Studies on salophen anchored micro/meso porous activated carbon fibres for the removal and recovery of uranium

Article abstract of DOI:10.1039/c5ra03168k

Stringent environmental regulations emphasize the removal of uranium from aqueous systems. Activated carbon fibers (ACF) were functionalized by oxidation (ACF-OX) and salophen ligand (ACF-Sal) and evaluated for the removal of uranium. The prepared sorbents were characterized by various techniques such as scanning electron microscopy (SEM), energy dispersive X-ray (EDAX), Fourier transform infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) surface area analyzer and X-ray photoelectron spectroscopy (XPS). The anchoring of salophen ligand onto ACF surface was evident from the FTIR and XPS studies. The adsorption properties of UO₂²⁺ as a function of pH and contact time were characterized by inductively coupled mass spectrometry (ICPMS). The adsorption kinetics fitted the pseudo second order kinetics and equilibrium was reached within 180 minutes. The experimental data were modelled with Langmuir and Freundlich isotherms and various isotherm parameters were evaluated. The maximum adsorption capacities of U(VI) at pH 6 for ACF, ACF-OX and ACF-Sal were found to be 22.2, 50.0 and 142.8 mg g^-1, respectively. Thermodynamic studies revealed the spontaneity of the reaction and influence of other cations and anions on the sorption behaviour of uranium has been studied. Studies have been conducted to demonstrate the recyclability of the sorbent for five consecutive sorption desorption cycles. Using FTIR and XPS studies, a suitable mechanism for uranium sorption has also been postulated.

Full text of DOI:10.1039/c5ra03168k

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PAPER
Studies on salophen anchored micro/meso porous
activated carbon fibres for the removal and
recovery of uranium
Cite this: RSC Adv., 2015, 5, 33023
b
c
a
Shruti Mishra,ab Jaya Dwivedi, Amar Kumar and Nalini Sankararamakrishnan
*
Stringent environmental regulations emphasize the removal of uranium from aqueous systems. Activated
carbon fibers (ACF) were functionalized by oxidation (ACF-OX) and salophen ligand (ACF-Sal) and
evaluated for the removal of uranium. The prepared sorbents were characterized by various techniques
such as scanning electron microscopy (SEM), energy dispersive X-ray (EDAX), Fourier transform infrared
(FTIR) spectroscopy, Brunauer–Emmett–Teller (BET) surface area analyzer and X-ray photoelectron
spectroscopy (XPS). The anchoring of salophen ligand onto ACF surface was evident from the FTIR and
2+
XPS studies. The adsorption properties of UO2
as a function of pH and contact time were
characterized by inductively coupled mass spectrometry (ICPMS). The adsorption kinetics fitted the
pseudo second order kinetics and equilibrium was reached within 180 minutes. The experimental data
were modelled with Langmuir and Freundlich isotherms and various isotherm parameters were
evaluated. The maximum adsorption capacities of U(VI) at pH 6 for ACF, ACF-OX and ACF-Sal were
found to be 22.2, 50.0 and 142.8 mg gꢀ1, respectively. Thermodynamic studies revealed the spontaneity
of the reaction and influence of other cations and anions on the sorption behaviour of uranium has been
studied. Studies have been conducted to demonstrate the recyclability of the sorbent for five
consecutive sorption desorption cycles. Using FTIR and XPS studies, a suitable mechanism for uranium
sorption has also been postulated.
Received 19th February 2015
Accepted 24th March 2015
DOI: 10.1039/c5ra03168k
www.rsc.org/advances
removal of uranium from large volumes of wastewater. Several
methods, including ion exchange, reduction, reduction fol-
1. Introduction
lowed by chemical precipitation, electrochemical precipitation,
membrane separation, solvent extraction, biosorption, and
adsorption, are utilized to remove uranium from wastewater
and process effluents. Among the various removal technologies
for U(VI) reported, adsorption is the most versatile technique
owing to its ease of operation, low waste generation and
considerably low recurring cost. The removal of U(VI) by various
adsorbents has been adequately reviewed.4,5 Carbon based
sorption materials offer various advantages such as higher
radiation and thermal resistance than commonly used organic
exchange resins and improved chemical stability than widely
used inorganic sorbents in strongly acidic solutions in the
majority of nuclear wastewaters.4 Carbonaceous materials,
including activated carbon,6,7 activated carbon bres, carbon
nanotubes8–10 and mesoporous carbon,11 have been reported in
the applications of U(VI) sorption. To improve the selectivity and
sorption capacity towards targeted metal ions, functionalization
with specic ligands are generally used.4 Among these carbo-
naceous materials, activated carbon bres (ACF) are unique
owing to their large porous surface area, controllable pore
structure, thermo-stability and low acid/base reactivity.
