Applied Surface Science 307 (2014) 665676

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Agglomerated nanoparticles of hydrous Ce(IV) + Zr(IV) mixed oxide:

Preparation, characterization and physicochemical aspects
on uoride adsorption
Abir Ghosh, Sharadindra Chakrabarti, Krishna Biswas 1 , Uday Chand Ghosh
Department of Chemistry and Department of Environmental System Management, Presidency University, 86/1 College Street, Kolkata 700073, India

a r t i c l e i n f o a b s t r a c t

Article history: Hydrous Ce(IV)Zr(IV) oxide (Ce/Zr 1:1, mol/mol) (HCZMO) prepared by simple chemical precipita-
Received 13 January 2014 tion was nanoparticles (6070 nm) agglomerate with irregular surface morphology. The BET surface
Received in revised form 12 April 2014 area, pore volume and pHzpc were estimated to be 185.04 m2 g1 , 0.1219 cm3 g1 and 5.8 (0.2), respec-
Accepted 14 April 2014
tively. Investigation of uoride adsorption over HCZMO from its aqueous phase at an optimized pH 6.0
Available online 24 April 2014
showed that the adsorption kinetics and equilibrium data described, respectively, the pseudo-second
order equation (R2 = 0.980.99) and the Langmuir isotherm (R2 > 0.99) very well. Values of the com-
Keywords:
puted Arrhenius activation energy, Ea (1.16 kJ mol1 ), Langmuir monolayer capacity,  (19.5 mg g1 ), DR
Adsorption
Fluoride
adsorption energy, EDR (15.05 kJ mol1 ) and isosteric heat of reaction, Hr (0.518 kJ mol1 ) suggested
Cerium(IV)zirconium(IV) mixed oxide that the uoride has high afnity for homogeneous HCZMO surface for adsorption. Evidences appeared
Removal from the equal distribution co-efcient values and too well Langmuir isotherm t. The uoride adsorp-
Thermodynamics tion reactions at 298313 K with HCZMO were spontaneous (G0 = negative) despite endothermic nature
Desorption (H0 , kJ mol1 = +3.53, +4.04), owing to the increase of entropy (S0 , J mol1 K1 = +12.4, 13.8). More than
95% uoride was released from F HCZMO (24.8 mg F g1 ) by 1.0 M NaOH, conrming the ion-exchange
adsorption mechanism inclining to chemisorption. 1 g HCZMO per liter of a groundwater (F : 4.40 mg L1 )
can reduce uoride level below 1.5 mg L1 in batch treatment.
2014 Elsevier B.V. All rights reserved.

1. Introduction and operation [1]. The purication possibility of water contam-

Rapid industrial growth with population meets the societal need
globally, but causes the scarcity of hygienic water owing to con-
tamination of the water sources with inorganic and organic toxic
species for discharging untreated or partially treated waste efu-
ent. The scarcity of hygienic water is most critical in third world
countries where ground waters are naturally contaminated with
uoride (>1.5 mg L1 ) and/or arsenic (>0.01 mg L1 ). Thus, the use
of surface and/or ground water is risky without prior treatment to
public health of the third world countries like India.
Amongst the technologies reported for wastewater treatment
and recycling, the adsorption is considered to be the best and
most universal option because it could be used for the removal
of a wide variety of organic and inorganic pollutants. It is also
a simple process with a low cost of construction, maintenance
Corresponding author. Tel.: +91 33 2241 3893; fax: +91 3322413893.
E-mail address: ucghosh@yahoo.co.in (U.C. Ghosh).
1
Maharaja Manindra Chandra College, Kolkata, India.
inated with different organic compounds had been explored by
adsorption over various low cost materials [29]. Occurrence of
uoride/arsenic in ground water has been established well since
long back. Thus uoride/arsenic adsorptions over different materi-
als were also reported from wastewater and ground water [10,11].
Some materials are reported to be efcient at least in lab bench
scale, but the materials when applied for the eld water treatment
showed poor performances encouraging continuation of investiga-
tion for the efcient materials. Thus the synthesis of new materials
for searching has been continued for searching materials, which
may be capable for the efcient treatment of uoride or arsenic
rich ground waters. In India, uoride concentration in groundwater
even at 30 mg L1 had been reported [1214], which is much above
its permissible value (1.5 mg L1 ). Materials over which uoride
adsorption from aqueous solutions studied are some geomateri-
als [12], coal based sorbents [13], manganese coated alumina [14],
waste carbon slurry [15], y ash [16], silica gel [17], bone char [18],
spent catalyst [19], zeolites [20], activated alumina [21], granular
calcite [22], mixed rare earth oxides [23] and alumina supported
carbon [24]. However, uoride adsorption over most materials was

http://dx.doi.org/10.1016/j.apsusc.2014.04.095
0169-4332/ 2014 Elsevier B.V. All rights reserved.
666 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676

