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International Journal of Biological Macromolecules 66 (2014) 125134

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International Journal of Biological Macromolecules
j our nal homepage: www. el sevi er . com/ l ocat e/ i j bi omac
Modication and characterization of cellulose cotton bers for fast
extraction of some precious metal ions
M. Monier

, M.A. Akl, Wael M. Ali


Chemistry Department, Faculty of Science, Mansoura University, Mansoura, Egypt
a r t i c l e i n f o
Article history:
Received 3 December 2013
Received in revised form19 January 2014
Accepted 28 January 2014
Available online 11 February 2014
Keywords:
Cotton bers
Grafting
Acrylonitrile
Phenyl thiosemicarbazide
Precious metals
a b s t r a c t
In this work, native cellulose cotton bers were rst modied through graft copolymerization of poly-
acrylonitrile (PAN) and then by insertion of phenyl thiosemicarbazide moieties to nally produce C-PTS
chelating bers, which were fully characterized using various instrumental techniques such as SEM,
FTIR, EDX and XRD spectra. The obtained C-PTS were employed in removal and extraction of Au
3+
, Pd
2+
and Ag
+
precious metal ions from their aqueous solutions using batch experiments. The kinetic studies
showed that the pseudo-second-order model exhibited the best t for the experimental data. In addi-
tion, the adsorption isotherm studies indicated that the adsorption follows the Langmuir model and the
maximum adsorption capacities for Au
3+
, Pd
2+
and Ag
+
were 198.31, 87.43 and 71.14 mg/g respectively.
2014 Elsevier B.V. All rights reserved.
1. Introduction
As a result of their unique chemical and physical properties,
precious metals like gold, platinum, silver and palladiumare exten-
sively utilized in many applications such as catalysis, electronics,
anti-corrosion materials and jewelry. In addition, with in the next
few years, precious metals are expected to be employed in some
new environmental, biotechnological and therapeutic uses [13].
For these reasons, many eco-friendly methods were developed for
efcient extractionandrecoveryof thesevaluablemetals fromtheir
limited sources and from industrial efuents. Among the efcient
process for the separationandisolationof these precious metal ions
from industrial wastewater, sorption onto active adsorbents such
as activated carbon [4,5], modied silicates [6,7], chelating poly-
meric resin [8,9], biopolymers and biomass [1012] considered as
a common and successful method.
Between all of the previously mentioned sorbents, chelating
materials derived from inexpensive natural or synthetic sources
considered of a great importance particularly from the economic
point of view [1318]. Usually, the chelating materials are uti-
lized in form of beads, resin or membranes [19,23]. However,
recently many studies had been focused on preparation and

Corresponding author at: Chemistry Department, Faculty of Science, Mansoura


University, Mansoura, 35516, Egypt. Tel.: +20 1003975988.
E-mail address: monierchem@yahoo.com(M. Monier).
applicationof brous chelatingmaterials whichderivedfromeither
natural bers such as wool bers [24] or synthetic bers such as
PET and polypropylene bers [21,22,25]. Actually the chelating
bers provides many advantages when compared to the conven-
tional chelating materials in form of beads or membranes, rst of
all, the ease of preparation, extraction and modication, also, the
ability to be applied as felts or fabrics which provides a high ef-
ciency and high surface area during the contact with the media and
subsequently enhance the rate of both reaction and regeneration
process.
In the past few years various studies focused on evaluation of
modiedcellulosic materials as anefcient andinexpensivebiosor-
bents. In addition to the great advantages of cellulose as a highly
abundant, cheap and biodegradable material, cellulose can also be
easily modied due to the high availability of the active hydroxyl
groups which play an important role in various types of reactions
like oxidation, ether formation, esterication and free radical graft
co-polymerization by which many cellulose derivatives are pre-
pared [2628].
In this article, brand new chelating bers based on cellulosic
cotton fabrics modied by insertion of phenyl thiosemicarbazide
moieties (C-PTS) had beenprepared for quick eliminationof Au(III),
Pd(II) and Ag(I) precious metal ions from aqueous solution. The
prepared C-PTS chelating bers were fully characterized using var-
ious instrumental techniques such as elemental analysis, scanning
electron microscope (SEM), FTIR and wide angle X-ray spectra.
Also, various parameters such as pH, temperature, kinetics and
http://dx.doi.org/10.1016/j.ijbiomac.2014.01.068
0141-8130/ 2014 Elsevier B.V. All rights reserved.
126 M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134
adsorption isotherms were investigated in order to evaluate the
optimum adsorption conditions and maximum adsorption capac-
ity.
2. Materials and methods
2.1. Materials
Cotton bers were collected from the high agriculture school
farmin Mansoura, Egypt and treated by desizing in 1% (v/v) H
2
SO
4
and scouring in 1% (w/v) NaOH. The bers were then washed
with distilled water and absolute ethanol and nally the cleaned
bers were dried in oven at 50