Furthermore, ACFs are microporous materials possessing high
surface area (ꢁ1200–1800 m2 gꢀ1), which is a prime factor for an
Uranium is the second heaviest naturally occurring radioactive
element. Uranium is the basic energy element of the present
Indian nuclear power programme. It starts as a source of the
fuel cycle and nally ends up as a waste component. Uranium is
a well-known nephrotoxic heavy metal. It is reported that an
exposure of 0.1 mg per kg body weight of natural U results in
transient chemical damage to the kidneys.1 The maximum
contaminant level of U(VI) in water set by the Environmental
Protection Agency (EPA) is 30 mg Lꢀ1, whereas the World Health
Organization's guideline value is set at 50 mg Lꢀ2. According to
the Atomic Energy Research Board (AERB) of India, the
maximum allowable concentration of U(VI) in water bodies is 60
mg Lꢀ1. In aquatic environments, uranium predominantly exists
in its hexavalent oxidation state, e.g. UO22+. These hexavalent
uranyl ions are highly mobile and migrate as stable uranyl
carbonate complexes under near surface conditions.3 Cost
effective remediation technology is required to tackle the
aCentre for Environmental Science and Engineering, Indian Institute of Technology
Kanpur, Kanpur, U.P. 208016, India. E-mail: nalini@iitk.ac.in; Tel:
+91915122596360
bDepartment of Chemistry, Banasthali Vidyapith, Rajasthan 304022, India
cBhabha Atomic Research Centre, Trombay, Mumbai, India
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adsorbent. In ACF, micropores which are responsible for
adsorption are connected to the external surface directly by
narrow diameter bres (10–20 mm). Thus, the diffusion length is
small, resulting in negligible mass transfer coefficient and the
removal rate of pollutants is adsorption controlled.12 ACFs have
been found useful for the removal of variety of pollutants like
Cd(II) and Pb(II),12–14 Ni(II) and Zn(II),15–17 SO2, NO and CO2,18 and
2-chloroethanol.19 Jung et al.20 have reported the electrosorption
of uranium (U(VI)) ions onto a porous ACF. However, there are
seldom any reports in the literature on the use of functionalized
ACFs towards U(VI) removal. It is well known that salophen is a
tetradentate ligand that can easily combine with uranyl cation
to form a stable uranyl–salophen complex21,22 and has been
found useful for the determination of trace U(VI). Thus, this
study pertains to the development of functionalized activated
carbon bres by oxidation (ACF-OX), graing of salophen ligand
(ACF-Sal) and its applicability for U(VI) removal. The systematic
structural characterization of the functionalized sorbents,
namely, ACF-OX and ACF-Sal, were performed using various
techniques and optimization of reaction parameters, including
pH and reaction time, were carried out. Isotherm, thermody-
namic and kinetic models were evaluated and a suitable
mechanism for the adsorption of U(VI) using FTIR and XPS has
also been postulated.
2. Materials and methods
All the chemicals including, sodium hydroxide (NaOH), nitric
acid (HNO3), uranyl(vi) nitrate (UO2(NO3)2$6H2O), and other
reagents and solvents (ethanol, acetone) used in this study were
of analytical grade and all the solutions were prepared using
Milli-Q puried water (resistivity > 18.2 MU cm). 4-Hydroxy-
salicylaldehyde, thionyl chloride and 1,2-diaminoethane were
acquired from Sigma Aldrich chemicals. Activated carbon bres
were purchased from Nippon Kynol In. (Osaka Japan).
2.1 Preparation of ACF-OX
Around 1 g of ACF samples were treated with 20 mL of 1 : 1
mixture of conc. HNO3 and water and heated at 60 ꢂC for 30
min, followed by a thorough washing with distilled water and
ꢂ
dried in an oven for 12 h at 120 C.
2.2 Preparation of salophen ligand
A stoichiometric amount of 4-hydroxysalicylaldehyde (0.02 mol,
2.76 g) in dissolved methanol (25 mL) was added dropwise to
1,2-diaminoethane solution (0.01 mol, 0.60 g) in 25 mL meth-
anol. The contents were reuxed for 4 h and a bright yellow
precipitate of symmetrical Schiff-base ligand, H2[(OH)2–salen],
was obtained.
Scheme 1 Schematic representation of ACF functionalization.
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2.3 Preparation of ACF-Sal
2.4 Batch studies
Initially, chlorinated ACFs were prepared. Around 100 mg of Adsorption experiments were carried out by a batch technique.
ACFs were suspended in a solution of SOCl2 (25 mL) and DMF About 0.05 g of adsorbent was placed in a beaker containing 20
(1 mL). The suspension was stirred at 65 ꢂC for 24 h. The solid mL of 0.1 to 500 mg Lꢀ1 of U(VI) solution for ACF and ACF-OX
was then separated by ltration, washed with anhydrous THF, and 0.1 to 1000 mg Lꢀ1 for ACF-Sal. The pH of the solution
and dried in vacuum. To a solution of salophen (100 mg) in was adjusted to 6.0 by adding 10% sodium hydroxide or 10%
degassed CHCl3 (8 mL), chlorinated ACFs were added (50 mg) sulphuric acid solutions. The suspension was stirred for 3 h at
and the suspension was stirred for 20 h under N2 atmosphere at an agitation speed of 110 rpm. At the end of the equilibrium
ꢂ
70 C. The solid was then separated by ltration, exhaustively time, the content was separated by ltration with a 0.22 mm pore
washed with THF and CH2Cl2, and dried under vacuum. The size lter paper and U(VI) in solution was analyzed by inductively
schematic of the preparation of ACF-OX and ACF-Sal is shown coupled plasma-mass spectrometry (ICP-MS) (Thermo Scien-
in Scheme 1.23
tic, XSERIES 2). All the experiments were repeated twice. The
Fig. 1 SEM images of (a) pristine ACF, (b) ACF-OX, (c) ACF-Sal, and (d) EDAX spectra of ACF-Sal-U.
