Synthesis and Evaluation Catalytic Efficiency of Perovskite-Type Oxide Nanopowders in Removal of Bromocresol Purple from Aqueous Solution

International Journal of Scientific Research in Knowledge, 2(7), pp. 340-351, 2014

Available online at http://www.ijsrpub.com/ijsrk

ISSN: 2322-4541; 2014 IJSRPUB

http://dx.doi.org/10.12983/ijsrk-2014-p0340-0351

340

Full Length Research Paper

Synthesis and Evaluation Catalytic Efficiency of Perovskite-Type Oxide

Nanopowders in Removal of Bromocresol Purple from Aqueous Solution

Haman Tavakkoli*, Arezoo Ghaemi, Mastaneh Mostofizadeh

Department of Chemistry, Khouzestan Science and Research Branch, Islamic Azad University, Ahvaz, Iran

*Corresponding author: [email protected], [email protected]

Received 10 May 2014; Accepted 25 June 2014

Abstract. A1xAxBO3 belongs to the perovskite oxides of the ABO3 structure. In this study, nanoparticles of La0.5Ca0.5FeO3 were fabricated by solgel citrate technique. A series of common analytical techniques were used to characterize the crystallinity, morphology, specific surface area, and grain size of the nanopowders. These properties were characterised by

means of XRD, SEM, EDX and FTIR. The calculated particles size using the Scherrer's formula was about 20 nm. Moreover,

the family of perovskite-type oxides could be considered as an adsorbent/catalyst material for the removal of dyes. This study

has also investigated the efficiency of La0.5Ca0.5FeO3, as an adsorbent for removal of dye (Bromocresol Purple (BP)), from an

aqueous solution. The adsorption studies were carried out at different pH values, various adsorbent dosages and contact time in

a batch experiments. The kinetic studies indicate that the removal process obeys the Pseudo-first-order kinetic equation. Also,

the isotherm evaluations reveal that the adsorption of BP by the nanoparticles follows the Langmuir model. In addition, this

nanoparticle with good specific affinity towards dye molecules was a promising adsorbent for dye removal from natural water.

Keywords: Perovskite oxides, Solgel method, Nanopowders, dye removal, bromocresol purple

1. INTRODUCTION

The structure of the LaMO3 perovskite oxide consists

of MO6 and LaO12. A1xAxBO3 belongs to the group

of perovskite oxides of the ABO3 structure with a

trivalent rare earth in the A position (La) and a

trivalent metal ion in the B position (Co, Fe or Ni).

When La+3

ions in LaMO3 are replaced by earth

alkaline ions such as Ca+2

to form La1xCax(Co, Fe,

Ni)O3 a positive charge can be generated. Since Fe+z

cations have different oxidation states, the charge

neutrality can be maintained by the formation of

oxygen vacancies and a change in the valence state of

the cations. Therefore, these structures have an

oxygen deficiency, , due to the high oxygen vacancy concentration and can show the fine electric

conductivity, catalytic, mechanical, and colossal

magnetoresistance (CMR) properties which have

attracted a lot of attention (Gao and Wang, 2010; Gao

et al., 2006; Chi et al., 2010). Furthermore, perovskite

oxide, La1xCaxFeO3 could be a mixed ionic and

electronic conductor. It has been widely investigated

for use in various high-temperature electrochemical

devices such as solid oxide fuel cells (Zhen et al.,

2006; Jiang, 2008) or oxygen permeation membranes

(Van Hassel et al., 1993). Moreover, they have been

proposed as alternative catalysts for oxidation of

carbon monoxide and hydrocarbons (Hu, 2005;

Hirano et al., 2007) and promising catalyst for multi

component reactions (Sanaeishoar et al., 2014).

A number of approaches such as solid-state

reactions (Zhou et al., 2006), mechanical-synthesis

(Szabo et al., 2002), coprecipitation (Nakayama et al.,

2003; Srdic et al., 2005), solution combustion or

thermal decomposition (Bansal and Zhong, 2006;

Berger et al., 2004; Berger et al., 2007) hydro-

thermal, and sol-gel technique (Pechini, 1967;

Cizauskaite and Kareiva, 2008) have been used to

synthesize LaMO3-based perovskite powders. The sol-

gel method is highly attractive because various metal

ions are chelated to form metal complexes in solution

and are uniformly distributed at the molecular level.

In this method, citric, oxalic and fatty acids and

EDTA (Ethylenediaminetetraacetic Acid) have been

utilized as complexing agents, among which, citric

acid is a good chelating agent for transition metal

cations for synthesizing ultra-fine powders of complex

oxide compositions (Raileanu et al., 2013).

