 1474 Overlapped C=C stretching in aromatic 1442
skeleton
1565 1589 1580 Overlapped C=C stretching in olefinic 1589
double bonds
1633 1650 Overlapped Overlapped N–H in-plane bending 1635
1758 1735 1742 1700–1748 C=O stretching in 1742
aldehydes, ketones, ester
and acetyl derivatives
1900–2082 1925–2150 1880–2130 1955–2225 N–H. . .O stretching and 1945–2200
bending intra-molecular
hydrogen bonding
2322, 2410 2350–2390 2325 2314 C=O stretching in ketene 2350–2380
group
Broad band 2822–2976 2914 overlapped 2864, 2926 2931, 2870 CH stretching 2942, 2864
with 2870
3099 3053–3048 Overlapped 3077 CH stretching in 3099
polynuclear system
3100–3500 3100–3446 3100–3500 3100–3593 OH, NH, CH stretching in 3100–3488
alkyl or aryl

Table 3
Textural characteristics of activated carbons prepared from date pits and olive stones
Sample SBET C VT d Vmicro Vmicro /VT αS Snon-micro Smicro Smicro /SBET
(m2 /g) (ml/g) (nm) (ml/g) (m2 /g)
DP 9.9 151.6 0.0083 3.34 0.0027 0.33 10.3 3.8 6.5 0.66
DP CZ 2:1 474.9 194.3 0.2573 2.17 0.1521 0.59 478.9 18.4 460.6 0.97
DP CZ 1:1 535.6 109.9 0.2732 2.04 0.1588 0.58 538.3 24.4 510.0 0.95
DP CZ 1:2 713.4 53.2 0.3960 2.22 0.2220 0.56 715.8 34.9 685.0 0.96
DP CS 27 495.7 76.5 0.2659 2.15 0.1367 0.51 499.2 142.3 359.0 0.72
DP CS 38 722.4 38.5 0.3605 2.00 0.2048 0.57 725.3 41.8 690.0 0.96
DP CS 56 1047.4 22.6 0.5797 2.21 0.2853 0.49 1050.0 106.3 955.0 0.91
OS 50.4 185.1 0.0342 2.71 0.0140 0.41 50.9 14.5 35.4 0.70
OS CZ 2:1 343.6 235.7 0.2140 2.49 0.0899 0.42 346.3 48.5 292.8 0.85
OS CZ 1:1 503.0 88.8 0.2744 2.18 0.1504 0.55 506.7 37.5 478.2 0.95
OS CZ 1:2 635.4 41.7 0.3068 1.93 0.1795 0.59 639.6 20.3 621.3 0.98
OS CS 27 455.3 89.9 0.2399 2.11 0.1211 0.50 458.9 48.6 417.3 0.92
OS CS 38 617.7 36.1 0.3232 2.09 0.1682 0.52 620.2 88.7 532.5 0.86
OS CS 56 836.1 20.0 0.4454 2.13 0.2200 0.49 839.7 124.6 715.1 0.86

Therefore, the produced pores during activation of pore size show two sections; the first passes through the origin and gives
≈2 nm, as listed in Table 2, are predominantly nearest to the total surface area, while the second is indicated by the up-
the micropore dimensions and exceed the half of total pores ward deviation and gives the surface area of non-micropores
(Vmicro /VT ). (meso + macropores). The values of Smico /SBET again indicate
An alternative approach used to determine the surface area, the predominance of micropore volumes, and they are consis-
Smicro and Snon-micro is αS method [29–32]. αS curves, Fig. 3, tent with the calculated values of Vmicro /VT .
E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508 503

Fig. 2. Adsorption/desorption isotherms of N2 adsorption onto activated carbons at 77 K.

3.4. Catalyst characterization Li et al. [36] identified the presence of Wx Ti1−x O2 spinel for
8% WOx -TiO2 /MCM-41 at 2θ of 20.45 and 22.83, which can-
XRD was used to identify the significant crystalline phase in not be assigned herein in the lower 2θ than 24. This phase may
the degradation process using solid catalysts. Fig. 4 depicts the be indicated by an exothermic DTA peaks (not represented) at
XRD patterns of pure TiO2 and MCM-41 supported TiO2 and 923 K. The absence of XRD characteristic lines of Wx Ti1−x O2
impregnated with 8 wt% WO3 (SiTW8 ). Pure titania calcined may indicate its amorphous nature, lower limit of XRD detec-
at 923 K is predominant in the rutile phase with small amounts tions and its high dispersion on MCM-41 support. MCM-41
of anatase phase. However, the higher thermal treatment of tita- exhibits XRD diffraction line at 2θ of 2–3.
nia enhanced the transformation of anatase phase titania to the
rutile phase during thermal treatment, the addition of Wn+ hin- 3.5. Adsorption of methylene blue
dered such transformation [23–35]. Therefore, our home-made
MCM-41 supported TiO2 catalyst lower fraction of rutile phase Methylene blue (MB) has been selected in the adsorption re-
than that in pure titania and mainly contains the anatase phase. searches, owing to its widespread, adsorbed by most surfaces
504 E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508

Fig. 3. αS plots of N2 adsorption onto activated carbons at 77 K. Fig. 5. Adsorption isotherms of methylene blue onto activated carbons at 77 K.

