Applied Surface Science 228 (2004) 8492

The HSAB concept as a means to interpret the adsorption

of metal ions onto activated carbons
Ahmad Alfarraa, Elzbieta Frackowiakb, Francois Beguina,*
a

CRMD, CNRS-University, 1B rue de la Ferollerie, 45071 Orleans Cedex 02, France

b
Poznan University of Technology, ul. Piotrowo 3 60-965 Poznan, Poland

Received 15 April 2003; received in revised form 23 December 2003; accepted 24 December 2003

Abstract
While activated carbons (ACs) are extensively used for metal ions trapping in aqueous medium, the physico-chemical factors
responsible of this phenomenon are not yet clearly understood, that is an important drawback for improving the adsorption
properties of these materials. The main interpretations are related either to a cationic exchange with the acid surface groups or to
an interaction with the p-orbitals of the surface polyaromatic units. However, it remains very unclear why some ions interact
mainly with one type of site and rather not the other, and why the interaction might depend whether the ions are coordinated or
not. In this paper, we show that the hard and soft acids and bases (HSAB) concept allows quite a large number of published data
dealing with ions adsorption on activated carbons to be interpreted. In this concept, the surface of the basal structural units of
carbon is soft and can trap soft ions, whereas the oxygen surface groups are the hard sites that fix hard metal ions. On the other
hand, using either special treatments for the activated carbon or the coordination of metal ions by various ligands allows the
hardness of the two interacting species to be matched for a better control of adsorption. According to the HSAB concept, one is
able to predict the potential sites of adsorption on the carbon surface as a function of the hardness of each ion. Changing the
experimental conditions, metal ions with a borderline hardness can be adsorbed by the hard and/or the soft sites of carbon.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Activated carbons; Adsorption; HSAB concept; Metal ions; Cationic exchange

1. Introduction
Activated carbons (ACs) are widely used for the
adsorption of metal cations in aqueous medium. This
phenomenon is controlled by different factors, such as
the contact time, the solution concentration and pH,
the structural and microtextural characteristics of
carbon. Most studies are applied to the removal of
one kind of ion where ACs are very often considered to
*

Corresponding author. Tel.: 33-2-38-25-53-75;

fax: 33-2-38-63-37-96.
E-mail address: beguin@cnrs-orleans.fr (F. Beguin).

have the behavior of a cationic exchanger [16] with

weak acidic surface groups. In this case, the adsorption
is almost independent of the carbon microtexture and
it increases with the pH value, the amount of surface
groups and the solution concentration. The desorption
of the trapped ions is only possible by cationic
exchange with other ions. This process works for
the adsorption of alkali, alkaliearth and several transition ions.
Some papers simplify the mechanism of cationic
exchange where it is presented as a physical interaction
[7,8]. In this concept, when the solution pH is higher
than the pH of zero charge, pHpzc, the surface groups are

0169-4332/$ see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2003.12.033

A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

ionized, that charges the AC negatively, allowing the

cations to be trapped by an electrostatic effect.
For other ions such as heavy metals, the adsorption
seems to be independent both of the pH value and the
surface groups concentration; since it only depends on
the specific surface area and porosity of carbon, it
means that the ions are rather trapped on the surface of
the basal planes [9,10].
An overall study which predicts whether a given ion
could be adsorbed on AC or not, and the kind of
mechanism among those mentioned above is absent.
The main question to which an answer should be given
is: why some ions are only trapped by surface groups,
others by the basal planes of carbon, or even by both
sites? In this paper we will show that the HSAB
principle can be applied as an universal concept to
interpret the adsorption properties of ACs for all kinds
of ions. Pearsons hard and soft acid and bases
(HSAB) principle, introduced in 1963 [11,12], has
become one of the fundamental constructs of modern
chemistry. It has been widely used because its bold
Lewis acid/base statement that soft likes soft, hard
likes hard is easily understood, straightforwardly
applied, and this idea rationalizes a range of otherwise
very disparate facts. The HSAB principle was first
applied to selective organic synthesis in 1967, and
then for homogenous catalysis in transition metal
coordination chemistry. Taking into account a documented review of ions adsorption studies on ACs, we
found that ions which are trapped by the surface
groups are always hard, whereas those which are
adsorbed on the basal planes surface are always
considered to be soft.
In this paper, we will remind the main statements of
the HSAB concept taken from a rich literature review
and it will be applied to interpret the peculiar adsorption properties of a wide range of ions on activated
carbons. Finally, we will see the possibilities to modify
the hardness of an ionic species in order to enhance or
to reduce its adsorption.

