Water Air Soil Pollut (2007) 184:141–155

DOI 10.1007/s11270-007-9404-2

Activated Carbon Produced from Waste Wood

Pallets: Adsorption of Three Classes of Dyes
Daniel C. W. Tsang & Jing Hu & Mei Yi Liu &
Weihua Zhang & Keith C. K. Lai & Irene M. C. Lo

Received: 31 October 2006 / Accepted: 1 April 2007 / Published online: 15 May 2007
# Springer Science + Business Media B.V. 2007

Abstract Activated carbon was derived from waste concentration, impregnation ratio, activation temper-
wood pallets in Hong Kong via phosphoric acid ature, and activation time could maximize the surface
activation and applied to adsorption of basic dye area and pore volume of activated carbon. An increase
(methylene blue), acid dyes (acid blue 25 and acid red of impregnation ratio or activation temperature signif-
151), and reactive dye (reactive red 23). The results icantly influenced the pore size distribution by expand-
showed that respective adjustment in phosphoric acid ing the porous structure and creating more macropores
than micropores. The characterization of the carbon
surface chemistry using Fourier-transform infrared
(FTIR) spectroscopy, however, revealed a decrease in
the amount of several functional groups with increas-
D. C. W. Tsang : J. Hu : M. Y. Liu ing activation temperature. The physical properties
Institute for the Environment,
The Hong Kong University of Science and Technology,
(surface area and pore volume) of the wood waste-
Clear Water Bay, derived activated carbon (using 36% phosphoric acid
Kowloon, Hong Kong with an impregnation ratio of 1.5 at an activation
temperature of 550°C for 1.5 h) were comparable to
W. Zhang
Department of Environmental Engineering,
those of commercial activated carbon (Calgon F400).
Sun Yat-sen University, The contrasting pH effects on the adsorption of dif-
135 Xin Gang Xi Road, ferent classes of dyes signified the importance of both
Guangzhou, China electrostatic interaction and chemical adsorption,
K. C. K. Lai
which correlated to pH-dependent dissociation of
Department of Civil Architectural and Environmental surface functional groups. It is noteworthy that the
Engineering Department – EWRE, physical properties of activated carbon were insuffi-
The University of Texas at Austin, cient to account for the observed dye adsorption be-
1 University Station C1786,
Austin, TX 78712-0280, USA
havior, whereas the surface chemistry of activated
carbon and the nature and chemical structure of dyes
I. M. C. Lo (*) were more important. The fast kinetics and high
Department of Civil Engineering, capacity of dye adsorption of wood waste-derived
The Hong Kong University of Science and Technology,
Clear Water Bay,
activated carbon suggest that production of activated
Kowloon, Hong Kong carbon from different types of wood waste should
e-mail: cedaniel@ust.hk merit further investigation.
142
Keywords Activated carbon . Adsorption . Dyes .
Phosphoric acid activation . Wood waste
1 Introduction
The application of activated carbon covers a wide
spectrum of systems such as air purification, water
and wastewater treatments, and food, beverage,
pharmaceutical and chemical industries (Marsh
2001; Moreno-Castilla 2004). It has been recently
extended to in-situ stabilization of marine and fresh-
water sediments contaminated by polychlorinated
biphenyls (PCBs) and polyaromatic hydrocarbons
(PAHs) (Zimmerman et al. 2004; Werner et al. 2005).
The aqueous concentrations and bioavailability of the
organic contaminants could be significantly reduced
by adsorption of contaminants on activated carbon
(Millward et al. 2005; Zimmerman et al. 2005).
Activated carbon is commonly manufactured from
coal, wood, peat, petroleum coke, and coconut shells.
For instance, Calgon Filtrasorb® 400 (F400), a widely
used commercial activated carbon, is produced from
metallurgical-grade bituminous coal (Calgon Carbon
Corporation 1999). In view of widespread engineer-
ing application and high efficacy of activated carbon,
an attempt to convert organic waste materials with
high carbon content into activated carbon is gaining
popularity, because wastes that are otherwise disposed
can be recycled and the raw materials for activated
carbon production can be conserved for other pur-
poses. It has been shown that activated carbon can be
successfully produced from a wide range of agricul-
tural wastes such as apricot stones, bagasse, grain
sorghum, nutshells, plum kernel, and rice husk (Gergova
and Eser 1996; Philip and Girgis 1996; Daifullah and
Girgis 1998; Toles et al. 1998, 1999; Ahmedna et al.
