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Adsorption of lead ions from aqueous solution using porous carbon derived
from rubber tires: Experimental and computational study
Tawk A. Saleh a, Vinod K. Gupta a,b,, Abdulaziz A. Al-Saadi a
a
b
Department of Chemistry, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia
Chemistry Department, Indian Institute of Technology Roorkee, Roorkee 247 667, India
a r t i c l e
i n f o
Article history:
Received 5 December 2012
Accepted 17 January 2013
Available online 31 January 2013
Keywords:
Porous carbon
Lead ion removal
FT calculations
a b s t r a c t
Effective activated porous carbon (AC) was prepared by thermal treatment of waste rubber tires and was
further activated using oxidizing agents like nitric acid and hydrogen peroxide. The tire-derived porous
carbon was characterized by means of FTIR and X-ray diffraction. Careful analysis of the IR spectra of the
synthesized AC reveals a number of bands centered at about 3400, 2350, 1710, 1650, and 1300
1000 cm1, proving the existence of hydroxyl and carboxylic groups on the surface of AC in addition to
C@C double bonds. The developed AC was tested and evaluated as a potential adsorbent for the removal
of lead (II) ions. Experimental parameters, such as contact time, initial concentration, adsorbent dosage,
and pH were optimized. AC was effective in a pH range between 4 and 7 with a highest uptake of lead
ions at pH 5 and 6. For further understanding of the chemistry behind the process, density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d) level adopting a functionalized pyrene
molecule as a model. The binding energy of Pb(II) ion toward carboxylic acid, carbonyl, and hydroxyl
groups was calculated. A binding energy in the range of 310340 kcal/mol, which is considered to be high
and to be indicative of a chemisorptions process, was predicted. The adsorption of the lead ion toward the
C@O groups in relatively all cases shows more stable binding compared to the sorption toward the alcohol groups.
2013 Elsevier Inc. All rights reserved.
1. Introduction
Contamination of the environment from different activities has
become an increasingly serious problem in recent years. Heavy
metals are one class of toxic pollutants released into the surface
and ground water as a result of various activities such as industries, mining, and agriculture [1]. The rapid development of industry has led to severe problems of water pollution. Industries and
municipal authorities have been forced to treat wastewater before
discharging. Various methods are available for water treatment.
However, adsorption technology is considered as an efcient and
universal method of water treatment as per the guidelines of
WHO and EPA. This is because of its cost effectiveness and environmental friendliness. The cost effectiveness of this technology is due
to the use of effective adsorbents by converting solid waste to value-added products.
Tire rubber is a mixture of different elastomers such as natural
rubber, butadiene rubber, and styrene butadiene rubber plus other
additives like carbon black, sulfur, and zinc oxide. Approximately
T.A. Saleh et al. / Journal of Colloid and Interface Science 396 (2013) 264269
industrial wastewater which releases lead into the aquatic and terrestrial systems is very important. Various adsorbents have been
reported for the removal of metal ions and organic compounds
from waters [1444]. Most of these adsorbents might not be efcient in removing heavy metal at very low concentrations and
could be relatively expensive. Therefore, it is essential to further
activate the adsorbent surface to enhance adsorption capacity.
The objective of the present study was to prepare activate porous carbon from waste rubber tire with a combination of physical
and chemical treatment in an attempt to develop surface porosity
as well as to incorporate desired functional groups on the surface
of the resultant activated carbon. The adsorption capacity of the
developed carbon was further evaluated for lead ions removal from
waste water. Factors that are likely to affect the adsorption capacity of the developed carbon were studied. In addition, a computational study was conducted.
2. Experimental section
265
2.1. Reagents
qe C 0 CV=W
where C0 and C are the initial and nal lead concentrations (ppm),
respectively, V is the volume of solution (L) and W is the weight
of adsorbent (g). All the experiments were repeated three times,
and average values were reported. The standard deviation was
found to be 0.2%; values of the correlation coefcient averaged 0.99.
The parameters considered for study were initial concentration
of adsorbate, contact time, adsorbent dose, pH, and temperature.
The representative calculations for Pb(II) ion adsorption on several functionalized pyrene systems have been carried out with the
G09 program package14 utilizing the DFT-B3LYP method with the
6-31+G basis set for H, C and O atoms and the SDD pseudo-potential for Pb(II) ion. Full geometry optimizations were performed on
the models shown in Fig. 8 without any constraint. The stationary
points have been conrmed by frequency calculation, and the initial binding energy was predicted from the following equation:
266
T.A. Saleh et al. / Journal of Colloid and Interface Science 396 (2013) 264269
Fig. 1. SEM image of the surface structure of the tire-derived activated carbon.
