Journal of Analytical and Applied Pyrolysis 89 (2010) 143151

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Review

A review on surface modication of activated carbon for carbon dioxide

adsorption
Mohammad Saleh Shafeeyan, Wan Mohd Ashri Wan Daud , Amirhossein Houshmand, Ahmad Shamiri
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

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

Article history: The inuence of surface modication of activated carbon with gaseous ammonia on adsorption prop-
Received 29 March 2010 erties toward carbon dioxide (CO2 ) was reviewed. It was apparent from the literature survey that the
Accepted 19 July 2010 surface chemistry of activated carbon strongly affects the adsorption capacity. In general, CO2 adsorption
Available online 19 August 2010
capacity of activated carbon can be increased by the introduction of basic nitrogen functionalities into the
carbon surface. Accordingly, in this review the impact of changes in surface chemistry and formation of
Keywords:
specic surface groups on adsorption properties of activated carbon were studied. Two different methods,
Activated carbon
heat treatment and ammonia treatment (amination) for producing activated carbon with basic surface
Surface properties
Amination
were compared. Amination was found to be suitable modication technique for obtaining efcient CO2
CO2 adsorption adsorbents. Finally, the common characterization methods were also mentioned.
Characterization 2010 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2. Activated carbon surface chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2.1. Acidic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2.2. Basic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3. Preparation of activated carbon with basic surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.1. Heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.2. Ammonia treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4. Characterization of activated carbon surface chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
4.1. Chemical titration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
4.2. Temperature programmed desorption (TPD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
4.3. X-ray photoelectron spectroscopy (XPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
4.4. Fourier Transform Infrared Spectroscopy (FT-IR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150

1. Introduction CO2 capture and sequestration from point source emissions

has been recognized as a potential way to stabilize CO2 in
Global warming is widely attributed to an increase in atmo- the atmosphere [35]. Various processes, such as liquid solvent
spheric level of greenhouse gases. Carbon dioxide (CO2 ) is absorption, cryogenic techniques, membrane separation, solid
considered as the most important greenhouse gas with the sorbents, and pressure (and/or temperature) swing adsorption
largest impact on climate change [1]. The gradual increase in have been proposed for the separation and recovery of CO2
the atmospheric concentration of CO2 due to burning of fos- emitted by power plants [611]. To date, most of commercial
sil fuels is becoming a serious environmental problem [2]. CO2 capture plants use amine-based processes and wet scrub-
bing systems [12], but they are energy intensive due to the
large amount of water needed in these systems [2,3]. Other
Corresponding author. Tel.: +60 3 79675297; fax: +60 3 79675319. problems associated with these processes are amine degrada-
E-mail addresses: ms.shafeeyan@gmail.com (M.S. Shafeeyan), ashri@um.edu.my tion by oxidation leading to corrosion of process equipments
(W.M.A.W. Daud). [1315].