2000; Juang et al. 2000; Diao et al. 2002; Kennedy
et al. 2004); and from various municipal wastes such
as PET waste, sewage sludge, discarded tyres, and
refuse derived fuel (Nagano et al. 2000; Nakagawa
et al. 2004; Rozada et al. 2005; Tanthapanichakoon
et al. 2005; Zhang et al. 2005).
In Hong Kong, daily generation of domestic,
commercial, and industrial wood wastes was 347 tons;
however, only about 11% (14,000 tons/year) was
recycled in practice and the rest was directly
discarded at landfills (Hong Kong Environmental
Water Air Soil Pollut (2007) 184:141–155
Protection Department (HKEPD) 2005). In consider-
ation of limited landfill capacity (Environment, Trans-
port and Works Bureau (ETWB) 2003), recycling
massive wood wastes into valuable products is a top
priority whenever it is possible. Enormous amount of
waste wood pallets that come from shipping industry in
Hong Kong may be fit for activated carbon production.
Therefore, this study assessed the feasibility of
chemical activation of waste wood pallets by means
of phosphoric acid activation. It has been noted that
high specific surface area and favorable pore structure
of activated carbon contribute to effective contaminant
sequestration (Zimmerman et al. 2004; Millward et al.
2005), on the other hand, surface chemistry of
activated carbon also plays key roles in adsorption
mechanisms and behaviors (Pereira et al. 2003;
Moreno-Castilla 2004). All these attributes depend on
the activation conditions, including phosphoric acid
concentration, impregnation ratio, activation tempera-
ture, and activation time. Therefore, the physical and
chemical characteristics of activated carbon synthe-
sized under a wide range of conditions were investi-
gated in this study.
The adsorption performance of the synthesized acti-
vated carbon for different classes of dyes was subse-
quently evaluated. Considerable amount of dye effluents
are discharged from textile, paper, and plastic industries,
for example, over 4.4×106 m3 per day in Mainland
China (Wong et al. 2003). It has been estimated that 5–
20% of acid dye, 0–5% of basic dye and 10–50% of
reactive dye leak to the effluent directly during the
industrial dyeing processes (Frank 2002). Dyes would
persist in natural settings due to their resistance to
chemical degradation and photodegradation, causing
aesthetical and environmental problems because their
strong colors block sunlight penetration and the toxic or
carcinogenic nature of many dyes endangers living
organisms (Banat et al. 1996; Vandevivere et al. 1998;
O’Neill et al. 1999; Robinson et al. 2001). Activated
carbon adsorption has proven to be more versatile and
cost-effective in removing a variety of dyes from
industrial wastewater than other technologies such as
advanced oxidation and membrane separation (Derbyshire
et al. 2001; Jain et al. 2003; Faria et al. 2004). Thus, the
adsorption kinetics and capacity of the wood waste-
derived activated carbon and F400 (as a reference) for
basic dye (methylene blue, MB), acid dye (acid blue 25,
AB, and acid red 151, AR), and reactive dye (reactive
red 23, RR) were studied.
Water Air Soil Pollut (2007) 184:141–155
2 Materials and Methods
2.1 Production of Activated Carbon from Waste
Wood Pallets
Waste wood pallets, which were obtained from a local
container terminal managed by HIDC Management
Limited in Hong Kong, showed 47.8% of carbon content
(by mass) in elemental analysis (Elementar vario EL III
CHNS-O, Germany), indicating that this wood waste can
be a suitable precursor for activated carbon production.
Direct phosphoric acid activation had been applied to
organic waste materials (Philip and Girgis 1996; Toles
et al. 1998; Diao et al. 2002; Diaz-Diez et al. 2004).
Preliminary study, however, showed that direct phos-
phoric acid activation of the waste wood pallets
required long activation time and only activated the
exterior portion, leaving hardened cores (i.e., resistant
to grinding) in the center that had to be discarded. A
carbonization step was, therefore, carried out prior to
phosphoric acid activation. About 300 g of the waste
wood pallets that had been sliced into small pieces and
dried at 105°C for 24 h were carbonized by partial
combustion at 300°C in a furnace (Carbolite CSF
1100) with a constant nitrogen gas flow of 250 mL
min−1 for 3 h at a heating rate of 4.5°C min−1, followed
by cooling down with a continuous flow of nitrogen
gas. No hardened cores were formed. The carbonized
wood was virtually free of volatile organic compounds