eco-friendly rout aiming to apply for purication of contaminated

Nomenclature water.
Therefore, this manuscript reports herein the synthesis and
HZCMO hydrous ceriumzirconium mixed oxide characterization of HCZMO with adsorption behavior of uoride
Ci initial uoride concentration (mg L1 ) from the aqueous solutions at diverse conditions.
Ce equilibrium uoride concentration (mg L1 )
Ct uoride solution concentration (mg L1 ) at time t
2. Materials and methods
(min)
Cf uoride concentration (mg L1 ) in nal solution
2.1. Reagents
S solid surface
M mass of solid added (g)
Sodium uoride (AR, BDH) was used for the preparation of stock
V solution volume (L)
solution of uoride (1000 mg L1 ) by dissolving an appropriate
qt adsorption amount (mg g1 ) at a time t (min)
quantity in deionized water. Sodium 2-(Para sulfo phenylazo)-
k1 pseudo-rst order rate constant (time1 )
1,8-dihydroxy-3,6-naphthalene disulfonate (SPADNS) (E. Merck,
k2 pseudo-second order rate constant (g mg1 min1 )
Germany) and zirconium oxy chloride (E. Merck, Germany) were
t time (min)
used for uoride estimation [45]. All other chemicals used were
qe equilibrium adsorption amount (mg g1 )
either of analytical or reagent grade.
 Langmuir monolayer adsorption capacity (mg g1 )
b Langmuir constant (L mg1 )
2.2. Synthesis of HCZMO
KF Freundlich constant (mg11/n L1/n g1 )
n dimensionless Freundlich constant
Different volume proportions of ammonium cerium(IV) nitrate
pHzpc zero point surface charge pH
(0.1 M in 0.1 M HNO3 ) and zirconium oxychloride (0.1 M in
T absolute temperature (K)
0.1 M HCl) solutions were mixed together with rigorous stirring
G0 standard Gibbs free energy change (kJ mol1 )
(500 rpm) by a mechanical stirrer. Each mixture was then treated
H0 standard enthalpy change (kJ mol1 )
with ammonia (1:1) solution with stirring (500 rpm) continu-
S0 standard entropy change (J mol1 K1 )
ously till the pH attained to 8.08.5. The yellowish jelly precipitate
Hr isosteric heats of adsorption (kJ mol1 )
in each container including the mother liquid was ltered after 24 h
R universal gas constant (8.314 J mol1 K1 )
through 0.45-m membrane lter, and washed repeatedly with
Kc the equilibrium constant
distilled water to remove excess alkali. It was then dried in an air-
DR DubininRadushkevick equation
oven at 100 (5) C. Each dried mass was then ground and sieved
Qm DR adsorption capacity (mol kg1 )
(B. S. Sieve) to obtain the mesh fraction of 50100 mesh (particle
Qe DR adsorption capacity (mol kg1 ) at equilibrium
size: 140290 m). Before using as-prepared HCZMO particles in
the constant of DR isotherm equation (mol2 kJ2 )
actual experiments, the agglomerated particles were stirred sep-
Polanyi potential
arately with different pH adjusted aqueous solutions so that the
EDR mean free energy of adsorption (kJ mol1 )
material particles reached to pH of the respective solution.
A Arrhenius temperature-independent factor
(g mg1 min1 )
2.3. Analytical tools
Ea Arrhenius activation energy of adsorption
(kJ mol1 )
The pH value of each sample solution was analyzed by the pH
R2 linear regression co-efcient
meter (model LI-127, ELICO) standardizing against pH 4.0, 7.0 and
C1 equilibrium concentration at temperature T1 (K)
9.2. Atomic force micrograph (AFM) of the sample was recorded
C2 equilibrium concentration at temperature T2 (K)
by commercial Nanoscope-III (Digital Instruments, Santa Barbara,
CA having spring constant value 80 N m1 ) using optical beam
deection to visualize the surface topography, surface roughness,
not encouraging despite low cost. It has been reported that La(III), particle size distribution, and approximate particle size analysis.
Ce(IV), and Zr(IV) oxides showed fairly high capacities of uo- The powder X-ray diffraction (XRD) analysis of samples was done
ride adsorption [23,25]. Consequently, several composite materials by the Phillips X-Ray diffractometer. Furier Transform Infrared
such as La(III)-modied chitosan [26], Zr(IV)-impregnated colla- (FTIR) spectroscopic analysis of HCZMO sample before and after
gen ber [27], Al3+ , La3+ and ZrO2+ loaded natural zeolite [28], uoride adsorption was recorded using Jasco 680 plus spectropho-
Fe-modied attapulgite adsorbent [29], Zr(IV)-doped chitosan bio- tometer (Japan) under resolution of 2 cm1 making thin lms of
composite [30], activated titanium rich bauxite [31], Fe(III)Al(III) samples with the specpure KBr (3:100). Scanning electron micro-
hybrid oxide [32], FeAlCe trimetal oxide [33], Fe(III)Zr(IV) graph (SEM) with EDAX spectra of the material sample were taken
hybrid oxide [34], Fe(III)Sn(IV) mixed oxide [35], Al(III)Ce(IV) by the Scanning Electron Microscope (Vega, Tescan, UK) for surface
hybrid adsorbent [36], Zn/Al hydrotalcite-like compound [37], alum morphology and composition. Transmission electron micrograph
sludge [38], La-incorporated chitosan beads [39], CaO nanoparticles (TEM) of the sample was taken by the Transmission Electron Micro-
[40], and FeAl based mixed hydroxide [41] were reported with scope (Techni, STWIN, Hillsboro, OR, USA) for exact particle size in
high uoride adsorption capacity. Enhanced adsorption of uoride agglomerates of HCZMO. The BET surface area and the pore vol-
over some mixed oxides [32,34,35] was reported from our labora- ume of HCZMO were analyzed after taking N2(v) adsorption and
tory. Fairly high for uoride adsorption amount of Ce(IV) and Zr(IV) desorption isotherms by Quatachrome Autosorb-1C surface ana-
oxides [23,25] indicated that the mixed Ce(IV) + Zr(IV) oxide might lyzer. The colorimetric analysis of uoride samples was done by
have higher uoride adsorption capacity compared to either Ce(IV) UV-Vis spectrophotometer (Hitachi, Model U-3210) of Japan.
or Zr(IV) oxide. Mixed oxide preparations comprising of Ce(IV) and
Zr(IV) were reported by the methods such as microemulsion [42], 2.4. Experimental procedures
sonohydrothermal [43] and solgel [44] for their selective applica-
tions. We have thus taken an attempt to synthesis of agglomerated Batch experiments were carried out by a series of steps for opti-
nanoparticles of hydrous Ce(IV) + Zr(IV) mixed oxide (HCZMO) by mization of the adsorbent material and efciency of adsorption
 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
process. In this respect, the effects of Ce to Zr mole proportions and
also the calcined temperatures on HCZMO were investigated for u-
oride adsorption for the material optimization. Variable parameters
such as pH, contact time, inuence of uoride concentration and
effect of some groundwater occurring ion on uoride adsorption
over optimized HCZMO sample were carried out by batch method.