0165-2370/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2010.07.006
144 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151
The goal in reducing CO2 emissions on an industrial scale is
the development of cost-effective techniques for the separation
and capture of CO2 [16]. Adsorption is considered as one of the
potential options because of the low energy requirement, cost
advantage, and ease of applicability over a relatively wide range
of temperatures and pressures [2,17]. However, the success of this
approach is dependent on the development of easily regenerable
and durable adsorbent with a high CO2 selectivity and adsorption
capacity [4,18]. Zeolites have shown promising results for separat-
ing CO2 from gas mixtures. However, the presence of water inhibits
the CO2 adsorption capacity of zeolites [1921]. Activated carbons
are being proposed as suitable candidates for CO2 capture: they
do not require any moisture removal, present a high CO2 adsorp-
tion capacity at ambient pressure and, moreover, they are easy to
regenerate [22]. It has been recognized that the surface chemistry
of activated carbon can strongly affect the adsorption capacity [7].
Due to acidic role of CO2 (weak Lewis acid), it is expected that the
introduction of Lewis bases onto the activated carbon surfaces may
favour the CO2 capture performance of these materials [18].
One of the popular ways used for the preparation of activated
carbon with increased basicity is to remove or neutralize the acidic
functionalities, and other way is to replace acidic groups with
proper basic groups (e.g., basic nitrogen functionalities). It has been
shown that introduction of nitrogen functional groups into the car-
bon surface can increase the capacity of activated carbon to adsorb
CO2 [1,3,7,1517,2326]. Nitrogen containing functionalities can
be introduced through either reaction with nitrogen containing
reagents (such as NH3 , nitric acid, and amines) or activation with
nitrogen containing precursors [17,2734]. The objective of ammo-
nia treatment is to increase the basicity of activated carbon by
introducing basic nitrogen functionalities to the carbon surface
[31,32,3537]. When the carbon materials are treated with ammo-
nia at high temperatures, ammonia will decompose to free radicals
such as NH2 , NH, and atomic hydrogen and nitrogen. Those free
radicals attack the carbon to form nitrogen containing functional
groups [3840]. Several authors have studied thermal treatment
of carbons in an ammonia atmosphere [3032,3842]. Economy
et al. [43] treated activated carbon bers (ACF) using NH3 at ele-
vated temperature to obtain a product with basic characteristics.
Plaza et al. [18,22] proposed the modication of activated carbon
with gaseous ammonia as a suitable technique to produce efcient
CO2 adsorbents. Various characterization methods have been used
to detect and verify the existence of surface functional groups of
the activated carbons [44,45]. The most common of these meth-
Fig. 1. Acidic and basic surface functionalities on a carbon basal plane [72].
ods are chemical titration, temperature programmed desorption
(TPD), X-ray Photoelectron Spectroscopy (XPS) and Fourier Trans-
form Infrared Spectroscopy (FT-IR).
The main objective of this review is how activated carbon should
be modied to enhance surface basicity for carbon dioxide adsorp-
tion.
2. Activated carbon surface chemistry
The chemical characteristics of activated carbons are largely
determined by a certain degree of surface chemical heterogene-
ity, which is related to the presence of heteroatoms, i.e. atoms
present in the carbon structure that are not carbon, such as oxygen,
nitrogen, hydrogen, sulfur, and phosphorus. The type and quantity
of these elements are derived either from the nature of starting
material or introduced during the activation process [46,47]. Sur-
face functional groups (which are formed from these heteroatoms)
and the delocalized electrons of the carbon structure determine the
acidic or basic character of the activated carbon surface [48].
2.1. Acidic surfaces
The acidic character of activated carbon surfaces is closely
related to the oxygen containing surface groups [4951]. These
groups which are mainly present on the outer surface or edge
of the basal plane contribute toward the chemical nature of the
carbon. As these outer sites constitute the majority of the adsorp-
tion surface, the concentration of oxygen on the surface has a
great impact on the adsorption capabilities of the carbon [5257].
Some examples of oxygen containing functionalities detected on
the carbon surface include the following: carboxylic, lactone, phe-
nol, carbonyl, pyrone, chromene, quinone, and ether groups (Fig. 1).
Carboxylic groups can also exist in the form of carboxylic anhy-
dride [52,5861]. The surface oxygen functional groups can be
classied into three classes according to their chemical properties:
acidic, basic, neutral. Functional groups such as carboxylic acid or
carboxylic anhydride, lactone, and phenolic hydroxyl have been
postulated as the sources of surface acidity [61,62].
Oxygen containing functionalities are created when the carbon
surface is oxidized. The most commonly used activation meth-
ods to introduce oxygen containing acidic groups are oxidation by
gases and aqueous oxidants [52,6366]. Oxygen, air, carbon diox-
ide, and steam can be used in the gas phase treatment. In these