2. The HSAB concept

At the same time that Brnsted proposed his acid
base theory, a broader theory was introduced by
Lewis. A Lewis base is a compound with an available
pair of electrons, either unshared or in a p-orbital,

85

whereas a Lewis acid is any species with a vacant

orbital. In a Lewis acidbase reaction, the base
unshared pair forms a covalent bond with the acid
vacant orbital. A specific example is given by the
following reaction:


BF3 NH3 ! F3 BNH3

Far fewer quantitative measurements have been made
of Lewis acid strength compared to that of Brnsted
acids. A simple estimation of Lewis acidity based on
any quantitative measurement is not feasible because
it is related with the nature of the parent base. The
facility for an acidbase reaction to take place depends
of course on the strength of both acid and base, and
also on quite another quality, called their hardness or
softness [1114]. Hard and soft acids and bases have
the following characteristics.
 Soft bases: the donor atoms have a low electronegativity and a high polarizability and they are
easy to oxidize. They hold their valence electrons
loosely: example I.
 Hard bases: the donor atoms have a high electronegativity and a low polarizability and they are
difficult to oxidize. They hold their valence electrons tightly: example F.
 Soft acids: the acceptor atoms are large, have a low
positive charge density, and contain unshared pairs
of electrons (p or d) in their valence shells. They
have a high polarizability and a low electronegativity: example Cu, Ag.
 Hard acids: the acceptor atoms are small, have a
high positive charge density, and do not contain
unshared pairs in their valence shells. They have a
low polarizability and a low electronegativity:
example Li, H, Mg2.
Relative hardness or softness of some acids and
bases are listed in Table 1.
To make a quantitative treatment of hardness, Parr
and Pearson used the density functional theory [15
17]. According to this, let E(N) to be the electronic
energy of the ground-state as a function of the number
of electrons N. It is known that the derivative of E(N)
with respect to N is the chemical potential m, or the
negative of the absolute electronegativity w:
 
@E
m
w
(1)
@N vr;T

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A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

Table 1
Hard and soft acids and bases [12,13]
Hard bases


Soft bases


H2O, OH , F , CH3COO , SO4 ,

Cl, CO32, NO3, RO,
RNH2, ROH, R2O
Hard acids

Borderline bases


2

H , Li , Na , K , Mg , Ca , Al ,
Cr3, Fe3, BF3, AlCl3, CO2, HX

R2S, RSH, RS , I , (RO)3P,

CO, C2H4, C6H6, H, R

ArNH2, pyridine, NO2

Soft acids

Borderline acids

Fe2, Co2, Cu2, Zn2, Cd2,

Sn2, Sb3, Bi3

Cu , Ag , Pd , Pt , Hg , I2

where vr is the potential acting on an electron at a

distance r due to the nuclear attraction plus other
external forces that may be present. The second
derivative of E(N) gives the hardness Z:
 
 2 
@m
@ E
2Z

(2)
@N vr;T
@N 2 vr;T
The corresponding operational definition is the difference finite formula:

rule is found in complexes between alkenes or aromatics (soft bases) and metal ions. Thus, complexes of
soft cations such as Ag, Pt2 and Hg2 are common,
whereas complexes of Na, Mg2, or Al3 are rare.
Chromium complexes are also common, however in
such complexes chromium is in low or zero oxidation
state, or softer being attached to other soft ligands, like
Cr(CO)3C6H6. In many cases, organic or aqueous
solution chemistry is based on an exchange reaction:

Z 12 I  A

A : B A0 : B0 A : B0 A0 : B

(3)

where Z, the absolute hardness (always positive), is

half the difference between I, the ionization energy,
and A, the electron affinity. The softness, s, is simply
the inverse of the hardness, s 1=Z. The form of
hardness in Eq. (3) can be further approximated to be
the difference of orbital energy between the lowest
unoccupied molecular orbital (LUMO) and the highest
occupied molecular orbital (HOMO), which is a measure of the stability. Values of Z for some molecules
and ions are given in Table 2. It is important to notice
that cations, due to their higher ionization energy, have
a higher hardness than atoms or anions. Eq. (3) cannot
be applied to anions, because their electron affinity A
is difficult to be measured. Instead, it is assumed that Z
for anions X is the same as that for the radical X .
Once acids and bases have been classified as hard or
soft, a simple rule of the HSAB principle can be given:
hard acids prefer to bond to hard bases, and soft acids
prefer to bond to soft bases [18]. This rule has nothing
to do with acid or base strength but merely says that
the product AB will be particularly stable if both A
and B are hard or if they both are soft. Another rule is
that a soft Lewis acid and a soft Lewis base tend to
form a covalent bond, while a hard acid and a hard
base tend to bond ionically. One application of the first

(4)

Taking into account the above rules, it can be concluded that such reactions occur as follows [19]:
HS H0 S0 HH0 SS0

DE < 0

(5)

Table 2
Experimental hardness values for ions and molecules (eV) [13,15]
Cations
Ion

H
Al3
Li
Mg2
Na
Ca2
Fe3
Mn2
Cr3
Cu2
Pb2
Pt2
Hg2
Fe2
Ag
Pd2
Cu
Au

Molecules
Z
1
45.8
35.1
32.6
21.1
19.5
13.1
9.3
9.1
8.3
8.5
8.0
7.7
7.2
6.9
6.8
6.3
5.7

Compound
HF
CH4
BF3
H2 O
N2
NH3
(CH3)2O
CO
C2H2
CO2
(CH3)3N
H2 S
C2H4
SO2
HI
Butadiene
Cl2

Anions
Z
11.0
10.3
9.7
9.5
8.9
8.2
8.0
7.9
7.0
6.9
6.3
6.2
6.2
5.6
5.3
4.9
4.6

Ion


F
H
OH
CN
Cl
Br
SH
I

Z
7.0
6.4
5.7
5.1
4.7
4.2
4.1
3.7

A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

where H, H0 and S, S0 are read as the harder and the

softer of the two acids (bases), respectively.
For a polyatomic system, the local softness s(r) (s is
the global softness) is proportional to the Fukui function f(r) [18]. This function represents the sensitivity
of the chemical potential of a system to an external
perturbation applied locally, such as a magnetic or an
electrostatic field. In this case, the HSAB principle is
locally applied: hard regions of a system prefer to
interact with hard reagents whereas soft regions prefer
soft species. This principle was applied by Lee et al.
[20] who calculated the local softness s(r) for three
speciesformaldehyde, the thiocyanate ion and carbon monoxide. They confirmed that: (1) a nucleophilic
reagent approaches the carbon atom in formaldehyde
from the direction perpendicular to the molecular
plane, while an electrophilic reagent approaches the
oxygen atom in the molecular plane; (2) the sulfur end
is softer than the nitrogen end in the thiocyanate ion;
and (3) carbon monoxide behaves like a Lewis acid in
bonding with transition metals. In another study,
Galva n et al. [21] could establish a formal relationship
between local softness and scanning tunneling microscopy (STM) images. They showed that, under appropriate conditions, the STM images can be used to
measure the local softness for surfaces and they presented a potential application of those images as
reactivity criteria within the context of the HSAB
principle. More recently, Krishnamurty et al. [22]
have demonstrated that in the case of gases interacting
with zeolite surfaces, the reactions follow the local
HSAB principle. In the next paragraph, we will
describe the surface of activated carbons in terms of
local hardness and softness to understand the adsorption of different species.