C till constant weight. Acryloni-


trile (AN) (SigmaAldrich) was puriedbytreatment with3%(w/w)
NaOHsolutionandthenwashedwithdistilledwater until free from
alkali. Potassiumpersulphate(KPS) (SigmaAldrich), Thiourea (TU)
(BDH-England); hydrazine hydrate (Adwic); phenylisothiocyanate
(SigmaAldrich), AuCl
3
, PdCl
2
and AgNO
3
were purchased from
Sigma Aldrich. All chemicals were used as received.
2.2. Synthesis of C-PTS chelating bers
The actual synthetic reactionhadbeenaccomplishedwithinthe
next few steps. Initially the native cotton bers were modied by
graft copolymerization with polyacrylonitrile (PAN) as in the fol-
lowing. 0.1g of the cotton bers was immersed into 100mL conical
ask containing the combined redox initiator systemcomposed of
25mL 2mmol KPS and 25mL 2mmol TU and to which, 0.5mL 1%
H
2
SO
4
was added. After which, the mixture was vigorously shaken
for 5min then, the ANmonomer (2mL) was added and the shaking
was continued up to 3h at 80

C. In order to terminate the graft


copolymerization reaction, 5mL of 3% hydroquinone solution was
added. The PANgraftedcotton(C-g-PAN) bers were thenremoved
from the reaction medium, washed with DMF to extract the PAN
homopolymer and nally dried at 50

C till constant weight.


Grafting percentage (GP) was evaluated according to the follow-
ing mathematical expression:
Graftingpercentage (GP) =

A B
B

100 (1)
where A and B are the weight of grafted product and native cotton
bers, respectively.
The resulted C-g-PANfromthe previous step, were then treated
with 100mL 10%(v/v) alcoholic hydrazine hydrate solution and the
mixture was reuxed for 4h at 80

C. The obtained modied C-g-


PAH bers were then eliminated from the mixture, washed with
ethanol and dried at 50

C.
The modied C-PTS chelating bers were nally manufactured
by reuxing the previously prepared C-g-PAN with 100mL 10%
(v/v) alcoholic phenylisothiocyanate solution at 80

C for 4h. The


bers were then removed, washed with ethanol and dried at 50

C.
Schematic presentation for the synthetic steps of the C-PTS is
shown in Scheme 1.
2.3. Characterization of the polymer samples
The elemental analysis (E.A.) of the native cotton bers, C-g-
PAN, C-g-PAH and C-PTS was obtained from a Perkin-Elmer 240C
Elemental Analytical Instrument (USA).
FTIR spectra were performed using a Perkin-Elmer spectrum.
Theber samples weredriedovernight at 60

Cunder reducedpres-
sure and pressurized with a glass slide on top of the quartz window
of the ATR instrument.
The surface morphologies of the native andmodiedbers were
observedusing a FEI Quanta-200scanning electronmicroscope (FEI
Company, The Netherlands) equipped with Oxford energy disper-
sive X-ray system(EDX) operating at 20kV.
ASAP 2010 Micrometrics instrument was utilized to anticipate
the specic surface area of the studied samples by N
2
adsorption
isothermand by BrunauerEmmettTeller (BET) method.
Crystallinity of the polymeric samples was determined
using X-ray powder diffractometer (Japanese Dmax-rA, wave-
length=1.54

A, CuK radiation). Generator intensity was 40kV,
generator current was 50mA. The sample was then scanned from
2 =570

, in step of 0.02

. The resultant graphs were printed out


on the Origin graph plotting package.
2.4. Metal ion uptake experiments using batch method
2.4.1. Instrumentation
A Perkin-Elmer Model 5000 atomic absorption spectrometer
(Perkin-Elmer, Shelton, CT-USA) was utilized for detection of the
precious metal ion concentrations. The instrument was set at Ag
328.068nm, Au 242.795nmand Pd 324.270nm.
2.4.2. Adsorption and desorption experiments
Inall adsorptionstudies, the experiments were performedusing
batch method. 0.03g of the studied ber samples were placed in a
small glass-stoppered bottles containing 30mL metal ion solution
with main concentration 100mg/L (except for adsorption isotherm
studies in which the concentration ranged from 10 to 400mg/L),
at 30