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amount of the U(VI) adsorbed (mg) per unit mass of sorbent (g), and equilibrated with 20 ml of 0.1 M H3PO4 for 30 min and the
qe, was obtained by mass balance using the following equation: adsorbent was ltered, thoroughly washed with water and used
for the consequent adsorption cycle.
ðCi ꢀ CeÞ
qe ¼
ꢃ V
(1)
m
where Ci and Ce are initial and equilibrium concentrations of
the U(VI) (mg Lꢀ1), m is dry mass of sorbent (g) and V is the
volume of the solution (L). Kinetic experiments were conducted
by equilibrating 20 mL of 100 mg Lꢀ1 of U(VI) at a dose rate of 5.0
g Lꢀ1 and the pH was maintained at 6.0 during equilibration.
The amount of uranium adsorbed was monitored at regular
time intervals. The effect of competing cations and anions were
examined by maintaining the initial concentration of uranium
at 100 mg Lꢀ1. Using the same conditions mentioned above,
thermodynamic studies were carried out by equilibrating the
solutions for 3 h at three different temperatures at 25 ꢂC, 35 ꢂC
and 45 ꢂC and the amount of uranium adsorbed was deter-
mined. Recyclability studies were performed using 0.1 M H3PO4
as the desorbent. Aer each cycle, the adsorbent was ltered
2.5 Analytical measurements
Fourier transform infrared (FTIR) measurements were made with
KBr pellets using a Tensor 27 (Bruker, Germany) in the attenu-
ated total reectance (ATR) mode. A FEI Quanta 200 machine was
used for scanning electron microscopy (SEM). XPS measure-
ments were performed using a PHI 5000 Versa Prob II (FEI Inc.)
spectrometer using nonmonochromatic Al Ka radiation (1486.6
eV). XPSPEAK41 soware with a Gaussian–Lorentzian line shape
was used for the deconvolution of individual spectral peaks. A
nonlinear Shirley background subtraction was applied for tting
each spectral region. The adsorbent was analyzed for the pore
size distribution (PSD), specic surface area and pore volume by
N2-physisorption using a Autosorb-1C instrument (Quantach-
rome, USA). Uranyl ions concentrations were determined by
Fig. 2 FTIR spectra of (a) plain ACF (b) ACF-OX and (c) ACF-Sal.
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Table 1 Surface area and pore volumes of virgin and functionalized ACF
Pore volume (cc gꢀ1
)
Surface area
Average diameter
(nm)
Total pore volume
Adsorbent
(m2 gꢀ1
)
(cc gꢀ1
)
Meso
Micro
ACF
ACF-OX
ACF-Sal
1337.0
1416.5
1410.0
2.10
0.95
0.98
0.7020
0.6737
0.6800
0.031
0.033
0.032
0.6320
0.6407
0.6480
Inductive coupled plasma mass spectroscopy ICP-MS (Thermo, X-
Series2). Calibration was carried out daily with freshly prepared
uranium standards before sample analysis.
3.1.3 BET measurements. The specic surface area of ACF,
ACF-OX and ACF-Sal was obtained over the relative pressure
range from 0.05 to 0.35 using the standard BET method. The
total pore, mesopore and micropore volumes were calculated
using the instrument's soware supplied by Quantachrome
using Barrett–Joyner–Halenda (BJH) and density functional
theory (DFT) methods. Table 1 summarizes the data for BET
surface area and pore volumes of various ACFs. The large
surface area and small pore size of these materials lead to the
strong connement of the adsorbed phase, together with strong
interactions with the surface. It is evident that the surface area
of the ACFs increased from 1337 m2 gꢀ1 to 1416.5 m2 gꢀ1 upon
oxidation with nitric acid and further graing with salophen
ligand does not affect the surface area of the sorbent. During
oxidation, the increased surface area could be attributed to the
opening of pores. The marginal decrease in pore volumes of
functionalized ACFs could be attributed to the blockage of inter-
bundle galleries and intra-bundle interstitial channels by
various functional groups.
3. Results and discussion
3.1 Characterization of adsorbent
3.1.1 SEM analysis. SEM images of ACF, oxidized ACF, and
ACF-Sal are shown in Fig. 1a–c, respectively. ACF are composed
of bundles of bres with a diameter of about 10 mm. It is evident
from the images that the surfaces of pristine ACF, ACF-OX and
ACF-Sal are found to be smooth. The loading of uranium on
ACF-Sal was conrmed from the Energy Dispersive X-ray anal-
ysis (EDAX), as shown in Fig. 1d.
3.1.2 FTIR spectra. FTIR spectra from the ACFs show a
broad peak at ꢁ3445 cmꢀ1, which is a characteristic of the O–H
stretch of the hydroxyl group (Fig. 2a), arising from the oscil-
lation of carboxyl groups. The peaks at 2891 and 2920 cmꢀ1
correspond to –CH2 and –CH symmetric stretch, respectively.