The adsorption data were fitted to Langmuir’s isotherm:


Ceqm 1 Ceqm
= + , (5)
Q bQmax Qmax
where Qmax is the monolayer coverage of MB adsorbed (mg/g)
and b is the Langmuir constant (L mg−1 ). The values of Qmax
and b were determined from linearized form of Eq. (4) by plot-
ting Ceqm /Q versus Ceqm , Fig. 6. Qmax values of MB enabled
to calculate the specific surface area occupied with MB mole-
cules, i.e. SMB (m2 /g), according to the equation applied by
Poots et al. [38,39]:
SMB = 2.79038Qmax . (6)
Listed in Table 4 are the adsorption parameters, namely Qm , b,
Fig. 4. XRD patterns of pre-calcinated catalysts. SBET , VT and SMB , which predict the following points:

(i) Non-activated carbons exhibit low adsorption of MB com-


in the form of ionic micelles and represents a medium sized ad- pared with the activated ones. The activation with zinc
sorbed molecule of pore size >13 Å. The adsorption isotherms chloride, e.g. CZ 2:1 or with steam CS 27, resulted in 2.5-
of MB onto activated carbons, Fig. 5, verified Freundlich’s ad- or 4-fold increase of Qmax for CZ 2:1 or CS 27, respec-
sorption relationship: tively. The values of Qm of MB on both date pits and olive
stones-activated carbons are comparable with other adsor-
1/n bents [40]. The value of Qm for hazelnut shells-activated
Q = KF × Ceqm , (4) carbons was 41.3–76.9 mg/g (SBET = 793 m2 /g), for
coconut shell-activated carbons was 48 mg/g, babassu-
where Q is the amount adsorbed (mg/g), Ceqm the equilibrium activated carbons 79 mg/g and coir pits was 120 mg/g
concentration (mg/L). and reduced upon carbonization, while activated carbons
The isotherms exhibit L-curves according to Gile’s classifi- made at our home were 166 mg/g.
cations [37] which are characteristic of an adsorption proceed- (ii) Steam-activated carbons are more effective in MB de-
ing through ionic bonding; the solute molecules lie parallel to colorization than zinc chloride-activated carbons, agreeing
the adsorbent surface. Further, the shape of the isotherms is in- thus with the evaluated surface area (SBET ) and total pore
dicative of strong affinity of the dye towards the adsorbents. volume (VT ), Fig. 7. However, the mean pore diameters
E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508 505

Table 4
Langmuir’s parameters, SBET , K0 and G0 of MB adsorption on prepared activated carbons at 298 K
Samples Qmax b SMB (m2 /g) SBET (m2 /g) VT (ml/g) K0 G0 (kJ mol−1 )
DP 17.04 0.016 47.55 9.9400 0.0083 71.302 −10.57
DP CZ 2:1 40.65 0.028 113.43 474.93 0.2573 523.55 −15.51
DP CZ 1:1 68.97 0.027 192.44 535.62 0.2732 658.87 −16.08
DP CZ 1:2 127.3 0.043 355.01 713.40 0.3960 1347.7 −17.85
DP CS 27 66.67 0.019 186.03 495.70 0.2659 432.18 −15.04
DP CS 38 119.9 0.049 334.58 722.40 0.3605 1519.1 −18.15
DP CS 56 155.3 0.063 433.26 1047.4 0.5797 2412.9 −19.30

OS 14.34 0.019 40.01 50.400 0.0342 61.781 −10.22


OS CZ 2:1 29.94 0.021 83.54 343.60 0.2140 213.45 −13.29
OS CZ 1:1 34.13 0.052 95.23 503.00 0.2744 592.17 −15.82
OS CZ 1:2 130.7 0.046 364.75 635.40 0.3068 1286.6 −17.74
OS CS 27 90.7 0.018 253.09 455.30 0.2399 96.127 −11.31
OS CS 38 92.59 0.010 258.37 617.70 0.3232 846.15 −16.70
OS CS 56 166.1 0.013 463.52 836.10 0.4454 2138.9 −19.00

Fig. 7. Qmax vs SBET and VT for adsorption of MB onto carbons investigated.