C (except for thermodynamic studies in which the temper-


ature ranged between 20 and 40

C), pH 5 (except in pH studies


in which the pH ranged between 1 and 5 using KCl/HCl for pH 1,
2, and 3; CH
3
COOH/CH
3
COONa for pH 4 and 5) and contact time
180min (except for the kinetic studies in which the reaction time
ranged between 10 and 120min). The bottles were equilibrated
on a thermostated shaker at 150rpm. The percent removal and
the amount adsorbed can be estimated according to the following
mathematical expressions:
Percent removal (%) =
(C
i
C
e
) 100
C
i
(2)
q
e
=
(C
i
C
e
)V
W
(3)
where C
i
(mg/L) and C
e
(mg/L) initial and equilibrated metal ion
concentrations, respectively; q
e
(mg/g) adsorption capacity; V (L)
volume of addedsolutionandW(g) the mass of the adsorbent (dry).
The desorption experiments were performed as in the follow-
ing: initially the precious metal ions loaded C-PTS chelating bers
were prepared by soaking 0.1g of the bers into 100mL (100mg/L)
metal ion solution at pH 5.0 for 3h and at 30

C. The batch was


equilibrated on a thermostated shaker adjusted at 150rpm. Then,
the metal ion loaded bers were removed, washed with distilled
water to get rid of the unadsorbed ions and then agitated with
100mL 0.1N HNO
3
solution for 60min. The concentrations of the
desorped metal ions were estimated utilizing atomic absorption
techniques. The reusability of the chelating bers were examined
by repeating the above adsorptiondesorption cycles for ve times
and the desorption percentage (D%) was calculated as Eq. (4).
D% =
C
HNO
3
C
ad
100 (4)
whereC
HNO
3
is themetal iondesorbedtotheHNO
3
solutions (mg/L)
and C
ad
is the metal ion adsorbed onto the resin (mg/L).
M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134 127
Scheme 1. Synthesis of C-PTS chelating bers.
Table 1
Elemental analysis of cotton, C-g-PAN, C-g-PAH and C-PTS.
Fibers C(%) H(%) O(%) N(%) S(%)
Cotton 42.2 6.01 51.79 0 0
C-g-PAN 57.2 5.8 21.5 15.41 0
C-g-PAH 42.9 6.1 16.1 34.7 0
C-PTS 52.7 5.5 7.6 21.7 12.4
3. Results and discussion
3.1. Characterization
Table 1 presents the E.A. results for native cotton, C-g-PAN,
C-g-PAH, C-PTS. As can be seen, the nitrogen content presents a sig-
nicant increase after grafting and hydrazine hydrate modication,
whichgives anevidence for the insertionof PANchains andconver-
sion of the vast majority of the CN groups into H
2
N C NH NH
2
.
Also, the appearance of sulfur in C-PTS may conrm the for-
mation of the functional phenyl thiosemicarbazide moieties on
the modied bers. The approximate estimation of the phenyl
thiosemicarbazide content on the C-PTS is 3.88mmol g
1
.
The surface morphologies of native and modied bers were
examined using scanning electron microscope (SEM) and the
photos of native cotton, C-g-PAN and C-PTS are shown in Fig. 1.
As can be noticed, the observed size increase of C-g-PAN could be
attributed to the insertion of the grafted PAN chains onto the main
cellulose bers backbone. In addition, the relatively rough surface
observed in C-PTS compared to both native and grafted bers may
be due to the further treatment steps during the insertion of the
active chelating phenyl thiosemicarbazide moieties. According to
the BET surface area measurements, both native cotton and C-PTS
bers exhibited a surface area 2.432m
2
/g and 6.235m
2
/g, respec-
tively. This relatively low surface area gives an indication that the
heavy metal ion adsorption is mainly due to the coordination with
the active functional groups inserted onto the bers.
The FTIR spectra of the modied and unmodied cotton bers
were presented in Fig. 2. The IR spectrum of the native cot-
ton bers (Fig. 2a) exhibited the main characteristic cellulose
peaks at approximately 10701150cm
1
due to C O stretching,
12601410cm
1
due to O H bending, and 36003100cm
1
due
to O H stretching [29]. On the other hand, the spectrum of the
grafted cotton bers C-g-PAN(Fig. 2b) conrms the insertion of the
PANonto the polysaccharide cellulose backbone by the appearance
of the CNspecic peakat 2350cm
1
. However, thefurther modi-
cation by turning the majority of CN groups into H
2
N N C NH
2
groups (Fig. 2c), was obviously cleared by the observed lowering
of the CN characteristic peak at 2350cm
1
and appearance of
peaks at about 1660cm
1
and 3200cm
1
corresponding to the
azomethine (C N) and NH
2
groups respectively, in addition to
the clear N N characteristic peak at about 1030cm
1
. Moreover,
the spectrumof the obtained chelating C-PTS bers (Fig. 2d) gives
an obvious evidence for the creation of the active phenyl thiosemi-
carbazide moieties by the appearance of the diagnostic C S peaks
at 1300cm
1
and 870cm
1
, in addition to the peaks at 1580cm
1
and 770cm
1
which are related to the C C and C Hof the inserted
aromatic units.
Usually the thiosemicarbazide derivatives can exhibit
thionthiol tautomerism (Structure 1) in solution as a result
of thioamide (NH C S) functional group [30]. The absence of the
thiol (S H) and C S bands at about 2300cm
1
and 1200cm
1
,
Fig. 1. SEMphotos of modied and unmodied cotton bers. (a) Native unmodied cotton bers, (b) C-g-PAN, and (c) C-PTS.
128 M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134
Fig. 2. FTIR spectra of (a) native cotton bers, (b) C-g-PAN, (c) C-g-PAH and (d) C-PTS.
Structure 1. Molecular modeling of the chelating bers active center (a) thione formand (b) thiol form.
M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134 129
respectively in addition to the presence of the sharp C S peaks
at 1330cm
1
and 870cm
1
suggests that the active phenyl
thiosemicarbazide moieties exist mainly in the thion form.
Geometry optimization of the PTC derivative moieties inserted
onto the modied cotton bers was performed using MM+ force-
eld in HyperChem software version 8.03 implemented on a Dell
core i5 personal computer and the molecularly modeled structure
was presented in Structure 1.
The changes in the crystalline structure resulted from the
chemical modications were examined using wide angle X-ray
diffraction (XRD). As can be seen in Fig. 3a the XRD pattern of the
native cotton bers exhibited crystalline peaks at approximately
15