Here, 50 mL uoride solution at a desired concentration level (Ci ,
mg L1 ) was mixed with 0.05 g of HCZMO (excepting dosage exper-
iment) inside the 100 mL polyethylene (PE) bottles and agitated
at 275 (5) rpm in a thermostated shaker for 2 h (excepting the
kinetic experiment). Since the pHzpc value of HCZMO was analyzed
to be 5.66.0, the batch adsorption experiments were conducted
with uoride solution at a pH 5.8 (0.2), excepting the pH inuence
experiments.
Inuences of pH on the uoride adsorption over HCZMO
were carried out separately at pH 3.0, 4.0, 5.0, 6.0, 7.0, 8.0
and 9.0 loading three separate uoride solutions of initial
concentrations (Ci , mg L1 ) = 5.0, 10.0 and 20.0 mg g1 , maintain-
ing other parameters for experiments as specied above kept
xed.
Inuences of contact time (for kinetics) on the uoride adsorp-
tion reaction with HCZMO were investigated from the solute
solutions of Ci = 5.0, 10.0 and 20.0 mg L1 (ionic strength, I: 0.1 M
NaCl solution) and pH = 5.8 0.2.
Isothermal equilibrium experiments were conducted separately
at 20 , 30 , 40 and 55 C using the uoride solution of C0 ranged
in (5.035.0) mg L1 at an I = 0.1 M NaCl and a pH 5.8 (0.2). Here,
50 mL portion of each uoride solution mixing with 0.05 g HCZMO
was successively agitated taking in seven separate PE bottles up
to an equilibrium time (2.0 h). Thermodynamic parameters (S0 ,
H0 , and G0 ) were evaluated from the analysis of the equilibrium
results.
For estimating the competitive inuences of some groundwa-
ter occurring ions on the present reaction, 50 mL uoride solution
(Ci = 10.0 mg L1 ) in the presence of 1.0 mM of a competing ion at
pH = 5.8 (0.2) was mixed with 0.05 g HCZMO in PE bottles and
agitated for 2.0 h. The competing ions were derived from Na2 CO3 ,
Na2 HPO4 , NaCl, Na2 SO4 , and Na2 SiO3 .
For the uoride desorption tests, 0.05 g of uoride-rich HCZMO
(24.8 mg F g1 ) was agitated (300 rpm) for 1.0 h with 50 mL NaOH
solution (concentrations: 0.14.0 M) taking into PE bottles (capac-
ity: 250 mL).
After each experiment, the HCZMO particles were separated
immediately after experiment by ltration through 0.45-m mem-
brane lter. Fluoride concentration of each ltrate (Cf , mg L1 ) was
analyzed by SPADANS method using UV-Vis spectrophotometer
[45]. The capacity of HCZMO for uoride adsorption (qe , mg g1 )
was calculated based on the following mass balance equation
(Eq. (1)):
(Ci Cf ) V
qe =
M negative at pH > 5.8 (0.2).
where V is the volume (L) of the solute solution and M is the mass
of the adsorbent (g) for conducting experiments. The signicance
of Ci and Cf are noted previously.
The zero point surface charge pH (pHzpc ) of optimized HCZMO
material was analyzed by the procedure as described by Babic
et al. [46]. Here 0.1 g of HCZMO was mixed to 50 mL 0.1 M
NaCl solution at an adjusted pH and agitated (300 rpm) for
48 h, and pH of each reaction mixture was analyzed. The nal
pH (pHf ) with respect to its pHi of each reaction mixture was
recorded.
667
3. Results and discussion
3.1. Material optimization for uoride adsorption
Some bimetallic hybrid oxides comprising of Ce, Zr, Mn and
Sn including single Ce and Zr oxides investigated only for uoride
adsorption from its aqueous solution at pH 7.0 have been shown in
supporting information (SI) section (Fig. SI-1). It shows that the
hydrous Ce(IV)Zr(IV) mixed oxide (HCZMO) showed the high-
est capacity of uoride adsorption supporting the pre-assumption
made.
For the optimization, Ce/Zr mole ratio in HCZMO was also varied
and investigated for the uoride adsorption. The results obtained
are presented in Fig. SI-2, which indicated the increase of uoride
adsorption amount (qe , mg g1 ) with increasing Ce/Zr (mol/mol)
value from 1.0:0.2 to 1:1, and remained nearly constant up to the
Ce/Zr ratio 1:4. Thus, the HCZMO having Ce/Zr value 1:1 could
be a novel material for uoride scavenging from the high uoride
waters.
Inuence of the calcined temperature of HCZMO (Ce/Zr = 1:1)
on uoride adsorption amount (qe , mg g1 ) was investigated using
the calcined (5 h) material at 100 , 200 , 300 , 400 and 500 C sep-
arately. Results obtained show nearly same qe value up to a calcined
temperature of 300 C (Fig. SI-3). Thus, the material which was used
calcining at 300 C showed highest capacity (qe = 9.8 1.0 mg g1 )
of uoride adsorption from a solution of Ci = 10.0 mg L1 , but that
material when employed calcining above 300 C at identical exper-
imental conditions showed a substantial decline of the qe -value
which is found to be similar with Wu et al. [33] and Liua et al.
[36]. Wu et al. [33] reported that the hydroxyl groups attached
to the surface of metal oxide are primarily responsible for the
uoride binding. Thus, the elimination of surface (S) hydroxyl
groups (2S OH 2S O + H2 O) with increasing calcined tempera-
ture causes the depletion of qe value. The as-prepared HCZMO when
calcined at temperatures > 300 C eliminates surface OH groups
as water giving anhydrous material, and causes the depletion of
qe value. Moreover, the decrease of surface area with increasing
calcined temperature may also diminish the adsorption capacity
[36]. Analyzed experimental results conrmed that the as-prepared
HCZMO (Ce/Zr 1:1, mol/mol) calcined at 300 C is an optimized
material for uoride adsorption. Thus, the HCZMO (Ce/Zr 1:1,
mol/mol) calcined at 300 C was characterized properly by different
physicochemical tools, and used for evaluating the uoride adsorp-
tion behavior.
3.2. Physicochemical characterization of HCZMO (Ce/Zr 1/1,
mol:mol)
The changes of equilibrium solution pH (pHf ) with respect to
initial solution pH (pHi ) are shown in Fig. SI-4, indicating the pHzpc
of HCZMO analyzed to be 5.8 (0.2). This must have a signicant
role on the adsorption reactions as the material surface should be
(1) (i) positive at pH < 5.8 (0.2), (ii) neutral at pH = 5.8 (0.2) and (iii)
Fig. 1 shows the AFM images of HCZMO surface at 2D and 3D
topographic views. A small portion of the 2D image was further
extracted to note the surface prole, particle size approximation
and their distribution pattern. The surface appeared to be irregular
and undulatory in nature. The 3D topographical AFM image indi-
cated porous nature of the sample and absence of any conspicuous
structural feature, which is found to be similar with the result as
reported by Debnath et al. [47]. From the particle size distribution
curve, it is evident that the average size of HCZMO particles was
ranged in 5060 nm indicating majority of 50 nm.
Fig. 2 shows the XRD pattern of HCZMO sample between start
and end angles (2) of 10 and 70 . The moderate peaks at 28.7 ,
668 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676