Growing concern for public health and

environmental quality has prompted a wide interest in

developing and implementing various materials and

methods for removing the toxic organic and inorganic

Tavakkoli et al.

Synthesis and Evaluation Catalytic Efficiency of Perovskite-Type Oxide Nanopowders in Removal of Bromocresol

Purple from Aqueous Solution

341

pollutants from water (Senthilnathan and Philip,

2010). Dyes from the effluent of textile, paper,

printing, and leather industries are the major sources

of water contamination. There are more than ten

thousand types of commercially available dyes with

over seven hundred tons of dyestuff produced

annually worldwide and used extensively in industries

(Banat et al., 1996; Spadaro et al., 1994; Robinson et

al., 2001). It is estimated that about 1015% of the dyes were lost in industrial effluents (Forgacs et al.,

2004).

The traditional physical, chemical and biologic

means of wastewater treatment often have little

degradation effect on this kind of pollutants. On the

contrary, the technology of nanoparticulate

photodegradation has been proved to be effective to

them. Compared with the other conventional

wastewater treatment means, this technology has such

advantages as: 1) wide application, especially to the

molecule-structure complexed contaminants which

cannot be easily degraded by the traditional methods;

2) the nanoparticles itself has no toxicity to the health

of our human livings and 3) it demonstrates a strong

destructive power to the pollutants and can mineralize

the pollutants into CO2 and H2O. Due to the excellent

features of this technology, it appears promising and

has drawn the attention of researchers of at home and

abroad (Tavakkoli et al., 2013; Yazdanbakhsh et al.,

2011; Carbajo et al., 2006).

In the present study, La0.5Ca0.5FeO3 (LCFO)

component with perovskite structure was prepared via

the sol-gel method and characterized by different

techniques such as XRD, FTIR, SEM and EDX.

Moreover, its efficiency as an adsorbent for removal

of dye, bromocresol purple (BP), from an aqueous

solution was evaluated. The effect of different

variables including concentration of dye, different pH

values, adsorbent doses and reaction time, for removal

of BP on LCFO nanopowders has been investigated

and two kinetic models have also been analyzed.

2. MATERIALS AND METHODS

2.1. Reagents

La(NO3)3.9H2O (99.99% purity), Ca(NO3)2.4H2O

(99.99% purity), Fe(NO3)3.9H2O (99.99% purity)

were all obtained from Merck, Germany; citric acid

(CA) (99.5% purity), was purchased from Aldrich,

USA. The commercial color index (CI) dye (BP,

molecular weight = 540.22 g/mol) was generously

provided by Sigma company, T8154-20ml USA

which was used without further purification (Fig. 1).

All the reagents were of analytical grade and thus

used as received. Deionized water was used

throughout the experiments.

2.2. Preparation and characterization of

La0.5Ca0.5FeO3

For the preparation of the nanoperovskite in this work,

Proportional amounts of, La(NO3)3.9H2O,

Ca(NO3)2.4H2O and Fe(NO3)3.9H2O , were dissolved

in 20 ml of deionized water, Citric acid (CA) was

proportionally added to the metal solution by stirring

at room temperature. The solution was concentrated

by evaporation at approximately 75C to remove

excess water. Then, the dry gel was obtained by

letting the sol into an oven and heated slowly up to

110C and kept for 10 h in baking oven.Then, it was

ground in agate mortar and turned into powder and

calcinated at 750C in air for 9 h. The annealing of the

amorphous precursor allows removing most of the

residual carbon and the orthorhombic perovskite

phase was obtained.

The complex polymeric gel and derived powders

have been analyzed by Fourier transform infrared

(FTIR) spectroscopy on Perkin Elmer BX II FTIR

spectrometer. The crystallization and microstructure

of the oxide powders have been characterized with an

X-ray diffractometer employing a scanning rate of

0.02 S-1

in a 2 range from 20 to 70, u ing a pert, 200, Equinox 3000, France, equipped with CuK

radiation. The data have been analyzed using JCPDS

standards. The microstructure and elemental

distribution on the surface were investigated using

KYKY EM3200 (V=30kV) scanning electron

microscopy and energy dispersive X-ray spectroscopy

(EDX, Inca 400, Oxford Instruments). A UVVis spectrophotometer (Perkin Elmer lambda 35) was

employed to monitor adsorption of dyes.

