Advanced Powder Technology 25 (2014) 17211727

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Advanced Powder Technology

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

Original Research Paper

Na0.5Li0.5CoO2 nanopowders: Facile synthesis, characterization

and their application for the removal of methylene blue dye
from aqueous solution
Iman Khosravi , Melika Eftekhar
Department of Chemistry, Qeshm Branch, Islamic Azad University, Qeshm, Iran

a r t i c l e

i n f o

Article history:
Received 27 January 2014
Received in revised form 14 June 2014
Accepted 24 June 2014
Available online 5 July 2014
Keywords:
Delafossite-type
Solgel
Adsorption
Na0.5Li0.5CoO2
Methylene blue

a b s t r a c t
In this paper, delafossite-type Na0.5Li0.5CoO2 nanoparticles (NPs) with an average particle size of 50 nm
were successfully synthesized by solgel method. Prepared NPs were characterized by differential thermal analysis, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy,
and scanning tunneling microscopy. The nanoparticles showed the excellent adsorption properties
towards methylene blue dye (MBD) as a reactive dye. The kinetics of removal of MBD in aqueous solutions was studied in a series of experiments which were varied in the amount of NPs, contact time,
pH, and temperature. The experimental data were tted very well in the pseudo-second order kinetic
model and the Freundlich adsorption isotherm model. 92% of dye was successfully removed in 10 min
using 0.02 g Na0.5Li0.5CoO2 NPs in a pH = 11. Thermodynamic study indicates that the adsorption of
MBD is feasible, and spontaneous in nature.
2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction
Environmental problems associated with organic pollutants and
toxic water pollutants provide the impetus for sustained fundamental and applied research in the area of environmental remediation [1]. Most of these contaminants exist in industrial
wastewater and even drinking water which are extremely dangerous to the environment for their toxicity and resistance to natural
degradation [2]. Among the pollutants, dyes from the efuents of
textile, paper, printing, and leather industries are the major
sources of water contamination. The presence of dyes in water
reduces light penetration and hinders photosynthesis in aquatic
plants [3]. Various physical, chemical, and biological techniques
have been developed for eliminating the negative environmental
impact of dyes. Traditional treatments such as coagulationocculation [4], reverse osmosis [5], and membrane technologies [6]
merely make the wastes concentrated or otherwise transported.
Destructive techniques such as chemical and other advanced oxidation processes could overcome the problems but they suffer
from high costs and incomplete degradation. Heterogeneous photocatalyst has been considered as a cost-effective alternative for
water remediation [7]. Among all the approaches proposed,
Corresponding author. Tel.: +98 7635263309; fax: +98 7635263598.
E-mail address: khosraviiman@yahoo.com (I. Khosravi).

adsorption is one of the most popular methods which are currently

considered as an effective, efcient, and economic method for
water purication.
The family of Delafossite-type oxides generally formulated as
ABO2 (A is a rare metal of alkali metals; B is a transition metal with
a small ionic radius) could be considered as an adsorbent material
for the removal of dyes. Many methods have been used for the
preparation of delafossite such as chemical coprecipitation, hydrothermal synthesis, and hydrolysis of metal carboxylates in organic
solvents, aerosolization, solgel, and shock wave method [8].
Several articles have investigated the effectiveness of spinel
[9,10] and perovskite [11,12] oxides as adsorbent for removal of
water-soluble dyes. Yazdanbakhsh et al. [13] evaluated the effectiveness of LiCo0.5Fe0.5O2 powder as an adsorbent/catalyst material
for the removal of Reactive blue 5 (RB5). They showed nanoparticles of delafossite-type powder possess the excellent adsorptive
properties towards RB5 at pH < 2. However, to our knowledge,
the conrmation and optimization of the efciency of the delafossite oxides adsorbents and the adsorption pathway for the removal
of reactive dyes from aqueous solution have received little attention in the literature.
This study has investigated the efciency of delafossite-type
oxide Na0.5Li0.5CoO2 NPs as an adsorbent for removal of methylene
blue dye from an aqueous solution. The kinetics of removal of MBD
was studied in a series of experiments which were varied in the

http://dx.doi.org/10.1016/j.apt.2014.06.020
0921-8831/ 2014 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

