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Desalination
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / d e s a l
a r t i c l e i n f o a b s t r a c t
Article history: In this study, two series of functionalized samples were prepared by means of oxidation of a commercially
Received 18 August 2009 available activated carbon with either HNO3 or H2O2. The effect of the liquid-phase oxidation on the Pb2+
Received in revised form 10 January 2010 adsorption capacities of activated carbon was investigated. The porous structure of the functionalized
Accepted 16 January 2010
activated carbon was characterized using N2 adsorption at 77 K. The surface functional group characteristics
Available online 6 February 2010
were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, Zeta potential as well
as the point of zero charge (pHPZC) measurement. The adsorption capacity for lead ions in aqueous solution
Keywords:
Activated carbon was found to depend on the amount of acidic oxygen functional groups. The isothermal adsorption data were
Modification measured and were fitted with the Langmuir and Freundlich isotherm model. The adsorption capacity of
Liquid-phase oxidation activated carbon oxidized with HNO3 (10 mol L− 1) at 363 K was about 2.5 times higher than that of the
Adsorption original activated carbon. The increase in the adsorption capacity of the oxidized activated carbons is
Lead ions attributed to the increased oxygen groups, which enhanced the hydrophilicity of the activated carbon,
lowered the pHPZC, made the surface more negatively charged, and increased the amount of homogeneous
active sites available for lead ions.
© 2010 Elsevier B.V. All rights reserved.
0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.01.011
X. Song et al. / Desalination 255 (2010) 78–83 79
condition for a specific activated carbon only on the basis of results transform spectrophotometer (Nicolet Model Nexus 670, U.S.A) using
from literature without experimental determination because the pellets of KBr containing about 0.5% finely ground activated carbon
activated carbons reported are derived from different precursors and samples. These pellets were dried overnight at 393 K before the
their physical and chemical properties vary considerably. spectra were recorded and the spectra were the results of averaging
The objective of this work is to investigate the effect of surface 32 scans with a spectral resolution of 2 cm− 1 in the range of 400–
modification on the adsorption of trace lead ions from aqueous 4000 cm− 1.
solution. Two series of samples were prepared by means of oxidation
of a commercially obtained activated carbon with either HNO3, or 2.4. Acid/base titrations
H2O2. Prior to oxidation treatment, the activated carbon was deashed
with HCl because ash constituents usually give hydrophilic sites on The amphoteric characteristics of the treated activated carbon
the activated carbon surface. The changes of physicochemical samples were characterized by measuring the amount of the surface
properties of the activated carbons upon the treatment were functional groups using the acid–base titration method proposed by
investigated by N2 adsorption, Fourier transform infrared (FTIR) Boehm [23]. According to this method, activated carbon samples each
spectroscopy, acid/base titrations, Zeta potential and point of zero with 0.2 g were placed into 50 mL conical flasks containing 25 mL
charge (pHPZC). An optimal treatment condition was obtained based aqueous solution of the following material respectively: sodium
on the analysis of the relationship between the properties of surface hydroxide, sodium carbonate, sodium bicarbonate and hydrochloric
functional groups and adsorption capacity of the activated carbons. acid. The concentration of the aqueous solution was 0.05 M. The
containers were then sealed with rubber caps and shaken for 24 h at
2. Experimental section 298 K, after which the resulting suspensions were filtered and 10 mL
of accurately withdrawn aliquot of filtrates were titrated up to pH 4.5
2.1. Liquid-phase oxidation treatment by 0.05 M hydrochloric acid in order to estimate the residual base or
up to pH 11.5 by 0.05 M sodium hydroxide for the residual acid. The
A commercial coconut-shell derived activated carbon (obtained titration value was measured three times for each sample and then
from Shanghai Xinhuoli Activated Carbon Co., Ltd, China) was used as the amount of acidic/basic functional groups was calculated using the
the precursor. This activated carbon was ground and sieved to a final average of the three titration data.