2.3. Dye removal experiments

A prepared solution of BP was distributed into

different flasks (1 L capacity) and pH was adjusted

with the help of the pH meter (HORIBA F 11 E, Japan

made). The initial pH value of the dye solution was

adjusted to the desired levels, using either HCl (0.5

M) or NaOH (0.5 M). A known mass of nano-LCFO

powder (catalyst dosage) was then added to 10 mL of

the BP aqueous solution, and the obtained suspension

was immediately stirred for a predefined time. All

experiments were done at the room temperature. The

investigated ranges of the experimental variables were

as follows: dye concentration (50-250 mg/L), pH of

solution (1-13), catalyst dosage (0.005, 0.01, 0.02 and

0.03 g) and mixing time (1- 40 min). After a

preselected time of decolorization, samples were

collected and absorbance of the olution at a max = 450 nm for pH = 1 to 5 and max = 530 nm for pH = 6 to 13 was measured to monitor the residual BP

concentration.


342

Fig. 1: Chemical structure of Bromocresol Purple

3. RESULTS AND DESCUSIONS

3.1. X-ray Diffraction

XRD patterns of the synthesized nanopowder which

calcined at 700C for 9 h (heating rate: 3

C/min) is

shown in Fig. 2. XRD results reveal the existence of a

perovskite-type phase for sol-gel method at this

temperature. When the precursor was calcined at

700C for 9 hours, several sharp peaks were observed

attributed to the perovskite La0.5Ca0.5FeO3 by

comparison with standard XRD spectra. The

diffraction peak at 2 angel appeared in the order of 22.65

, 32.30

, 39.85

46.36

, 57.65

, and 67.66

can be

assigned to scattering from the (0 2 0), (2 0 0), (2 2

0), (2 0 2), (3 2 1), and (4 0 0) planes of the

La0.5Ca0.5FeO3 perovskite type crystal lattice,

respectively. XRD data also shows La0.5Ca0.5FeO3 crystallizes in an orthorhombic phase with a = 5.5408,

b = 7.843, c = 5.544 . The crystallite sizes were

calculated using XRD peak broadening of the (2 0 0)

peak u ing the Scherer formula (1):

hklhkl

hklD

cos

9.0 (1)

where Dhkl is the particle size perpendicular to the

normal line of (hkl) plane, hkl is the full width at half maximum, hkl i the Bragg angle of (hkl) peak, and is the wavelength of X-ray. The particle sizes of

LCFO nanoparticles calcinated at 700C is about 20

nm.

3.2. SEM and EDX Analysis

The surface and textural morphology of LCFO

nanopowder by SEM image is illustrated in Fig. 3.

According to the SEM image, the size of LCFO

particles was found to range between 20 to 50 nm.

The surface looks scaly and nearly fully covered with

the particles that have grown on it. Moreover, the

porosity of the surface is evident and it seems that the

particles have grown with uniform size. The pores

size varied from 0.1 to 0.3 m. It mu t be mentioned that pores with large geometric dimensions are more

suitable for water treatment. Also, the existence of

these meso-pores facilitates the sorption of hazardous

chemicals to the surface. This phenomenon improved

the efficiency and workability of LCFO as a

promising adsorbent.

The surface looks scaly and nearly fully covered

with the particles grown on it. Further, it can also be

seen from the SEM image that in addition to the larger

particles, the surface contains also rather smaller

particles. Nonetheless, the dominant particles on the

surface were the larger ones. When smaller particles

(in the nm range) aggregate, this may lead to the

formation of bigger LPMO NPs on the surface.

The EDX analysis was performed to further

confirmation of the obtained product composition.

Fig. 4 shows EDX spectrum which indicates the

existence of La, Ca, Fe and O elements in this

nanoparticle.

Tavakkoli et al.



343

Fig. 2: XRD pattern of La0.5Ca0.5FeO3 nanopowder

Fig. 3: SEM images of LCFO nanopowders.

Fig. 4: Energy dispersive X-ray (EDX) spectrum of the LCNO nanoparticles.


344

3.3. FT-IR Spectroscopy

The FT-IR spectra of the LCFO fresh xerogel and

calcinated xerogel in the range of 500-4000 cm-1

were

shown in Fig. 5 (a,b). The dried gel of the sample

shows the characteristic bands at about 1725, 1617

and 1385 cm-1

corresponds to the symmetric and anti-

symmetric stretching mode of carboxylate group

(Kuznetsov et al., 2002; Kim and Honma, 2004). The

band at about 1230 cm-1

assigned to the NO3

stretching vibration (Lui et al., 2007). The absorption

band around 1080 cm-1

is attributed to CO bond

(Nakamoto, 1978). As can be seen in Fig.5 b, the

bands correspond to OH group, NO3, and carboxylate ligand disappear as the gel was calcinated

at 700C.

The FTIR spectra of calcined sample shows the

vanishing of bands related to organic and hydroxyl

groups. Two bands are observed at 400-650 cm1 in the FTIR spectrum of sample, one of them is strong at

~ 617 cm1 and other weak peak at 431 cm1. The e peaks are characteristics of perovskite oxides and can

be attributed to MO tretching and OMO bending mode of vibrations, respectively.