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I. Khosravi, M. Eftekhar / Advanced Powder Technology 25 (2014) 17211727

amount of Na0.5Li0.5CoO2 NPs, contact time, pH, dye concentration,

and temperature. The experimental data were tted very well in
the pseudo-second order kinetic model and the Freundlich adsorption isotherm model.
2. Materials and methods
2.1. Adsorbate
Methylene blue [MB, chemical formula = C16H18N3SCl,
MW = 319.85 g/mol, kmax = 661 nm] is a heterocyclic aromatic
chemical compound. It has many uses in a range of different elds,
such as biology and chemistry. The structure is as illustrated in
Fig. 1.
2.2. Preparation of Na0.5Li0.5CoO2 NPs
All chemicals were of analytical grade and were used without
further purication. The chemicals were obtained from Merck,
Germany.
A stoichiometric amount of Li:Na:Co nitrate salts with the cationic ratio of 0.5:0.5:1 respectively, were dissolved in distilled
water and mixed well with an aqueous solution of maleic acid
(the ratio of maleic acid to total metal ions is 2:1). Maleic acid
was used as a chelating agent in making a gel. The resultant solution was then evaporated at 70 C with magnetic stirring for 4 h.
The gel precursors were decomposed at 400 C for 1 h in air to
eliminate organic contents. The powders were heated to 700 C
to obtain the single phase Na0.5Li0.5CoO2 powders.
2.3. Instruments
The reaction process and decomposition of the dried polymeric
gel were analyzed by thermogravimetry analysis using a TGA-50
SHIMADSU from room temperature up to 900 C in air with a heating rate of 10 C/min. The powder X-ray diffraction (XRD) pattern
of Na0.5Li0.5CoO2 NPs was recorded by means of a Bruker/D8
Advanced diffractometer in the 2h range from 10 to 70, by step
of 0.04, with graphite monochromatic Cu Ka radiation
(k = 1.541 ).
The morphology and dimension of the nanoparticles were
observed by LEO 912 AB transmission electron microscope (TEM)
using an accelerating voltage of 120 kV, and the morphology of
the particles was investigated using LEO 1450 VP (V = 30 kV) scanning electron microscopy (SEM) and SS1 STM, scanning tunneling
microscopy (STM). All images were recorded in the constant current mode at room temperature using a Remanium tip with a bias
voltage of around 2 V in atmosphere.
2.4. Batch adsorption experiments
The dye removal by Na0.5Li0.5CoO2 NPs was studied by
monitoring the adsorption of the MBD in an aqueous solution.
Different amounts of NPs (0.010.04 g) were added into the reactor

containing 10 ml aqueous solution of MBD (50 mg L1) and the

experiments were done at different temperatures (15, 25, 35 and
45 C), and pH (111). Sample was taken out and centrifuged for
analysis by a UVvis spectroscopy at different time intervals. The
characteristic absorption at 661 nm was used to determine the
MBD concentration [14]. The dye removal efciency (DRE%) is
dened as:

DRE%

Co  Ct
 100
Co

where Co and Ct are the initial concentration and the concentration

of dye at time t, respectively.
2.5. Desorption study
Desorption studies are important since they contribute to elucidate the nature of adsorption process and adsorbent regeneration.
For repeated use of an adsorbent, adsorbed dye should be easily
desorbed under suitable conditions. Desorption process was conducted by mixing 0.05 g of MBD loaded Na0.5Li0.5CoO2 with 25 ml
of different concentration of HCl solutions (0.050.50 M) and shaking for 30 min. It was found that desorption of MBD from loaded
nanoparticles started at pH = 5.
The desorption efciency calculated as:

Desorption %

amount of desorbed MBD

 100
amount of adsorbed MBD

To evaluate the possibility of regeneration of Na0.5Li0.5CoO2

adsorbent, we have performed desorption experiments. The cycles
of adsorptiondesorption experiments were carried out up to 3
times. The calculated desorption efciency are given in Table 1.
Therefore, the MBD could be desorbed from the loaded nanoparticles by higher concentration of HCl. It can be seen that the adsorption capacities decrease for each new cycle after desorption with
three cycles. As shown in Fig. 2, Na0.5Li0.5CoO2 NPs keep high
adsorption efciencies (79%) during all the three adsorption
desorption cycles. These results show that Na0.5Li0.5CoO2 can be
potentially used as adsorbent to remove dye contaminants from
water for avoiding the secondary pollution.
3. Results and discussion
Fig. 3 shows the TGA (a) and DTA curve (b) for the Na0.5Li0.5CoO2
NPs. During the heating of the dried polymeric gel from room temperature to 900 C, several thermal features take place leading to a
better knowledge of the delafossite formation reaction mechanism.
The endothermic peak and weight loss at about 110 C corresponds
to the removal of supercial and structural waters in the gel precursor. The exothermic peak around 350 C involving weight loss
is due to the combustion of maleic acid and nitrate ions. It seems
that maleic acid acts as a fuel in the pyrolysis of the gel precursors
and accelerating the decomposition of nitrate ions [15]. The exothermic peak is formed at 700 C which is a reaction and crystallization of the decomposed complex to form the delafossite-type

Table 1
Desorption of MBD from Na0.5Li0.5CoO2 NPs.