and contained some pores that were too small or
restricted to be useful as an adsorbent. It was then
crushed through a 180-μm sieve (U.S. standard sieve no. 80).
The subsequent activation step created an active
surface and a highly porous structure by selectively
oxidizing part of the structure. In order to investigate
the influence of activation conditions on the character-
istics of the wood waste-derived activated carbon,
Table 1 Activation conditions for the production of activated carbon from waste wood pallets
Activation conditions under investigation Experimental parameters
H3PO4 concentration
(%)
H3PO4 concentration (%) 20;36;60
Impregnation Ratio 36a
Activation temperature (°C) 36a
Activation time (h) 36a
a
Conditions determined by preceding experiments.
143
various phosphoric acid concentrations, impregnation
ratios (i.e. H2PO3 to carbonized wood ratio by weight),
activation temperatures, and activation times were
applied (Table 1). Four sets of experiments were run
in sequence with respect to each experimental param-
eter, under an implicit assumption of independent and
non-interacting parameters. A 10 g of carbonized wood
powder was firstly impregnated with phosphoric acid
solution (20, 36, or 60%) at a designated impregnation
ratio (1, 1.5, 2, 2.5, or 3) for 2 h. The mixtures were
then heated to a certain activation temperature (450,
500, 550, 600°C) for a given duration (1, 1.5, 2, or
2.5 h) in a furnace with purging of nitrogen gas of
25 mL min−1 at a heating rate of 7.8°C min−1, and
cooled to room temperature afterwards. Excess phos-
phoric acid was removed from the carbon using a
Soxhlet extraction system. The synthesized activated
carbon was dried at 105°C and stored in a desiccator.
2.2 Physical and Chemical Characterization
Microscopic images of the waste wood pallets and the
synthesized activated carbon were obtained by Scanning
Electron Microscope (JEOL-6300 SEM). The physical
properties (i.e., surface area and pore structure) of the
activated carbon were determined by the nitrogen gas
adsorption at 77 K using a Brunauer, Emmett, Teller
(BET) surface area analyzer (Coulter SA-3100, USA;
Huang et al. 2006). The samples were degassed at 120°
C in vacuum for 1.5 h prior to the adsorption measure-
ments. Nitrogen adsorption isotherms were measured at
a relative pressure (P/P0) ranging from approximately
0.001 to 0.995. The BET surface area (SBET) was
calculated by applying the BET equation to the
adsorption data (P/P0 =0.05–0.35) and the total pore
volume (Vtotal) by the Dubinin-Raduskhevich equation
at P/P0 =0.9814. The micropore volume (Vmicropore) and
Impregnation Activation temperature Activation time
ratio (°C) (h)
2 500 1.5
1; 1.5; 2; 2.6; 3 500 1.5
1.5a 450;500;550;600 1.5
1.5a 550a 1; 1.5; 2; 2.5
144
micropore surface area (Smicropore) were obtained by the
t-plot method and the pore size distribution of meso-
pores by BJH analysis.
In addition, the chemical properties of the activated
carbon were characterized using Fourier-transform infra-
red (FTIR) spectroscopy. The transmission FTIR spectra
were acquired using a FTIR spectrometer (Perkin Elmer
Spectrum BX, USA) by averaging 32 scans in the 400–
4,000 cm−1 spectral range at 4 cm−1 resolution. The
activated carbon was homogenized with KBr at a mass
ratio of 1:99 to prepare pellets. Pellet thickness was kept
constant by pelletizing the equal-weight samples at the
same pressure and time using a hydraulic press.
2.3 Batch Adsorption Experiments
Batch adsorption experiments were carried out to study
the dye adsorption efficiency of the synthesized activat-
ed carbon. The wood waste-derived activated carbon and
F400 were applied to adsorb four selected dyes (Sigma-
Aldrich): methylene blue (MB), acid blue 25 (AB), acid
red 151 (AR), and reactive red 23 (RR). The properties
of these water-soluble dyes are summarized in Table 2.
A 0.5 g of activated carbon was mixed with 100 mL of
dye solution using an orbital shaker at 400 rpm at room
temperature (21°C). The mixtures were filtered after
various reaction times. The dye concentrations in the
filtrate were determined using a UV-visible spectropho-
tometer (Ultraspec 4300 pro, Denmark) at respective
wavelengths of maximum absorbance (Table 2). The
adsorption kinetics was studied using 3,000 mg L−1 dye
solution. A 50-h equilibration time was then used in the
equilibrium study. The pH effect on the dye adsorption
efficiency was investigated using an initial pH range of
2–12. The final pH was reported and generally