Fig. 1. Atomic force microscopic images of HCZMO surface in (a) 3D view (b) 2D view, (c) an extracted prole from the 2D image and (d) the particle size distribution of
HZCMO.

33.1 , 47.6 and 56.4 indicated the presence of crystalline CeO2
[48]. The XRD peak patterns also indicated the presence of tetrago-
nal ZrO2 phase [49]. Approximate size of particles calculated from
XRD peak data (inset of Fig. 2) using Scherers formula (a standard
equation of solid-state physics) was ranged in 5565 nm. The par-
ticle size as-calculated by the Scherers equation using XRD peak
data agreed well to the inference drawn from the AFM image.
Fig. 3 shows the FTIR spectrum of HCZMO sample compar-
ing with HZO and HCO. It is seen that the bands appeared for
HCZMO were at wave number () values 1051, 1133, 1389, 1623,
2361 and 3325 cm1 . The broad band at  = 3466 cm1 in the spec-
trum of HCZMO can be assigned to the stretching vibration of
adsorbed water, and that at  = 1641 cm1 is attributed to the bend-
ing vibration of OH group [34,50]. The FTIR band at  = 1623 cm1
showed the presence of Zr O bond, while that at  = 2361 cm1
and 1380 cm1 were the characteristic peaks of Ce O vibration,
suggesting the presence of Ce O and Zr O bonds in HCZMO
[50].
Fig. 4 shows the SEM micrograph (image-A) of HCZMO including
EDAX analysis (spectrum-B). It has been found from the image-
A that the material showed an irregular surface morphology with
agglomerized particles and porous structure. The surface composi-
tion of that material analyzed from the EDAX spectrum showed to
be nonstoichiometry with empirical formula CeZr1.729 O7.257 .

Fig. 2. XRD analysis of HCZMO with particle size calculation from XRD peak in inset.
 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
Fig. 3. FTIR spectra of HCZMO comparing with pure hydrous cerium(IV) oxide (HCO)
and hydrous zirconium(IV) oxide (HZO).
Fig. 5 shows the TEM images of HCZMO. It shows that the particle
sizes of this material were ranged in 6070 nm, which is close to the
particle size as-calculated from the XRD peak data. The BET surface
area and the pore volume of this material analyzed (Fig. SI-5) to be
185.03 m2 g1 and 0.1219 cm3 g1 , respectively.
Fig. 4. (A) The scanning electron micrograph of HCZMO, and (B) EDX spectrum with atomic percentages and empirical composition of HCZMO in inset.
669
Thus, the synthetic HCZMO was characterized as hydrous crys-
talline porous material with irregular surface morphology and
fairly high surface area. The size of particles was ranged in
6070 nm with pHzpc value 5.8 (0.2). The high BET surface area
and pore volume encourage us that the present material could be
used as an adsorbent.
3.3. Effect of pH
Fig. SI-6 shows uoride adsorption capacity (qe , mg g1 ) of
HCZMO as a function of the solution initial pH (pHi ). It is found
that the qe had enhanced with increasing pHi from 3.0 to 5.0, which
was highest at pHi between 5.0 and 7.0. The qe declined notably at
pHi > 7.0 and above. The results are found to be similar with many
other workers [12,23,37,38], but dissimilar with Wu et al. [33] and
Bansiwal et al. [39]. This observation can be attributed based on
the fact that the HCZMO surface becomes positive at pH < 5.8 0.2
(pHzpc ) owing to protonation, and uoride ions from the solution
will be bound over the material surface with Columbic forces (R1 ).
Lowering of qe in the strong acid pH range (pH 3.0) is due to the
presence of F in solution as HF (pKa = 3.3). Enhancement of qe
with increasing pH (>3.0) is due to the increased F concentration
appeared from the HF dissociation in aqueous solution.
SOH(S) + H+ + HF(aq) SOH2 + (S) F H+ + aq (pH < 3.0)
(R1 )
670 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676

Fig. 5. The transmission electron microscopic (TEM) image of HCZMO.

In the present study, the KD values were constant indicating homo-

At pH > pHzpc , the solid surface becomes negative triggering geneous nature of the HCZMO surface [52], which is found to be
columbic repulsion between aqueous F and negative surface of similar with Sujana et al. [38] and also with Patel et al. [40].
solid, indicating the decrease of qe value. Lowering of qe may be
explained by the reactions (R2 ) and (R3) as the equilibrium pH
3.5. Kinetic modeling
reduced.