, 16

in addition to a sharp intense peak at about 23

, which
is in accordance with previous report [31]. On the other hand,
the crystalline pattern of the modied C-g-PAN and C-PTS (Fig. 3b
and c) present a sharp intensive peak at approximately 17

which
attributed to the crystalline pattern of the grafted PAN chains [32],
this may give an evidence that during the graft copolymerization,
the PAN grown to relatively long chains and forma well organized
crystalline pattern. In addition, the intensities of the characteristic
cotton bers peaks at 15

, 16

, and 23

present an obvious decrease


upongraftingandmodicationwhichmay indicatethecrystallinity
decrease.
Fig. 4ac presents the EDX spectra of native unmodied cot-
ton bers, C-g-PAN and C-PTS chelating bers, respectively. It is
obvious that the spectrum of C-g-PAN (Fig. 4b) showed an addi-
tional nitrogen peak in addition to the original carbon and oxygen
peaks observed in the native cotton bers spectrum(Fig. 4a), which
conrmthesuccessful graftingreaction. Inaddition, theC-PTSspec-
trum (Fig. 4c) exhibited the characteristic sulfur peak at 2.3keV.
This may gives an evidence for the further modication of the
grafted chains via insertion of the functional phenyl thiosemicar-
bazide chelating groups.
3.2. Metal ions uptake studies
3.2.1. Effect of functionalization
The inuence of cotton functionalization on the precious metal
ions removal capabilities was explored at 30

C, while maintaining
all other circumstances xed. The outcomes are demonstrated in
Fig. 3. X-ray diffraction pattern of (a) native unmodied cotton bers, (b) C-g-PAN,
and (c) C-PTS.
Table 2. As can be observed, the original unmodied cotton bers
as well as C-g-PAN bers did not showany characteristic potential
for the studied precious metal ion extraction, which caused by
the lack of functional groups that may possibly bind with these
metal ions. Alternatively, C-g-PAH displayed a relatively elevated
potential for metal ion removal. For the phenyl thiosemicarbazide
functionalized C-PTS bers, the percent removal of the three
metal ions Au
3+
, Pd
2+
and Ag
+
presented a noticeable increase and
these can be resulting from a greater surface area with abundant
Fig. 4. EDX analysis of (a) native cotton bers, (b) C-g-PAN, and (c) C-PTS.
130 M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134
Table 2
Effect of the functionalization on the percent removal of Au
3+
, Pd
2+
and Ag
2+
.
Fibers Percent removal (%)
Au
3+
Pd
2+
Ag
+
Cotton 1.8 1.5 1.1
C-g-PAN 6.7 5.6 3.2
C-g-PAH 70.2 66.3 37.5
C-PTS 98.4 76.3 62.5
1 2 3 4 5
0
20
40
60
80
100
P
e
r
c
e
n
t