decreased to a larger extent at a higher initial pH.
Adsorption isotherms were determined using initial
concentrations ranging from 500 to 5,000 mg L−1,
which resulted in an equilibrium concentration range of
0–2,650 mg L−1. The average values of duplicate
experiments were reported.
3 Results and Discussion
3.1 Phosphoric Acid Activation of Waste Wood
Pallets
It is known that acid treatment can modify the physical
and chemical properties of carbonaceous materias. A
Water Air Soil Pollut (2007) 184:141–155
comparison of the SEM images of the waste wood
pallets and the synthesized activated carbon (Fig. 1)
illustrates that phosphoric acid activation generated a
highly porous and platelet structure. The physical
characteristics (SBET, Smicropore, Vtotal, and Vmicropore) of
the activated carbon produced under different con-
ditions are listed in Table 3. It should first be noted
that the effectiveness of activated carbon for contam-
inant adsorption is a function of the physical proper-
ties (surface area, pore volume, and pore size
distribution) and surface chemistry of activated car-
bon, the nature and functional groups of the contam-
inants, and the solution characteristics (e.g., pH). The
findings shown in Table 3 (i.e., physical properties of
activated carbon) were, therefore, taken into account
to select the appropriate activation conditions that
deserve further investigation of corresponding surface
chemistry and dye adsorption behavior.
A 36% concentration of phosphoric acid was first
selected as it produced the activated carbon of
comparatively higher values of total surface area and
total pore volume (SBET and Vtotal). On the other hand,
varying the impregnation ratio, activation tempera-
ture, and activation time, respectively, led to similar
parabolic variations of SBET and Vtotal. The values of
SBET and Vtotal were greater with an initial increase in
each of these parameters (i.e., impregnation ratio from
1 to 1.5, activation temperature from 450 to 550°C,
activation time from 1 to 1.5 h), but then became
smaller with a further increase (i.e., impregnation
ratio from 1.5 to 3, activation temperature from 550 to
600°C, activation time from 1.5 to 2.5 h). There may
be two contrary processes in action during activation:
development of pores and breakdown of the pore
wall. The former process increases the SBET and Vtotal,
whereas the latter decreases. It is plausible that under
certain activation conditions, the pore volume estab-
lishment can exceed the collapse of pore walls,
resulting in maximum surface area and pore volume.
Therefore, 36% phosphoric acid was employed at an
impregnation ratio of 1.5 to activate the waste wood
pallets at an activation temperature of 550°C for
1.5 h. It is noteworthy that the surface area and pore
volume of the wood waste-derived activated carbon
(SBET =1,227 m2 g−1, Smicropore =710 m2 g−1, Vtotal =
0.58 mL g−1, and Vmicropore =0.30 mL g−1) were
comparable to those of commercial activated carbon,
F400 (SBET =1,174 m2 g−1, Smicropore =718 m2 g−1,
Vtotal =0.60 mL g−1, and Vmicropore =0.32 mL g−1).
Water Air Soil Pollut (2007) 184:141–155
Table 2 Properties of commonly used industrial dyes
These favorable physical properties provided a strong
ground for subsequent FTIR spectroscopy and dye
adsorption study.
Table 3 also shows the ratios of micropore surface
area to total surface area and micropore volume to
total pore volume (Smicropore:SBET and Vmicropore:Vtotal)
that reflect the distribution of the porosity. The
variation of phosphoric acid concentrations or activa-
tion times did not appreciably change the ratios,
indicating that pore size distribution did not correlate
to these activation conditions. On the contrary, raising
the impregnation ratio from 1 to 3 significantly
lowered the Smicropore:SBET and Vmicropore:Vtotal ratios
145
from 72 to 60% and 61 to 52%, respectively.
Analogously, increasing the activation temperature
from 450 to 600°C reduced the Smicropore:SBET and
Vmicropore:Vtotal ratios from 73 to 57% and 64 to 48%,
respectively. These changes corresponded to a shift in
pore size distribution between micropores and non-
micropores (i.e., meso- and macropores). A higher
impregnation ratio or activation temperature appears
to considerably expand (open up) the porous structure
of the synthesized activated carbon, creating more
meso- and macropores than micropores. The presence
of mesopores was evident from hysteric nitrogen
isotherm (Fig. 2a), though the magnitude of hysteresis
146 Water Air Soil Pollut (2007) 184:141–155