S OH(s) + OH (aq) S O (s) + H2 O (R2 ) 3.5.1. Effect of concentration

Fig. 6 shows the time-dependent adsorption amount (qt , mg g1 )
S O (s) + F (aq) + Na+ (aq) S O Na+ F (s) + aq (R3 ) of uoride over HCZMO at 303 (2) K and pH 5.8 (0.2) from uo-
At pH = pHzpc (5.8 0.2), the M OH surfaces will have the equal ride solutions of Ci = 5.0, 10.0 and 20.0 mg L1 , respectively. It is seen
distribution of both positive and negative charges indicating neu- that about ninety percent of the adsorbed uoride at equilibrium
tral surface. The uoride adsorption by the solid at pH = pHzpc can (qe , mg g1 ) took place in 30 min from the start of reaction. How-
thus be described by either ion-exchange mechanism (R4 ) or simply ever, the time required to attain the equilibrium (te , min) increased
(R5 ). with increasing Ci in solution. Results show (Fig. 6) that the values
of te were about 45, 60 and 85 min for uoride adsorption from the
S OH(s) + F (aq) S F(s) + OH (aq) (R4 ) solution of Ci = 5.0, 10.0 and 20.0 mg L1 , respectively. Increase of
S OH(s) + F
S O
H +
F
+ aq (R5 ) te to attain the dynamic equilibrium with increasing Ci indicated
(aq) (s)
the decrease of rate constant value. The data shown in Fig. 6 were
analyzed by the non-linear t method with pseudo-rst order (Eq.
3.4. Effect of adsorbent dosage
(3)) [53] and pseudo-second order (Eq. (4)) [54] equations.
Fig. SI-7 shows the inuence of HCZMO dosage which was var-
Pseudo-rst order equation : qt = qe {1 exp(k1 t)} (3)
ied from (10 to 50) mg per 50 ml of aqueous uoride solution
(Ci = 10.0 mg L1 ) for the adsorption reaction at 30 C and at pH = 5.8 (t k2 q2e )
(0.2). It has indicated that the adsorbent dosage optimized to be Pseudo-second order equation : qt = (4)
{1 + (t k2 qe )}
50 mg/50 mL of uoride solution for the maximum removal. The
result obtained herein is found to be better than Gupta et al. [15],
and also than Gopal and Elango [51]. It is evident that the per-
centages of uoride adsorption had increased from 40 to 98.0 with
increasing adsorbent dosage from 10 to 50 mg/50 mL of uoride
solution (Ci = 10.0 mg L1 ). The increase of adsorption amount with
increasing concentrations of particle is nothing but a direct conse-
quence of a greater amount of available binding sites for uoride.
The distribution coefcient (KD ) for uoride on adsorbent was cal-
culated by Sujana et al. [38].
  
[F ] adsorbed 1
KD = (2)
[F ] dissolved Cp

where Cp is the solid concentration in kg L1 and KD has the units

of L kg1 . The distribution coefcient KD which reects the bind-
ing ability of solid surface for uoride mainly depends on the pH
and the type of solid surface. Here, it is observed (Fig. SI-8) that
the KD values were unchanged despite increase of the adsorbent
dose. It was clear from the plot (Fig. SI-8) that the surface bind-
ing ability, as reected in the KD values, remained constant with
increasing adsorption. If the surface was heterogeneous, the KD val- Fig. 6. The kinetic data on uoride adsorption by HCZMO at 303 (2) K and at pH
ues should change with adsorbent concentration at a constant pH. 5.8 (0.2) under varying uoride concentration in the presence of 0.1 M NaCl.
 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676 671

Table 1
Kinetic parameters for the uoride adsorption reaction with HCZMO (pH 5.8 0.2)
in the presence of 0.1 M NaCl at three different uoride concentrations and temper-
ature 303(2) K.

Kinetic equation Parameters Fluoride concentration

(mg L1 )

5 10 20

Pseudo-second order k2 (g mg1 min1 ) 0.020 0.014 0.006

qe (mg g1 ) 5.41 10.57 18.08
R2 0.990 0.985 0.984
2 0.01 0.18 0.21

Pseudo-rst order k1 (min1 ) 0.085 0.102 0.086

qe (mg g1 ) 4.80 9.60 16.17
R2 0.971 0.966 0.970
2 0.06 0.34 0.28

where k1 (time1 ) and k2 (g mg1 time1 ) are pseudo-rst order

and pseudo-second order rate constants, respectively. The signi-
cances of qe and qt have been noted earlier in this section.
The parameters estimated relating to pseudo-rst order and
pseudo-second order kinetic models are presented in Table 1.
It is seen that the present reaction kinetic data had described
the pseudo-second order equation (R2 = 0.99, 0.985 and 0.984;
2 = 0.01, 0.18 and 0.21) better slightly than the pseudo-rst order
equation (R2 = 0.971, 0.966 and 0.970; 2 = 0.06, 0.34 and 0.28). It is
also realized that the value of k2 decreased, despite the value of qe
increased (Table 1) with increasing Ci (mg L1 ) of uoride solution.
It indicates that the uoride adsorption rate is faster from the dilute
solution than from the concentrated one, which is similar with the
results of some other workers [15,54,55].
Rapid uptake at initial stages is presumably due to the ion-
exchange or strong Columbic attraction between uoride in
solution and surface OH group of solid and, slow uptake at latter
stages is due to the penetration of solute inside the pores of solid
matrix. The present data (Fig. 6) were also analyzed by the linear
form of pseudo-second order equation (4), (t/qt =1/v0 + t/qe , where
v0 = k2 qe 2 represents the initial adsorption rate) to evaluate the u-
oride adsorption rate over HCZMO surface to have information on
chemisorption possibility [5658]. The values of v0 calculated were
0.585, 1.564 and 1.961 mg g1 min1 for Ci of uoride solution 5.0,
10.0 and 20.0 mg L1 , respectively. Increase of v0 with increasing Ci
suggested the increase of mass transfer at initial stages from liquid
to solid phase, indicating the increase of chemisorption possibility
[57,58] of uoride over HCZMO surface.
3.5.2. Effect of temperature
Fig. 7 shows the variation of time dependent adsorption amount
(qt , mg g1 ) of uoride over HCZMO against t (min) at tempera-
tures 288, 303 and 318 K from a uoride solution of Ci = 5.0 mg L1
at pH 5.8 (0.2). It is seen that the qt increased with increase
of temperature on the reactions. It is also noted that the qt at
t = 30 min was about 90% of the qe of uoride at the time te
(min), and the te increased with increase of temperature on the
reaction. This is presumably due to the increase of thermally acces-
sible adsorption sites on HCZMO surface for adsorption. Again,
the data shown in Fig. 7 were also analyzed by the nonlinear t
method with the kinetic Eqs. (3) and (4) specied earlier. The
Fig. 7. The temperature dependent uoride adsorption kinetics data obtained on
HCZMO at pH 5.8 (0.2) and C0 = 5.0 mg L1 in the presence of 0.1 M NaCl.
pseudo-second order rate constant (k2 , g mg1 min1 ) from 0.012
to 0.026 with increasing temperature from 288 (2) to 318 (2) K
has indicated the increase of rapidness of uoride adsorption by
HCZMO with increasing temperature [54].
3.6. Isotherm modeling
Fig. 8 shows the equilibrium isotherm data as point for uo-
ride adsorption over HCZMO at pH 5.8 (0.2) and at temperatures
303 (2) K and 293 (2) K in the presence of 0.1 M NaCl. Analy-
ses of equilibrium data by the non-linear t (shown in Fig. 8) and
the linear t (not shown) of Langmuir isotherm (Eq. (5)) [59] and
Freundlich isotherm (Eq. (6)) [60] were done carefully on origin soft
ware spread sheet of computer.
b  Ce
Langmuir equation : qe = (5)
1 + b Ce
1/n
Freundlich equation : qe = KF Ce (6)
where qe and Ce have their usual signicance and given elsewhere.
 is the Langmuir monolayer capacity (mg g1 ), b the Langmuir con-
stant (L mg1 ) and KF , the Freundlich capacity (mg g1 ) and n is a
dimensionless constant of the Freundlich equation.
From the values of regression coefcient (R2 ), it can be said
that the ts of equilibrium data were much better with the
Langmuir model (R2 non-linear = 0.993 and R2 linear = 0.999) than with
the Freundlich model (R2 non-linear = 0.905 and R2 linear = 0.859). It
indicates that the adsorption sites on HCZMO surfaces are homo-
geneous and, the adsorption which occurred took place with
monolayer surface coverage. The Langmuir monolayer capacity (,
mg g1 ) evaluated from the linear and the non-linear analyses of
equilibrium data by Langmuir model was ranged in (19.419.5)
Table 2
Kinetics parameters for uoride adsorption reaction with HCZMO at pH = 5.8
(0.2) in the presence of 0.1 M NaCl and at three different temperatures (Ci of
F = 5.0 mg L1 ).