The C]C stretching vibration was found at 1632 cmꢀ1. An
additional peak at 1720 cmꢀ1 corresponding to C] O stretching
was found aer the oxidation of ACF with nitric acid (ACF-OX)
(Fig. 2b).24 In the salophen anchored ACF (Fig. 2c), the peaks
at 1510 and 1620 cmꢀ1 are attributed to the absorption of
carbon–nitrogen double bond of the azomethine group.23
Furthermore, additional peaks at 1210 cmꢀ1 and 1116 cmꢀ1 are
due to the C–O and C–N stretching vibration, respectively.21
3.2 Effect of initial pH
The effect of the variation of initial pH in the range of 1–9 on
adsorption using ACF, ACF-OX and ACF-Sal was examined. The
initial concentration of U(VI) was maintained at 100 mg Lꢀ1
.
Efforts were made not to maintain the pH throughout the
sorption experiments. The results obtained are shown in Fig. 3.
It is evident from the gure that the sorption of U(VI) increased
greatly from pH 4 to pH 6 and further increases in pH resulted
2+
in decreased sorption. At pH # 3, UO2 is the predominant
species of ions and sorption is found to be very low owing to the
competition of H+ ions for the active binding sites of the
sorbent.9 In the pH range of 5.5–7.5, the hydrolysis of uranyl
ions occurs and various multinuclear hydroxyl complexes are
2+
prevalent,
including
UO2(OH)+,
(UO2)2(OH)2
and
+
(UO2)3(OH)5 .25 Thus, the maximum adsorption of U(VI) was
found at pHꢀ6. At pH values greater than 7, anionic U(VI) species
(UO2)3(OH)7 were prevalent, which resulted in low sorption
capacity.26 Furthermore, the amount of U(VI) increased from
18.56 mg gꢀ1 to 35.2 mg gꢀ1 aer functionalization with salo-
phen ligand. This can be explained by the complexation of U(VI)
and salophen ligand, which are detailed in section 3.9.
3.3 Effect of contact time
Sorption of U(VI) on ACF-Sal as a function of contact time was
carried out at pH 6.0 ꢄ 0.1. The results obtained are shown in
Fig. 4a. The sorption of U(VI) on ACF-Sal was shown to be rapid and
Fig. 3 Effect of initial pH on ACF, ACF-OX and ACF-Sal with U(VI).
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Fig. 4 (a) Effect of equilibration time, (b) pseudo first order kinetic model, (c) second order kinetic model, (d) pseudo second order kinetic model,
and (e) Web–Morris model of ACF-Sal and uranium system.
a contact time of 3.5 h was enough to reach sorption equilibrium.
Thus, all the experiments were carried out at 4 h equilibration
time. The kinetics of U(VI) adsorption onto ACF-Sal was modelled
using the Lagergren model27 or pseudo rst order, second order28
and pseudo second order,29 as shown in eqn (2)–(4), respectively.
Table 2 Kinetic parameters of ACF-Sal and U(VI) systems
Pseudo rst order Second order Pseudo second order
kl (minꢀ1
)
R2
k2
R2
k20
R2
kl
logðqe ꢀ qtÞ ¼ log qe ꢀ
t
(2)
(3)
(mg gꢀ1 minꢀ1
)
(mg gꢀ1 minꢀ1
)
2:303
0.0069
0.951 0.001
0.833 0.0007
0.986
1
1
¼
þ k2t
qe ꢀ qt
qe
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the U(VI) adsorbed and the intraparticle rate constant (kint) given by
eqn (5)
t
1
t
¼
þ
(4)
k20 qe
qe
2
qt
pffiffi
qt ¼ kint t þ C
(5)
where kL is the Lagergren rate constant of adsorption (minꢀ1);
k2 the second-order rate (g mgꢀ1 minꢀ1) and k20 the pseudo-
second-order rate constant of adsorption (g mgꢀ1 minꢀ1); qe
and qt are the amounts of U(VI) ion (mg gꢀ1) at equilibrium and
at time t, respectively. The plots of various models are depicted
in Fig. 4b–d. The rate constants obtained for various kinetic
models are given in Table 2. It is evident that among the pseudo
rst order, second order and pseudo second order plots, the
pseudo second order plot of t/qt vs. t, Fig. 4c, yielded a straight
line with correlation coefficients of >0.98. Thus, it could be
concluded that the sorption of U(VI) with ACF-Sal followed
pseudo second order kinetics. Since this model is based on the
assumption that the rate-limiting step may be chemical sorp-
tion, involving valency forces through sharing or exchange of
electrons between sorbent and analyte, it is postulated that
complex formation between the salophen ligand and U(VI) ions
is the rate limiting step for the sorption of U(IV) onto ACF-Sal.
It is generally known that a typical solid/liquid sorption
involves lm diffusion or intraparticle diffusion as well. The
probability of intraparticle diffusion could be modelled by the
Weber and Morris model30 and this model relates the amount of
The plot of qt against Ot results in an intercept (Fig. 4e). If the
intraparticle diffusion is the sole rate determining step, then
the plot of qt vs. Ot should pass through the origin with zero
intercept. However, in the present scenario (Fig. 4e), qt vs. Ot
does not pass through the origin. Hence, we can conclude that
intraparticle diffusion is not the sole rate determining step for
the sorption of U(VI) on ACF-Sal. The value of intraparticle
diffusion constant (kint) of U(VI) was found to be 1.021 (g mgꢀ1
(min0.5 ꢀ1
)
)
.