Fig. 6. Linear Langmuir’s plots of methylene blue onto activated carbons at


77 K.
chloride-activated carbons may be attributed to the pres-
ence of excess H+ ions competing with the dye cations
for dye cations [42]. The increase of pH values, i.e. for
for all preparations are not comparable and are within steam-activated carbons, reduce the electrostatic repulsion
micro–mesopore types, the de-colorization of MB was between MB cation and the adsorption sites, increasing
much recognized with activated carbons of higher surface therefore the adsorption capacities of carbons investigated
areas. Moreover, the adsorption degree of ionic dyes de- [43,44].
pends on the acid–base nature of the surface [40,41]. Sus- (iii) Date pits-non-activated carbons have higher SMB com-
pended system of steam-activated carbons in water exhib- pared with SBET , while olive stones-non-activated samples
ited pH ≈ 9 (basic), while that of zinc chloride-activated own SBET of the same magnitude as SMB . This may be ex-
carbons in water exhibited pH ≈ 4 (acidic). A good agree- plained on the basis of interacting MB molecules with the
ment between the obtained data and that of literature re- surface functional groups, which was destructed via the
ported which approved a maximum adsorption of MB in activation [40,45].
basic pH and reduced upon increasing of pH values. This (iv) Regarding the estimated values of SBET and SMB , they are
behavior depends on H+ concentration in the adsorption well comparable and manifest the correlation between the
media. In other words, the lower Qm values of MB on zinc porous texture and the adsorption of bulky molecules. The
506 E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508

Table 5
Qmax , b, K0 and G0 of MB adsorption onto DP CZ 1:1 and OS CZ 1:1
samples at 298 and 318 K
Samples Qmax b K0 G0 (kJ mol−1 )
DP CZ 1:1 at 298 K 68.97 0.0274 658.866 −16.0807
DP CZ 1:1 at 318 K 78.74 0.0441 691.311 −16.1998
OS CZ 1:1 at 298 K 34.13 0.0515 592.166 −15.8163
OS CZ 1:1 at 318 K 56.18 0.0280 698.800 −16.2270

estimated values of {(SMB /SBET ) × 100} are being of 22–


65. On the basis of these foundations, one cannot expect to
measure a higher surface area with the bulky molecule ad-
sorption, indicating the presence of different types of pores
and only fraction of pores are accessible to MB molecules.

Thermodynamic parameters of MB adsorption onto DP CZ


Fig. 8. Photolysis and photocatalytic degradation of MB using home-made cat-
1:1 and OS CZ 1:1 was determined at 298 and 318 K. The given
alysts.
parameters in Table 5, namely thermodynamic equilibrium con-
stant K0 , Gibb’s free energy (G0 ), enthalpy change (H 0 )
indicates that MB was not degraded completely when irradiated
and entropy change (S 0 ) were calculated using the following
equations: with UV in the absence of catalyst and 37% remained without
decomposition after 25 h. The curve shows that the further ir-
K0 = CS /Ce , (7) radiation for long time may become un-effective. The uses of
titania led to the complete degradation of MB within 22 h, while
where CS is the surface concentration of MB and Ce the equi-
SiTW4 and SiTW8 reduced the time of complete degradation
librium concentration (mg/L).
to 10 and 14.5 h, respectively. The primary factor of photo-
G0 = −RT ln K0 , (8) catalytic degradation is the adsorption of MB onto the catalyst
surface via the interaction of surface hydroxyl groups, particu-
where R is the universal gas constant (8.314 × 10−3 kJ K−1 - larly onto high surface area support, i.e. MCM-41 [47]. In other
mol−1 ). words, the adsorption of cationic dye on oxide surface is fa-
 