kinetic parameters estimated relating to each analyzed equation Kinetic models Parameters 288 K 303 K 318 K
was calculated from the slope and the intercept are presented
Pseudo-second order k2 (g mg1 min1 ) 0.012 0.0204 0.026
in Table 2. The values of regression co-efcients (R2 ) and chi qe (mg g1 ) 4.230 5.410 5.740
squared (2 ) have indicated that the pseudo-second order equation R2 0.985 0.994 0.995
described the temperature dependent kinetic data somewhat bet- 2 0.034 0.016 0.015
ter (R2 = 0.9850.995, 2 = 0.0150.034) than the pseudo-rst order Pseudo-rst order k1 (min1 ) 0.051 0.086 0.074
equation (R2 = 0.970.98, 2 = 0.0210.044). The experimental qt qe (mg g1 ) 3.520 4.690 5.020
values were found too close to the modeled qt from pseudo-second R2 0.971 0.984 0.980
2 0.044 0.021 0.022
order kinetics at any given time and temperature. Increase of the
672 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676

Fig. 8. The plot of equilibrium adsorption capacity versus equilibrium concentration of uoride on HCZMO in the presence of 0.1 M NaCl at 303 (2) K and 293 (2) K at pH
5.8 (0.2) and the non-linear data ts with the Langmuir and Freundlich isotherm models.

Table 3
Non-linear and linear isotherm parameters of uoride adsorption equilibrium data on HCZMO at 303 (2) K and pH = 5.8 (0.2) in the presence of 0.1 M NaCl.

Isotherm model Non-linear Linear

Langmuir  (mg g1 ) b (L mg1 ) R2  (mg g1 ) b (L g1 ) R2

19.515 0.744 0.993 19.400 0.725 0.999

Freundlich KF (mg11/n L1/n g1 ) n R2 KF (mg11/n L1/n g1 ) n R2

8.566 3.465 0.905 7.240 2.770 0.737

mg g1 (Table 3). The performance on uoride adsorption by
HCZMO was assessed comparing with some literature available
materials (Table 4). It can be said that the present material has good
prospect for ltration of high uoride groundwater.
An essential feature of the Langmuir isotherm can be expressed
by the separation factor (KL ), the dimensionless constant which is
expressed by the relation (Eq. (7)).
1
KL =
1 + b Ci
The signicance of each term of equation (7) has already been
given elsewhere. An adsorption reaction should be (i) favorable if KL
ranged in 0 < KL < 1.0, (ii) unfavorable if KL > 1.0, and (iii) irreversible
if KL = 1.0 [61]. Values of the KL for the present adsorption reaction
calculated to be ranged in 01.0 even for the Ci of uoride lesser
than 1.0 mg L1 . Thus, the uoride adsorption over HZCMO is a
favorable process even at the level of uoride concentration that
occurs commonly in groundwater [62,63].
3.7. Heat of the reaction
The isosteric heat of adsorption is mainly a function of
adsorption density. It can also provide further evidence for site
homogeneity and indicates the reaction nature as endothermic or
exothermic. The isosteric heat of adsorption can be calculated from
adsorption isotherms at two or more temperatures taking two dif-
ferent adsorbent dose using ClausiousClapeyron Eq. (8) [52].
(7)
R ln(C2 /C1 )
Hr = (8)
1/T1 1/T2
where Hr is the isosteric heat (kJ mol1 ) of adsorption at a given
adsorption density, R is the gas constant in SI unit; C1 and C2 are
equilibrium concentrations of the adsorbate at temperatures T1
and T2 , respectively. At the reaction temperatures 293 and 303 K,
the value of Hr was calculated for any two adsorption densi-
ties to be 0.518 kJ mol1 (Table 5). Thus, the Hr is independent
of adsorption density, which signies the homogeneous nature of

Table 4
Comparative assessment of uoride adsorption capacity of HCZMO with some reported materials.

Adsorbents pH Equilibrium concentration (mg L1 ) Adsorption capacitya (mg g1 ) Reference

Activated alumina 7.0 1.0 0.96 [21]

Bone Char 7.0 1.0 2.71 [18]
Carbon slurry 7.58 1.0 4.86 [15]
FeSn oxide 7.0 1.0 8.50 [35]
Zr(IV)-impregnated collagen ber 5.5 1.0 2.29 [27]
HCZMOb 5.8 1.5 12.4 Present work
Titanium rich bauxitesb 6.0 1.0 1.2 [31]
Ironaluminum mixed oxide 6.9 1.5 12.0 [32]
FeAlCe trimetal oxideb 7.0 1.0 12.2 [33]
AlCe hybrid adsorbentb 6.0 1.0 27.5 [36]
a
Calculated from the sorption isotherms or Langmuir equation.
b
Powder adsorbent.
 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676 673

Table 5
Thermodynamic parameters for the uoride adsorption reaction with HCZMO at pH = 5.8 (0.2) in the presence of 0.1 M NaCl.