Fig. 1 SEM images:

a Waste wood pallets and
b Synthesized activated
carbon

Table 3 Physical properties of activated carbon derived from waste wood pallets under different activation conditions

H3PO4 Impregnation Activation Activation SBET Smicropore Vtotal Vmicropore Smicropore: Vmicropore:
concentration ratio temperature time (h) (m2 g−1) (m2 g−1) (mL g−1) (mL g−1) SBET (%) VBET (%)
(%) (°C)

20 2 500 1.5 910.4 614.6 0.467 0.260 67.5 55.6

36 2 500 1.5 1,053.9 673.7 0.522 0.290 63.9 55.6
60 2 500 1.5 916.8 604.6 0.467 0.267 65.9 57.1
36 1 500 1.5 856.7 617.5 0.430 0.264 72.1 61.4
36 1.5 500 1.5 1,093.0 736.9 0.553 0.308 67.4 55.7
36 2 500 1.5 1,054.0 673.7 0.522 0.290 63.9 55.6
36 2.5 500 1.5 870.3 579.0 0.434 0.247 66.5 57.0
36 3 500 1.5 946.0 567.0 0.475 0.245 59.9 51.6
36 1.5 450 1.5 856.9 620.9 0.423 0.269 72.5 63.6
36 1.5 500 1.5 1,093.0 736.9 0.553 0.308 67.4 55.7
36 1.5 550 1.5 1,226.7 709.5 0.582 0.303 57.8 52.0
36 1.5 600 1.5 1,025.2 582.7 0.513 0.246 56.8 48.0
36 1.5 550 1 1,109.1 669.7 0.562 0.280 60.4 49.8
36 1.5 550 1.5 1,226.7 709.5 0.582 0.303 57.8 52.0
36 1.5 550 2 1,008.7 602.0 0.511 0.252 59.7 49.2
36 1.5 550 2.5 883.8 514.8 0.444 0.219 58.2 49.2
F400 1,174 718 0.600 0.320 61.2 53.3
Water Air Soil Pollut (2007) 184:141–155 147

was moderate. The pore size distribution of meso- 2005). A direct measurement of organic diffusion into
pores (Fig. 2b) was obtained by BJH analysis. The the activated carbon was faster than the prediction of
mesopore volume (0.062 mL g−1), however, only diffusion model using single domain and diffusivity
accounted for about 10% of total pore volume (Ahn et al. 2005), displaying the significance of fast
(0.582 mL g−1); thus, micropores (0.303 mL g−1) macropore diffusion. The pore size distribution was
and macropores (0.217 mL g−1) were more important shown to play a key role in competitive adsorption,
than mesopores. for it determined the degree of direct site competition
It has been emphasized that the high efficacy of and pore blockage mechanisms (Pelekani and
activated carbon is attributed to high specific surface Snoeyink 1999, 2001; Li et al. 2003). Because dyes
area and favorable pore structure that facilitates fast are usually too large (Table 2) to penetrate into small
mass transfer (or diffusion) kinetics into the activated pores, larger pores of the synthesized activated carbon
carbon (Zimmermann et al. 2004; Millward et al. are important. The dependence of the adsorption

Fig. 2 Activated carbon 400

synthesized using 36%
a
Adsorbed amount (mL g STP)

phosphoric acid with an

impregnation ratio of 1.5 at
an activation temperature of 350
-1

550°C for 1.5 h: a Nitrogen

isotherm (straight line: ad-
sorption; broken line: de-
300
sorption); b Pore size
distribution of BJH analysis
of nitrogen adsorption
250

200

150
0 0.2 0.4 0.6 0.8 1
P/P0
0.030

b
0.025
Pore Volume (mL g )
-1

0.020

0.015

0.010

0.005

0.000
Under 6 6-8 8 - 10 10 - 12 12 - 16 16 - 20 20 - 80 Over 80

Pore Diameter (nm)

148 Water Air Soil Pollut (2007) 184:141–155

kinetics and capacity on the adsorbent pore size and
adsorbate molecular size would be discussed in the
following adsorption studies of different dyes.
3.2 FTIR Characterization
Infrared spectroscopy provides qualitative informa-
tion of characteristic functional groups on the surface.
Figure 3 presents the FTIR spectra of the waste wood
pallets, wood waste-derived activated carbon (at
different activation temperatures), and F400. For
waste wood pallets, the bands at 1,300–1,400 cm−1
may reflect the aromatic CH and carboxyl-carbonate
structures and the peaks at 1,020–1,130 cm−1 may
correspond to C–OH stretching and –OH deformation
values. After activation, the peak at 1,022 cm−1 nearly
diminished because phosphorous acid activation can
convert hydroxyl groups into acid oxygen-containing
functional groups on the carbon surface. The spectra
of F400 showed fewer peaks with weaker intensity,
indicative of comparatively less amount of surface
functional groups, which was probably because of
different types of precursor materials and different
activation processes (F400 is produced from bitumi-
nous coal by thermal activation using water vapor and
carbon dioxide as activating gases).
The broad absorption band at 3,400 cm−1 indicated
the presence of both free and hydrogen bonded –OH
groups on the surface. Its intensity decreased after
activation, especially at higher temperatures. The spectra

