Separation and Purification Technology 52 (2007) 403415

Review

Review of modifications of activated carbon for enhancing

contaminant uptakes from aqueous solutions
Chun Yang Yin a, , Mohd Kheireddine Aroua b , Wan Mohd Ashri Wan Daud b
a

Faculty of Chemical Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
Received 18 April 2006; received in revised form 15 June 2006; accepted 15 June 2006

Abstract
Due to its versatility and wide range of applications, activated carbon is widely used as contaminant removal media. Recent research have focused
on enhancing the effectiveness of activated carbon by modifying their specific properties in order to enable the carbon to develop affinity for certain
contaminants. In view of this, a comprehensive list of literatures on chemical, physical and biological modification techniques of activated carbon
pertaining to enhancement of contaminant removal from aqueous solutions was compiled and reviewed. Acidic treatment to introduce acidic
functional groups onto surface of activated carbon was by far, the most studied technique. It was apparent from the literature survey that the
beneficial effects of specific modification techniques on activated carbon adsorption of targeted contaminant species from aqueous solutions were
profound, with some studies reported increase of contaminant uptake factors of more than 2. Concurrently, considerable decreases associated with
certain contaminant uptakes can also occur depending on the technique used.
2006 Elsevier B.V. All rights reserved.
Keywords: Activated carbon modification; Surface functional groups; Impregnation; Contaminant; Aqueous solution

Contents
1.
2.

3.

4.
5.

6.
7.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modification of chemical characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Acidic treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Basic treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Impregnation of foreign material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Recent studies on AC impregnation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. Surfactant modified AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4. Functionalization method of graphitic layers using ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modification of physical characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Removal of organic-based compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2. Adsorption of fungicides and herbicides on modified AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3. Adsorption of dyes on modified AC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bioadsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Corresponding author. Tel.: +603 55436348; fax: +603 55436300.

E-mail address: yinyang@salam.uitm.edu.my (C.Y. Yin).

1383-5866/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.06.009

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C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

1. Introduction
Activated carbon (AC) has been proven to be an effective
adsorbent for the removal of a wide variety of organic and inorganic pollutants dissolved in aqueous media, or from gaseous
environment. It is a widely used adsorbent in the treatment of
wastewaters due to its exceptionally high surface areas which
range from 500 to 1500 m2 g1 , well-developed internal microporosity structure as well as the presence of a wide spectrum of
surface functional groups [1]. As an inert porous carrier material,
it is capable of distributing chemicals on its large hydrophobic internal surface, thus making them accessible to reactants
[2]. While the effectiveness of ACs to act as adsorbents for a
wide range of contaminants is well noted [3,4] more and more
research on AC modification are gaining prominence due to the
need to enable ACs to develop affinity for certain contaminants
to cater for their removal from varying types of wastewater in
the industries.
It is, therefore, essential to understand the various factors
that influence the adsorption capacity of AC prior to their modification so that it can be tailored to their specific physical and
chemical attributes to enhance their affinities toward metal, inorganic and/or organic species present in aqueous solutions. These
factors include specific surface area, pore-size distribution, pore
volume and presence of surface functional groups. Generally,
the adsorption capacity increases with specific surface area due
to the availability of adsorption site while pore size, and micropore distribution are closely related to the composition of the AC,
the type of raw material used, the degree of activation during
production stage and the frequency of regeneration [5]. Recent
research have placed emphasis on modifying these physical and
chemical attributes and this paper aims to review and summarize the various AC modification techniques and their effects on
adsorption of chemical species from aqueous solutions. In order
to facilitate a more focused discussion, only studies on modification of AC in granular or powdered form were reviewed.
Also, it should be noted that the term modification in this paper

Fig. 1. Categories of activated carbon modification techniques.

represents treatment applied to as-received commercial AC or

carbonaceous materials after activation. Studies on activation of
carbonized material that incorporated modifying chemicals are
not presented. Based on extensive literature reviews, the authors
have categorized the techniques into three broad groups, namely,
modification of chemical, physical and biological characteristics which are further subdivided into their pertinent treatment
techniques (Fig. 1). These techniques were intended to significantly alter a characteristic and not two or more characteristics
concurrently, even though in actual fact, all treatment effected
to AC to modify a single characteristic may cause unintended
minor alteration in other characteristics. Table 1 lists and compares the advantages and disadvantages of existing modification
techniques with regards to technical aspects which are further
elucidated in the following sections. While these characteristics
are reviewed separately as reflected by numerous AC modification research, it should be noted that there were also research
with the direct intention of significantly modifying two or more
characteristic and that the techniques reviewed are not intended
to be exhaustive. For information pertaining to detailed experimental methodology and conditions, readers are referred to the
full articles listed in the references.
2. Modication of chemical characteristics
It is an established fact that the AC surface can display acidic,
basic and/or neutral characteristics depending on the presence of
surface functional groups [6]. As such, modification of chemical

Table 1
Technical advantages and disadvantages of existing modification techniques
Modification

Treatment

Advantages

Disadvantages

Chemical characteristics

Acidic

Increases acidic functional groups on AC

surface. Enhances chelation ability with
metal species

May decrease BET surface area and pore

volume

Basic

Enhances uptake of organics

Impregnation of
foreign material

Enhances in-built catalytic oxidation

capability

Has adverse effect on uptake of organics

May give off undesired SO2 (treatment
with H2 SO4 ) or NO2 (treatment with
HNO3 ) gases
May, in some cases, decrease the uptake
of metal ions
May decrease BET surface area and pore
volume