processes, low temperature oxidations lead to formation of strong
 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151
acidic groups (e.g., carboxylic) while high temperature oxidations
can be used to create a considerable amount of weak acid groups
(e.g., phenolic) [6365]. Liquid phase oxidations can introduce a
higher amount of oxygen into the carbon surface at much lower
temperatures compared to the gas phase treatment [65]. Nitric
acid or nitric and sulfuric acid mixture have been shown to be
very effective oxidizing agents due to introduction of a signicant
number of oxygenated acidic functionalities onto the carbon sur-
face that mainly include carboxylic, lactone, and phenolic hydroxyl
groups [49,52,6771]. It has been demonstrated that oxidation of
activated carbon in the gas phase increases mainly the concentra-
tion of hydroxyl and carbonyl surface groups while oxidation in
liquid phase can incorporate a higher amount of oxygen in the form
of carboxylic and phenolic hydroxyl groups onto the carbon surface
at much lower temperatures compared to the gas phase oxidation
[65,67].
2.2. Basic surfaces
Basicity of activated carbon can be associated with: (i) resonat-
ing -electrons of carbon aromatic rings that attract protons, and
(ii) basic surface functionalities (e.g., nitrogen containing groups)
that are capable of binding with protons [7276]. It was pro-
posed that certain oxygen containing surface functionalities such as
chromene [77], ketone [78], and pyrone [79] can contribute to the
carbon basicity (Fig. 1). However, the basic character of activated
carbons arises primarily from delocalized -electrons of graphene
layers [50,72,73]. It was pointed out that the -electrons of these
layers could act as Lewis bases [80]. Some researchers studied the
contribution of basal planes to the carbon basicity [8082]. Leon y
Leon et al. [73] studied the surface basicity of two series carbons
and demonstrated that oxygen-free carbon sites can adsorb pro-
tons from solution. These sites are located in -electron rich regions
on the basal plane of carbon crystallites. Therefore, basic sites are
Lewis type associated with the carbon structure itself [62].
It has been shown that introduction of nitrogen functional
groups into the carbon surface can increase the capacity of activated
carbon to adsorb CO2 [13,7,1517,2326]. Nitrogen containing
functionalities can be introduced through either reaction with
nitrogen containing reagents (such as NH3 , nitric acid, and amines)
or activation with nitrogen containing precursors [2729,33,34].
Possible structures of the nitrogen functionalities include the fol-
lowing: amide group, imide group, lactame group, pyrrolic group,
and pyridinic group [36,37,83]; which are shown in Fig. 2. Nitro-
Fig. 2. Types of nitrogen surface functional groups: (a) pyrrole, (b) primary amine, (c) secondary amine, (d) pyridine, (e) imine, (f) tertiary amine, (g) nitro, (h) nitroso, (i)
amide, (j) pyridone, (k) pyridine-N-oxide, (l) quaternary nitrogen [85].
145
gen functionalities generally provide basic property, which can
enhance the interaction between carbon surface and acid molecules
such as, dipoledipole, H-bonding, covalent bonding, and so on
[84].
3. Preparation of activated carbon with basic surface
In the presence of a large number of oxygen containing acidic
groups on carbon surface, the contribution of resonating -
electrons to carbon basicity is overshadowed. Therefore, one way
of increasing basicity is to remove or neutralize the acidic function-
alities, and other way is to replace acidic groups with proper basic
groups (e.g., basic nitrogen functionalities).
3.1. Heat treatment
High temperature (>700 C) heat treatment under inert atmo-
sphere might be used to selectively remove some of surface acidic
functionalities from the activated carbon surface [57,8690]. The
majority of oxygen functionalities on a carbon surface can be
decomposed at 8001000 C [67].
Heat treatment will create unsaturated surfaces as a result of
thermal desorption of acidic functional groups. Several researchers
have conrmed that the decomposition of oxygen functional
groups at elevated temperatures increases basicity of the carbon
surface [49,82,91]. This is due to the fact that strongly acidic func-
tionalities (such as carboxylic, anhydrides and lactones) decompose
at lower temperatures, while the weakly acidic functionalities
(such as carbonyl, phenol and quinone) decompose at higher tem-
peratures [92,93]; which are shown in Fig. 3. Therefore the large
amount of CO2 releasing groups are removed and only a small
amount of CO releasing groups remains in the carbon surface, which
can be assigned to pyrone and chromene type structures [92,94].
Heat treatment of carbon under hydrogen or inert atmosphere
(nitrogen or helium) can increase carbon hydrophobicity by remov-
ing hydrophilic surface functionalities [57,8688,95]. Hydrogen is
usually the preferred gas since it is more effective for removing the
oxygen functionalities and it can also effectively stabilize the car-
bon surface by deactivation of active sites (i.e., forming stable CH
bonds and/or gasication of unstable and reactive carbon atoms)
(see Fig. 4) [57,86,87,90,96].
The temperature of heat treatment is limited to 1000 C and
resulting material usually shows a low degree of activity for
reacting with oxygen or chemical agents and a high degree of basic-
146 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151