r
e
m
o
v
a
l
pH
Au
3+
Pd
2+
Ag
+
Fig. 5. Effect of pH on the uptake of Au
3+
, Pd
2+
, and Ag
+
ions by C-PTS (initial con-
centration 100mg/L; C-PTS 1g/L; contact time 3h; shaking rate 150rpm, 30

C).
accessibility to considerably more active sites to which the heavy
metal ions can possibly bind.
3.2.2. Inuence of pH
Fig. 5 presents the pHinuence on the percent removal of Au
3+
,
Pd
2+
and Ag
+
by the modied C-PTS chelating bers. As can be
noticed, the adsorption experiments were performed in a pHrange
15 prior to the precipitation limits of the studied metal ions. As
expected, the percent removal of the metal ions exhibited a signif-
icant increase at high pH value; this could be attributed to the low
H
+
concentration which may compete with the metal ion for the
coordination with active phenyl thiosemicarbazide moieties and
subsequently lower the percent removal at lowpH values.
In order to understand the mechanismthrough which the stud-
ied metal ions coordinated to the C-PTS bers, the FTIR spectra of
the C-PTS loadedwithAu
3+
, Pd
2+
andAg
+
were performedandcom-
pared with the spectra of the metal free bers to investigate the
active sites involved in the coordination. The characteristic peaks
of the inserted phenyl thiosemicarbazide moieties are expected to
change upon coordination with the studied metal ions. Table 3 lists
these guide peaks before and after the coordination. For both Au
3+
and Pd
2+
, the absence of v(S H), v(C S), appearance of v(C S) and
v(C N)
b
, in addition to the lower shift of the v(C N)
a
stretching
Table 3
Assignments of characteristic IR spectral peaks (cm
1
) of C-PTS and M-C-PTS.
Fibers v(C N)
a
v(C N)
b
v/(C S) v/(C S) v(N N)
C-PTS 1660 1300, 870 1030
Au-C-PTS 1610 1630 1150, 650 1095
Pd-C-PTS 1614 1635 1173, 670 1112
Ag-C-PTS 1622 1220, 805 1055
a
Azomethine.
b
New.
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
y = -0.3665 + 1451.8074x
R
2
= 0.9975
y = -6.07442 + 3411.41086x
R
2
= 0.9998
y = -22.41883 + 8660.82896x
R
2
= 0.9987
l
n
K
C
1/T (K
-1
)
Au
3+
Pd
2+
Ag
+
Fig. 6. Plot of lnK
C
as a functionof reciprocal of temperature (1/T) for the adsorption
of Au
3+
, Pd
2+
, and Ag
+
by C-PTS bers.
vibration of the complexes, suggested the coordination through
the deprotonated thiol and azomethine nitrogen atomand forma-
tion of ve membered ring as shown in the molecularly modeled
Structures 2 and 3. This suggestion supported by the marked pH
lowering after the Au
3+
and Pd
2+
adsorption from5 to about 3. On
the other hand, the spectrumof Ag-C-PTS exhibited a lower shift of
both v(C S) and v(C N)
a
in addition to the absence of both v(C S)
andv(C N)
b
, whichsuggest the coordinationof the Ag
+
throughthe
thione sulfur and azomethine nitrogen atoms in a ve membered
chelation mode as presented in Structure 4.
3.2.3. Effect of temperature
The thermodynamic parameters for the adsorptionof Au
3+
, Pd
2+
and Ag
+
were anticipated by equilibrating 0.03g C-PTS chelating
bers with 30mL of the studied metal ion solution with concen-
tration 30mg/L at 293, 303 and 313K. In all studied cases, raising
temperature lowers the adsorption, whichmay give anevidence for
the exothermic nature of the adsorption. In addition, we can esti-
mate the thermodynamic parameters (free energy (G

