Professional Documents
Culture Documents
a r t i c l e i n f o a b s t r a c t
Article history: An extremely small size novel adsorbent, nickel hydroxide nanoplate loaded on activated
Received 15 October 2015 carbon (Ni(OH)2 -NP-AC) was synthesized using a simple, low cost and highly efficient
Received in revised form 18 January method. The developed adsorbent was used for the removal of hazardous MG dye from the
2016 aqueous solution. To evaluate the importance of Ni(OH)2 nanoplates on the adsorption and
Accepted 20 February 2016 removal process, the contact time of virgin AC and Ni(OH)2 -NP-AC were compared (under the
same conditions) that the results showed Ni(OH)2 nanoplate had a crucial role in the removal
or adsorption process. The surface unique textural and morphological properties such as
Keywords: high surface area (>960 m2 g−1 ) and low pore size (<3.5 nm) made it possible for efficient and
Nickel hydroxide nanoplates, rapid removal of MG. Subsequently, the impact of various influential variables such as pH,
Activated carbon adsorbent dosage, initial dye concentration, contact time and temperature were examined
Adsorption and optimized. The adsorption kinetic and equilibrium data of MG were found well fitted
Malachite Green and found to be in good agreement with pseudo-second-order and Langmuir models, respec-
Liquid phase tively. Finally, antibacterial activity of the synthesized nanoplates was evaluated by testing
Antibacterial study against some Gram-negative and Gram-positive bacteria. The results of this antibacterial
testing indicated that the synthesized nanoplates showed effective bactericidal activity.
© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction life due to their mutagenic and carcinogenic effects. The dyes
discharging in environment are produced by textile, paper
One of main environmental pollution or hazard is the indus- and printing activities. So, increasing demand and shortage
trial effluents containing highly color dyes with significant of clean water sources due to the rapid development of
amount of organic solids (Crini, 2006). The presence of such industrialization, population growth and long-term droughts
toxic contaminants in aqueous body leads to generation of have become an issue worldwide. With this growing demand,
several detrimental and hazardous impacts on the aquatic various practical strategies and solutions have been adopted
∗
Corresponding author at: Indian Institute of Technology Roorkee, Chemistry Department, Roorkee 247667, Uttarakhand, India.
Tel.: +91 1332285801; fax: +91 133227356.
∗∗
Corresponding author. Tel.: +39 081674281/+39 3273378505.
E-mail addresses: F.nekouei@hotmail.com, Farzin.nekouei@unina.it (F. Nekouei), vinodfcy@gmail.com, vinodfcy@iitr.ac.in
(V. Kumar Gupta).
http://dx.doi.org/10.1016/j.psep.2016.02.011
0957-5820/© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
86 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97
to yield more viable water resources (Chong et al., 2010). S1 in the Supporting Information) with chemical formula
The discharge of highly colored waste is not only aestheti- of C52 H54 N4 O12 (Sigma-Aldrich sdn Bhd, Malaysia) with
cally displeasing, but it also impedes light penetration, thus Max = 617 nm was used for the preparation of the solu-
upsetting biological processes within a stream. In addition, tions of MG in desired concentrations. The working solutions
many dyes are toxic to some organisms and may cause direct were prepared by diluting the stock solution with distilled
destruction of aquatic communities (Mohammadi et al., water. Nickel chloride (NiCl2 ), ammonium (NH3 ), ammo-
2011). nium chloride (NH4 Cl) and 4-(1,1,3,3-tetramethylbutyl)phenyl-
Various methods have been proposed for removal of polyethylene glycol (Triton X-100 or TX-100) were purchased
dyes from wastewaters such as coagulation and flocculation from Sigma-Aldrich Co.
(Panswed and Wongchaisuwan, 1986), oxidation or ozonation
(Malik and Saha, 2003; Koch et al., 2002), membrane separa-
tion (Ciardelli et al., 2000), adsorption (Sadegh et al., 2015a,b; 2.1.1. Precipitation method for preparation of Ni(OH)2
El-Bindary et al., 2014). Among these methods, adsorption is a nanoplates
reliable method due to its simplicity, high efficiency and low Nanoplates were synthesized by precipitation method using
cost (Wei et al., 2014). NiCl2 as initial chemical and ammonium as precipitation
Malachite Green (MG) has numerous industrial applica- agent. 0.3 g of NiCl2 was dissolved in 50 mL distilled water
tions namely dyeing of silk, leather, plastics, paper and others in a 100 mL flask. Then, after adding 1 mL of 0.02 M Triton
and their appearance leads to detrimental effect on flora X-100, 9 mL NH3 4 M and 1 mL NH4 Cl 1 M were added slowly
and fauna ecosystem following inhalation and/or ingestion under magnetic stirring at 50 ◦ C (pH ≤ 11). The green suspen-
(Ghaedi et al., 2014; Culp and Beland, 1996) and produce tox- sion remained under a constant and strong stirring for 45 min.