(a)

(b)

Fig. 5: FT-IR spectra of LCFO precursor (a), and the calcinated powders at 700 C (b).

3.4. Adsorption experiment

The efficiency of the prepared and characterized

LCFO nanoparticle as an adsorbent for removal of BP

from liquid solutions was investigated using a batch

equilibrium technique placing different amount of

adsorbent in a glass bottle containing 10 ml of a dye

solution at 50 mg/L concentrations. The adsorption

studies were carried out for different pH values,

contact time, catalyst dosage and dye solution

concentrations and results are presented in the

following sections.

Tavakkoli et al.



345

3.4.1. Effect of pH

Solution pH is an important parameter that affects

adsorption of dye molecules. The effect of the initial

solution pH on the dye removal efficiency of BP by

LCFO nanoparticles was evaluated at different pH

values, ranging from 0.5 to 13, with a stirring time of

30 min. The initial concentrations of dye and

adsorbent dosage were set at 50 mg/L and 0.01 g,

respectively. The percentage of dye removal is

defined as (2):

100)(

% rateRemoval

o

o

C

tCC (2)

where C0 and C(t) are the initial concentration and

concentration of BP at time t, respectively.

As shown in Fig. 6, the dye removal was much higher

in acidic pH and decreased when the pH was

increased from 3 to 13. Since the removal of BP

increased to its maximum value at pH 1 (the removal

of BP above 97% was achieved) the electrostatic

attraction between the dye molecules (negatively

charged) and LCFO surface (positively charged)

might be the predominant adsorption mechanism [Al-

Degs et al., 2008]. Therefore, to have the optimized

condition to remove BP, acidic pH should be applied

and pH 1 seems to lead to the best result; so this pH

was selected to run further experiments.

Fig. 6: Effect of initial pH of dye solution on removal of BP (LCFO dosage = 0.01 g, initial dye concentration = 50 mg/L,

stirring time = 30 min).

3.4.2. Effect of contact time and adsorbent dosage

To further assessing of dye removal, the effects of

mixing time and adsorbent concentration on the

removal of BP by LCFO nanoparticles were

examined. Initial dye concentrations and pH of the

solutions were fixed at 50 mg/L and 1, respectively,

for all the batch experiments.

Results are shown in Fig. 7. As indicated,

increasing of mixing time in different dosages of

adsorbent led to decrease in the concentration of BP.

This behavior was also observed when catalyst dosage

increased from 0.005 to 0.03 g. This decreasing in the

concentration is due to the adsorption of BP on LCFO

nanoparticles and the greater number of adsorption

sites for dye molecules made available at greater

LCFO dosages (Erdem et al., 2005; Wang et al.,

2008). The removal efficiency of BP at the initial

dosage of 0.01 g, increased from 77% at the second

minute of contact to 95% at time equals to 30 min by

keeping constant stirring, however, with rising LCFO

dosage to 0.03 g the percentage of removal obtained

in the second minute of stirring was 88%, and the

most percent of removal (98%) was attained when the

stirring was continued till time equals to 15 min. The

adsorbent dosage obtained in this study for complete

removal of BP on to LCFO nanopowder is less than

most of the reported values in the literatures for dye

adsorption using other adsorbents (Moussavi and

Mahmoudi, 2009; Song et al., 2008; Kong et al., 2009;

Zhang et al., 2006).

83.21

97.94

72.57

59.63 59.48 59.41 59.33 59.11 58.6

40

60

80

100

0 2 4 6 8 10 12 14

Re

mo

val(

%)

pH


346

Fig. 7: Effect of stirring time on removal of BP in different doses of LCFO (initial dye concentration = 50 mg/L, initial pH 1).

3.4.3. Effect of dye concentration

The initial dye concentration is another important

variable that can affect the adsorption process. The

effect of initial BP concentration on dye removal

efficiency by LCFO particles was studied by varying

the initial dye concentration from 50 to 300 mg/L at

pH 1, a catalyst dosage of 0.01g and contact time of

30 min, as shown in Fig. 8. Results show that removal

of textile dye BP decreases with increasing initial

concentration. As it is obvious, the percentage

removal of BP decreased from around 95% at a

concentration of 50 mg/L to 50% when the

concentration was increased to 300 mg/L. This

behavior reveals the dependency of adsorption to

initial concentration of BP.

Fig. 8: Effect of initial dye concentration on removal of BP (LCFO dosage = 0.01 g, initial pH 1, stirring time = 30 min).