Physical characteristics

Heat

Increases BET surface area and pore

volume

Decreases oxygen surface functional

groups

Biological characteristics

Bioadsorption

Prolongs AC bed life by rapid oxidation

of organics by bacteria before the
material can occupy adsorption sites

Thick biofilm encapsulating AC may

impede diffusion of adsorbate species

C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

characteristics in this paper is taken to mean treatment to modify

the inherent surface functional groups of AC. It has been widely
recognized that chemical species removal by AC adsorption is
due predominantly to the surface complex formation between
the species and the surface functional groups. This is especially
significant in the case of removing inorganics and metals from
aqueous solutions where ACs are generally less effective as compared to removing organic compounds [7]. This is due to the fact
that metals often exist in solution either as ions or as hydrous
ionic complexes.
Yang [4] described the existence of surface functional groups
on the surface of AC as follows: AC can be represented by
a model of a twisted network of defective hexagonal carbon
layer planes (typically 5 nm wide), which are cross-linked by
aliphatic bridging groups. Heteroatoms are incorporated into
the network and are also bound to the periphery of the planes.
The heteroatoms bound to the surfaces assume the character of
the functional groups typically found in aromatic compounds,
and react in similar ways with many reagents. Acidic and basic
functional groups impart a polar character to the AC surface
by interaction with water [6,8,9]. Ionization of these surface
groups depends strongly on the pH of the solution and leads to
a build up of a charged interface between the AC and the bulk
of the solution. The formation of complexes occurs in addition
to simple ionization of surface functional groups by the association/dissociation reaction of protons and hydroxyl ions [9,10].
These theories suggest that the existence of surface functional
groups on the carbon matrix can be manipulated by thermal or
chemical treatments to produce adsorbents that are tailored for
particular functions [1] since addition or reduction of these functional groups imply elevated or reduced ionization capability of
the AC. This results in enhanced or reduced adsorption capacity
and selectivity on a certain adsorbate in the gaseous or liquid
phase [11].
Predominant types of surface functional group on AC are
surface oxygen complexes such as carbonyl groups. The surface
oxygen complexes of AC can be created via two major oxidation methods, namely, dry and wet oxidations. Dry oxidation
is a method involving reactions with oxidizing gases (such as
steam, CO2 , etc.) at high temperatures (>700 C) [12,13] while

405

Fig. 3. Cation exchange mechanism with the carbon surface carboxylic group
[34].

wet oxidation involves reactions between AC surfaces and oxidizing solutions (such as aqueous solutions of HNO3 , H2 O2 ,
NaOCl and ((NH4 )2 S2 O8 ) under relatively mild reaction conditions (20100 C) [13,14]. Table 2 lists the recent research on
modification of carbon surfaces for creation of specific surface
functional groups to enhance removal of chemical species.
2.1. Acidic treatment
Many investigations, with emphasis on metal removal from
aqueous solutions, are directed towards modifying carbon surfaces to increase their acidic surface functional groups [33],
which are types of oxygen complexes. Examples of these acidic
surface functional groups are carboxyl, quinone, carbonyl, lactone, hydroxyl and carboxylic anhydride and they are illustrated
in Fig. 2.
These specific functional groups are essential for the adsorption of heavy metals due to chelating attribute of these groups
where alkaline-earth metal cations can be integrated with the
groups to form complexes as indicated in the following equation [2,22]:
Mn+ + n(COOH) (COO)n M + nH+
The reaction above occurs due to cation exchange mechanism
where the metal cation exchanges site with the hydrogen ion
previously attached as a whole carboxylic group as illustrated
in Fig. 3.
In general, acidic reactions with regards to AC have
been associated with oxide structures, which are part of the

Fig. 2. Simplified schematic of some acidic surface groups bonded to aromatic rings on AC [4].

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C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

chemisorbed oxygen found on all carbon surfaces, which

have been exposed to air or other oxidizing media [35].
In addition to usage of strong acid oxidizers such as nitric
acid, other oxidization agents such as hydrogen peroxide,

oxygen and acetic acid are also used to increase acidic

functional groups albeit exhibiting a lesser effect as indicated in studies by Aggarwal et al. [15] and Hoang et al.
[36].

Table 2
Recent research on modification of carbon surfaces for creation of specific surface functional groups to enhance removal of metal species
Researchers

Type(s) of surface functional

group created

Technique used

Metal species removed

Effect on adsorption capacity

Aggarwal et al. [15]

Weakly acidic and non-acidic

(quinones-postulated)

Oxidization using nitric acid

(solution), ammonium
persulphate (solution),
oxygen gas at 350 C

Cr(III) and Cr(IV)

Ali et al. [16]

Weakly acidic (carboxylic)

Cu2+

Alvarez-Merino et al. [17]

Weakly acidic (carboxyl,

lactone and phenolic)

Goel et al. [18]

Weakly acidic (carboxylic,

lactonic and phenolic) and
sulphur (C S, S O and
SS)
Sulfur-based (CS, SS, C S
and S O)
Weakly acidic

Oxidization using nitric,

hydrofluoric acids
Oxidization using saturated
solution of ammonium
persulphate in 1 M H2 SO4
Treatment using Na2 S

Pb2+

Increased by factors of
approximately 3.7 (HNO3 ),
2.2 ((NH4 )2 S2 O8 ), 1.7 (O2 )
for Cr(III), decreased by
factors of approximately 4.3
(HNO3 ), 2.1 ((NH4 )2 S2 O8 ),
1.6 (O2 ) for Cr(VI)
Increased by factors of 1.4
(for pH 3) and 1.2 (for pH 5)
Increased by factors of 1.7
(without presence of KNO3 )
and 1.9 (with KNO3 )
Increased by a factor of 1.35