Initial uoride concentration (C0 , mg L1 ) H0 (kJ mol1 ) S0 (J mol1 K1 ) G0 (kJ mol1 ) at various temperature (K) Hr (kJ mol1 )

293 303 313 328

20.0 +4.04 +13.8 0.015 0.164 0.360 0.567 0.518

15.0 +3.53 +12.4 0.012 0.259 0.410 0.614

the adsorbent surface [41]. The positive heat of adsorption is thus

indicated endothermic nature of the adsorption reaction [64].

3.8. Thermodynamic parameters

Thermodynamic parameters such as G0 (Gibbs free energy

change), H0 (enthalpy change), S0 (entropy change) and Kc
(equilibrium constant at temperature T, K) for this adsorption
process in solution can be calculated using the standard thermody-
namic relations (Eqs. (9) and (10)) assuming the activity coefcient
as unity at low level of solute concentration [52].

G0 = H 0 TS 0 (9)

G0 = 2.303 RT log Kc (10)

From these Eqs. (9) and (10), the Eq. (11) can be obtained.
 
S 0 H 0 1 Fig. 9. The plot of log (qe /Ce ) against 1/T (K) 103 for thermodynamic parameters.
log Kc = (11)
2.303R 2.303R T

The thermodynamic equilibrium constant, Kc was calculated by
using Eq. (12),
qe
Kc =
Ce
where qe /Ce is called the adsorption afnity (L g1 ).
Here, qe
(mg g1 ) signies the adsorption capacity and Ce (mg L1 ) is the
remaining/equilibrium uoride concentration in the solution. So
the above relation (Eq. (11)) can be written as (Eq. (13))
q   
e S 0 H 0 1
log = (13)
Ce 2.303R 2.303R T
Assuming S0 and H0 to be constant within the range of tem-
perature studied, the values of H0 and S0 can be computed from
the slope and intercept of the straight line plot of log(qe /Ce ) versus
1/T, and G0 , the free energy change for the reaction, at various
temperatures can also be calculated from Eq. (9).
Taking the values of qe (mg g1 ) and Ce (mg L1 ) over a range of
temperature for uoride solution of Ci = 15.0 and 20.0 mg L1 , the
values of log(qe /Ce ) are plotted against 1/T (Fig. 9) which shows
a straight line with good regression coefcient value (R2 = 0.99).
The thermodynamic parameters estimated are shown in Table 5,
which indicated the spontaneous nature (G0 = negative) of the
reaction despite the uoride adsorption over HCZMO surface was
an endothermic (H0 = positive) process. Thus, the uoride adsorp-
tion over HCZMO occurs spontaneously, because the entropy (S0 ,
J mol1 K1 = +12.8 and +13.4) increased at the solidliquid inter-
face when uoride adsorbed over HCZMO from the Ci = 15.0 and
20.0 mg L1 and also the gain of energy from the surroundings
[65,66]. The signicant increase of entropy is due to the release of
H2 O molecules at the solidliquid interface with F (aq) adsorption
by the solid surface.
3.9. Energy of adsorption
The mean free energy of adsorption (EDR ) is important for dis-
tinguishing physical and chemical adsorption process, which is
dened as the change of free energy when 1 mol of a solute is trans-
ferred to the surface of an adsorbent from innity i.e. from solution
[67] and can be calculated by the relation (Eq. (14)).
(12)
1
EDR = (14)
1/2
(2)
where is a DubininRadushkevich (DR) isotherm constant. It
can be evaluated by tting of the equilibrium data (Fig. 8) with the
DubininRadushkevich (DR) isotherm (Eq. (15)) [67]. It is a more
generalize isotherm than the Langmuir as there is no assumption
of homogeneity and constancy of adsorption potential [68].
ln Qe = ln Qm 2 (15)
where Qe and Qm are the equilibrium and saturation capacities
(mol kg1 ) of uoride adsorption a uoride by HCZMO, respec-
tively. Again, the is related with the equilibrium concentration
(Ce / , mol L1 ) by Eq. (16),
 