3.5. Adsorption kinetic studies

To find the suitable chemical removal model for

describing the experimental kinetic data, the obtained

data were evaluated using pseudo-first and pseudo-

second-order reaction rate models (Santos et al., 2008;

Ho and McKay, 1999).

For the first and second order kinetic model, the

experimental data have been fitted with the following

equations:

first-order equation: tkCtC o 1ln)(ln (3)

second-order equation:

oCtk

tC

1

)(

12

(4)

where k1 and k2 are the first-order and second-order

rate constant, respectively; C0 stands for the initial BP

concentration and C(t) is the concentration of BP at

time t. Higher value of R2 were obtained for first-

order (0.98) than for second-order (0.92) adsorption

rate models, indicating that the adsorption rates of BP

on to the LCFO nanoparticles can be more

appropriately described using the first-order rate

rather than second-order rate. The values of the rate

constant, k1 and k2 are 0.055 and 0.014 (M1

min1

),

respectively.

0

20

40

60

80

100

120

0 50 100 150 200 250 300 350

Dye

re

mo

vale

(%

)

Initial concentration (mg/L)

Tavakkoli et al.



347

3.6. Adsorption isotherms studies

The equilibrium isotherm of a specific adsorbent

represents its adsorptive characteristics and analysis of

isotherm data is so important to predict the adsorption

capacity of the adsorbent, which is one of the main

parameters required for designing the adsorption

processes (Afkhami and Moosavi, 2010).

The amount of dye adsorbed onto LCFO nanoparticles

has been calculated based on the following mass

balance equation:

m

CCVq ee

)( 0 (5)

where qe is equilibrium dye concentration on

adsorbent (mg/g), V is the volume of the dye solution

(L), C0 and Ce (mg/L) are the initial and equilibrium

dye concentrations, respectively, and m (g) is the mass

of LCFO nanoparticles.

Various isotherm models, such as Langmuir,

Freundlich, and Temkin were applied to describe the

nonlinear equilibrium relationship between the solute

adsorbed onto the adsorbent and that left in the

solution. An adsorption isotherm is characterized by

certain constants which values express the surface

properties and affinity of the adsorbent.

The Langmuir model equation, assuming monolayer

adsorption on a homogeneous adsorbent surface, can

be presented as follows (Langmuir, 1918):

maxmax

1

q

C

qKq

C e

Le

e (6)

where the qmax (mg/g) is the surface concentration at

monolayer coverage which illustrates the maximum

value of qe and it can be attained as Ce is increased.

The values of qmax and KL can be determined from

the linear regression plot of (Ce/qe) versus Ce.

The linearized form of the Freundlich isotherm is

expressed as follows [Freundlich, 1906]:

eFe Cn

Kq log1

loglog (7)

where KF and n are constants of the Freundlich

equation. The constant KF represents the capacity of

the adsorbent for the adsorbate and n is related to the

adsorption distribution. A linear regression plot of log

qe versus log Ce gives the KF and n values.

The derivation of the Temkin isotherm assumes that

the fall in the heat of adsorption is linear rather than

logarithmic, as implied in the Freundlich equation.

The Temkin isotherm is as following

ee CBAq ln (8)

where A and B are isotherm constants (Fu et al.,

1994).

Table 1: Isotherm constants for BP adsorption on LCFO nanoparticles

Temkin

model

Freundlich

model

Langmuir

model

Adsorben

t

R2

BT

(j/mol)

AT (L/g)

R2

n

Kf (mg1-1/n

L1/n

g-1

)

R2

b (L mg-1

)

qmax (mg g-1

)

La0.5Ca0.5FeO3

0.951

64.536

1.351

0.975

2.583

35.974

0.991

0.074

250

The experimental results of this study were fitted

to the aforementioned models. The calculated

adsorption parameters and correlation coefficient (R2)

for the three isotherm models by linear regression are

listed in Table 1. The value of correlation coefficient

(R2) for Langmuir isotherm is greater than that of the

Freundlich and Temkin isotherm for the adsorption of

investigated dye. This indicates that the adsorption of

BP on LCFO nanoparticles is better described by the

Langmuir model than the others and generally it has

been found better suited for characterizing monolayer

adsorption process onto the homogeneous adsorbent

surface. The linearized form plot of the Langmuir

isotherm is shown in Fig. 9


348

Fig. 9: Langmuir isotherm plot of BP adsorption onto LCFO nanoparticles: LCFO dosage=0.01 g, initial pH 1, stirring

time=30 min, initial dye concentration=50, 100, 150, 200, 250 mg/L.