3.4 Sorption isotherms
The U(VI) adsorption isotherms for ACF, ACF-OX, and ACF-Sal
are presented in Fig. 5a. The adsorption data of U(VI) over
various functionalized ACFs were modelled using various
isotherms. The most commonly used Langmuir model
describes the formation of homogeneous monolayer on the
sorbent surface. The adsorption of U(VI) ions from the bulk to
functionalized ACF surface could be expressed by Langmuir
expression31 as follows:
Fig. 5 (a) Equilibrium isotherm, (b) linearized Langmuir plot, (c) two site Langmuir plot, (d) Freundlich plot.
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Table 3 Isotherm parameters of ACF, ACF-OX and ACF-Sal with U(VI) systems
Freundlich
model
Langmuir model
Two site Langmuir model
qmax
b
qm0
b0
q0m0
b00
KF
Adsorbent
(mg gꢀ1
)
(L mgꢀ1
)
R2
(mg gꢀ1
)
(L mgꢀ1
)
R2
(mg gꢀ1
)
(L mgꢀ1
)
R2
(L gꢀ1
)
ACF
ACF-OX
ACF-Sal
22.22
50.00
142.86
0.8640
0.0149
0.0029
0.96
0.94
0.99
—
—
204.08
—
—
0.0023
—
—
1.00
—
—
101.01
—
—
0.0043
—
—
0.99
2.673
2.138
0.916
Further analysis of the Langmuir model could be achieved
based on a dimensionless equilibrium parameter called sepa-
ration factor (RL):38
qmbCe
qe ¼
(6)
1 þ bCe
where qe is the amount of U(VI) adsorbed (mg gꢀ1) at equilib-
rium and Ce is the equilibrium concentration (mg Lꢀ1). The
empirical constants qm and b denote the maximum adsorption
capacity and energy of adsorption, respectively, and were
calculated from the slope and intercept of plot between 1/Ce and
1/qe (Fig. 5b). The constant ‘b’ is attributed to the affinity
between the adsorbent and analyte in the given system. The
values obtained for the various constants are given in Table 3. It
is evident from Fig. 5a that an “S-isotherm” curve was obtained
using ACF-Sal as an adsorbent. The curve obtained is sigmoidal
with a point of deection. At low U(VI) concentrations, the
adsorption is limited by the presence of the salophen ligand.
Aer the complexation of U(VI) with the salophen ligand,
normal adsorption occurs.32 The point of inection illustrates
the concentration, for which the other process of sorption
overcomes the complexation. To further explain this behaviour,
the data obtained was modelled by the two site Langmuir
isotherm,33 given by eqn (7).
1
RL ¼
(8)
1 þ bC0
where C0 is the initial concentration of U(VI) and ‘b’ is the
Langmuir adsorption equilibrium constant (mL mgꢀ1). The
value of RL indicates that the isotherm represents a favourable
(0 < RL < 1), unfavourable (RL < 1), linear (RL ¼ 1), or irreversible
process (RL ¼ 0). For an initial concentration of 100 mg Lꢀ1, the
U(VI) RL values for ACF, ACF-OX and ACF-Sal were found to be
0.0115, 0.4016, and 0.7752, respectively. These values suggest
that the adsorption of uranyl ions by ACF and functionalized
ACFs is a favourable process.
The heterogeneity of the system is described by the
Freundlich model and its linearized form is represented below39
1
log qe ¼ log Ce þ log Kf
(9)
n
Fig. 5d denotes the Freundlich plots of various sorbents. n
and Kf are the Freundlich parameters, which represent the
adsorption capacity and adsorption intensity, respectively. For a
good adsorbent, the values of n ranged between 1 and 10. It is
evident from Table 3 that the ‘n’ values ranged between 1.335
and 2.024 with a regression coefficient of 0.93 to 0.98, indicating
the strong interaction of U(VI) ions with the adsorbent.
q0mb0Ce
1 þ b0Ce 1 þ b00Ce
q0m0 b00Ce
qe ¼
þ
(7)
The two-site Langmuir isotherms t the adsorption data well
when there are two types of adsorption sites with different
binding energies on the adsorbents.33 qm0 (mg gꢀ1) and qm00 (mg
gꢀ1) are the maximum absorption capacities and b1 (L mgꢀ1
)
and b2 (L mgꢀ1) in eqn (7) are the affinity coefficients to sites 1
and 2 on the adsorbents, respectively. The total maximum
adsorption capacity can be obtained by adding qm0 and qm00 . It is
evident from the data that the maximum adsorption capacity of
the three sorbents towards U(VI) is in the order ACF-Sal > ACF-
OX > ACF. It is evident that the sorption capacity of ACF-Sal
from the two site Langmuir model is 13.68 times higher than
plain ACF. The high sorption capacity of ACF-Sal towards U(VI)
could be attributed to the complex formation between salophen
ligand and U(VI) ions. The adsorption capacity of ACF-Sal is
signicantly higher than the adsorption capacity of various
carbon adsorbents such as plain oxidized MWCNT26 (43.32 mg
gꢀ1), carboxymethyl cellulose graed CNT34 (112.0 mg gꢀ1),
diglycolamide functionalized MWCNTs35 (133.7 mg gꢀ1), palm
shell activated carbon36 (51.81 mg gꢀ1) and imine functionalized
carbon spheres37 (113 mg gꢀ1).