3. Local softness and hardness of a carbon

surface
In active carbons, atoms are grouped into stacks of
flat aromatic sheets (basic structural units, BSU)
which are randomly crosslinked [23]. The mutual
arrangement of these aromatic sheets, called the
microtexture, is irregular and therefore leaves free
interstices (pores) between the sheets making active
carbons excellent adsorbents. Their adsorption capacity is determined by the porous microtexture but is

87

also strongly influenced by the chemical structure of

the surface. Active carbons are almost invariably
containing appreciable amounts of heteroatoms such
as oxygen and hydrogen, and in addition, chlorine,
nitrogen and sulfur. These heteroatoms are derived
from the starting material and become a part of the
chemical structure as a result of imperfect carbonization, or they become chemically bonded to surface
during activation or subsequent treatments. They
either form surface groups at the edge of the aromatic
sheets, or they can be incorporated in the microtexture
forming heterocyclic ring systems within the carbon
layers or bridges connecting the BSUs.
Carbonoxygen surface functional groups are by far
the most important structures that influence the surface characteristics and behavior of activated carbons.
They are easily introduced by oxygen chemisorption
even on mere exposure to air or oxygen. Oxygen is
fixed firmly and comes off only as carbon oxides at
relatively high temperature. Similarly all carbons have
chemically bonded hydrogen. Activated carbons can
also bond nitrogen under ammonia treatment, sulfur
under hydrogen sulfide, carbon sulfide or sulfur treatment, and halogens under gas or solution phase treatment. Hence, carbonnitrogen, carbonsulfur and
carbonhalogen surface groups give rise to some
specific adsorption properties as well.
According to their electronegativity, heteroatoms
form more or less polar bonds with carbon. The p
orbitals of all the given examples of heteroatoms
except hydrogenoverlap with those of carbon and
form bonding and antibonding molecular orbitals
(MOs) extended on the whole basic structural unit.
Nevertheless, being more electronegative than carbon,
heteroatoms have lower energies for their valence
orbitals. Therefore, bonding MOs have their highest
contribution at heteroatoms, giving them a partial
negative charge d. The opposite charge d will be
delocalized over all the carbon atoms of the graphene
layer.
There are two reasons for considering that an
activated carbon has soft sites on the BSUs surface
and hard sites on the edge carbonoxygen bonds
(Fig. 1).
1. The difference between carboncarbon and carbonoxygen bonds. Table 2 shows that carbon
monoxide or dimethylether are harder than

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A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

Soft sites
O
H

OH

Hard sites
O

O
C

O
C

O
O

O
H

Fig. 1. Hard and soft zones of a graphene layer.

ethylene or butadiene. Generally, the CO or CO

bonds are more polar and less polarizable, hence
harder, than the CC or CC bonds. One can
deduce that the edges which contain electronegative heteroatoms are harder than the graphene
layers surface.
2. The strong delocalization of MOs on the BSUs
and donor or acceptor groups. In Table 3 we can
see the effect of MOs delocalization on compounds hardness. Polyaromatic hydrocarbons are
softer than benzene, and hardness decreases with
the number of cycles. Hence, it is reasonable to
attribute a very strong softness to the surface of
graphene layers, especially far from the edge
heteroatoms.
By application of the Hu ckel method of calculation
for aromatic compounds, the energies of the HOMO
and LUMO orbitals a xb and a  xb are practically
symmetric, i.e. the layers present approximately an
amphoteric acidbase character. Furthermore, by
comparison of different substituted aromatic compounds in Table 3 we observe that the electronegativity is increased by acceptor groups like COOH, NO2
compared to benzene whereas it is decreased by donor
groups like OH, NH2 or OCH3. Experimentally, at low
pH (pH < 3) most carbons are positively charged,
primarily due to the acceptor/donor interactions
between the graphene layers and the hydronium ions
in spite of their hardness [24]. We observe here how

the HSAB principle gives a tendency for a reaction

course. It does not allow to conclude that a reaction
between the soft graphene layers and the hard hydronium ions is excluded, but simply says that the product
of this reaction can decompose easily by the presence
of another hard base (for example, OH) or a soft acid
(like polyaromatic compounds which will be trapped
by graphene layers). On the other hand, the conductivity of activated carbons decreases after their oxidation because this treatment destroys the large BSUs to
produce smaller ones with a higher amount of ether
bridges. Hence, the polarizability of BSUs is reduced,
and the electron transfer is more difficult along the
ether bridges due to their hardness.
Table 3
Experimental parameters for aromatic and polyaromatic molecules
(eV) [17]
Molecule