Fig. 1. Chemical structure of methylene blue dye (MBD).

Concentration of HCl (M)

Desorption (%)

0.05
0.10
0.20
0.30
0.40
0.50

11.53
18.15
24.91
29.03
32.70
36.44

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1723

Fig. 4. XRD patterns of the Na0.5Li0.5CoO2 powders sintered at 700 C.

Fig. 2. The removal efciencies of MBD onto Na0.5Li0.5CoO2 NPs during three
adsorptiondesorption cycles.

Dhkl

0:9k
bhkl cos hhkl

where Dhkl is the particle size perpendicular to the normal line of

(h k l) plane, bhkl is the full width at half maximum of the (h k l) diffraction peak, hhkl is the Bragg angle of (h k l) peak, and k is the wave
length of X-ray. The crystallite size was about 50 nm for 2h = 46 corresponds to (1 0 4) plane.
Fig. 5(a) shows the TEM image and the histogram of particle
size distribution of the as-prepared sample. According to the
observation, the average particle size of Na0.5Li0.5CoO2 quantum
dots was 50 nm in diameter. It can be seen that the obtained value
was in agreement with the result achieved from XRD measurement
[17,18].
Fig. 5(b) shows the SEM images of NPs. These images also
exhibited typical morphologies for prepared powder. The particles
showed uniform particle distribution. As the SEM images showed

Fig. 3. (a) TGA curve of the Na0.5Li0.5CoO2 precursor obtained by the maleicmetalnitrate polymerized complex and (b) DTA curve of the Na0.5Li0.5CoO2 precursors.

phase. No obvious change was observed above 700 C. Hence, it is

plausible to conclude that the calcination temperature is about
700 C.
The XRD pattern of delafossite implies the formation of single
phase Na0.5Li0.5CoO2 NPs with good crystallinity (Fig. 4). The analysis of the diffraction pattern using (0 0 3), (1 0 1), (0 0 6), (1 0 2),
(1 0 4), (0 1 5), (0 1 8), (1 1 0) and (1 1 3) reection planes conrmed
the formation of rhombohedral delafossite structure with (R3m)
space group of the Na0.5Li0.5CoO2. The average crystallite size of
Na0.5Li0.5CoO2 quantum dots was estimated using the Scherrers
equation [16]:

Fig. 5. (a) TEM micrograph and calculated histogram of the Na0.5Li0.5CoO2 and (b)
SEM micrograph of the NPs.

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the nanoparticles had regular shapes with well-dened crystal

faces.
Fig. 6 shows the scanning tunneling microscopy (STM) images
(500 nm  500 nm) of Na0.5Li0.5CoO2 NPs which can be used to
determine the particles size and height. In Fig. 6(a), the bright spots
were higher than the dark ones and particles distribution on the
surface was mapped obviously. In Fig. 6(b), three particles were
selected for quantitative measurements and results showed that
their average size and height were obtained around 50 and
10 nm, respectively.
Fig. 7. Zeta potentials of the Na0.5Li0.5CoO2 NPs at different pH.

3.1. Zeta potentials analysis

The zeta potential, which is the overall charge a particle
acquires in a specic medium, is a good indicator of the stability
of the colloidal system. The zeta potential of colloidal dispersions
of Na0.5Li0.5CoO2 NPs in water (Fig. 7) was measured. The pHIEP
(the pH of zero point charge) was found to be pH = 6. The colloidal
system was the least stable at this point due to the absence of particle surface charges. The zeta potential of the suspensions of Na0.5Li0.5CoO2 NPs nanoparticles in water reached as high as 25 mV at
basic pH.
3.2. Adsorption studies
3.2.1. Effect of pH
The most important parameter inuencing adsorption was the
pH of solution [19]. The effect of pH on the adsorption of MBD is
given in Fig. 8. The results showed that the degradability in basic
and neutral pH is higher than that of acidic pH. MBD is cationic
dye because of the sulde group. With increasing pH, the negative

Fig. 8. Effect of pH on MBD removal by Na0.5Li0.5CoO2. Experimental conditions:

mass of adsorbent, 0.02 g; initial dye concentration, 50 mg L1; volume of dye
solution, 10 ml; time, 10 min; temperature 25 C.

charges on Na0.5Li0.5CoO2 NPs were expected to adsorb the cationic

dye and an increase in the efciency of adsorption with increasing
pH was observed.

Fig. 6. (a) STM images of Na0.5Li0.5CoO2 NPs for the area of 500 nm  500 nm and (b) height prole along the white line.