), enthalpy
(H

) and entropy (S

)) according to the following mathematical


equations:
K
C
=
C
ad
C
e
(5)
where C
ad
is the concentration of solute adsorbed on the bers at
equilibrium(mg/L) andC
e
is the equilibriumconcentrationof metal
ion in the solution (mg/L).
Free energy of the adsorption (G
ads

) can be calculated using


the following equation:
G
ads

= RT lnK
C
(6)
The adsorption standard enthalpy (H
ads

) and entropy (S
ads

)
can be evaluated using the following equation:
ln K
C
=
S
ads

R

H
ads

RT
(7)
where R (8.314J/mol K) is the gas constant.
By plotting lnK
C
vs 1/T (Fig. 6), the values of the slope H
ads

/R
and the intercept S
ads

/R were employed in calculating both


H
ads

and S
ads

for Au
3+
, Pd
2+
and Ag
+
adsorption onto the mod-
ied C-PTS chelating bers.
The calculated thermodynamic parameters were collected in
Table 4, and as can be noticed in all cases, the G
ads

exhibited
negative values, which means that the adsorption is a spontaneous
M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134 131
Structure 2. Molecular modeling of Au-C-PTS.
Structure 3. Molecular modeling of Pd-C-PTS.
Structure 4. Molecular modeling of Ag-C-PTS.
Table 4
Thermodynamic parameters for the adsorption of Au
3+
, Pd
2+
and Ag
+
on C-PTS bers.
Metal ion K
C
G
ads

(kJ/mol) H
ads

(J/mol K) S
ads

(J/mol K)
293K 303K 313K 293K 303K 313K
Au
3+
1499 332.33 229.76 17.812 14.626 14.148 72.006 186.39
Pd
2+
271.7 165.66 129.43 13.651 12.872 12.654 28.362 50.502
Ag
+
99.01 82.33 72.17 11.193 11.111 11.009 12.070 3.047
132 M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134
0 20 40 60 80 100 120
30
40
50
60
70
80
90
100
q
t

(
m
g
g
-
1
)
Time (min
-1
)
Au
3+
Pd
2+
Ag
+
Fig. 7. Effect of contact time on the uptake of Au
3+
, Pd
2+
, and Ag
+
ions by C-PTS
(initial concentration 100mg/L, C-PTS 1g/L, pH 5.0, shaking rate 150rpm, 30

C).
process. In addition both H
ads

and S
ads

are also negative indi-


cating that the process is an exothermic process with a decrease
in entropy, which could be attributed to the aggregation of the
metal ion onto the surface of the chelating bers. This is a common
observation during the metal ion removal process [23].
3.2.4. Kinetic studies
Theinuenceof theadsorptiontimeontheremoval of Au
3+
, Pd
2+
and Ag
+
by modied C-PTS chelating bers is presented in Fig. 7. As
can be seen, the removal exhibited a rapid rate for the rst 20min
where the percent removal reached about 85%, 70% and 55% with
initial rate of approximately 5.5, 4.0 and 2.8mg g
1
min
1
for Au
3+
,
Pd
2+
and Ag
+
, respectively.
For better evaluation of the kinetic mechanism which governs
the whole removal process, the resulted experimental data were
tted with the well known kinetic pseudo-rst-order and pseudo-
second-order models according to the following equations [20,21]:
1
q
t
=
k
1
q
et
+
1
q
e
(8)
where k
1
is the pseudo-rst-order rate constant (min
1
) of adsorp-
tion and q
e
and q
t
(mg/g) are the amounts of metal ion adsorbed
at equilibriumand time t (min), respectively. The value of 1/q
t
was
calculated from the experimental results and plotted against 1/t
(min
1
). The linear form of pseudo-second-order equation can be
written as
t
q
t
=
1
k
2
q
2
e
+