3.5 Thermodynamic studies
The commonly used thermodynamic parameters, such as DG0,
DH0 and DS0, were calculated from the adsorption data.40 Initially,
Kc, the equilibrium constant, was determined by eqn (10)
Fig. 6 Thermodynamic studies of ACF-Sal and U(VI) systems.
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Table 4 Thermodynamic parameters
Table 5 Effect of competing cations on sorption of U(VI) by ACF-Sal
qmix/q0
Ce
DG
DS
DH
T (K)
(g Lꢀ1
)
Kc
(kJ molꢀ1
)
(J molꢀ1
)
[kJ (molꢀ1 Kꢀ1)]
Cations
100 mg Lꢀ1
200 mg Lꢀ1
298
308
318
0.2476
0.2309
0.2131
1.0192
1.1649
1.3463
ꢀ0.0472
ꢀ0.3909
ꢀ0.7863
Ni2+
0.91
0.82
0.97
0.90
0.99
1.00
0.89
0.76
0.94
0.86
0.92
1.00
4.439
10.96
Cd2+
Ca2+
Pb2+
Cu2+
Mn2+
Table 6 Effect of competing anions on sorption of U(VI) by ACF-Sal
Anions (0.1 M)
qmix/q0
Sulphate
Chloride
Nitrate
0.97
0.93
1.00
1.10
Phosphate
Table 7 The experimental stability constants (Kass) for the uranyl sal-
Fig. 7 Recyclability studies.
ophene (US1) complexation with anionsa
Complex
Kass [Mꢀ1
]
CA
Ce
Kc ¼
(10)
Sal–UO2–Clꢀ
Sal–UO2–NO2
Sal–UO2–HSO4
4.5 ꢃ 102
3.1 ꢃ 102
5.0 ꢃ 101
1.1 ꢃ 104
ꢀ
ꢀ
where CA (g Lꢀ1) is the concentration of solute in the aqueous
phase and Ce is the equilibrium concentration (g Lꢀ1). DG0 was
calculated using the following equation:
ꢀ
Sal–UO2–H2PO4
a
Adapted from ref Stauthammer, W. Ph.D. Thesis, University of Twente,
The Netherlands, 1994.
DG0 ¼ ꢀRT ln Kc
(11)
where R is the gas constant and T is the temperature in Kelvin.
Using the Van't Hoff eqn (12) the value of DS and DH was
determined:
adsorbed by ACF-Sal for ve consecutive sorption–desorption
cycles are depicted in Fig. 7. It is evident from the gure that
around a 20% and 40% decrease in U(VI) uptake was observed at
the end of the 3rd and 5th cycle, respectively. A similar result has
been reported using ordered mesoporous carbon as an
adsorbent.11
DS0
DH0
logKc ¼
ꢀ
(12)
2:303 2:303RT
Based on the above-calculated data, a linear plot of ln Kc vs. 1/T
was drawn for the U(VI) and ACF-Sal system (Fig. 6). Using these
plots, DS0 and DH0 were determined from the intercept and slope,
respectively. The data obtained are presented in Table 4. The
negative free energy values indicate the spontaneity and feasibility
of the process, while the positive DH0 values indicate the endo-
thermic nature of the process. Furthermore, positive values of the
entropy (DS0) of adsorption could be attributed to metal ion
dehydration due to surface sorption on ACF-Sal.
3.7 Effect of competing ions
Uranium sorption by ACF-Sal in the presence of other cations
and anions was studied. Initially, 100 ppm of U(VI) was spiked
with known concentrations of anions/cations and pH was
adjusted to 6 and equilibrated for 3 h. Aer equilibration, the
solution was ltered and the amount of U(VI) adsorbed was
analyzed using an ICP-MS instrument. The effect of these ions
on the sorption process may be represented by the ratio of
adsorption capacity in the presence of interfering ion (qmix) and
without interfering ion (q0), as shown below.41
3.6 Recyclability studies
qmix/q0 > 1, increased adsorption in the presence of other
Uranium desorption studies were conducted aer the sorption interfering ions; qmix/q0 ¼ 1, adsorption is not inuenced in the
of U(VI) using ACF-Sal as a sorbent. The conditions for adsorp- presence of other interfering ions; qmix/q0 < 1, adsorption is
tion were maintained as prescribed in Sec 2.4. Aer the suppressed in the presence of other interfering ions.
adsorption of U(VI) ions, the sorbents were ltered, washed with
The effect of cations and anions on the sorption capacity of
water, and 0.1 M H3PO4 was used as a desorbent. The sorption– ACF-Sal is detailed in Tables 5 and 6, respectively. The order of
desorption cycle was repeated for 5 cycles. The amount of U(VI) interfering effect of the various cations tested is Cd2+ > Ni2+ > Pb2+
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C 1s, and U 4f of the sorbents are demonstrated in Fig. 8. In the
survey spectra (Fig. 8), the characteristic doublet peaks of U 4f5/2
and U 4f7/2 were observed for all the loaded sorbents. The
binding energies of the various peaks and the splitting values of
uranium peaks are depicted in Table 8. The peak positions of
U(VI) adsorbed on ACF-Sal shied to relative high binding
energies as compared to those of U(VI) adsorbed onto ACF and
ACF-OX, which could be attributed to the stronger interaction of
U(VI) with ACF-Sal compared to ACF and ACF-OX. A similar
observation was observed by other researchers on uranyl sorp-
tion onto chitosan modied CNTs.43 Upon further comparison
of the splitting values of 4f5/2 and 4f7/2 peaks of U(VI) ions onto
ACF, ACF-OX, and ACF-Sal, an increasing trend is observed,
which could be attributed to stronger interaction of U(VI) with
salophen ligand.