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3.2.2. Effect of temperature and contact times

Fig. 9 shows dye removal of MBD solutions with Na0.5Li0.5CoO2
NPs as a function of time at different temperatures. The amount of
dye removal increased rapidly in initial times (10 min). Dye
removal efciency was about 90% when the experiment was done
at 45 C but it decreases to 60% for the experiment at 15 C. Therefore, by increasing the temperature, the dye removal increased
[20].

Table 2
Kinetics of removal dye by Na0.5Li0.5CoO2 NPs.

Pseudo-rst order
Pseudo-second order

R2

K (M1 min1)

0.888
0.997

0.019
0.041

3.2.3. The effect of adsorbent concentration

The effect of adsorbent dosage of MBD adsorption onto
Na0.5Li0.5CoO2 NPs was investigated (Fig. 10). The results showed
that as the adsorbent dose increases, the percentage removal of
dye also increases. This is due to increase in binding sites in the
adsorbent [21].

equilibrium concentration of adsorbate, Ce, (Fig. 11) is fundamental

in describing the interactive behavior between adsorbate and
adsorbent. 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 system.
The amount of dye adsorbed onto Na0.5Li0.5CoO2 nanoparticles
has been calculated based on the following mass balance equation
as:

3.3. Kinetics of dye removal

qe

To investigate the kinetics of color removing, the experiments

were compared with pseudo-rst order and pseudo-second order
kinetics models by plotting ln C/C0 and 1/C versus time, respectively [22]. Higher value of the correlation factor (R2) were
obtained for pseudo-second-order than for pseudo-rst-order
adsorption rate models, indicating that the adsorption rates of
MBD on to the NPs can be more appropriately described using
the pseudo-second-order rate rather than pseudo-rst-order rate
(Table 2).

where qe is the adsorption capacity (mg dye adsorbed onto the mass
unit of Na0.5Li0.5CoO2, mg g1), V is the volume of the dye solution
(L), Co and Ce (mg L1) are initial and equilibrium dye concentrations, and m (g) is the mass of dry Na0.5Li0.5CoO2 added. The adsorption isotherm of a specic adsorbent represents its adsorptive
characteristics and is very important to the design of adsorption
processes. To simulate the adsorption isotherm, two commonly
used models, the Langmuir [23] (Eq. (5)) and Freundlich [24] (Eq.
(6)) isotherms were selected to explicate dyeNPs interaction.

3.4. Adsorption isotherms

Ce
1
Ce

qe bqmax qmax

The equilibrium adsorption isotherm model, which is the

number of mg adsorbed per gram of adsorbent (qe) versus the

VC o  C e
m

log qe log K F

5
1
log C e
n

where qmax is the maximum amount of adsorption with complete

monolayer coverage on the adsorbent surface (mg g1), and b is
the Langmuir constant related to the energy of adsorption (L mg1).
The Langmuir constants b and qmax can be determined from the linear plot of 1/Ce versus 1/qe. KF and n are the Freundlich adsorption
isotherm constants, being indicative of the extent of the adsorption
and the degree of nonlinearity between solution concentration and
adsorption, respectively. KF and 1/n values can be calculated from
intercept and slope of the linear plot between log Ce and log qe.
The Freundlich isotherm was employed to describe heterogeneous systems and reversible adsorption, which does not restrict
to the monolayer formations. Unlike the Freundlich isotherm, the
Langmuir isotherm is based on the assumption that a structure
Fig. 9. Removal of MBD versus time at different temperatures. Experimental
conditions: mass of adsorbent, 0.02 g; initial dye concentration, 50 mg L1; volume
of dye solution, 10 ml; pH = 7.

Fig. 10. Effect of adsorbent dosage of MBD adsorption onto of Na0.5Li0.5CoO2.

Experimental conditions: initial dye concentration, 50 mg L1; volume of dye
solution, 10 ml; time, 10 min; temperature, 25 C; and pH = 7.

Fig. 11. Plots of qe versus Ce for the adsorption of MBD adsorption onto of
Na0.5Li0.5CoO2. Experimental conditions: mass of adsorbent, 0.02 g; initial dye
concentration, 25, 50, 75, 100, 125, 150, 175, 200 and 225 mg L1; volume of dye
solution, 10 ml; temperature, 25 C; and pH = 7.

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I. Khosravi, M. Eftekhar / Advanced Powder Technology 25 (2014) 17211727

Table 3
Freundlich and Langmuir model parameters for adsorption MBD.