Fig. 3. Surface oxygen containing groups on carbon and their decomposition by TPD [67,84].

ity [49,57,82,86,87,95]. The basicity of thermally treated samples
arises from the oxygen-free Lewis basic sites on the graphene lay-
ers and from the few basic oxygen containing groups (pyrone and
chromene) remaining in the carbon surface [92,94].
Summary of research studies on the heat treatment under inert
atmosphere are given in Table 1.
3.2. Ammonia treatment
The objective of ammonia treatment is to increase the basicity
of activated carbon by introducing basic nitrogen functionalities
to the carbon surface [31,32,3537]. Apart from the incorpora-
tion of basic nitrogen functionalities during heat treatment under
ammonia ow, the removal of oxygen containing functionalities
can signicantly improve the basicity of ammonia treated carbons
[30,31,97,98].
Several authors have studied thermal treatment of carbons in an
ammonia atmosphere [3032,3842]. Economy et al. [43] treated
activated carbon bers (ACF) using NH3 at elevated temperature
to obtain a product with basic characteristics. They also reported
that such bers were effective in adsorbing acidic gases such as
SO2 . Sthr et al. [39] observed that ammonia treatment at ele-
vated temperature (600900 C) resulted in considerable increase
in activated carbons activity.

Fig. 4. Proposed model for the stabilization of carbon surfaces upon heat treatment () in N2 (inert gas) and H2 . For simplicity and illustrative purposes, only two types of
oxygen surface groups (pyrone and lactone) and three types of carbon active sites are shown. These three types are in the order of increasing stability: (i) type I, isolated
unpaired-electron sites Ar (where Ar represents the aromatic (graphene) layer); (ii) type II, ArC C ; and (iii) type III, divalent in-plane pairs, Ar * (where * represents
a localized electron). Structures C and D are formed in N2 , while structures D and E are formed in H2 . (Structure D is much more abundant in H2 -treated carbons because
of the higher concentration of CH2 radicals.) [57].
 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151 147

Table 1
Summary of research studies on the heat treatment under inert atmosphere.

Starting material Treatment Ref.

Granular activated carbons (GACs) Under H2 ow at 900 C [90]
Activated carbon ber (ACF) Under H2 ow at 900 C
Granular activated carbons (GACs) Under H2 ow at 900 C [97]
under He ow at 900 C
Norit ROX activated carbon Under N2 ow at 700 C [75]
under H2 ow at 700, 900 C
Commercial activated carbon (AC) Under N2 ow at 1000 C [99]

Norit C-Granular (Nc) activated carbon Under N2 ow at 950, 500 C [57]

under H2 ow at 950, 800, 650 C
Norit C-Granular (Nc) activated carbon Under N2 , H2 ow at 950 C [86]

Activated carbon bres (ACFs) Under N2 ow at 600, 800 C [100]
Norit C-Granular (Nc) Under H2 ow at 600, 950 C [87]
Activated carbon Under N2 ow at 600, 950 C
Norit Corp activated carbon Under H2 ow at 950 C [93]
Carbon black Under N2 ow at 800 C
Porous phenolformaldehyde resin (PF-polymer) Under N2 ow at 1000 C [49]

Fig. 5. Reaction scheme for conversion of chemisorbed oxygen (ether-like) into imine and pyridine surface groups in the reaction with ammonia [39].