T 1 T2 b2 vored, leading to an increase of the dye concentration on the
H 0 = R 2.303 log , (9)
T 2 − T1 b1 surface and facilitate the photocatalytic degradation of the dye
investigated [14–16]. Li et al. [36] approved that W in WOx
where b1 and b2 are the Langmuir’s constants at 298 and 318 K,
shows different oxidation states, namely W6+ , W5+ and W4+ .
respectively.
The doping of TiO2 with Wn+ led to an ionic exchange between
H 0 − G0 W4+ and Ti4+ , depending on the similar ionic radii of W4+ and
S 0 = . (10) Ti4+ as well as the bond length Ti–O and W–O. Moreover, the
T
The values of K0 increase with the increase of the amount of formation of Wx Ti1−x O2 spinel as examined with XRD could
activator. Date pits-activated carbons have higher values of K0 reduce the band energy compared with the pure TiO2 (3.2 eV),
compared with olive stones-activated carbons. The inspection Scheme 1.
of Table 5 reveals that: (i) the negative values of G0 indi- The presence of transition metal cations doped titania may
cate the spontaneous adsorption of MB onto the active carbon prevent the recombination between the photo-generated holes
investigated. (ii) The positive values of H 0 confirm the en- and electrons or elongate the time of charge separation, because
dothermic nature of adsorption and the highest affinity of the it acts as an electron acceptor center [7,48,49]. In agreement
adsorption sites to adsorb MB molecules than H2 O molecules with Fujishima et al. [50,51], one can assumed that the hydroxyl
[46]. (iii) The positive value of S 0 may indicate that the ad- groups on the surface of prepared catalysts act as an electron
sorbed MB molecules are more free on the adsorption sites of donor for photo-generated H+ , forming a reactive hydroxyl rad-
activated carbons than in aqueous medium. In water, MB mole- icals (·OH) which attack MB.
cules possess low kinetic energy owing to its attraction with the The kinetics of photocatalytic degradation of MB in aqueous
solvent molecules and therefore look like as they were in cage. solution was investigated. The reaction rate (R, mg L−1 min−1 )
of the degradation is expressed as
3.6. Photocatalytic degradation of methylene blue  
R = dc/dt = kKC/(1 + KC) , (11)
Photocatalytic degradation of MB on the prepared cata- where C is the concentration of MB (mg/L), t the irradiation
lysts was studied at 25 ◦ C and pH 8. The concentration of time, k the reaction rate constant and K the adsorption coeffi-
un-decomposed MB at various time intervals during UV irradi- cient of MB (L/mg). For the lower initial concentration of MB,
ation was determined, Fig. 8. Control experiment (photolysis) i.e. ppm, the latter equation can be simplified through the first
E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508 507

Scheme 1. Schematic diagram of band energy for the investigated photocatalysts. (DP is the degradation products of MB.)

tal surface area. Steam-activated carbons own a higher surface


area compared with zinc chloride-activated ones.
Non-activated carbons exhibit low adsorption of MB. The
activation with zinc chloride or with steam causes an enormous
increase of the adsorption capacity. Steam-activated carbons
are more effective in MB de-colorization than zinc chloride-
activated carbons, agreeing thus with the evaluated surface area
(SBET ) and total pore volume (VT ). Moreover, the basic nature
of the surface of steam-activated carbons leads to a less adsorp-
tion of H+ compared with MB cation.
The values of thermodynamic equilibrium constant (K0 ) in-
creases with the increase of the amount of activator, i.e. ZnCl2
or steam. The negative values of G0 indicate the spontane-
ity of adsorption process. H 0 is positive, confirming the high
affinity of MB molecules to the adsorption sites compared with
H2 O molecules. The positive value of S 0 may indicate that
Fig. 9. Kinetics of photolysis and photocatalytic degradation of MB using cat-
alysts investigated. the adsorbed MB molecules are more free on the adsorption
sites of activated carbons than in aqueous medium.
Methylene blue is efficiently degraded in the presence of ti-
order equation: tania as a semi-conducting oxide or WOx -TiO2 /MCM-41. The
order of activity of prepared samples can be SiTW4 > SiTW8
log C0 /Ct = kKt/2.303 = Kapp t/2.303. (12)
> T. The role of Wn+ is the formation of Wx Ti1−x O2 spinel
The plot of log C0 /Ct versus time, Fig. 9, gives a fairly good which reduces the band energy compared with that of pure TiO2
straight line passing through the origin, indicating the photo- (3.2 eV). The photocatalytic degradation is found to be a first-
catalytic degradation of MB is a first-order kinetics. The slopes order kinetic.
of these lines enabled us to calculate the apparent first-order To compare the removal of methylene blue via adsorption
rate constant, Kapp . The deduced values of Kapp are 0.1571, and photocatalytic degradation, a preliminary experiment for
0.0989, 0.0634 and 0.0209 for SiTW4 , SiTW8 , T and photolysis the desorption of MB is performed and conducted that the des-
process, respectively; indicating therefore the order of photocat- orbed amount not exceeds 10% of the pre-adsorbed amount.
alytic activity can be ordered as SiTW4 > SiTW8 > T. This means that the adsorbed MB onto activated carbons may
not be easily recovered and therefore causes severe environ-
4. Conclusion mental problems. On the other hand, the complete removal of
MB via photocatalytic degradation takes place within the in-
Steam-activated carbons prepared from date pits or olive tervals 10–22 h and in some reported literature within a few
stones are basic, while zinc chloride-activated carbons are minutes, depending on the irradiation source. The photocat-
acidic. The activation process of the carbonized precursors in- alytic degradation is therefore favored method in the de-colored
creased the porosity and therefore increased the surface area. In of MB from aqueous solution compared with the adsorption,
all cases, the micropore volume is predominant and the surface particularly if the degradation products are mainly CO2 , H2 O
area of micropore represents the major contribution of the to- and other non-hazardous materials.
508 E.A. El-Sharkawy et al. / Journal of Colloid and Interface Science 310 (2007) 498–508

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