Heat treatment in H2 S

Mercury (as HgCl2 )

Oxidization using nitric acid,

ammonium persulphate
Oxidization using nitric acid

Cu2+

Loading of ZnO on AC

Pb2+

Helium-oxygen plasma
treatment to produce oxygen
resulting in creation of
surface functional groups
Oxidization using nitric acid
on two commercial AC (BPL
and WPL)
Treatment at ambient
temperature and 900 C in
SO2 and/or H2 S
Treatment using hydrochloric
acid
Ozonation at 298 K and 1 atm

Fe2+

Gomez-Serrano et al. [19]

Goyal et al. [20]
Jia and Thomas [21]
Kikuchi et al. [22]
Lee et al. [23]

Weakly acidic (carboxylic,

quinones and phenolic)
Hydroxyl (on ZnO as
impregnated on AC)
Weakly acidic (carboxylic
and carbonyl)

Li et al. [24]

Weakly acidic (carboxylic,

lactone and carbonyl)

Macias-Garcia et al. [25]

Sulfur surface complexes

Park and Jang [26]

Weakly acidic

Rivera-Utrilla and
Sanchez-Polo [27]

Weakly acidic (carboxylic,

lactonic, phenolic and
carbonic)
Not specified/identified,
possibly acidic
Not specified/identified,
possibly acidic
Not specified/identified,
possibly acidic

Tai et al. [28]

Ucer et al. [29]
Ucer et al. [30]

Vladimir and Malik [31]

Yantasee et al. [32]

Zhao et al. [11]

Weakly acidic (carboxylic,

lactonic, phenolic and
carbonic)
Amine (NH2 )

Weakly acidic (carboxylic,

lactonic and phenolic)

Zn2+

Cd2+

Elemental mercury (Hg )

Cd2+

Increased by a factor of 1.4

(approximation)
Increased by a factor of 3.0
(approximation)
Increased by a factor of up to
34 (approximation)
Increased by a factor of up to
4.5
Increased by a factor of 3.8

Increased by a factor of 38.0

(BPL). Decreased by a factor
of 0.76 (WPL)
Increased by 70.3% (heat
treatment at 900 C in SO2 )

Cr(VI)

Increased by a factor of 1.7

Cr(III)

Increased by a factor of up to
2.6

Oxidation using nitric acid or

air
Treatment using tannic acid

Cu2+ , Ni2+ and Zn2+

Treatment using tannic acid

Cu2+ , Cd2+ , Zn2+ and Fe3+

Oxidization using nitric acid

Cu2+ , Mn2+ , Ni2+ and Zn2+

Increased by 50 times (for

Cu2+ )
Increased by a factor of
approximately 1.2 (20%)
Increased by 23.5% (Cu2+ ),
17.8% (Cd2+ ), 14.0% (Zn2+ )
and 17.9% (Fe3+ )
Increased by a factor of up to
4 (for Cu2+ )

Electrophilic aromatic
substitution of nitro groups
onto AC followed by
reduction of NO2 to NH2
Oxidization using HNO3 ,
H2 O2 or Fe(NO3 )3 followed
by heat treatment

Cu2+ , Pb2+ , Cu2+ and Ni2+

Fe3+

Cr(VI)

Distribution coefficient, Kd
was increased by a factor up
to 140 (for Cu2+ ) and 4 (for
Pb2+ )
Increased by a factor of up to
1.4

C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

While acidic treatment of AC displays beneficial effects on

adsorption of metal ions, it is, however, detrimental to the physical aspects of AC such as BET surface area and pore volume. In
most cases, treatment with oxidizing agents produces modification of the textural characteristics of the original AC, which can
be a drawback in carbon materials with a narrow microporosity
or a well-defined porosity [37]. Maroto-Valer et al. [38] reported
that treatment with nitric acid reduced the BET surface area and
total pore volume by 9.2% and 8.8%, respectively in which they
postulated partial or complete blockage with additional oxygen
complexes as the reason for the reduction. This effect was also
reported by Rios et al. [34] and Aburub and Wurster [39] where
AC treated with concentrated nitric acid and equimolar mixture
of nitric/sulfuric acid for 38 and 24 h, respectively, experienced
reduced BET surface area by 33.7% and 6.5%. They suggested
that the reduction may be attributed to destruction of porous
structure within AC as caused by severe nitric acid oxidation.
As conventional treatments using oxidizing agents in a carrier medium can reduce the AC surface area, researchers are
looking into alternative methods to increase acidic surface functional groups without the undesirable effect of pore blockage.
One promising method is oxygen plasma treatment as initially
studied by Garcia et al. [40]. Their findings indicated that the
method was capable of modifying the external surface of AC
with formation of acidic functional groups, while the internal
surface was practically unaffected. There is a general hypothesis
that plasma species do not penetrate into the internal structure
of the carbon because of the high reactivity of mono-oxygen
radicals, which etch the surface without affecting microporosity. This hypothesis was supported by a study conducted by
Domingo-Garcia et al. [37] where they found out that chemical surface groups introduced by oxygen plasma treatment are
on the external surface, whereas those produced by treatments
in aqueous solutions of (NH4 )2 S2 O8 and H2 O2 are located on
both the external and internal surface. In another study, Lee et
al. [23] treated AC with heliumoxygen plasma generated in a
dielectric-barrier discharge reactor. In that study, it was found
out that even though adsorbability of Fe2+ was increased by 3.8
after treatment, the BET surface area was nonetheless, reduced
by as much as 22.5% due to destruction of pore walls by gasification of carbon and pore blockage. These two separate plasma
treatment experiments indicate that not all plasma treatments can
provide favorable treatment outcomes with regards to textural
characteristic which may change as a result of different experiment designs and therefore a more concerted focus on improving
this shortcoming is desirable in future studies.
While acidic treatment is favorable for enhancing uptakes
of metal ions, it impairs uptake of organics (especially phenol)
from aqueous solution. A postulate as to why acidic treatment is
detrimental to uptake of organics such as phenol is that treatment
with acids can lead to destruction of existing basic groups on the
surface of AC. This hypothesis was put forward in a study conducted by Santiago et al. [41] where AC treated with nitric acid
destroyed basic sites considerably and subsequently decreased
the uptake of phenol from aqueous solution. In that study, it
was believed that destruction of basic sites eventually led to
reduced catalytic activity of phenol and this trend is consistent