Fig. 3 FTIR spectra of

F400, waste wood pallets, 3420 3280
and synthesized activated o
450 C
carbon (at different activa-
1540
tion temperatures) 1180
1690
o
500 C

o
550 C
Absorbance

o
600 C

1022
3400 1260
1720 1420 590
Waste Wood Pallets 1620

3430
F400 1560 1150

4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )
Water Air Soil Pollut (2007) 184:141–155 149

also showed the definite bands at 1,620–1,700 cm−1,
which may be assigned to C=O stretching vibrations of
aldehydes, ketones, lactones or carboxyl groups, to the
stretching modes of hydrogen-bonded P=O, to O–C
stretching vibrations in P=O–C linkage, and to P=OOH
(Corbridge 1956; Socrates 1994). The 1,050–
1,290 cm−1 adsorption band was attributed to the
vibration of the C=O group in lactones. The 1,500–
1,560 cm−1 region spectra showed considerable over-
lapping of different absorption bands, which were
attributed to quinonic and carboxylate groups (Bellamy
1954). These spectroscopic results were consistent with
preliminary chemical analysis by Boehm’s titration, in
which the synthesized activated carbon exhibited more
surface acidity (carboxylic, phenolic, and lactonic
groups) but less surface basicity than F400.
The varying extent of thermal treatment (450–600°C)
during the activation process altered the surface
chemistry of the activated carbon. A more intensive
heating treatment would result in a greater reduction in
the quantity of the acid oxygen-containing functional
groups (Fig. 2). It was reported that oxygen may be
evolved from the oxygen-containing functional
groups on the carbon surface at temperatures higher
than 170°C (Randtke and Snoeyink 1983), and that
700°C heating completely removed carboxylic groups
and 900°C heating removed almost all carbonyl
groups of activated carbon (Pereira et al. 2003). The
surface chemistry of activated carbon is a decisive
factor of contaminant adsorption. The association/
dissociation of surface functional groups would deter-
mine the density of surface charge for electrostatic

Fig. 4 a Adsorption kinet- 100

ics of dyes on the synthe-
sized activated carbon; b 90
Second-order kinetic model 80
fitting
70
Removal eff. (%)

3000 mg/L AB
60
3000 mg/L AR
50 3000 mg/L MB
40 3000 mg/L RR
30
20
10
a
0
0 10 20 30 40 50 60
Time (h)
0.30

3000 mg/L RR
RR
0.25
3000 mg/LAB
AB
3000 mg/LAR
AR
0.20
3000 mg/L MB
t/q (h*g/mg)