C6H6
Naphthalene
Anthracene
Fullerene C60
Graphite

4.1
4.0
3.8
4.8
4.6

5.3
4.2
3.3
2.0
0.0

C6H5OH
C6H5NH2
C6H5OCH3
C6H5CO2CH3
C6H5CO2H
C6H5COCH3
C6H5NO2

3.8
3.3
3.55
4.7
4.9
4.8
5.5

4.8
4.4
4.65
4.6
4.8
4.5
4.4

A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

Hence, according to the previous remarks, we may

generally predict that hard acids or bases would be
adsorbed on surface groups of carbon, and that the
trapped amount would depend on the nature and
concentration of surface groups. Soft acids or bases
would be adsorbed on basal planes and their adsorption is supposed to be a function of the specific surface
area. In the following part of this paper, taking experimental results from literature, we will demonstrate the
possibility of an overall interpretation of ions adsorption by activated carbons, applying the HSAB concept. Especially this concept may explain why some
ions are exclusively trapped by surface groups, others
by the surface of basal planes, or even on both sites.

4. Application of the HSAB concept to cations

and anions adsorption on activated carbons
All the data of Tables 1 and 2 correspond to isolated
ions or molecules in the gas phase. To apply the HSAB
principle in water medium, it is essential to take the
ions hydration into account. In 1987, Pearson suggested the maximum hardness principle which
states that there seems to be a rule of nature that
molecules arrange themselves so as to be as hard as
possible [25]. Chattaraj et al. proved the validity of
this observation for over 40 different reactions eventually involving cations hydration or complexation
[26]. Water is a hard base, and it is easy to predict
that its reaction with hard alkali or alkaliearth cations
(Tables 1 and 2) would produce hard hydrated cations
as well. Therefore these cations may be preferentially
adsorbed by surface groups and cannot be trapped by
the graphene layers in water medium.
Generally, the formation of complexes between
hydrated metal ions and ligands in aqueous solution
in terms of HSAB concept is complicated. Taking into
account the reaction
A B ! AB
the most accurate treatment for a quantitative work can
be given by the equation:
log K EA EB CA CB  DA DB

(7)

where K is the equilibrium constant (in H2O, at 25 8C)

for reaction (6), the energetic non-dimensional parameters EA and EB measure the ionic bonding, CA and

89

CB the covalent bonding; the D parameters are necessary to account for steric effects. The last term in
Eq. (7) can be neglected for large cations, but it is
important for small cations. It emphasizes the important difference between reactions in solution and in
gas phase. In an aqueous solution, a Lewis acid is
multicoordinated by a number of water molecules.
Hence, the steric effects arise when the ligands replace
these water molecules [19]. The E, C and D parameters are related to hardness, but not in any simple
way, since they represent electrostatic and covalent
bonding, primarily. However, when ions have the
same coordination with water molecules, the terms
EB, CB and DB (B is H2O) are the same and the values
of ions hardness between the gas phase and water
medium are simply shifted. This is the case of
hydrated transition metals that always have an octahedral coordination with six water molecules. They
conserve their relative order of hardness in aqueous
solutions.
The main conclusion from Pearsons notes about
hydrated ions is that complexes of soft cations with
soft ligands are also soft while complexes of these ions
with hard ligands like water (which is the reference
ligand of complexation reactions) would be borderline
between soft and hard.
4.1. Trapping of ions by a redox process
The most simple mechanism for ions trapping by
activated carbons is the chemical adsorptionreduction. It occurs when the redox potential of metal ions is
high compared to that of carbon; platinum [27], gold
[2830] and silver [29,30] ions (E0(AuCl4/Au)
1.00 V), (E0(Ag/Ag) 0.80 V) and (E0([PtCl4]2/
Pt) 0.755 V) are trapped by this mechanism, according to the following reaction taken as an example:
PtCl4 2 2e ! Pt 4Cl
However, these metal ions behave more or less differently. The soft AuIII ions are strongly trapped by the
basal planes of the activated carbon where they are
extensively reduced because of their high redox potential, independently of the activation degree and concentration of surface groups. On the other hand,
Ag(NH3)2 ions have a borderline behavior. While
they are weakly trapped and reduced by activated
carbon fibers, this phenomenon is strongly enhanced