particle between 50 and 60 mesh. Then, a fraction of it was purified
(mainly for elimination of ash impurities) by treatment with 2.5. pH at the point of zero charge (pHPZC)
HCl (2 mol L− 1) at room temperature for 12 h. The amount of HCl
solution used was 2 ml g− 1. After the HCl-purification, the activated The pH at the point of zero charge (pHPZC) of the activated carbon,
carbon was washed with deionized water until no further change in namely the pH value required to give zero net surface charge, was
pH could be detected, and then it was dried at 383 K for 24 h (denoted measured using mass titration method proposed by Noh and Schwarz
as AC0). The HCl-treated activated carbon was subsequently subjected [22]. For the measurement of the pHPZC, three solutions with different
to liquid-phase oxidation treatment as follows: (i) oxidation of initial pH values, pH = 3, 6, 11, were prepared with addition of 0.05 M
sample AC0 with 10 mol L− 1 H2O2 at room temperature and at 363 K aqueous solution of HNO3 or NaOH. NaNO3 was used as the
for 24 h (samples labeled as AC1 and AC2, respectively); (ii)oxidation background electrolyte. For each initial pH, ten containers were filled
of sample AC0 with 10 mol L− 1 HNO3 at room temperature and at with 20 ml of the solution and different amounts of activated carbon
363 K for 4 h (samples labeled as AC3 and AC4 respectively) and with were added (0.05, 0.1, 0.25, 0.5, 1, 1.5, 2.5, 4, 6, and 10% by weight).
5 mol L− 1 HNO3 at 363 K for 4 h (labeled as AC5). The oxidation was The containers were sealed under N2 and placed on a thermostatic
conducted under stirring in a three-necked flask equipped with a swing shaker for 24 h. Then the carbon was separated and the pH was
stirrer and a reflux condenser and heated in a thermostat water bath. measured. A plot of the equilibrium pH versus mass fraction yields a
The amount of the oxidizing solution used was 10 ml g− 1. The curve showing a plateau and the pHPZC is identified as the point at
oxidized activated carbons were washed repeatedly with deionized which the change of pH is zero. The pHPZC is then taken as the average
water until the pH of the effluent water was constant, dried at 383 K of the three asymptotic pH values.
for 24 h and stored in a desiccator for later use. For the determination
of pHPZC and pHIEP, the measurement was carried out 10 min after the 2.6. Zeta potential measurement
oxidation treatments in order to avoid atmospheric oxidation as much
as possible. Zeta potential was obtained using a Zeta Potential Analyzer
(Coulter Delsa440SX, U.S.A). Samples prepared for determination of
2.2. Textural characterization pHPZC were also used for the zeta potential measurements. Approx-
imately 0.5 g of fresh sample with a particle size below 0.038 mm
The textural characterization of the activated carbons was carried (400 mesh) was added to a plastic bottle containing 1 L of freshly
out using N2 adsorption at 77 K with a Quantachrome Autosorb-1 outgassed CO2-free deionized water, sealed under N2 and hand-
apparatus. Prior to the N2 adsorption measurement, samples were shaken periodically during 24 h to ensure complete wetting of the
outgassed under vacuum at 423 K for 6 h. The cross sectional area of sample. The suspension was dispersed by ultrasonic before being
nitrogen at 77 K was taken as 0.162 nm2. Specific surface areas were transferred to the electrophoresis cell. The pH of the slurries measured
calculated via the BET model at relative pressures of P/P0 = 0.01–0.1. by a pHS-3C pH meter was adjusted by adding either HCl or NaOH. In
The total pore volume was estimated from the uptake of nitrogen at a each case, the zeta potential was measured three times for each pH to
relative pressure of P/P0 = 0.99. Surface area and pore volume of provide an average value.
micro-pores were calculated via t-plot analyses as a function of
relative pressure using the Carbon Black model for thickness curves 2.7. Adsorption of lead ions
measured between 4.5 and 7.0 Å.
The stock solution of Pb2+ was prepared from lead nitrate
2.3. Fourier transform infrared (FTIR) spectroscopy (analytical reagent grade) at a concentration of 1 g L− 1. Experimental
solutions of lead were prepared by appropriately diluting a different
The surface functional groups of some selected samples were volume of stock solution to achieve the desired concentration. The pH
investigated by transmission infrared spectra obtained from a Fourier of the working solutions was adjusted to 4 by adding different
80 X. Song et al. / Desalination 255 (2010) 78–83
3.3. Acid/base titrations basic character such as ACO will readily adsorb protons from solution,
whereas those with acidic character and lower pHPZC value will
The acid/base titration results of the samples are shown in Table 2. release protons to form net negative surface charges, which is
Taking into account that NaOH titrates carboxyl, lactone and phenolic beneficial for the aqueous lead cation adsorption.