1
q
e

t (9)
where k
2
is the pseudo-second-order rate constant of adsorption
(g/(mgmin)).
The kinetic parameters of the removal process were summa-
rized in Table 5. According to the resulted correlation coefcients
(R
2
), the experimental date exhibited the best t with the pseudo-
second-order equation model, which means that the chemical
coordination step considered as the rate determining step without
involvement of a mass transfer in solution [33,34]. Generally, C-PTS
is characterized by its relatively high nitrogen and sulfur percent-
age related to the azomethines (C N) and thione/thiol (C S/C SH)
of the inserted phenyl thiosemicarbazide moieties, which are able
to coordinate with the precious metal ions as previously presented
in Structures 14.
Table 5
Kinetic parameters for Au
3+
, Pd
2+
and Ag
+
ions adsorption by C-PTS bers.
Metals First-order model
k
1
(min
1
) q
e1
(mg/g) R
2
Au
3+
8.743 98 3 0.9324
Pd
2+
6.983 75 4 0.9221
Ag
+
7.349 61 3 0.8998
Metals Second-order model
k
2
(g/(mgmin)) q
e2
(mg/g) R
2
Au
3+
7.110
3
99 1 0.9998
Pd
2+
5.210
3
76 1 0.9999
Ag
+
4.910
3
62 1 0.9988
The pseudo-second-order kinetic model also showed the best
t with the experimental data in the studies carried out by Monier
and Abdel-Latif [22] on adsorption of Hg
2+
, Cu
2+
and Co
2+
onto che-
lating bers based on PET; by Hajeeth et al. [27] on removal of Cu
2+
and Ni
2+
ions onto cellulose-g-acrylic acid copolymer; by Jia and
Demopoulos [4] on adsorption of Ag
+
ions onto activated carbon;
Kanget al. [6] onremoval of Pt
2+
andPd
2+
usingthiol-functionalized
mesoporous silica whichwere inagreement withthe kinetic results
found in our study.
3.2.5. Adsorption isotherms
The adsorption isotherm studies are essential for anticipa-
tion of the characteristic relationship between the adsorbate and
the adsorbent [35] and subsequently, provide valuable informa-
tion about the adsorption mechanism, which is very important
in designing the adsorption system. The adsorption isotherms of
Au
3+
, Pd
2+
and Ag
+
ions were performed under the optimumcondi-
tions of pH, temperature, contact time and a range of concentration
between 10 and 400mg/L. As can be seen in Fig. 8, the adsorption
of the three studied precious metals was increased gradually by
raising the initial concentration until the C-PTS reached the max-
imum saturation capacity at high concentration. Both Langmuir
and Freundlich models were employed to evaluate the adsorption
parameters. The Langmuir adsorption isotherm model assumes
that the adsorbate form monolayer on the adsorbent surface, the
surface is homogeneous with energetically equivalent adsorption
sites and there are no intermolecular forces between the adsorbed
0 50 100 150 200 250 300 350
0
50
100
150
200
q
e

(
m
g

g
-
1
)
C
e
(mg L
-1
)
Au
3+
Pd
2+
Ag
+
Fig. 8. Adsorption isotherms of Au
3+
, Pd
2+
, and Ag
+
ions by C-PTS (initial concentra-
tion 10400mg/L, C-PTS 1g/L, pH 5.0, shaking rate 150rpm, 30

C).
M. Monier et al. / International Journal of Biological Macromolecules 66 (2014) 125134 133
Table 6
Parameters for Au
3+
, Pd
2+
and Ag
+
ions adsorption by C-PTS bers according to
different equilibriummodels.
Metals Langmuir isothermconstants
KL (L/g) qm (mg/g) R
2
Au
3+
29.710
2
198.31 0.9997
Pd
2+
25.210
2
87.43 0.9999
Ag
+
15.010
2
71.14 0.9999
Metals Freundlich isothermconstants
KF n R
2
Au
3+
29.057 3.423 0.8997
Pd
2+
20.253 3.783 0.9012
Ag
+
18.287 4.002 0.9112
species [35]. The mathematical expression of Langmuir adsorption
model is represented according to the following equation:
C
e
q
e
=