407

with dilute phenol solutions. However, at high phenol concentrations, several authors have observed the opposite behaviour.
As a case in point, Terzyk et al. [42] (along with references cited)
observed an increase in phenol uptake at high phenol concentrations after treatment with HNO3 . This effect was attributed to
the prevalence of adsorbateadsorbate interactions in the high
phenol concentration zone, which could even be enhanced by
the presence of oxygen groups [41].
2.2. Basic treatment
There were studies carried out to determine the effect of basic
treatment of ACs on metal adsorption capacity. Park and Jang
[26] reported that adsorption of Cr(VI) reduced by a factor of
about 2 at a contact time between NaOH-treated AC and the
metal ion at over 170 min. They suggested that this reduction
may be due to the decrease of specific surface area or micropore
volume. Under alkaline environment (basic components in aqueous solutions), it is expected that OH ion will react with the
surface functional groups of AC. This was verified in the study
conducted by Chiang et al. [43] where AC treated with NaOH
showed major increase in concentration of phenolic functional
groups on the surface.
Review on studies pertaining to basic treatment seems to
indicate that basic treatment is beneficial in enhancing uptake
of organic-based substances from aqueous solution. Przepiorski
[44] studied the influence of AC treatment with gaseous ammonia from 400 to 800 C on adsorption toward phenol from aqueous solution. It was found that the adsorption capacity toward
phenol was enhanced by as much as 29% at the optimum treatment temperature at 700 C. In a separate study, Chen et al.
[45,46] investigated the modification of AC surface with ammonia thermal treatment to achieve higher adsorption capacity for
perchlorate from aqueous solution, without undermining the
pore structure that was beneficial to the perchlorate adsorption.
They reported that the most favorable improvement occurred
between temperatures of 650 and 700 C in which a four-fold
increase in perchlorate adsorption.
3. Impregnation of foreign material
3.1. Denition
It is generally accepted that the adsorptive capacity of activated carbon to remove hazardous substances can be substantially boosted by impregnation with suitable chemicals [47].
The term impregnation, however, is rather vaguely defined
by researchers. Henning and Schafer [48] defined impregnation as fine distribution of chemicals on the internal surface of
AC. However, there are researchers [49,50] that associate AC
treatment with acids or bases to increase acidic/basic surface
functional groups as impregnation techniques. In this context,
the authors construe that impregnation methods exclude acidic
or basic treatment in which the effect of impregnate AC with
substance(s) that generally, does not exert significant influence
on pH of surface of AC. These substances can be metals or
polymeric materials, which are generally not associated with

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C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

significant pH changes. There are also researchers who used

the term immobilisation [2] and coating [51] which, in the
authors opinion, denoted similar techniques as impregnation.
As chemical treatment has already been discussed, we will hereafter present review on impregnation based on the aforestated
definition, which excludes acidic/basic treatment.
Henning and Schafer [48] specified that the three main reasons for impregnating AC are to optimise the existing properties
of AC via enhancement of its in-built catalytic oxidation capability, promote synergism between AC and impregnating agent
to augment adsorption capacity as well as to boost the capacity of AC as inert porous carrier. The last reason is particularly
significant as impregnated material can be distributed on large
internal surface area, making them accessible to incoming reactants. They further elucidated general processing methods to
manufacture industrial-grade impregnated AC where virgin AC
are sprayed with impregnating material in a rotary kiln or fluidized bed. In some applications, the impregnating material are
present in forms of hydroxides, carbonates, chromates or nitrates
by which the impregnated AC must be subjected to thermal after
treatment at elevated temperatures (150200 C) to decompose
the anions.
3.2. Recent studies on AC impregnation
Monser and Adhoum [2,7,47] are active researchers in investigating the impregnation of AC with foreign materials. In 2002,
they reported their study on adsorption of copper(II), zinc(II),
chromium(VI) and cyanide (CN ) ions onto the surface of
AC immobilized with tetrabutyl ammonium (TBA) and sodium
diethyl dithiocarbamate (SDDC) [2]. It was found that the TBAimmobilized AC had an effective removal capacity of approximately five times that of virgin AC while the SDDC-immobilized
AC had an effective removal capacity for copper(II) (four times),
zinc(II) (four times), chromium(VI) (two times) greater than
virgin AC. It was reported that the overall ion removal was a
combination adsorption capacity of the virgin AC and the extent
of exchange of ions with the immobilizing agent molecules
adsorbed on the AC. In the same year, they also presented their
findings on the efficiency of silver and/or nickel impregnated
AC for removing cyanide from aqueous solutions [7]. It was
found that silver impregnated AC had a cyanide removal capacity of nearly two times that of nickel-impregnated AC and of
four times that of untreated AC. They concluded that uptake of
cyanide on impregnated AC could be attributed to either adsorption, exchange with positively charged groups existed in the
surface of AC and/or complexation in the forms of Ag(CN)2
and Ni(CN)4 2 . Recently, in 2004, they investigated the efficiency of AC impregnated with tetrabutylammonium (TBA) and
copper in the removal of phthalate from industrial wastewater
[47]. Their result indicated that copper impregnated AC had a
removal capacity of nearly two times that of untreated AC while
TBA impregnated AC enhanced the phthalate adsorption capacity with a factor of 1.7 times that of untreated AC.
Impregnation of AC with metals to improve its adsorptive
capacity was also of interest to other researchers. Huang and
Vane [52] evaluated the effectiveness of pretreating AC with iron