groups, Na2CO3 titrates carboxyl and lactone, and NaHCO3 titrates
only carboxyl groups, one can therefore obtain the amount of the
different acid groups present on the activated carbons [26]. The data 3.5. Zeta potential measurement
presented in Table 2 indicate that the original carbon AC0 does not
react with Na2CO3 and NaHCO3 due to the absence of strongly acidic As mentioned above the activated carbons show amphoteric
surface groups such as carboxylic groups. Oxidation treatment results property, therefore, it is possible to evaluate their isoelectric point
in an increase in the total surface acidity and a decrease in the total (pHIEP), i.e. the pH at which the zeta potential is zero. Fig. 2 gives the
surface basicity. This phenomenon is due to the presence of different results of zeta potential measurements and Table 2 gives the pHIEP
types and concentrations of functional groups which give the values of the original and the oxidized carbons. The pHIEP value of the
amphoteric characteristics to activated carbons in aqueous solution. original carbon is 3.5. Oxidation results in a decrease of the pHIEP
The greatest surface acidity was obtained after drastic nitric acid values, especially those of AC4 and AC5, which pHIEP could not be
oxidation treatment. An intermediate surface acidity and basicity was detected in the pH range of 2–12 due to the presence of weakly acidic
obtained with a treatment by concentrated hydrogen peroxide at carboxylic functional groups with lower dissociation pH values. Thus,
363 K. The concentration of lactone and carboxylic groups on the dissociation of the groups in the pH range of 2–5 renders the
activated carbon surface after different oxidation treatment follows surface of AC4 and AC5 to be negatively charged.
the sequence AC4 > AC5 > AC2 > AC3 > AC1 > AC0. It has been suggested that the isoelectric point value is represen-
It is generally accepted that oxidization treatment leads to the tative of the external charges of carbon particles in solution, whereas
incorporation of a great number of acidic oxygen-containing groups the point of zero charge varies in response to the net total (external
on the surface of the activated carbon. However, as shown in Table 2, and internal) surface charge of the particles [23,35]. The difference
the oxidized activated carbons always contain basic surface sites in between pHPZC and pHIEP values would give an indication of the
addition to the acidic sites, though their number is usually smaller surface charge distribution of the porous activated carbon. As shown
than that of the original carbon (AC0). The basic sites are of Lewis type in Table 2, when the original sample was oxidized with HNO3 and
and are associated with the presence of basic oxygen and nitrogen H2O2, both the pHPZC and pHIEP values became lower than those
functional groups, such as pyrone-like structures, and with π electron- observed for the original sample, indicating an increase in acidic
rich regions within the basal planes of activated carbon [23,34]. In oxygen-containing surface groups [36–38]. However, for these
contrast, the acidic oxygen functional groups, incorporated by liquid- samples, as pHPZC > pHIEP, the internal surface is always more basic
phase oxidation show characteristics of Brønsted acid. than the external surface. Upon oxidation, the pHPZC values, all in the
acid range, decrease to a greater extent than the pHIEP values,
although pHPZC is still higher than pHIEP and the difference between
3.4. pH at the point of zero charge (pHPZC) pHPZC and pHIEP decreases sharply from the original carbon to the
oxidized carbons. This means that the external surface is somewhat
The point of zero charge describes the condition when the more acidic than the internal surface, but the introduction of the
electrical charge density on a surface is zero. The pH of point of zero acidic oxygen-containing groups essentially takes place on the
charge (pHPZC) of an activated carbon depends on the chemical and internal surface, showing a uniform oxidation. In the cases of AC4
electronic properties of the functional groups on its surface and is a and AC5, the lowest {pHpzc–pHIEP} difference shows that more
good indicator of these properties. Table 2 gives the pHPZC values of uniform oxidation took place, and will render more acidic sites to
the original and the oxidized activated carbons. The original carbon release protons for exchange with lead ions in the adsorption process.
AC0 has a pHPZC value of 10.1. Upon oxidation treatment, the pHPZC of
the activated carbons decreased markedly due to an increase in the
amount of the surface acidic oxygen-containing groups. Carbons
oxidized with nitric acid at 363 K (AC4 and AC5) give the lowest pHPZC
values about 3.1. The pHPZC of AC3 oxidized with nitric acid at ambient
temperature is 4.9, which is significantly higher than that of AC4 and
AC5. This means that oxidation of the activated carbon at higher
temperature produce higher amount of acidic groups. This is also the
case for the carbons oxidized with H2O2 (AC1 and AC2).
As shown in Table 2, the amount of the basic sites on AC1, AC2, and
AC3 is much more than that on AC4 and AC5. Activated carbons with
Table 2
Acid/base titration and pHPZC and pHIEP of the activated carbons used in this study.
Q0 KL Ce
qe = ð2Þ
1 + KL Ce
1=n
qe = KF Ce ð3Þ
Where
Table 3
Values of the parameters for Langmuir model and Freundlich model.
a
Activated pHads Initial concentration Langmuir parameters Freundlich parameters
carbon (mg L− 1)
Q0 (mg g− 1) KL (L mg− 1) b 2
R KF (mg g− 1 (L g− 1)1/n) 1/n b 2
R
Acknowledgements
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