When the carbon materials are treated with ammonia at high
temperatures, ammonia will decompose to free radicals such as
NH2 , NH, and atomic hydrogen and nitrogen. Those free radicals
attack the carbon to form nitrogen containing functional groups
[3840]. The reaction of ammonia with carboxylic acid sites present
in the carbon can form ammonium salts that through dehydration
reaction lead to amides and nitriles:
H O H O
COO NH4 +
2 2
CONH2 C N
Amines can also easily formed by the substitution of OH groups:
OH + NH3 NH2 + H2 O
In the reaction with ammonia at elevated temperatures ether-
like oxygen surface groups are easily replaced by NH on the
carbon surface that through dehydrogenation reaction could read-
ily lead to imine and pyridine functionalities as shown in Fig. 5
[35,38,39,41,101]:
Mangun et al. [33] modied activated carbon ber (ACF) with
dry ammonia at various temperatures from 500 to 800 C and
demonstrated that nature of nitrogen functionalities differed with
the temperature of ammonia treatment. It has been reported that
amides, imides, imines, amines and nitriles dominated at low tem-
perature (<600 C) while thermally stable aromatic rings such as
pyrrole and pyridinic-like functionalities dominated at higher tem-
perature (>600 C) [7,18,22,30,32,33,35,102,103].
Reviewing literature shows development of ammonia modi-
cation as an alternative pathway to increase the adsorption ability
of activated carbon toward CO2 [7,16,18,22,25]. In these modi-
cations, since the introducing of nitrogen functionalities made
activated carbon more alkaline therefore carbon dioxide adsorption
capacity expected to be increased [25]. Plaza et al. [18,22] proposed
the modication of activated carbon with gaseous ammonia as a
suitable technique to produce efcient CO2 adsorbents. They also
studied the effect of temperature on ammonia treatment and found
that the optimum temperature to reach the maximum CO2 adsorp-
tion capacity and nitrogen incorporation values was 800 C. Their
study highlighted the merits of the method as the ammonia was
treated without any preliminary oxidation of the samples.
Summary of research studies on the modication of activated
carbon with gaseous ammonia are given in Table 2.
4. Characterization of activated carbon surface chemistry
Characterization of functional groups on porous carbon is com-
plicated due to the complexity of surface functional groups and
incomplete understanding of their behaviour on the carbon surface.
Elemental analysis is the primary method to obtain the elemen-
tal kinds and it amount. This method is employed in most studies
because it is convenient, easy and inexpensive, but it cannot give
the functional groups, so the results from this test should not
simply be treated as a reection of surface chemistry [84]. Vari-
ous characterization methods have been used to detect and verify
the existence of surface functional groups of the activated carbons
[45,67]. Details of the most common of these methods are as fol-
lows:
4.1. Chemical titration
Classical acid/base titration, such as proposed by Boehm
[62,69,79,115,116,117], used to determine the basic and acidic
functional groups of the carbon surface. In this method specic
acids or bases are contacted with the basic or acidic functional
groups on the carbon surface then titrated to determine the quan-
tity of acid or base that has reacted with these functionalities
[51,118].
The basic principle of Boehm titration is that different
basic/acidic functionalities can be distinguished by their neutraliza-
tion behavior [58,119]. The amounts of various oxygen containing
acidic groups on the activated carbon were measured under the
assumption that NaOH neutralizes carboxylic, phenolic and lac-
tone groups; Na2 CO3 neutralizes carboxylic and lactone groups;
and NaHCO3 neutralizes only carboxylic groups [62,74,120]. The
number of the surface basic sites can be calculated from the amount
of HCl that is consumed by the carbon [74,92]. The amount of each
acid/base neutralized by the basic/acidic functional groups on the
carbon surface can be determined by back titration using NaOH and
148 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151

Table 2
Summary of research studies on the modication of activated carbon with gaseous ammonia.

Starting material Treatment Application Ref.

Carbon adsorbents from biomass residue (almond Amination at 800 C for 2 h Producing CO2 capture adsorbents [18]
shells)