salt solution to improve its arsenic removal capacity in which a

10-fold increase, over the untreated AC, can be achieved under
optimal pre-treatment procedure. They found out that enhancement in arsenic removal were attributed to adsorption of ferrous
ions and formation of arsenate complexes. Leyva Ramos et al.
[53] investigated the efficiency of aluminium-impregnated AC
for removing fluoride from aqueous solutions which was prepared by impregnation with an aluminium nitrate solution at a
fixed pH, followed by calcinations in an inert environment at
temperatures above 300 C. They found that the impregnated
AC had a fluoride adsorption capacity of three to five times that
of virgin AC and that the pH of solution affected the adsorption
of aluminium onto AC and the optimum impregnating pH was
determined to be 3.5. At pH below 3.0, the aluminium did not
adsorb onto the AC and at pH above 4.0, impregnation was not
possible due to precipitation of aluminium. In a separate study,
Dastgheib et al. [54] investigated impregnation of AC with iron
to enhance removal of dissolved natural organic matter (DOM)
from natural waters. They reported that iron impregnation followed by high temperature ammonia treatment enhanced the
DOM uptake about 50120% (on a mass basis). Ghorishi and
Keeney [55] investigated the effect of impregnating AC with
Cl (hydrogen chloride) on adsorption of elemental mercury
and reported that the adsorption capacity increases by factors
from 2 to 3 over virgin AC in fixed-bed capture of these mercury species.
3.3. Surfactant modied AC
There were numerous studies on adsorption of both anionic
and cationic surfactants onto AC [5660] in which comprehensive elucidation of adsorption mechanisms was the primary objective. A general consensus among the studies was
that hydrophobic interactions between surfactants and AC were
the primary mechanism that govern surfactant adsorption onto
AC. Conversely, direct application surfactant-modified AC in
removal of other contaminants from aqeuous solutions was comparatively rare. As such, the study conducted by Parette and Cannon [61] represented a rather recent approach in AC modification
in which granular AC was preloaded with cationic surfactants to
enhance removal of ppb levels of perchlorate from groundwater
in small-scale column tests. They reported that AC tailored with
cetyltrimethylammonium chloride (CTAC) was able to increase
the time to perchlorate breakthrough by 30 times over virgin
AC when operated at a simulated 2022 min empty bed contact
time.
3.4. Functionalization method of graphitic layers using
ligands
A novel and unique functionalization method of graphitic
layers of AC was recently conceived by Garcia-Martin et al.
[62] where N-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxo2-pyrimidinyl)-l-lysine (AMNLY) and N-(4-amino-1,6-dihydro-1-methyl-5-nitroso-6-oxopyrimidin-2-yl)-N -[bis(2-aminoethyl)]ethylenediamine (AMNET) were supported (or
impregnated) on basic AC with low oxygen and nitrogen con-

C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

tents which was subsequently used for removing chromate(VI)

anion from aqueous solution. They postulated that impregnation
of AMNLY and AMNET would enhance the -electron density
in the graphene layers, so favoring the adsorptive capacity
of the receptors, via dispersive and/or donoracceptor
interactions between the pyrimidine moiety of the receptors and
the basic arene centers of the graphene layers. It was found that
the adsorption of Cr(VI) on the compound AMNET supported
on the AC was approximately increased by a factor of 1.7 as
compared to virgin AC. They attributed the enhancement of
adsorptive capacity to the stronger and selective interaction
of chromate anions with the NH3 + functions existing in this
compound once firmly anchored at the arene centers. In contrast,
impregnation of AMNLY reduced the uptake of Cr(VI) by
75% and this was due to prevention of interaction between the
chromate anion and NH3 + group existing at the amino acid
moiety as a direct result of proximity of a carboxylate center
that carried a negative charge.