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A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

by the oxidation of carbon with nitric acid, giving

surface groups on which these ions are first trapped
before being reduced to the metal state. Finally
[PtCl4]2 has the behavior of a soft base. The adsorption step on the carbon surface determines the amount
of reduced ions and it is independent of the concentration of surface groups. In this case, the amount of
trapped platinum increases considerably with the specific surface area [27]. Actually, on the economical
point of view, the deposited metals are more difficult
to recover after this reaction than using cyanide complexes, Au(CN)2 and Ag(CN)2, that is the base of the
industrial method for silver and gold extraction. The
redox potential of these complexes (E0(Ag(CN)2/
Ag) 0.31 V, E0(Au(CN)2/Au) 0.58 V) is
low enough for their reversible trapping without reduction by the activated carbon. Jia et al. indicated two
possible sites of chemical adsorption for Au(CN)2
and Ag(CN)2: the surface of basic structural units,
and surface groups, but they did not mention the HSAB
concept [9]. They noticed that the adsorption of these
ions is independent of oxygen and nitrogen contents
and it increases with the BET specific surface area of
carbon, demonstrating that it occurs on the BSU surface. Accordingly to the HSAB concept, these complexes are soft bases due to their delocalized MOs, and
they are adsorbed on the surface of graphene layers
through pp interactions.
4.2. Trapping on the BSUs surface
The mercuric ion, Hg2, is a typical example of soft
acid. It seems to be less adsorbed on an activated
carbon of acidic character when the pH increases [10].
However, if the adsorption would occur on surface
groups, which are more dissociated by a pH increase,
one would expect a better trapping at high pH. On the
other hand, after a post treatment of carbon by CS2 the
adsorption of Hg2 ions is considerably enhanced. No
interpretation for this result was given by the reference
[10]. Hence, the sulfur organic compounds are soft
bases (Table 2) such as RS, and their reaction with
the soft acid, Hg2, produces a steady covalent bond.
The HSAB concept also explains that in aqueous
medium HgS is insoluble (pKs 53) because the
dissociation of the Hg S covalent double bond is
difficult. For the same reason, when activated carbons
contain phosphonic groups, they have a better affinity

for lead than for nickel or cadmium because the lead

phosphate is insoluble [4]. A kind of similar effect is
observed when some metal ions, such as copper, zinc
or lead, are complexed by EDTA. They are better
adsorbed on activated carbons, and it has even been
proved that the formed complexes are trapped by the
BSUs surface [31]. Hence, using the organic EDTA
ligand, containing delocalized MOs, for the complexation of metal ions, the hardness of the ions is reduced,
and consequently their adsorption on the BSUs is
enhanced.
4.3. Trapping by cationic exchange
Most of the metal ions are adsorbed by cationic
exchange with the weak acid surface groups of activated carbons [3234]. The higher the pH value, the
stronger the dissociation of surface groups and the
higher the amount of trapped ions from a solution.
Many studies in this field showed the profitable effect
of carbon oxidation on the ionic exchange adsorption
of transition metal ions like zinc Zn2 [1], copper
Cu2 [2], chromium III and VI [3] or nickel Ni2 [4],
or rare earth metal ions like dysprosium Dy3 [5]. In
this mode of adsorption, the effect of specific surface
area is almost negligible, and even using a charcoal
with a BET surface as low as 46 m2/g, the cations
trapping is effective and it increases with the surface
oxygen content [6].
The cationic exchange phenomenon is compatible
with the HSAB concept. Indeed, all the hard acids
like Cr3 [3], Na (the acidbase titration of
surface groups is a cationic exchange reaction) or
even borderline acids like Zn2 (they are relatively
hard in the hydrated form) are trapped by the dissociated surface groups that can be considered as hard
bases [1].
In some papers, a more physical vision of adsorption is presented, that hinders the true mechanism
because of the global vision of the activated carbon.
This interpretation is based on the fact that a carbon
rich in surface groups has a negative charge above a
certain pH, known as the pH of zero charge (pHpzc)
due to the dissociation of acid surface groups, and a
positive charge below the pHpzc. Hence, cations like
Co2 [7] and Pb2 [8] are considered to be electrostatically trapped by the negatively charged surface of
activated carbons at high values of pH.