4. CONCLUSION

In present study, a nanoparticle La0.5Ca0.5FeO3 powder

was produced and tested as a novel adsorbent for the

removal of dye. A systematic study on the structural,

morphological and adsorption properties of

La0.5Ca0.5FeO3 samples has been carried out by means

of various analytical techniques. The effects of LCFO

dosage, initial pH, contact time and initial dye

concentration on the removal of BP was investigated

through batch experiments. Results indicated that the

synthesized powder could effectively remove high

concentrations of dye in a short contact time. The

optimum dosage, pH and contact time were obtained

to be 0.01 g, pH 1 and 30 min, respectively. Isotherm

modeling revealed that the Langmuir equation could

better describe the adsorption of BP dye onto the

LCFO as compared to other models.

Acknowledgements

This research project was supported and funded by

Khouzestan Science and Research Branch, Islamic

Azad University, Ahvaz, Iran

REFERENCES

Afkhami A, Moosavi R (2010). Adsorptive removal

of Congo red, a carcinogenic textile dye, from

aqueous solutions by magnetite nanoparticles. J.

Hazard. Mater., 174: 398403. Ahmad AL, Puasa SW (2007). Reactive dyes

decolourization from an aqueous solution by

combined coagulation/micellar-enhanced

ultrafiltration process. Chem. Eng. J., 132: 257265.

Al-Degs YS, El-Barghouthi MI, El-Sheikh AH,

Walker GM (2008). Effect of solution pH, ionic

strength, and temperature on adsorption

behavior of reactive dyes on activated carbon.

Dyes Pigments, 77: 1623. Banat IM, Nigam P, Singh D, Marchant R (1996).

Microbial decolorization of textile-dye-

containing effluents. Bioresour. Technol., 58 :

217227. Bansal NP, Zhong Z (2006). Combustion synthesis of

Sm0.5Sr0.5CoO3x and La0.6Sr0.4CoO3x nanopowders for solid oxide fuel cell cathodes.

J. Power Sources., 158: 148-153.

Berger D, Fruth V, Jitaru I, Schoonman J (2004).

Synthesis and characterization of

La1xSrxCoO3 with large urface area. Mater. Lett., 58: 2418-2422.

Berger D, Matei C, Papa F, Voicu G, Fruth V (2007).

Pure and doped lanthanum cobaltites obtained

by combustion method. Solid State Chem., 35:

183-191.

Carbajo M, Beltran FJ, Medina F, Gimeno O, Rivas

FJ (2006). Catalytic ozonation of phenolic

compounds: The case of gallic acid. Appl. Catal.

B: Environ., 67: 177-186.

Chatterjee S, Lee DS, Lee MW, Woo SH (2009).

Congo red adsorption from aqueous solutions by

chitosan hydrogel beads impregnated with

nonionic or anionic surfactant. Bioresour.

Technol., 100: 38623868. Chi QG, Li WL, Zhao Y, Fei WD (2010). Low

temperature preparation and electric properties

of highly (100)-oriented

Pb0.8La0.1Ca0.1Ti0.975O3 thin films prepared

by a solgel route. J. Sol-gel Sci. Tech., 54: 286-291.

Tavakkoli et al.



349

Choy KKH, McKay G, Porter JF (1999) Sorption of

acid dyes from effluents using activated carbon.

Resour. Conserv. Rec., 27: 5771. Cizauskaite S, Kareiva A (2008). Sol-gel preparation

and characterization of non-substituted and Sr-

substituted lanthanum cobaltates. Cent. Europ. J.

Chem., 6: 456-464.

El Qada, EN, Allen SJ, Walker GM (2008).

Adsorption of basic dyes from aqueous solution

onto activated carbons. Chem. Eng. J., 135,

174184. Erdem E, Colgecen G, Donat R (2005). The removal

of textile dyes by diatomite earth. J. Colloid

Interf. Sci., 282: 314319. Forgacs E, Cserhati T, Oros G (2004). Removal of

synthetic dyes from wastewaters. a review,

Environ. Int., 30: 953971. Freundlich HMF (1906). Over the adsorption in

solution. Z. Phys. Chem. A., 57: 385471. Fu XC, Shen WX, Yao TY (1994). Physical

Chemistry (Fourth edition), Higher Education

Press, China. 303321. Gao J, Hu FX, Yao H (2006). Impact of electric

currents on the insulatormetal phase transition in epitaxial thin film of La1xAxMnO3 (A = Sr, Ca, and Ba). Appl. Surf. Sci., 252: 5521-

5524.

Gao Z, Wang R (2010). Catalytic activity for methane

combustion of the perovskite-type

La1xSrxCoO3 oxide prepared by the urea decomposition method. Appl. Catal. B:

Environ., 98: 147-153.

Hirano T, Purwanto H, Watanabe T, Akiyama T

(2007). Self-propagating high-temperature

synthesis of Sr-doped LaMnO3 perovskite as

oxidation catalyst. J. Alloys Compd., 441: 263-

266.