409

of AC with no appreciable reduction in other ranges of pore

size.
A significant drawback of thermal treatment of AC is that
oxygen surface functional groups (which are thermally unstable)
can be destroyed at high temperatures [64]. As such, destruction
of these groups may indicate lesser capacity to form chelates
with metal species and thus reduces their uptakes onto the modified AC. However, carbons generally acquire a basic character
after high temperature (above 700 C) heat treatment in an inert
atmosphere [6,9]. Thus, it can be argued that heat-treated AC is
generally favourable for enhancing adsorption of organic compounds from aqueous solutions since basic characteristic of the
AC is amplified at high temperature conditions. This conclusion is further supported by findings of various research listed
in Table 3.
5. Removal of organic-based compounds
5.1. Mechanism

4. Modication of physical characteristics

All AC modification techniques sometimes constitute at
minor changes in its physical characteristics (as exemplified
by acidic treatment). However, there are research specifically
aimed at significantly modifying the physical characteristics
such as BET surface area and pore volume so that magnitude of these characteristics can be increased to enhance contaminant removal, especially in the case of organic adsorptions. It should be noted that the majority of these studies utilized thermal treatment as a sole technique to achieve
the required physical characteristic enhancements. However,
there are also other distinctive treatment techniques utilized by
researchers to gain similar effects such as the one conducted
by Torregrosa-Macia et al. [63] where carbohydrates (d-glucose
and d-glucosamine) were impregnated into AC prior to carbonisation at 1173 K and activation with CO2 . It was reported that
this technique produced an increase in the macropore volume

It is of common knowledge that AC is more effective in

removing organics than metal species from aqueous solutions.
However, the specific mechanism by which the adsorption of
many organic compounds takes place on AC remains ambiguous [69]. As such, numerous researchers [6972] have attempted
to modify AC either by chemical or thermal treatment to provide
an avenue where this mechanism can be determined experimentally. There are several factors that play significant roles
in determining the adsorbability of organics onto AC such as
the presence of surface functional groups. It is widely recognized that acid oxygen-containing surface groups decrease the
adsorption of organic compounds in aqueous solution, while
their absence favors adsorption, independently of the polarity of
the compounds [69,7380]. As such, while at the elevated concentrations of weakly acidic functional groups on the surface of
AC augment their metal adsorptive capacities, the presence of
these functional groups seems to be unfavourable for adsorption

Table 3
Recent techniques used to significantly modify physical characteristics of AC
Researchers

Technique(s) used

Physical characteristic(s) improved

Changes in physical
characteristic(s)

Chemical species removed as

enhanced by modification

Attia et al.[64]

Heat treatment at 400 and

600 C

Specific surface area and total pore

volume

Acid dyes (acid red 73 and

acid yellow 23)

Chiang et al. [65]

Ozonation

Chingombe et al. [66]

Heat treatment via

annealing at 1173 K in a
quartz reactor
Heat treatment by steam
or methane and stream at
1000 C
Heat treatment at 350 C

Specific surface area (micropore

size) and total pore volume, total
pore volume (+9.0%)
Specific surface area (micropore size)

Bet surface area (+7.2% for

400 C; +6.6% for 600 C),
total pore volume (+ 6.8% for
400 C; +8.6% for 600 C)
Bet surface area (+8.7%)

Rangal-Mendez and
Cannon [67]
Yoo et al. [68]

Micropore and mesopore volumes

Specific surface area (micropore

size) and total pore volume

Bet surface area (+21.5%)

Micropore volume
(+5070%), mesopore
volume (+65-90%)
Bet surface area (+ up to
19.4%), total pore volume (+
up to 19.2%)

Methylethylketone and
benzene
Herbicides
(2,4-dichlorophenoxyacetic
acid and benzolin)
2-Methylisoborneol

Maltooligosaccharide
(carbohydrate)

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C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

Table 4
Recent research on adsorption of aromatic compounds on modified ACs
Researchers

Aromatic compound(s) removed

Technique(s) used
25 C

Effect on adsorption capacity

Alvarez et al. [75]

Phenol, p-nitrophenol, p-chlorophenol

Ozonation at

Haydar et al. [70]

p-nitrophenol

Oxidization using HNO3 , NaOCl

Nouri and
Haghseresht [85]

p-nitrophenol

Treatment using H2 , H2 SO4 or urea

Przepiorski [44]

Phenol

Villacanas et al. [69]

Phenol, aniline and nitrobenzene

Treatment with gaseous ammonia

from 400 to 800 C
Oxidation using HNO3 following by
heat treatment to 700 C under H2

of phenolic compounds. This was evident in a study conducted

by Leng and Pinto [81] where increased concentrations of surface carboxylic groups were found to decrease physisorption
of phenol, possibly due to the increase in water adsorption and
weaker dispersion interactions with basal plane carbons. Their
research, to a certain extent, reinforced an earlier finding by
Mahajan et al. [82] in which the latter argued that phenol adsorption increased when more -electrons were available on the
basal plane surfaces of the crystallites and reduced by oxygen
complexes on edge sites. Recent studies [73,74] also justified
the aforementioned studies where it was concluded that water
is mainly adsorbed on the surface establishing hydrogen bonds
with the oxygen groups, which can produce clusters that may
block the passage of the adsorptive molecules into the micropores as well as the presence of these oxygen groups reduced
adsorptive capacity by localizing free electrons of the carbon
basal plane. Other studies [83,84] suggested the adsorption of
some organics on AC was generally determined by dispersion interaction between the electrons of AC surface and the
aromatic ring of the adsorbate and by electrostatic interactions
between ions attached to the ring and the surface charge of AC.
Research on removal of organics from aqueous solutions onto
AC are more focused on aromatic compounds such as phenol and
benzene-derivatives are frequently used as model compounds
for aromaticorganic contaminants in wastewaters. The possible reason for this is that phenolic and benzene-derivatives
compounds are, arguably, the predominant organics in a wide
spectrum of industrial wastewaters ranging from pharmaceutical to oil refineries as well as pesticides. Numerous factors
have been known to have significant effects on the adsorption of
phenol, namely, pH of solution, type of carbon, carbon surface
functionalities, oxygen availability, mineral contents and addition of electrolytes [4]. Table 4 summarizes the recent research
on adsorption of aromatic compounds on modified ACs, which