Commercial activated carbon Amination at 200 C, 400 C, 600 C, Enhancement of CO2 adsorption [25]
800 C, 1000 C for 2 h
Commercial activated carbons (wood-based and Amination at 200 C, 400 C, 600 C, Surface modication of AC for CO2 [7]
peat-based) 700 C, 800 C for 2 h capture
Bituminous granular activated carbon (GAC) Amination at 500 C, 600 C, 650 C, Enhancement of perchlorate removal [104]
700 C, 800 C for 1hr
Commercial activated carbon Amination at 200 C, 400 C, 600 C [105]
for 3 h
Carbon adsorbents from biomass residue (olive Amination at 400 C, 600 C, 800 C, Development of adsorbents for CO2 [22]
stones) 900 C for 2 h capture
Carbon materials (biomass residues, sewage Amination at 400 C for 2 h Development of CO2 adsorbents [16]
sludge, pet coke)
Viscose-based activated carbon cloth (ACC) Amination at 800 C for 2/3 h Adsorption of acidic gas (H2 S and SO2 ) [106]
Commercial granular activated carbons Amination at 385 C for 3 h Adsorption of model aromatic [89]
compounds (aniline and nitrobenzene)
Commercial activated carbon bers (ACFs) from Amination at 500 C, 600 C, 700 C, Adsorption of sulfur dioxide [107]
Nippon Kynol 800 C for 1 h
Activated carbon bers (phenolformaldehyde Amination at 500 C, 600 C, 700 C, Adsorption of acidic gas (HCl) [33]
polymer ber (Kynol)) 800 C for 1 h
Activated carbon bers (pitch-based carbon ber) Amination at 915 C for 1 h Removal of SO2 [108]
Activated carbon bres (pitch, PAN and phenolic Amination at 800 C for 1/4 h Enhancement of SO2 capture [100]
resin)
Activated carbons from bituminous coal, lignite Amination at 300 C for 1 h Sulfur removal [109]
Granular activated carbons (GACs) Amination at 300 C, 400 C, 800 C Enhancement removal of natural [97]
for 1 h organic matter from natural waters
Amination at 300 C, 400 C, 800 C
for 2 h
Granulated and powdered activated carbon Amination at 900 C for 2 h [110]
Commercial activated carbon Amination at 400 C, 600 C, 700 C, Adsorption of phenol from water [103]
800 C for 2 h
Commercial activated carbon (Norit) Amination at 200 C for 2.5 h Adsorption of dyes [75]
Viscose-based activated carbon cloth (ACC) Amination at 800 C for 2/3 h [111]
Bituminous granular activated carbon (GAC) Amination at 700 C for 1 h Perchlorate adsorption [112]
Commercial activated carbon (based coconut shell) Amination at 800 C for 3 h Adsorption of metal ions [74]
Activated carbons (from polyvinylidene chloride Amination at 800 C for 1 h [113]
and a phenolic resin)
Bituminous granular activated carbon (GAC) Amination at 500 C, 600 C, 650 C, Enhancement of perchlorate removal [114]
700 C, 800 C for 1 h
Commercial granulated activated carbon Amination at 800 C, 900 C for 2 h [31]
Activated carbon from peat Amination at 300 C, 500 C, 700 C, Enhancement of catalytic activity of AC [39]
900 C for 4 h in oxidation reactions
Activated carbon from sulfonated Amination at 600 C for 1.5 h Enhancement of molybdenum [42]
styrenedivinyl-benzene copolymer adsorption

HCl, respectively [74,121,122]. The Boehm titrations are not prac-
tical when dealing with small amount of samples. In addition, this
technique only could determine about half of the total oxygen con-
tent available in activated carbon. These are the main drawbacks
are presented in Boehm titration [119,123].
Currently, the total basic groups are measured as a single value
because the nature of basic surface functionalities is not well
known. The amount of total basic functionalities on the carbon sur-
face can be determined by HCl uptake. The difference between the
HCl consumption by the blank and samples was considered as the
surface basicity of the activated carbon [97].
4.2. Temperature programmed desorption (TPD)
The relative thermal stability of surface functional groups
is often used as a measurement of the concentration of these
functionalities on the carbon surface under a process called tem-
perature programmed desorption (TPD) [45,74]. This technique has
become rather popular for the characterization of the surface oxy-
gen functionalities of activated carbon [45,49,79,84,94,124132].
During a TPD experiment, surface oxygen groups on carbon
materials are decomposed upon heating by releasing CO2 at
lower temperatures and predominantly CO at higher tempera-
tures and in some cases H2 O and H2 , at different temperatures
[45,49,52,61,67,84,93,132135]. The main oxygen functionalities
detected on the carbon surface and their decomposition by TPD
were shown in Fig. 3.
It is well established [45,56,67,79,94,136140] that a CO2 peak
is mainly due to the decomposition of carboxyl and lactone groups,
while decomposition of carbonyl, quinone, phenol and ether groups
produce a CO peak in monitoring. Basic functionalities like pyrone
and chromene are thermally decomposed and generate a CO peak
[94]. During TPD, while the temperature is slowly raised, the sam-
ples show completely different TPD spectra. Pereira et al. [75]
demonstrated that at high temperatures (above 1000 C) the CO2
releasing groups have been almost completely removed and only a
small amount of CO releasing groups remains in the carbon surface,
which can be assigned to pyrone and chromene type structures.
The exact nature of different surface groups can be determined
by the decomposition temperature, quantities of devolved gases
and the knowledge of the chemistry behind the creation of the
released gas (e.g., carbonyl groups devolve as CO) [73,115,132,141].
Yet the interpretation of TPD spectra in the literature is somewhat
ambiguous [62,142] because of the overlapping of desorbed prod-
ucts generated from different oxygen complexes [45]. In order to
identify each surface group individually, CO and CO2 peaks must be
deconvoluted (separated) because TPD spectra, especially at high
temperature where surface mobility is signicant, represents com-
 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151 149