MB

0.15

0.10

0.05
b
0.00
0 10 20 30 40 50 60
Time (h)
150
interactions and reactive sites for chemical interac-
tions (e.g., ligand exchange) between the carbon
surface and the specific contaminants. It has been
shown that adsorption of cationic organics depends
on the acid oxygen-containing surface functional
groups; whereas adsorption of non-ionic or anionic
organics is closely correlated to the surface basicity
and oxygen-free Lewis basic sites (Toles et al. 1999;
Pereira et al. 2003; Moreno-Castilla 2004). Selective
modifications of surface chemistry of activated carbon
via chemical treatments (Pereira et al. 2003) may be
combined with quantitative characterization using
nuclear magnetic resonance (NMR) spectroscopy
(Huang et al. 2006) to elaborate the influence of
surface chemistry on contaminant adsorption mecha-
nisms and behaviors.
3.3 Adsorption Kinetics
The adsorption kinetics of the dyes on the synthesized
activated carbon is shown in Fig. 4, where an initial fast
adsorption was followed by a much slower adsorption.
This biphasic adsorption pattern was also observed in
other studies (Khraisheh et al. 2002; Dogan et al.
2004). The slow adsorption is likely due to external
film diffusion or intraparticle diffusion that encom-
passes surface diffusion on the pore wall surface and
pore diffusion into the polymeric matrix, of which
surface diffusion may be the primary rate-limiting
mechanism (Weber and Smith 1987; Sparks 1999).
The apparent equilibrium was reached after 24 h.
Although several diffusion models can be used to
interpret the adsorption kinetics, it is not currently
possible to make independent parameter estimations
for intraparticle diffusion in activated carbon due to
the system complexity, such as parallel macropore
and micropore diffusion and concentration-dependent
diffusivity (Ahn et al. 2005). Thus, mathematically
simple kinetic models may suffice for practical
operation. Having considered several empirical mod-
els for describing the overall adsorption kinetics (Ho
et al. 2000; Senthilkumaar et al. 2006), the second-
order model was found to be most appropriate.
dq
¼ k ð qe
qÞ 2 ð1Þ
dt
where q (mg g−1) represents the adsorbed dye
concentration on the activated carbon; qe (mg g−1) is
Water Air Soil Pollut (2007) 184:141–155
the corresponding value at equilibrium; t (h) is the
contact time; and k (g·L−1·mg−1) is a second-order
reaction rate coefficient. After integration with an
initial condition of q=0 at t=0, the following linear
equation can be obtained:
t 1 t
¼ þ ð2Þ
q kq2e qe
Table 4 shows the fitted values of the second-order
model for rate comparison. It should be noted that a good
fitting of empirical second-order model (r2 >0.99) does
not verify any particular rate-limiting mechanisms. The
rate coefficients (k) followed an order of: RR < AR <
AB < MB; in other words, the adsorption of RR reached
equilibrium slower than the other three dyes. The
kinetics did not negatively correlate with the equilibrium
adsorption capacity of different dyes (RR < MB < AR <
AB, Table 4), but probably with the molecular size that
determines the diffusion coefficient. A molecule of high
molecular weight and large structure (RR dye, Table 2)
exhibited slow adsorption kinetics (Table 4), whereas a
small molecule of low molecular weight (MB dye) was
able to undergo fast adsorption. Given that intraparticle
diffusion controls the adsorption rate, the pore size
distribution of activated carbon is important for fast and
effective adsorption of large molecules. Besides, anionic
dyes (AB, AR, and RR) consistently showed far lower
rates compared with cationic dye (MB). It appears that
electrostatic repulsion between anionic dyes and nega-
tively charged surface of the synthesized activated
carbon (pHPZC =2.89) significantly retarded the adsorp-
tion process. Nevertheless, the synthesized activated
carbon demonstrated a faster dye adsorption compared
with the reported findings of commercial activated
carbon, chitosan and natural clay (Allen 1996; Monteiro
and Airoldi 1999; Kacha et al. 2003). Fast adsorption
kinetics, which implies shorter reaction time and smaller
reactor volume, is critical in engineering application.
Table 4 Second-order kinetic model parameters for dye
adsorption on the synthesized activated carbon
Dyes Initial pH k (g mg−1min−1) qe (mg g−1)
MB 2.8 1.613 454.5
AB 3.5 0.072 588.2
AR 3.2 0.041 555.6
RR 6.2 0.008 169.5
Water Air Soil Pollut (2007) 184:141–155
3.4 Effect of pH on Adsorption
Figure 5 illustrates the effect of initial solution pH (2–
12) on the dye adsorption of the synthesized activated
carbon, which correlates with the surface chemistry of
the adsorbent (surface charge and functional groups)
and the nature of the adsorbate (cationic form, anionic
form, and the presence of reactive substituent).
Activated carbon is known to be amphoteric, that is,
its variable-charge surface can develop positive or
negative charge depending on solution pH. It is
negatively charged at pH > 3 since the carboxylic
groups (dissociation constant, pKa of 3–5) and
phenolic groups (pKa of 5–7) can deprotonate (i.e.,
dissociate H+ ions) and develop negative surface
charge. The surface charge of activated carbon is
increasingly negative with increasing pH. Based on the
understanding of electrostatic interactions, it is not
surprising that the adsorption of cationic dye (basic
dye, MB) was correlated to solution alkalinity, whereas
the adsorption of anionic dyes (acid and reactive dyes,
AB, AR and RR) was correlated to solution acidity.
The proton competition for adsorption sites wisth
cationic dyes at low pH and hydroxyl competition
with anionic dyes at high pH may also be accountable.
In addition to electrostatic interactions, a fraction
of dye adsorption appears to occur via chemical
adsorption that is of high binding strength. This was
evidenced by the observation that at least 25–40% of
Fig. 5 Effect of pH on 100
adsorption of dyes
90
80
70
Removal eff. (%)
60
50
40
30
20
10
0
0 2
151
the dyes can be adsorbed regardless of solution pH
and corresponding electrostatic repulsion (Fig. 5). It is
probable that some components of the dye molecules
such as N, S, O, and benzene rings can perform
hydrogen bonding or ligand exchange with the
surface functional groups. Chemical (specific) adsorp-
tion is particularly important for the reactive dye
(RR), which contains substituent reactive groups (e.g.,
triazine, pyrimideine and vinyl sulphone) that are
activated to directly react with the hydroxyl groups on
the surface forming covalent bond. The adsorption of
RR increased with pH in an alkaline range because
the surface hydroxyl group deprotonates to a greater
degree at a higher pH, allowing more formation of
covalent bond with the reactive dye. This suggests
that the solution pH affects the degree of chemical
adsorption besides electrostatic interaction. Future
study may attempt to quantify the relative significance
of electrostatic (weak) and chemical (strong) inter-
actions as a function of system settings.
3.5 Adsorption Isotherms
Figure 6 shows the fitted adsorption isotherms
(without pH adjustment). It is known that Freundlich
equation was frequently used (Randtke and Snoeyink
1983; Crittenden et al. 1985), however, the linear
form of Langmuir equation for a high range of con-
centrations (Wong et al. 2003; Senthilkumaar et al.
5000 mg/L MB
5000 mg/L AB
3000 mg/L RR
3000 mg/L AR
4 6 8 10 12 14
Solution pH
152 Water Air Soil Pollut (2007) 184:141–155
Fig. 6 Adsorption iso- 900
therms of dyes on the syn-
thesized activated carbon 800
(5 g L−1 at 400 rpm for
50 h) 700