Ho YS, McKay G (1999). Pseudo-second-order model

for sorption processes. Process Biochem., 34:

451465. Hu Z, Yang Y, Shang X, Pang H (2005). Preparation

and characterization of nanometer perovskite-

type complex oxides LaMnO3.15 and their

application in catalytic oxidation. Mater. Lett.,

59: 1373-1377.

Jiang SP (2008). Development of lanthanum

strontium manganite perovskite cathode

materials of solid oxide fuel cells. J. Mater. Sci.,

43: 6799-6833.

Kasiri MB, Khataee AR (2011). Photooxidative

decolorization of two organic dyes with

different chemical structures by UV/H2O2

process: experimental design. Desalination, 270:

151159. Kim J, Honma I (2004). Synthesis and proton

conducting properties of zirconia bridged

hydrocarbon/phosphotungstic acid hybrid

materials. Electrochim. Acta, 49 : 31793183. Kuznetsov PN, Kuznetzova LI, Zhyzhaev AM,

Pashkov GL, Boldyrev VV (2002). Ultra fast

synthesis of metastable tetragonal zirconia by

means of mechanochemical activation. Appl.

Catal. A., 227: 299307. Kong JZ, Li AD, Zhai HF, Li H, Yan QY, Ma J, Wu

D (2009). Preparation, characterization and

photocatalytic properties of ZnTiO3 powders, J. Hazard. Mater., 171: 918923.

Labanda J, Sabate J, Llorens J (2009). Modeling of

the dynamic adsorption of an anionic dye

through ion-exchange membrane adsorber. J.

Membr. Sci., 340: 234240. Langmuir I (1918). The adsorption of gases on plane

surfaces of glass, mica and platinum. J. Am.

Chem. Soc., 40: 13611403. Lui S, Qian X, Xiiao J (2007). Synthesis and

characterization of La0.8Sr0.2Co0.5Fe0.5O3 nanopowders by microwave assisted solgel route. J. Sol-gel Sci. Tech., 44: 187-193.

Raileanu M, Crisan M, Nitoi I, Ianculescu A, Oancea

P, Crisan D, Todan L (2013). TiO2-based

Nanomaterials with Photocatalytic Properties

for the Advanced Degradation of Xenobiotic

Compounds from Water, A Literature Survey.

Water, Air & Soil pollut., 224: 1548-1593

Mezohegyi G, Goncalves F, Orfao JJM, Fabregat A,

Fortuny A, Font J, Bengoa C, Stuber F (2010).

Tailored activated carbons as catalysts in

biodecolourisation of textile azo dyes. Appl.

Catal. B: Environ., 94: 179185. Moussavi G, Mahmoudi M (2009). Removal of azo

and anthraquinone reactive dyes from industrial

wastewaters using MgO nanoparticles. J.

Hazard. Mate., 168: 806812. Nakamoto K (1978). Infrared and Raman Spectra of

Inorganic and Coordination Compounds.

Plenum Press, New York.

Nakayama S, Okazaki M, Aung YL, Sakamoto M

(2003). Preparations of perovskite-type oxides

LaCoO3 from three different methods and their

evaluation by homogeneity, sinterability and

conductivity. Solid State Ionics., 158: 133-139.

Osugi ME, Rajeshwar K, Ferraz ERA, de Oliveira DP,

Arojo R, Zanoni MVB (2009). Comparison of

oxidation efficiency of dispersed dyes by

chemical and photoelectrocatalytic chlorination

and removal of mutagenic activity. Electrochim.

Acta, 54: 20862093. Pechini M (1967). Method of preparing lead and

alkaline earth titanates and niobates and coating

method using the same to form a capacitor. US

Patent. No. 3: 330,697.


350

Robinson T, McMullan G, Marchant R, Nigam P

(2001). Remediation of dyes in textile effluents:

a critical review on current treatment

technologies with a reposed alternative.

Bioresour.Technol., 77: 247255. Sanaeishoar T, Tavakkoli H, Mohave F (2014). A

facile and eco-friendly synthesis of imidazo[1,2-

a]pyridines using nano-sized LaMnO3

perovskite-type oxide as an efficient catalyst

under solvent-free conditions. Appl. Catal. A.,

470: 56 62. Santos SCR, Vilar VJP, Boaventura RAR (2008).

Waste metal hydroxide sludge as adsorbent for a

reactive dye. J. Hazard. Mater., 153: 9991008. Senthilnathan J, Philip L (2010). Removal of Mixed

Pesticides from Drinking Water System Using

Surfactant-Assisted Nano-TiO2. Water, Air &

Soil pollut., 210: 143-154.