In order to further probe the mechanism of U(VI) sorption on
to ACF-Sal at the molecular level, the XPS spectra of survey and
high resolution scans for O 1s, N 1s, and U 4f on ACF-Sal were
recorded. The O 1s, N 1s, and U 4f of the ACF-Sal before and
aer U(VI) sorption (denoted as ACF-Sal-U) are demonstrated in
Fig. 9. The peak tting results of the U 4f, O 1s, and N 1s before
and aer U(VI) sorption on ACF-Sal are listed in Table 9. As
shown in Fig. 9e, the U 4f7/2 spectrum was resolved into two
peaks: the peak at 379.5 eV corresponded to the free uranyl
adsorbed on ACF-Sal, and the peak at 381.08 eV was attributed
to covalent bond of azomethine N–U(VI).44 Fig. 9b shows that the
O 1s spectra could be resolved into three main peaks, occurring
at 530.54, 531.94 and 532.77 eV corresponding to O]C, C–O–C
and H–O–H bonds,45 respectively. Thus, XPS studies have been
used to study the efficient anchoring of salophen ligand onto
the CNT back bone.46 Aer U(VI) sorption (Fig. 9d) four different
peaks occurred at 529.47, 529.97, 530.53, 531.85 eV. An addi-
tional peak aer U(VI) sorption could be attributed to the pres-
ence of the U]O bond.46,47 Furthermore, the shi in the
binding energies of O 1s before and aer U(VI) loading indicated
that U(VI) sorption onto ACF-Sal occurred by the complexation
of oxygen-containing functional groups. The calculation of the
content of elements on the surface of ACFs by the area of each
element showed that the weight content of N is about 3.2%,
indicating the presence of Schiff-base groups. Fig. 9a and c
show the core level N 1s of ACF-Sal before and aer U(VI) sorp-
tion, respectively. The N 1s spectrum was resolved into two
individual component peaks at 395.5 and 402.0 eV.48 Aer
uranyl sorption, the peaks shied to higher binding energies
due to the charge transfers occurring from nitrogen containing
salophen ligand to U(VI) ions.
Fig. 8 Uranium loaded XPS wide scans of ACF, ACF-OX and ACF-Sal.
Table 8 Binding energies (eV) of ACF, ACF-OX and ACF-Sal after
uranium adsorption
Splitting
Type
C 1s
O 1s
N 1s
U 4f5/2 U 4f7/2 values
ACF-U
284.35 530.80
—
—
390.87 381.00
391.57 381.25 10.32
9.87
ACF-OX-U 284.48 530.43
ACF-Sal-U 285.30 531.35 398.53 391.67 381.30 10.37
> Cu2+ > Ca2+ \ Mn2+. An increased interfering effect was
observed for Cd2+, Ni2+ and Pb2+ ions. This could be attributed to
their complexation with salophen ligand and non-availability of
these complexing sites for U(VI) sorption. Among the various
anions tested, it is interesting to observe that a slight increase of
the sorption of U(VI) ions is observed in the presence of phos-
phate ions. Coordination around uranium is pentagonal bipyra-
midal with the four donor atoms of the salophen ligand
occupying the equatorial plane and the uranyl oxygen atoms in
the axial positions. The h equatorial site of the metal remains
available for coordination by an additional group, either an anion
2+
or a neutral molecule. Due to the high affinity of UO2 to
phosphate anions,42 the stability constants of Sal–UO2–H2PO4ꢀ is
larger than other anions (Clꢀ, SO42ꢀ, NO3ꢀ) tested and the data is
furnished in Table 7. This explains the increased uptake of U(VI)
by ACF-Sal in the presence of phosphate ions. Furthermore, it
should be noted that when desorption studies were conducted
with 0.1 M H3PO4, around 85% of U(VI) was found to be desorbed
(Sec 3.6). This is probably because the acidity of the desorbing
solution is around pH 1 and at this acidity, the U(VI) salophen
complex is unstable and uranyl–phosphate complexation takes
place, which results in leaching of U(VI) from the sorbent surface.
Thus, the results from XPS studies suggest that the salophen
ligand is efficiently anchored onto the ACF surface and U(VI)
complexation occurred with the tetradentate N(2)O(2) donors
derived from the phenolic oxygen and azomethine nitrogen of
the saplohen ligand.