1
K
L
q
m

C
e
q
m

(10)
where q
e
is the amount of metal ion adsorbed on one gram of the
adsorbent (mg/g) at equilibrium, C
e
the equilibriumconcentration
inthesolution(mg/L), q
m
themaximumadsorptioninmonolayered
adsorption systems (mg/g) and K
L
is the adsorption equilibrium
constant related to adsorption energy (L mg
1
). The adsorption
parameters (q
m
and K
L
) were evaluated fromthe slop and intercept
of C
e
/q
m
vs C
e
plot.
For Freundlich isothermmodel, the adsorbate assumed to form
a multilayer on energetically nonequivalent heterogeneous adsor-
bent surface. The model can be mathematically expressed as in the
following equation:
lnq
e
= lnKF +
1
n
(lnC
e
) (11)
where K
F
is a constant related to the adsorption capacity and 1/n is
an empirical parameter related to the adsorption intensity, which
depend on the material heterogeneity. Both K
F
and n can be esti-
mated by plotting lnq
e
vs lnC
e
.
Both Langmuir and Freundlich parameters were collected in
Table 6. According to the correlation coefcients, the experimen-
tal results exhibited the best t with Langmuir model suggesting
a monolayer homogeneous adsorption of the three precious metal
ions onto the modied C-PTS chelating bers. As can be seen in
Table 6, the maximumadsorption capacities for Au
3+
, Pd
2+
and Ag
+
were 198.31, 87.43 and 71.14mg/g, respectively, indicating a high
potential of the prepared bers for removal of these metal ions
from aqueous solution. In addition, the higher tendency for Au
3+
compared to Pd
2+
and Ag
+
could be attributed to the fact that triva-
lent ions have a higher coordination power than both divalent and
monovalent ions. Also, gold is considered as a soft Lewis acid due
to its high polarizability. It forms strong covalent bonds with soft
Lewis bases, notably with reduced sulfur [22].
The suitability of the adsorption process could be evaluated
by calculating the separation factor constant (R
L
): R
L
>1.0, unsuit-
able; R
L
=1, linear; 0<R
L
<1, suitable; R
L
=0, irreversible [21]. The
R
L
value can be estimated according to the following equation:
R
L
=
1
1 +C
0
K
L
(12)
where K
L
is the Langmuir equilibrium constant and C
0
(10400mg/L) is the initial concentration of the metal ions.
The values of R
L
lie between 0.252 and 0.0083, indicating the
suitability of the synthesized chelating bers as adsorbents for
Au(III), Pd(II) and Ag(I) fromaqueous solution.
Table 7 lists the maximum adsorption capacities of Au
3+
, Pd
2+
and Ag
+
adsorbed onto some previously prepared adsorbents. As
Table 7
Maximumadsorption capacities for the adsorption of Au
3+
, Pd
2+
and Ag
+
onto vari-
ous adsorbents.
Adsorbent Maximumadsorption
capacity
Reference
Au
3+
Pd
2+
Ag
+
Modied rice husks 250.2 [36]
Glycine-chitosan resin 169.9 120.3 [37]
Basic anion exchange resins 121.5 [38]
Thiourea modied chitosan 112.4 [39]
Pd-ion-imprinted resin 38.9 [40]
Thiourea modied chitosan 235.2 [41]
2-Mercaptobenzimidazole-TiO
2
128.2 [35]
Present study 198.31 87.43 71.14
Table 8
Repeated adsorption of Au
3+
, Pd
2+
, and Ag
+
ions by C-PTS (initial concentration
100mg/L, C-PTS 1g/L, pH 5.0, contact time 3h, shaking rate 150rpm, 30

C).
Cycle number Adsorption capacity (%)
Au
3+
Pd
2+
Ag
+
1 100 100 100
2 99.7 98.5 98.8
3 98.1 97.7 98.2
4 96.8 95.7 96.4
5 94.9 94.2 94.8
canbe noticed, by comparison, the preparedC-PTS exhibiteda good
capacity for the studied precious metal ions.
3.2.6. Desorption and regeneration of C-PTS chelating bers
Desorption experiments are signicant to evaluate both metal
ions recovery and adsorbent regeneration for reusability require-
ments. In the current study 0.1N HNO
3
solution was used as
eluent for desorption experiments, the process was repeated for
ve adsorptiondesorption cycles and the results were presented
in Table 8. As can be seen, desorption efciency did not exhibit a
signicant decrease, after the fth cycle, the bers still maintain
more than 94% of its original capacity. The obtained results con-
rmed that there is no appreciable loss in activity over at least ve
cycles.
4. Conclusions
Removal of Au
3+
, Pd
2+
and Ag
+
was carried out using a novel
phenyl thiosemicarbazide modied cotton bers (C-PTS) as adsor-
bent. The adsorption capacity follows the order Au
3+
>Pd
2+
>Ag
+
.
The adsorption kinetic studies indicated that the adsorption pro-
cess ts with the pseudo-second-order model. On the other hand,
the adsorption isotherm studies conrmed that the experimental
results followtheLangmuir model. Various techniques suchas SEM,
FTIR, SEM, XRD and EDX were utilized for characterization of the
modied C-PTS chelating bers. Also, FTIR spectra were performed
to understand the mechanismof the precious metal ion coordina-
tion with the active phenyl thiosemicarbazide moieties inserted
onto the modied chelating cotton bers.
Acknowledgements
The authors are grateful to Dr. S. Das for supplying us with some
chemicals. Also, theauthors appreciatetheefforts of Dr. M. Shamma
for the assistance in performing the instrumental analysis.
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