Table 3
Reported C1s binding energy assignment for carbon and carbonoxygen functional groups on activated carbon [31,158160], carbon bers [108,137,151] and coal-derived
carbon [153,154] surfaces.

Functional group Binding energy reference (eV)

[137] [108] [159] [160] [151] [31] [153] [158] [154]

Hydrocarbon CC, CH 284.6 284.5284.7 284.7 284.6 284.6 284.9 284.7 285.0 285.0
Hydroxyl or ether CO 286.0 286.2286.4 286.3 286.3 286.3 287.0 286.2 286.1 286.6
Carbonyl C O 287.3 287.4287.7 287.6 287.7 287.5 288.1 287.6 287.7 288.0
Carboxyl or ester OC O 288.9 289.1 289.6 290.0 288.6 290.0 289.4 288.8 289.0

Table 4
Possible FT-IR peak assignments of functional groups on carbon surfaces.

Group or functionality Wave number assignments (cm1 ) Ref.

Carboxylic acids
C O (stretching) 1710, 1717, 1720, 16001800, 17201750, 1712 [31,74,175,176,180,181]
OH (stretching) 3530, 3500 [169,182]
Quinones 1645, 1635, 15501680, 1650, 15801620 [31,74,135,172,175]
CH (stretching) 26003000, 2924 [135,183]

Phenolic groups
COH (stretching) 10001220, 10001400, 11001400, 12001300 [135,175,184,185]
OH (stretching) 25003620, 3605, 3393 [135,169,183]
Lactones (C O stretching) 1710, 1750, 1720, 1760 [175,186188]
Ketones (C O stretching) 1570, 1560, 1700, 1707, 1705 [31,175,185,188,189]
Ethers (CO stretching) 10001300, 10001400, 11001400 [135,175,176]
OH (stretching) 32003600, 31003600 [31,190]
C N 1570, 1600, 1600 [25,33,191]
Pyridine-like groups 14801610, 15121570 [31,74]
CN 1190, 1250, 1250 [25,31,33]
Cyclic amides 1676, 14611685, 1670 [33,103,188]
NH 1480, 1560 [25,103]
Nitro groups 13301530, 1574 [192,193]