Langmuir
Freundlich

Table 5
Adsorption capacities of different dye on various adsorbents.

b (L mg1)

qmax (mg g1)

R2

KF (mg g1)

0.006

502.11

0.85
0.99

1.11

1.00

of adsorbent is homogeneous, where all sorption sites are identical

and energetically equivalent. The Langmuir and Freundlich equation parameters for the Na0.5Li0.5CoO2 NPs adsorption were summarized in Table 3. The value of correlation coefcient (R2) for
Freundlich isotherm is greater than that of the Langmuir isotherm.
This indicates that Freundlich model can describe the adsorption of
MBD on Na0.5Li0.5CoO2 NPs better than the Langmuir model and
generally it has been found better suited for characterizing
multi-layer adsorption process [25].
3.5. Thermodynamic parameters

DG RT ln K e

DS DH 

R
RT

where Ke is equilibrium constant which can be calculated by plotting ln (qe/Ce) versus qe and extrapolating to zero qe, T is the temperature (K), R is the universal gas constant (8.314 J K1 mol1). The
slope and intercept of the plot of lnKe versus 1/T gives the DHo
and DSo, respectively [26]. Table 4 shows the thermodynamic
parameters of the MBD onto the NPs. The negative values of DG
indicate that the sorption of the cationic dyes onto Na0.5Li0.5CoO2
NPs was spontaneous and thermodynamically favorable. The
increase in the value of DG with increasing temperature indicates
that the sorption process was more favorable at higher temperature. A positive DH suggests that the sorption of MBD onto NPs
was endothermic, which is supported by the increasing sorption
of these dyes with the increase in temperature. In addition, the
positive value of DS suggests an increase in degree of freedom at
the solidliquid interface during sorption process, which reects
increased randomness at the solid/solution interface and dyes afnity to Na0.5Li0.5CoO2 NPs.
3.6. Performance evaluation
The qmax of Na0.5Li0.5CoO2 for MBD calculated from the Langmuir isotherm model are listed in Table 5 with literature values
of qmax of different adsorbents for reactive dyes adsorption. It
shows that qmax of MBD on Na0.5Li0.5CoO2 in this work is high.
Table 4
Thermodynamic parameters for removal of MBDa.
T (C)

DG (kJ mol1)

15
25
35
45

14.15
18.42
21.98
26.27

qmax (mg g1)

Reactive dye

Reference

Activated carbon
Clay
Silica xerogel
CoFe2O4
Na0.5Li0.5CoO2
ZnCr2O4
NiMn0.05Fe1.95O4
NiMnFeO4
CoFe2O4
LiCo0.5Fe0.5O2
CuFe2O4

131.93
434.78
40.86
244.50
502.11
41.32
212.76
476.19
89.29
76.92
86.80

Reactive blue 4
Congo red
Congo red
Congo red
Methylene blue
Reactive blue 5
Reactive black 5
Reactive blue 5
Malachite green
Reactive blue 5
Acid red B

[31]
[33]
[32]
[28]
Present study
[2]
[19]
[10]
[30]
[13]
[29]

Therefore, it can be concluded that Na0.5Li0.5CoO2 is a ne adsorbent with good adsorption capacity [27].
4. Conclusion

Thermodynamic parameters provide in-depth information of

inherent energetic changes associated with sorption. The change
in standard free energy DG, enthalpy DH and entropy DS were
calculated using the experimental data obtained at various temperatures by the following equations.

ln K e

Adsorbent

DH (kJ mol1)

DS (J mol1 K1)

120.45

460.89

a
Experimental conditions: mass of adsorbent, 0.02 g; initial dye concentration,50 mg L1; volume of dye solution, 10 ml; pH = 7.

In summary, Na0.5Li0.5CoO2 NPs have been fabricated by solgel

method. A systematic study on the structural, morphological and
removal dye efciency of Na0.5Li0.5CoO2 was carried out by means
of various analytical techniques. X-ray powder diffraction and
microscopic analysis reveal that the nanoparticles have good crystallinity with rhombohedral delafossite structure. In addition, the
present investigation has shown that the Na0.5Li0.5CoO2 can be a
promising surface material to remove MBD from water over a wide
range of dye concentrations. The processing parameters such as
dosage of adsorbent, temperatures and pH value can all affect
the adsorption process signicantly. Isotherm modeling revealed
that the Freundlich equation could better describe the adsorption
of MBD dye as compared to the Langmuir model. Thermodynamic
study indicates that the adsorption of MBD is feasible, and spontaneous in nature. Also results suggest that Na0.5Li0.5CoO2 nanospinels are a kind of efcient and reusable adsorbent.
Acknowledgment
This work was supported by the Islamic Azad University,
Qeshm Branch, Iran, and the authors acknowledge the nancial
support for this project.
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