at

100 C

Ozonation at 25 C decreased
adsorption capacity for all
compounds while ozonation at 25 C
increased adsorption capacity for
phenol and p-nitrophenol
Decreased by approximately 20%
(both HNO3 and NaOCl)
At pH 2: increased by 1.3%(H2 ),
decreased by 3.8% (urea) and 16.3%
(H2 SO4 ). At pH 12: increased by
22.9%(H2 ) and 6.3% (urea),
decreased by 22.9% (H2 SO4 )
Increased by 29% at the optimum
treatment temperature at 700 C
At pH 2: increased by approximately
40% (nitrobenzene), marginal
fluctuations for phenol and aniline.
At pH 12: increased by
approximately 38% (aniline) and
43% (nitrobenzene). Marginal
fluctuations for phenol

include techniques that enhanced or reduced the uptakes of

aromatic compounds. It should be noted that biological modification of AC for removal of aromatic compounds are discussed
separately in Section 6 and therefore excluded from this list.
5.2. Adsorption of fungicides and herbicides on modied
AC
In addition to removal of organics from industrial wastewaters, there were also applications of modified AC in removing
agricultural-based herbicides as well as fungicides from aqueous solutions. Chingombe et al. [66] reported that heat treatment via annealing the AC in a quartz reactor increased the
micropore content and hence the BET surface area from 790 to
960 m2 g1 which was attributed to the loss of oxygen containing functional groups. As such, it was found that the uptakes of
2,4-dichlorophenoxyacetic acid and benzolin (both organic herbicides) onto the heat-treated AC were increased. Adam et al.
[86] found out that basic treatment of AC with NaOH increased
the adsorption of propiconazole (a type of fungicide) while AC
treated with HNO3 and H2 O2 had propiconazole removal capacities lesser than untreated AC. They surmised that the presence
of oxygen-containing functional groups, which are electronwithdrawing groups, had a negative effect on the adsorption of
propiconazole, thus decreasing the adsorption potential for the
pollutant.
While the presence of oxygen-containing functional groups
have a somewhat significant effect on adsorption of some organics such as propiconazole, adsorption of other organic compounds are not influenced by acidic treatment of AC. Yoo et al.
[68] reported that AC treated with nitric acid introduced more
carboxylic groups on its surface but the treatment did not affect
much on the adsorption rate of oligosaccharides (carbohydrate
compounds) from aqueous solution.

C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

5.3. Adsorption of dyes on modied AC

Utilization of modified AC for removal of industrial dyes
from aqueous solutions was the subject of study for several
researchers. Faria et al. [87] studied the effect of AC oxidized
with 6 M nitric acid and 10 M hydrogen peroxide as well as
heat treatment at 700 C in H2 or N2 on adsorption capacity
of anionic and cationic dyes where they found out that thermal
treatment with H2 is the most effective technique for optimising
the removal of the dyes. Orfao et al. [88] investigated adsorption
of two textile reactive dyes, namely, Rifafix Red 3BN and C.I.
reactive red 241 on acidic as well as thermal treated AC. They
reported that irrespective of the solution pH, the adsorption of
reactive dye on basic AC (thermal treated) is favored, mainly
due to the dispersive interactions between the localized electrons in the carbon basal planes and the free electrons in the dye
molecules while AC treated with nitric acid were found to be
detrimental to the adsorption of reactive dyes due to the repulsive forces developed between acid oxygenated groups and dye
molecules. However, not all dyes experience increased uptake
on thermal treated AC as reported by Attia et al. [64] where
heated AC at either 400 or 600 C exhibited increased uptakes
of Acid Red 73, Acid Yellow 23 but reduced uptake of Acid
Blue 74.
As dyes are predominantly, if not entirely, consisted of
organic components, it can be hypothesized that increased acidic
functional groups on AC due to acidic treatment impair uptake of
dyes. This notion is reinforced by studies conducted by Valdes et
al. [89] and Wang et al. [90]. Valdes et al. [89] reported that prolonged exposure of AC to ozone gas (oxidiser) transformed basic
sites into acid sites which reduced the capacity of AC to adsorb
methylene blue (a type of textile dye). They attributed this phenomenon to extraction of electrons from band of AC by oxygen
which weakened the dispersion forces between the electron
system of the aromatic ring of methylene blue and the band
of the graphitic planes of the AC. This effect was also reported
by Wang et al. [90] where they concluded that AC treated with
2 M hydrochloric and nitric acids resulted in reduced uptakes
of methylene blue by up to 10.6% (HCl) and 13.5% (HNO3 ).