600

qe (mg/g)
500 AB MB

400 AR RR

300

200
100

0
0 500 1000 1500 2000 2500 3000
Ce (mg/L)

2006) was employed to determine the adsorption
capacity of the activated carbon for different dyes.
Ce Ce 1 difference may be attributed to the molecular size and
¼ þ ð3Þ
qe qm qm b
where Ce is the equilibrium concentration in mg L−1;
qe is the amount adsorbed at equilibrium in mg g−1;
qm and b are the empirical constants that are related to
the adsorption capacity (mg g−1) and the energy of
adsorption (L mg−1), respectively. The goodness of fit
of Langmuir isotherm was above 0.99. It should be
reminded that this does not necessarily or sufficiently
confirm the underlying assumptions of Langmuir
isotherm about adsorption mechanism (e.g., mono-
layer adsorption and identical sites) (Sparks 2003;
Benjamin 2002).
The adsorption capacity (qm) of different classes of
dyes on the synthesized activated carbon decreased in
the order of: AB > MB > AR > RR, demonstrating
the importance of the chemical structure of dye. The
number of functional group (e.g., sulphonate group)
of each dye (Wong et al. 2003). A smaller molecular
size (MB < AB < AR < RR, Table 2) can penetrate
deeper into the microporous interior of activated
carbon with less steric hindrance. In addition, AB
and AR have only one sulphonate group (D–SO3Na)
while RR comprises three sulphonate groups. That
means the same quantity of surface functional groups
on activated carbon can bind with more AB and AR
molecules than RR molecules, while there is a higher
tendency for stronger, bidentate or tridentate binding
with RR via substituent reactive groups.
Despite the comparable molecular weights of
AB and AR (Table 2), a significant difference in
their adsorption capacities (Table 5) illustrated that

Table 5 Langmuir isotherm parameters for dye adsorption on the synthesized activated carbon and F400

Dyes Activated carbon Initial pH qm (mg g−1) b (L mg−1)

MB Synthesized 2.8 625.0 0.157

F400 3.7 416.7 0.112
AB Synthesized 3.5 769.2 0.684
F400 6.6 476.2 0.028
AR Synthesized 3.2 344.8 0.029
F400 6.4 256.4 0.033
RR Synthesized 6.2 208.3 0.023
F400 4.5 555.6 0.075
Water Air Soil Pollut (2007) 184:141–155
the long-chain molecular structure of AR was
unfavorable for adsorption, probably because its
adsorbed molecule would be more spatially oriented
on the surface. On the other hand, the dyes can be in
part adsorbed via π–π dispersive interaction between
the delocalized ð electron of the carbon surface and
the free electrons of the dye (aromatic rings and
double bonds of –N=N– or –N=C–C=C–) (Pereira
et al. 2003; Moreno-Castilla 2004), of which the
magnitude is less easily explained by the molecular
size and structure.
The comparison of the adsorption capacity of the
synthesized and commercial activated carbon (Table 5)
revealed higher dye adsorption capacity (except for
RR) of the synthesized activated carbon than F400.
The dye adsorption on activated carbon was more
dependent on the surface chemistry of activated
carbon and the nature of contaminant than the porous
structure of activated carbon. In this study, the
effective use of wood waste-derived activated carbon
in dye adsorption suggests that production of activat-
ed carbon from wood waste should merit further
investigation. It has been reported that activated
carbon manufactured from different sources of woods
or coals tends to have different porous structures, for
example, lignite-based activated carbon has larger
pore diameter than bituminous coal-based activated
carbon (Calgon Carbon Corporation 1999; Macias-
Garcia et al. 2003; Diaz-Diez et al. 2004). It is
plausible that activated carbon made from different
types of wood wastes would possess specific charac-
teristics of surface chemistry (e.g., surface acidity/
basicity and functional groups), which make them
better-suited for particular class of contaminants (e.g.,
cationic, anionic, or molecular forms). In addition, it
is important to take into account competitive adsorp-
tion on the wood waste-derived activated carbon. In
particular, heavy metals may form precipitates with
residual phosphate in the activated carbon, while
organic contaminants and natural organic matter may
impose negative effects through direct competition for
sites and pore blockage.
Acknowledgements The authors gratefully acknowledge the
financial support of the University Grants Council for Emerg-
ing High Impact Area (project no. HIA 04/04.EG03).
153
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