3.9 Mechanism of interaction
3.8 XPS evaluation
Adsorption of U(VI) onto ACF and ACF-OX might be attributed to
In order to study the sorption of U(VI) onto ACF, ACF-OX and both ion exchange and electron donating acceptor complexa-
ACF-Sal, XPS spectra were recorded aer U(VI) loading. The O 1s, tion reactions at the surface sites. At pH 6.0, where in the
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Fig. 9 Curve fitted high resolution XPS scans of ACF-Sal for (a) O 1s, (b) N 1s before U(VI) loading and (c) O 1s, (d) N 1s and U 4f (e) after U(VI)
loading.
Table 9 Core level binding energies of ACF-Sal and U(VI) loaded ACF-Sal systems
Core levels
N 1s
ACF-Sal
ACF-Sal-U
Binding energy (eV)
FWHW (eV)
1.00
6.386
1.69
1.37
1.51
—
Area
Binding energy (eV)
400.50
406.09
531.85
530.53
529.47
529.97
379.5
381.08
FWHW (eV)
3.520
0.592
2.230
1.766
1.000
0.810
3.543
1.263
Area
82.12
0.59
2154.16
2002.55
243.86
252.97
1148.07
735.34
395.5
402.0
530.54
531.94
532.77
—
143.38
336.99
2326.78
982.99
186.71
—
O 1s
U 4f7/2
—
—
—
—
—
—
maximum removal of U(VI) is observed (Fig. 3), 95% of the with U(VI) are shown in Fig. 10. It is evident from the spectra that
2+
uranyl ions exist as (UO2)3(OH)5+ species and few as UO2
.
49 It is aer U(VI) loading in ACF (Fig. 10a), the hydroxyl peak shis
well known that at pH 6.0, the carboxyl groups are deprotonated from 3437 cmꢀ1 to 3418 cmꢀ1, which conrms the involvement
and there exists a strong complexation between the hydrolyzed of OH group and a sharp peak at 920 cmꢀ1 conrms the y3 band
uranyl ions [(UO2)3(OH)5+] and carboxyl groups. The FTIR of uranyl ions.50,51 In U(VI) loaded ACF-OX, the shiing of the
spectra of ACF, ACF-OX and ACF-Sal before and aer loading carbonyl stretching peak from 1721 to 1715 cmꢀ1 is observed. In
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Fig. 10 FTIR spectra of (a) ACF (b) ACF-OX and (c) ACF-Sal before and after loading uranyl ions.
Scheme 2 Schematic of complexation of U(VI) with ACF-salophen.
addition, a uranyl band appears at 906 cmꢀ1, which is a char- Sal. The shiing of the frequencies of the uranyl band
acteristic of the y3 band of uranyl ions described earlier. depends on the ligands present in the equatorial plane. In
Moreover, the U(VI) removal might be attributed to the electron general, the asymmetrical uranyl stretching frequency ranges
donating acceptor (EDA) complexation between the de-localized from 885 cmꢀ1 to 899 cmꢀ1 for uranyl complexes with Schiff
+
p-electron of graphene layers of ACF and (UO2)3(OH)5 by base.53–57 This further conrms the complexation between
dispersive forces.52
U(VI) and salophen ligand.
The main mechanism governing the sorption of U(VI) onto
Based on the discussions of the FTIR and XPS studies, a
ACF-Sal is the complexation reaction occurring between the mechanism has been suggested in Scheme 2, depicting the
salophen ligand and the uranyl ions. Aer complexation with complexation of uranium and salophen ligand.
U(VI) (Fig. 10c), the environment of C]N changes and a shi
from 1620 to 1615 cmꢀ1 is observed. Furthermore, the
4. Conclusions
stretching vibrations of –C–O and C–N exhibited a slight
upeld shi to 1220 cmꢀ1 and 1124 cmꢀ1, respectively, owing
Functionalized activated carbon bres were prepared by
to the complexation.21 As observed in ACF and ACF-OX, a y3
oxidation and graing salophen ligand. The prepared sorbent
materials were characterized by various spectral techniques.
The kinetics followed a pseudo second order model and
uranyl band appeared around 890 cmꢀ1 for U(VI) loaded ACF-
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maximum removal of U(VI) was found at pH 6. The experimental 17 M. S. Berber-Mendoza, R. Leyva-Ramos, F. J. Cerino-
data obtained were analyzed by various isotherms, including
Langmuir and Freundlich. The adsorption capacities of the
Cordoba, J. Mendoza-Barron, H. J. Amezquita Garcia and
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functionalized ACFs were in the order of ACF-Sal > ACF-OX > 18 X. Zhou, H. Yi, X. Tang, H. Deng and H. Liu, Chem. Eng. J.,
ACF. The observed high capacity (142.8 mg gꢀ1 for ACF-Sal by
2012, 200–202, 399.
Langmuir and 305.09 mg gꢀ1 by two site Langmuir model) 19 M. Bikshapathi, S. Mandal, G. N. Mathur, A. Sharma and
could be attributed to the bonding of U(VI) and the salophen N. Verma, Ind. Eng. Chem. Res., 2011, 50, 13092–13104.
ligand. The effect of other commonly occurring cations and 20 C.-H. Jung, H.-Y. Lee, J.-K. Moon, H.-J. Won and Y.-G. Shul, J.
anions on the sorption U(VI) by ACF-Sal was studied. Thermo- Radioanal. Nucl. Chem., 2011, 287, 833.
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Acknowledgements
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