1
= RT ln 1+ (16)
/
Ce
where R is the molar gas constant (8.314 J mol1 K1 ) and T is the
absolute temperature.
Like other authors [65,66], the equilibrium data were ana-
lyzed with the DR isotherm (Eq. (15)) for evaluating the average
energy of adsorption. Here, the values of Qm (mol kg1 ) and
(mol2 kJ2 ) were evaluated from the intercepts and the slopes
of the linear plot of ln qe versus 2 (Fig. SI-9, R2 = 0.976), which
were 2.11 and 2.20 103 , respectively. Inserting the value of
in Eq. (14), the value of EDR obtained was 15.07 kJ mol1 . It is
known that an adsorption reaction will occur by (i) physisorption if
EDR = 8.0 kJ mol1 , (ii) ion-exchange if EDR = 8.016.0 kJ mol1 and
(iii) chemisorptions if EDR > 16.0 kJ mol1 [6567]. As the value of
EDR estimated for the present reaction is 15.07 kJ mol1 and closer
to 16 kJ mol1 , the uoride adsorption reaction with HCZMO will
be predicted to be an ion-exchange [65] process with inclination to
the chemisorptions.
674 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
3.10. Activation parameters
The activation energy of a reaction can be evaluated from the
Arrhenius equation (Eq. (17)) [52]
 E 
a
k2 = A exp (17)
RT
where k2 is the rate constant (g mg1 min1 ), A is the temperature-
independent factor (g mg1 min1 ), Ea is the activation energy
(kJ mol1 ) of a reaction. The signicances of R and T are known
well and given earlier.
Taking logarithm of Eq. (17), the following Arrhenius type linear
relationship (Eq. (18)) can be obtained.
 E  1
a
ln k2 = ln A + (18)
R T
Taking the pseudo-second order rate constant value (best t
model), when the value of ln k2 was plotted against 1/T showed
a straight-line plot (Fig. SI-10) with good regression coefcient
value (R2 = 0.99). The values for A and Ea calculated from intercept
and slope of the plot were 7.2 104 g mg1 s1 and 1.16 kJ mol1 ,
respectively. Very low value of each parameter suggested that the
uoride has high combining afnity with HCZMO surface.
3.11. Adsorption mechanism
Fig. SI-11 shows the FTIR spectra of HCZMO and F adsorbed
HCZMO. It is seen that the bands at  = 1051 and 1133 cm1 of
HCZMO shifted to 1089 cm1 , respectively, indicating the forma-
tion of M F linkage [50]. It is exciting that the three new peaks
at  = 1744, 2851 and 2926 cm1 appeared in the spectrum of
uoride-rich HCZMO, which might be for the formation of Ce F
and Zr F bonds those arose owing to uoride adsorption. In addi-
tion, the estimated pH-effect (Section 3.3), binding constant and
the EDR (15.07 kJ mol1 ) values suggested previously that the pos-
sible adsorption mechanism of uoride by HCZMO can be expressed
by the reactions (R4 ) and (R5 ) presented in effect of pH sub-section.
This agrees well with (i) the small change of the solution pH and (ii)
the existence of S F bond in the FTIR spectrum of uoride adsorbed
HCZMO. The mechanism proposed is similar with other researchers
[33,68] for uoride adsorption over metal oxide surface.
3.12. Competitive effect of some ground water occurring ions
Common ground water occurring anions are phosphate, chlo-
ride, sulphate, carbonate, and silicate which may inuence
uoride adsorption over HCZMO. Fig. SI-12 displays the result
of uoride adsorption over HCZMO in the presence of ions
specied above. It is found that the sequence of adverse inu-
ence on uoride adsorption over HCZMO can be given as
HPO4 2 > Cl > SO4 2 > HCO3 > SiO3 2 . It has been seen that the
phosphate ion has stronger adverse effect comparing to others on
uoride adsorption over HCZMO. It appears also that the chloride
might compete well with uoride to get adsorbed on HCZMO sur-
face. The signicantly strong adverse inuence of phosphate on
uoride adsorption was also reported for the case of adsorbents
such as chitosan beads [63], granular ferric hydroxide [69], and
CeAl mixed metal oxide [70]. Fortunately, the phosphate concen-
tration in groundwater is very low [70]; hence its effect on uoride
adsorption by HCZMO could hardly be a limiting factor.
3.13. Desorption study
According to the pHzpc of HCZMO and initial pH-effect on the
uoride adsorption by HCZMO, it was found that the uoride
adsorption by HCZMO decreased signicantly with increasing pH
and, the uoride adsorption is too low in alkaline pH range. Based on
this observation, the uoride desorption from F-HCZMO was con-
ducted separately by the batch process varying 0.14.0 M NaOH
solution. The results obtained are presented in Fig. SI-13. It has
been found that the desorption percentage increased with increas-
ing alkali concentration and more than 95% desorption took place
with 1.0 M NaOH solution. The present result has been found to be
better than the results that reported by Patel et al. [40].
4. Field validation
Groundwater sample was collected from a tube well (Location:
Pitidiri village, 23 02.867 N, 86 35.123 E,) of district Purulia in
West Bengal (India) and analyzed for some water quality param-
eters before treatment with HCZMO. The parameters estimated
(mg L1 except pH) were pH (7.1), total hardness (as CaCO3 ) (620),
total alkalinity (385), Ca2+ (86.17), Mg2+ (98.42), Fetotal (0.09),
TDS (871), Turbidity (1.8), Na+ (28.9), K+ (4.7), Cl (234.93), F
(2.45), PO4 3 (0.05), NO3 (48.82), SO4 2 (286.17) and electrical
conductivity (1340). This groundwater sample was spiked with u-
oride to increase its concentration to 4.4 mg L1 . The solid material
(HCZMO) of a denite amount ranged in 0.21.0 g was mixed per
liter of water sample for estimating the efciency of the material as
uoride scavenger by batch procedure. Here, the reaction mixture
was stirred by a digital mechanical stirrer (speed: 1000 rpm) for
2.0 h and ltered. The ltrate of each experiment was analyzed for
uoride. The results obtained are shown in Fig. SI-14. It has been
seen that 1.0 g HCZMO per liter of water can reduce the uoride
level from 4.4 mg L1 to below 1.50 mg L1 , which is below the per-
missible level of uoride in drinking water for the countries of cold
climate. Increase of HCZMO dose from 1.0 g to 1.5 g per liter of water
reduced to uoride level to below 1.0 mg L1 , which is below the
permissible level for the countries of hot climate.
5. Conclusion
In the present study, HCZMO was prepared by low tempera-
ture and green method; and characterized as a microcrystalline
nanostructured material with irregular surface morphology. The
pHzpc (5.8 0.2) and BET surface area (185.04 m2 g1 ) has indicated
good possibility to be used as an adsorbent for water treatment.
This material when used for uoride adsorption showed highest
capacity at pH 5.56.0. The kinetic of uoride adsorption over
HCZMO occurred according to the pseudo-second order kinetic
model. The Langmuir isotherm which described the equilibrium
well showed the monolayer adsorption capacity 19.5 mg g1 .
Low activation energy (1.16 kJ mol1 ) and high adsorption energy
(15.05 kJ mol1 ) indicated high afnity of uoride for HCZMO sur-
face. Surface homogeneity and endothermicity indicated from
isosteric heat of reaction (Hr ) had been conrmed from the
Langmuir isotherm t and positive H0 , respectively. The spon-
taneity of uoride adsorption over HCZMO (G0 = negative) despite
endothermic (H0 = positive) is owing to the increase of entropy
(S0 = positive) of this reaction. 50 mL of 1.0 M NaOH solution is
regenerated the 0.1 g uoride-rich material up to >95%. Batch treat-
ment of 1.0 L eld sample with 1.0 g of HCZMO reduced the uoride
level from 4.4 mg L1 to well below of 1.5 mg L1 , indicating good
application possibility of HCZMO for the treatment of high uoride
ground water.
Acknowledgements
Authors wish to extend their sincerest thanks to the Depart-
ment of Science and Technology, Govt. of India, New Delhi for
awarding JRF to Abir Ghosh. Authors are also grateful to the Head,
 A. Ghosh et al. / Applied Surface Science 307 (2014) 665676
Department of Chemistry, Presidency University, Kolkata for lab-
oratory facilities. The Heads of the Department of Physics and
Geology of the same university are also acknowledged, respec-
tively, for the XRD and other analytical studies.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.apsusc.2014.
04.095.
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