A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

4.4. Trapping of cations with a borderline behavior

An interesting example is the adsorption of cadmium Cd2 which is trapped even at a pH of 1.1 on an
activated carbon. Furthermore, the amount of trapped
ions is almost independent of pH when it is lower than
3. At higher values of pH, cadmium ions are progressively trapped by the surface groups which are more
and more dissociated and the amount of fixed ions
increases with pH. The result at low pH was attributed
to the physisorption of cadmium, but this cannot
explain why an isotopic exchange of trapped cadmium
is slower at a pH of 1.1 than 4.05 [35]. This behavior is
easily interpreted taking into account that cadmium
Cd2 is a borderline acid. In this case the reaction
between Cd2 and the surface of BSUs (soft base)
produces bonds with a marked covalent character,
which are dissociated with difficulty. On the other
hand, at higher pH, the cationic exchange between the
oxygenated surface groups (hard base) and Cd2 gives
ionic bonds which are more easily dissociated.

5. How to modify the hardness and the

acid/base character of activated carbons for
a better control of adsorption
As shown before, the adsorption process of cations
on the activated carbons surface is controlled by the
relative hardness of the two species. The hardness of
ACs is generally increased by oxidation with classic
reagents like nitric acid, ammonium peroxodisulfate,
hydrogen peroxide, etc. The ammonia treatment at
high temperature allows an important part of oxygen
to be substituted by nitrogen. Since pyrones are transformed into pyridine groups, the activated carbon has a
stronger basic character, but the hardness of the surface groups is unchanged. The reduction of the oxygenated surface groups by di-hydrogen treatment or by
sodium borohydride reduces the amount of hard sites
on carbon. Some other chemical treatments may also
produce a softer carbon, like carbon disulfide, nitrogen
dioxide or iodine.
Electrochemical grafting of organic species allows
a specific group to be fixed at the carbon surface,
which should enable to obtain a better control of the
adsorption process [36,37]. By choosing a precise
ligand to be fixed, it is possible to reduce or to

91

increase considerably the ACs hardness. Unfortunately, applications of this method are still missing
in literature.
A direct complexation of metal ions by hard
ligands like NH3 and amines or by soft ligands like
EDTA, thio-urea, cyanide, iodide or organic ligands
with strongly delocalized orbitals is certainly easier
than the modification of the activated carbon hardness.
Generally, the modification of the ACs hardness is
often difficult to realize, but it is required for some
applications such as water treatment. Complexation of
metal ions is more easy to apply, as it is well known in
industrial applications for the metals separation or
recovery.

6. Conclusion
The hard and soft acids and bases concept was
successfully used to interpret literature data on the
adsorption behavior of different metal ions on activated carbons. The surface groups of ACs are considered to be their hard sites whereas the surface of
basal planes represents their soft sites. Using this
concept permits to explain whether a given ion may
be adsorbed on the surface of basal planes or by
oxygen surface groups, and also to explain qualitatively the efficiency of adsorption. On the other
hand, one should be able to control the adsorption
of metal ions modifying either their hardness or that
of ACs.
The use of the HSAB concept would be also interesting for the optimization of molecules adsorption by
activated carbons, and for a better control of their
removal as well. Several additional parameters intervene in this phenomenon, compared with ions adsorption. Among them, the most important is the molecular
size that determines a different number of adsorption
sites on the molecule, and which is also responsible of
steric effects with the activated carbon surface. In
other words, the trapping is in this case controlled
by the competition between the different sites of the
molecule for its adsorption on particular sites of the
activated carbon. In the future, more experimental
results will be needed to verify the applicability of
the HSAB concept to a wide range of adsorption
phenomena on ACs.

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A. Alfarra et al. / Applied Surface Science 228 (2004) 8492

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