Song S, Xu L, He Z, Ying H, Chen J, Xiao X, Yan B

(2008). Photocatalytic degradation of C.I. Direct

Red 23 in aqueous solutions under UV

irradiation using SrTiO3/CeO2 composite as the

catalyst. J. Hazard. Mater., 152: 13011308. Spadaro JT, Isabelle L, Renganathan V (1994).

Hydroxyl radical mediated degradation of azo

dyes: evidence for benzene generation. Environ.

Sci. Technol., 28: 13891393. Srdic VV, Omorjan RP, Seydel J (2005).

Electrochemical performances of (La, Sr) CoO3 cathode for zirconia-based solid oxide fuel cells.

Mater. Sci. Eng. B., 116: 119-124.

Szabo V, Bassir M, VanNeste A, Kaliaguine S (2002).

Perovskite-type oxides synthesized by reactive

grinding. Appl. Catal. B: Environ., 37: 175-180.

Tavakkoli H, Yadanbakhsh M (2013) Fabrication of

two perovskite-type oxide nanoparticles as the

new adsorbents in efficient removal of a

pesticide from aqueous solutions: Kinetic,

thermodynamic, and adsorption studies.

Micropor. Mesopor. Mater., 176: 8694.

Tehrani-Bagha AR, Mahmoodi NM, Menger FM

(2010). Degradation of a persistent organic dye

from colored textile wastewater by ozonation.

Desalination, 260: 3438. Van Hassel BA, Kawada T, Sakai N, Yokokawa H,

Dokiya M, Bouwmeester HJM (1993). Oxygen

permeation modelling of La1-yCayCrO3.5.

Solid State Ionics, 66: 41-47.

Wang X, Zhu N, Yin B (2008). Preparation of sludge-

based activated carbon and its application in dye

wastewater treatment. J. Hazard. Mater., 153:

2227. Xia C, Jing Y, Jia Y, Yue D, Ma J, Yin X (2011).

Adsorption properties of Congo red from

aqueous solution on modified hectorite: kinetic

and thermodynamic studies. Desalination, 265:

8187. Yazdanbakhsh M, Tavakkoli H, Hosseini SM (2011).

Characterization and evaluation catalytic

efficiency of La0.5Ca0.5NiO3 nanopowders in

removal of reactive blue 5 from aqueous

solution. Desalination, 281: 388-395.

Yi F, Chen S, Yuan C (2008). Effect of activated

carbon fiber anode structure and electrolysis

conditions on electrochemical degradation of

dye wastewater. J. Hazard. Mater., 157: 7987. Zhang G, Gong J, Zou X, He F, Zhang H, Zhang Q,

Liu Y, Yang X, Hu B (2006). Photocatalytic

degradation of azo dye acid red G by KNb3O8

and the role of potassium in the photocatalysis.

J. Chem. Eng., 123: 5964. Zhen YD, Jiang SP, Zhang S, Tan V (2006).

Interaction between metallic interconnect and

constituent oxides of (La,Sr) MnO3 3l3ctrodes

of solid oxide fuel cells. J. Eur. Ceram. Soc., 26:

3253-3264.

Zhou AJ, Zhu TJ, Zhao XB (2006). Thermoelectric

properties of perovskite-type oxide

La1xSrxCoO3 (x = 0, 0.1) prepared by solid state reactions. Mater. Sci. Eng. B., 128: 174-

178.

Tavakkoli et al.



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Dr. Haman Tavakkoli is an assistant professor in inorganic chemistry in Islamic Azad University,

Khouzestan Science and Research Branch, Iran. He received his M.Sc and Ph.D degree in inorganic

chemistry from Ferdowsi University of Mashhad, Iran in 2007 and 2012, respectively. He has published

17 refereed articles in valid ISI journals and 20 scientific articles in conference proceedings. Dr.

Tavakkoli field of experti e are in coordination chemi try, nanomaterial chemi try and phy ic and environmental chemistry.

Dr. Arezoo Ghaemi obtained her Bachelor degree from the Ferdow i Univer ity of Ma hhad, Iran in chemi try in 2004. She later bagged her Ma ter and Doctorate degree in Analytical chemi try from Ferdowsi University of Mashhad, Iran in 2006 and 2012, respectively. She has graduated with first grade

in Ph.D degree. At present, Dr. Ghaemi is an assistant professor in analytical chemistry in Islamic Azad

University, Khuzestan Science and Research Branch, Iran. She has published numerous articles in ISI

journals and conference proceedings.

Mastaneh Mostofizadeh has MSc degree in Inorganic Chemistry from Khouzestan Science and Research

Branch, Islamic Azad University, Ahvaz, Iran.

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