The IR spectra of the tire-derived activated carbon were measured by recorded on a PerkinElmer FTIR 180 spectrophotometer
using KBr pellets over the range 4000400 cm1. The spectrum,
not shown, displays a number of bands. The assignment of the carbonyl band to an ester is conrmed by observation of a strong band
in the CAO stretching region at about 1180 cm1 (broad band
11001300 cm1) [52]. The band at 1580 cm1 is attributed to
C@C double bonds [53]. The carboxylic acid group is usually presumed to take part in the adsorption of metal ions from aqueous
solution [54]. The bands at 1710 and 1650 cm1 are ascribable in
turn to stretching (m) (C@O) vibrations of carboxyl and carbonyl
in acidic oxygen surface groups. The band at 3400 cm1 is attributed to stretching (OAH) vibration in hydroxyl groups. The band
at 2350 cm1 is attributed to CC stretching vibration of the alkyne group [55].
Element
Weight%
Atomic%
1
2
CK
OK
Total
93.95
6.05
100.00
95.39
4.61
Fig. 3. The effect of contact time on the amount of lead ions adsorbed on the tirederived activated carbon. (Conditions: initial lead concentration 20 ppm; dosage of
adsorbent = 0.5 mg; pH 5; agitation speed = 150 rpm; contact time = variable.)
267
T.A. Saleh et al. / Journal of Colloid and Interface Science 396 (2013) 264269
150 rpm keeping all other experimental variables (initial lead concentration 20 ppm; dosage of adsorbent = 0.5 mg; pH 5; contact
time = 80 min) constant. It was observed that the percentages of
lead adsorbed increased as the agitation speed was increased,
Fig. 5. The removal ratio of lead increased from about 25% to
around 85% by increasing the speed between 20 and 150 rpm.
The adsorption capacity was greatest when agitation speed of
120 and 150 rpm was used. Fig. 5 shows that the extent of adsorption is not independent of agitation rate until the latter exceeds
120 rpm. Thus, at slower agitation rates, equilibrium is not attained in 80 min.
the adsorbent surface metal binding sites and the metal chemistry
in water [56].
As a function of solution pH, Pb2+ is the dominant species below
pH value of about 6. Between pH 6 and 8, Pb undergoes hydrolysis to
Pb(OH)+. Above pH 9, solid lead hydroxide Pb(OH)2 is thermodynamically the most stable phase, while PbOH
3 is predominant at
pH above 11 [57,58]. In order to nd the optimal pH value for the
sorption process, the pH of feed solution was examined using solutions of different pH levels, covering a range of 2.09.0. At
pH > 7.0, the Pb(II) gets precipitated due to hydroxide anions
forming a lead hydroxide precipitate. As shown in Fig. 7, the range
between 2 and 7 was chosen to avoid metal solid hydroxide precipitation. The results indicate that the removal of lead ions onto the
activated carbon is pH dependent. At low pH range between 2.0
and 3.0, hydrogen ions compete with lead ions for the surface of
the adsorbent which would hinder Pb(II) ions from reaching the
binding sites of the sorbent caused by the repulsive forces. The
increase in metal removal as pH increases to 4 can be explained on
the basis of a decrease in competition between protons (H+) and
positively charged metal ions at the surface sites. The maximum
uptake of lead ions is obtained at pH 5 and 6 with highest efciency
of 85%. This can be explained by the point of zero charge of the
developed activated carbon which was measured and found to be
at 4.5 (pHpzc = 4.5). According to the Pb(II) speciation diagram and
in this range of pH, the dominant species of sorption are Pb2+ [59].
At pH of 5 or 6, the adsorbent surface is negative and the lead presents as Pb2+ which reect the electrostatic adsorbate/adsorbent
interactions.
3.3. Computational study
For further understanding of the chemistry behind the process,
density functional theory (DFT) calculations were performed at the
Fig. 5. The effect of agitation speed on the amount of lead adsorbed on the tirederived activated carbon. (Conditions: initial lead concentration 20 ppm; dosage of
adsorbent = 0.5 mg; pH 5; agitation speed = variable; contact time = 80 min.)
Table 2
Binding energies (kcal/mol) and bond distances (angstroms) of the adsorption of
mono-binding lead ion on functionalized pyrenes as calculated at the B3LYP/6-31+G
level of theory.
Site type
Fig. 6. The effect of dosage on the amount of lead ions adsorbed on the tire-derived
activated carbon. (Conditions: initial lead concentration 20 ppm; dosage of adsorbent = variable; contact time = 80 min; pH 5; agitation speed = 150 rpm.)
Pyr-COOH
Pyr-C@O
Pyr-OH
Pyr-COOH
BE (kcal/mol)
Bond distance ()
Ecorrected
337
333
330
319
337
334
329
319
2.446
2.185
2.498
2.519
268
T.A. Saleh et al. / Journal of Colloid and Interface Science 396 (2013) 264269
Fig. 8. Optimized models of mono-binding of Pb(II) ion with (a) carbonyl oxygen of the carboxylic acid, (b) carbonyl oxygen, (c) alcoholic oxygen, and (d) alcoholic oxygen of
the carboxylic acid.
the Science & Technology Unit at King Fahd University of Petroleum & Minerals (KFUPM) for funding this work through Project
No. 10-WAT1400-04 as part of the National Science, Technology
and Innovation Plan.
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