411

They surmised that the acidic treatment removed the hydroxide

groups and produced acidic oxygen functional groups on the carbon surface, which extracted electrons from the band of the
carbon, reducing the interactions between the methylene blue
molecules and carbon. They also postulated that higher adsorption of methylene blue on HCL-treated AC than of HNO3 -treated
AC was due to the adsorption of negative ions (Cl ) on the
positive sites on the surface, so that the surface becomes more
negatively charged, facilitating adsorption of positive charged
molecules of methylene blue. While these two studies on AC
seemed to indicate detrimental effect of AC oxidation on uptake
of methylene blue, there was a finding by Jiang et al. [13] which
reported that AC oxidation using heated concentrated H2 SO4
solution (150270 C) in a flask fitted with a water reflux condenser resulted in higher adsorption capacities of methylene
blue. These contrasting results were perhaps, due to the heated
condition of the oxidation solution, which increased the mesopore volumes of AC by a factor of 4.2 (at 270 C) as opposed to
the relatively unaltered or reduced physical attributes of AC in
studies done by Valdes et al. [89] and Wang et al. [90].
6. Bioadsorption
Both natural and residual waters contain microorganisms
that can be adsorbed on AC during water treatment, especially
sewage treatment due to its rough and fissured surface on which
microorganisms can settle and colonize easily [91]. Adsorption
of microorganism, intentionally or unintentionally, onto AC has
been the subject of research for the past several decades. Most
research on bioadsorption on AC are directed at removal of readily biodegradable compounds that have low molecular weight
[92] such as phenol from aqueous solutions. Bioadsorption can
give rise to the formation of bacteria colonies on the AC [9395]
due to (1) the adsorptive properties of carbon, which produce an
increase in the concentration of nutrients and oxygen as well
as the removal of disinfectant compounds; (2) the porous structure of the carbon particles, which provides the bacteria with
a protective environment; (3) the presence of a large variety of
functional groups on the surface of the carbon, which enhances

Table 5
Types of microorganism adsorbed on AC and chemical species removed
Researchers

Microorganism(s) adsorbed

Chemical species removed

Abu-Salah et al. [91]

Annadurai et al. [100]
Choi et al. [101]

Pseudomonas sp., Comamonas testosterone, Pseudomonas aeruginosa

Pseudomonas pictorum
Pseudomonas aeruginosa, Pseudomonas uorescens and Pseudomonas
putida (mixed culture)
Pseudomonas putida
Rhodococcus rhodochrous and Acinetobacter junii)
Rhodococcus rhodochrous
Escherichia coli
Pseudomonas putida and Cryptococcus elinovii (mixed culture)
Rhodococcus sp.
Escherichia coli
Pseudomonas sp.
Xanthobacter autotrophicus and Pseudomonas sp.
Pseudomonas putida
Arthrobacter globiformis and Comamonas testosterone

Phenol, p-nitrophenol, phenanthrene

Phenol
Benzene

Ehrhardt and Rehm [102]

Feakin et al. [103]
Jones et al. [104]
Moreno-Castilla et al. [98]
Morsen and Rehm [105]
Pai et al. [106]
Rivera-Utrilla et al. [96]
Scott et al. [107]
Stucki and Thuer [108]
Walker and Weatherley [92]
Zhi et al. [109]

Phenol
Atrazine, simazine
Atrazine
Nitrite
Phenol
Phenol
Lead
Copper, zinc, nickel, cadmium, atrazine
1,2 dichloroethane
Acid dyes
Naphthalene-2-sulfonic acid

412

C.Y. Yin et al. / Separation and Purication Technology 52 (2007) 403415

the adhesion of the microorganisms. As a result, the bacteria

adsorbed onto AC are highly resistant to disinfectants [96].
However, adsorption of these microorganisms onto AC can be
beneficial in several ways. One of such beneficial effect is that in
the biological AC process, carbon-bed life can be prolonged by
converting a portion of recalcitrant organics to biodegradable
organics by preozonation. The attached microorganisms then
convert the biodegradable portion to biomass, carbon dioxide
and waste products before this material can occupy adsorption
sites on the AC [3,96]. Moreover, the biofilm formed on AC can
change the surface charge density of the AC, mainly increasing
its negative value, which could enhance its adsorption capacity against some positively charged pollutant species, such as
most of the heavy metals [96,97]. This theory was further investigated by Moreno-Castilla et al. [98] in which they found out
that pH of the point of zero charge (pHPZC ) of activated carbonbacterial complex of Escherichia coli was decreased due to the
lower pHPZC of the bacteria. As such, it affected the electrostatic
interaction between ionic species in solution and the activated
carbon bacterial complex. However, there is one distinct disadvantage of bioadsorption, which is the formation of biofilm that
may have an encapsulating effect on AC. If this biofilm becomes
too thick, the adsorbate species may encounter difficulty in diffusing through the biofilm and thus reduces adsorption rate [99].
Table 5 lists the recent research on bioadsorption by types of
microorganism adsorbed and chemical species removed.
7. Concluding remarks
In this review, a wide spectrum of AC modification techniques along with their advantages and disadvantages have been
presented. Modification of AC via acidic treatment was by far,
the most studied technique, perhaps attributed to its simplicity,
availability of oxidizing agents (mostly as aqueous solutions)
and the established nature of the technique that has been used
for past several decades. Generally, oxidative treatment of AC is
very favorable for enhancing uptakes of metal ions while thermal
treatment of AC is generally favourable for enhancing adsorption of organic compounds from aqueous solutions since basic
characteristic of the AC is amplified at high temperature conditions. From the literature survey, it was evident that the effects of
specific modification techniques on AC adsorption of targeted
contaminant species from aqueous solutions were generally profound, albeit some effects may be detrimental to uptakes of
certain chemical species. Treatment to improve the chemical
characteristics of AC may, on the downside, adversely affect its
physical characteristics or vice versa. It is, therefore, the opinion
of the authors that novel and promising modification techniques
such as plasma treatment be developed further as these techniques enhance the chemical characteristics of AC while at the
same time ensuring that the techniques do not compromise its
physical characteristics. The relatively untapped application of
surfactant-tailored AC to remove contaminants from aqueous
solutions should also be studied further as knowledge in this field
is presently lacking. The simultaneous enhanced and reduced
uptake effects of groups of contaminant such as metals and
organics due to the aforesaid modification techniques present an

attractive avenue to increase selectivity of AC and subsequent

provide better optimisation in tertiary wastewater treatment
systems.
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