posite CO and CO2 peaks [132,134]. Some researchers presented
modied procedures to deconvolute the TPD spectra in order to
determine different types of surface oxygen complexes [45,67].
4.3. X-ray photoelectron spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) is a non-destructive (or
weak) surface technique in which the electron binding energies of
atoms presented in the surface are used to determine the elemental
composition and chemical states of the sample surface [143145].
There are several good review articles describing the basic princi-
ples of XPS [146149].
XPS was used to investigate the chemical composition of the
surface of carbon materials [31,94,128,137,150160]. This spectro-
scopic method has been extensively employed to study the oxygen
containing surface groups [31,137,151,153,154,158160]. Substan-
tial changes in the nature of the carbon due to changes in surface
chemistry such as oxidation can be identied through an examina-
tion of the C1s core region [161]. Analysis of the C1s region revealed
the presence of four functional groups: CC or CH, CO, C O and
OC O [31,108,137,151,153,154,158161]. The binding energies
reported for these functionalities are summarized in Table 3. The
differences in binding energies of CC and CH, or between COC
and COH for example are not large enough to be distinguished by
the spectrometer, in this way XPS cannot detect hydrogen directly.
This is one of the main drawbacks appeared using XPS.
XPS is a successful method for studying nitrogen contain-
ing functionalities in solid materials [30,32,35,127,162]. Several
researchers studied the effect of ammonia modication on changes
in surface chemistry of activated carbon [30,35,39,97]. In order to
obtain further insight into the nature of the functional groups on
the surface, they used XPS and quantied the binding energies
of the nitrogen (N1s), oxygen (O1s), and carbon (C1s) photoelec-
trons of the surface groups. Jensen and van Bekkum [35] found that
modication with gaseous ammonia led to formation of amides
(399.9 eV), and lactams and imides (399.7 eV). Mangun et al. [33]
concluded that pyridine with a binding energy of 398.4 eV was
the main nitrogen functionality when activated carbon bers were
treated in ammonia at high temperature. Sthr et al. [39] explained
that due to the chemisorptions of nitrogen in ammonia treatment,
XPS showed two N1s signals with binding energies of 401400 eV
and 399398 eV, which were assigned to amine and nitrile and/or
pyridine-like nitrogen, respectively. Results of XPS studies also
indicated that two main nitrogen functionalities in coals were
pyrrolic and pyridinic groups with binding energies of 400.3 eV and
398.7 eV, respectively [37,163168].
4.4. Fourier Transform Infrared Spectroscopy (FT-IR)
Infrared (IR) spectroscopy is another method that has been
employed to identify the functional groups present on activated
carbon surfaces [59,169176]. However, it is not easy to interpret
the IR spectra because the peaks obtained are usually a sum of the
interactions of different types of groups [67,130,173]. Furthermore,
IR does not provide quantitative information about the presence of
individual functionalities on the carbon surface [59]. These are the
main drawbacks appeared using IR spectroscopy.
The shortcomings of IR studies can be overcome using the
Fourier Transform Infrared (FT-IR) technique [135]. FT-IR spec-
troscopy is one of the most versatile and powerful analysis methods
for IR data and has been used as a qualitative technique for
the evaluation of the chemical structure of carbon materials
[30,32,33,138,172,173,177,178]. Using this technique the inher-
ent signal-to-noise (S/N) ratio and resolution was improved and
a greater accuracy of the frequency scale was obtained compared
to dispersive IR spectroscopy [179]. The FT-IR spectrum is a plot of
the measured infrared intensity (transmittance units) versus wave
number of light (inverse of wavelength). By measuring the FT-IR
spectra of the sample before and after treatment, surface func-
tional groups formed or consumed during that treatment can be
150 M.S. Shafeeyan et al. / Journal of Analytical and Applied Pyrolysis 89 (2010) 143151
identied. Some FT-IR assignments of functional groups on carbon
surface were listed in Table 4.
Besides the above techniques, other commonly used methods
to characterize the surface functional groups of carbon materials
include NMR spectra [194], Inverse Gas Chromatography [195],
surface imaging techniques, such as SEM and STM [94].
5. Conclusion
In this study the impact of changes in surface chemistry on
adsorption properties of activated carbon was reviewed. Two
methods for producing activated carbon with basic surface were
considered: heat treatment and ammonia treatment. It was found
that decomposition of oxygen containing acidic groups and intro-
duction of basic nitrogen functionalities on the carbon surface
improved CO2 adsorption ability of activated carbons. Amination
is an alternative pathway to increase the adsorption ability of acti-
vated carbon toward CO2 . From the literature survey, it was evident
that the nature of the nitrogen surface groups depends on the tem-
perature of ammonia modication. It was reported that amides,
imides, imines, amines and nitriles dominated at low tempera-
ture (<600 C) while thermally stable aromatic rings such as pyrrole
and pyridinic-like functionalities dominated at higher temperature
(>600 C). Various characterization methods such as Boehm titra-
tion, TPD, XPS and FT-IR were presented to detect and verify the
existence of surface functional groups of the activated carbons.
Acknowledgement
This study was carried out with the aid of a research grant from
University Malaya Research Fund.
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