icity to respiratory system and reduced fertility in humans Subsequently, the suspension was filtered and washed several
(Srivastava et al., 2004). MG with complex chemical structure times by a mixture of distilled water and ethanol to remove
is resistant to light and oxidizing agents and the efficiency impurities. Finally, the obtained precipitation was dried in
removal of MG by biological treatment and chemical precipi- an ambient condition, vacuum oven: 0.1 MPa, for 7 h before
tation is low (DoganUluozlu et al., 2008). being characterized. Scheme S1 (Supporting information)
Nanotechnology is one of the fast developing technologies reveals a possible formation mechanism for PbO nanosheet
with demanding products in various fields, due to their tiny networks.
size (10−9 m) and large surface area (White et al., 2006). The
research on nanoparticles has attracted wide attention during
the last decade thanks to their unusual and size depend-
2.1.2. Preparation of Ni(OH)2 -NPs-AC
ent and has been used in different fields (Taylor et al., 2013;
The precursor materials were mixed as explained in Section
Boisseau and Loubaton, 2011). Recently, nanoparticles have
2.1.1. 5 g of AC was added to the suspension of Ni(OH)2 in an
been used for modification of activated carbon as promising
ultrasonic bath, until the uniform and green suspension was
and effective new sorbents for removal of dyes form solu-
obtained. The mixture was maintained at room temperature
tions because of their large surface area (Nekouei et al., 2015;
over a night (ca. 10 h) after adjusting the pH at 11. After filter-
Gupta et al., 2015; Vitela-Rodriguez and Rangel-Mendez, 2013;
ing the alkaline solution, Ni(OH)2 -NPs-AC was washed several
Asfaram et al., 2015).
times with distilled water and dried in ambient condition and
Nickel hydroxide compounds stimulated a large interest
used as such for further experiments.
in industrial and technical applications, for example as the
active materials in electrochemical cycling and as a photocat-
alyst to remove organic dyes (Zhang et al., 2013). Furthermore,
the feasibility of Ni(OH)2 and NiO nanomaterials for their 2.1.3. Role of Ni(OH)2 nanoplates
application in water treatment is also reported and evaluated The Ni(OH)2 nanoplates loaded on AC can confer some crucial
(Song and Gao, 2008). properties to the AC. The three of the most important of those
In this work, the Ni(OH)2 nanoplate loaded on activated are (1) It results in the enhancement of the surface area and
carbon was used for the removal of malachite green dye from increasing the number of active sites leading to improve the
aqueous phase. Moreover, for the first time the role of Ni(OH)2 adsorption capacity and efficiency; (2) it decreases adsorption
nanoplates on the adsorption of MG was discussed by compar- time and causes very rapid adsorption of MG, only by using a
ing the result of contact time for virgin AC and Ni(OH)2 -NP-AC. very low amount of adsorbent dose i.e. 0.035, maximum 99.8%
Different analytical parameters affecting the adsorption like of the adsorption in 20 min for 20 mg L−1 of MG; (3) Improving
pH, initial dye concentration, temperature, contact time, and the antibacterial activity of AC (see Section 3.10). Therefore, it
adsorbent dose were evaluated. The adsorption kinetic and is needed to coat Ni(OH)2 nanoplates onto the AC to perform
equilibrium data of MG on this adsorbent were tested and an efficient and maximum adsorption. To further confirm the
discussed by different models. Furthermore, different ther- remarkable role of Ni(OH)2 nanoplates on the adsorption of
modynamic parameters were calculated. Finally, antibacterial MG, we performed a couple of studies under the same con-
activity of the synthesized nanoplates loaded on activated car- ditions of Ni(OH)2 -NPs-AC for the virgin AC (20 mg L−1 of MG,
bon was evaluated. 0.035 g of AC, 323.15 K) in the pH range of 4 to 9. The results
showed that the maximum removal (94.1%) was achieved
2. Experimental around 165 h at pH 8. With regard the fact that one of the
most important parameters in designing a low cost wastewa-
ter treatment system is equilibrium time (Taghizadeh et al.,
2.1. Materials and chemicals
2013); Hence, the role of Ni(OH)2 nanoplates is crucial to save
All chemicals used were analytical grade and solutions time and cost as well as increasing the efficiency of adsorption
were prepared with distilled water. Malachite Green (Table (99.8% > 94.1%).
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97 87
2.2. Instrumentation where C0 (mg L−1 ) and Ct (mg L−1 ) are the dye concentration at
initial and after time t, respectively.
2.2.1. X-ray diffraction The amount of adsorbed MG at equilibrium (qe (mg g−1 ))
X-ray diffraction (XRD) measurement was conducted using a was calculated by
Bruker AXS-D8 Advance model system. The diffracted inten-
sity of the Cu K␣ radiation (0.154 nm, 40 kV, and 40 mA) was V
qe = (C0 − Ce ) (2)
measured over a 2 range between 5.0 and 80. W
where C0 (mg L−1 ) and Ce (mg L−1 ) are the initial and equi-
2.2.2. Microscopy librium dye concentrations in solution, respectively. V is the
The field emission scanning electron microscopy (FE-SEM) volume of the solution (L), and W is the mass (g) of the used
was performed on Zeiss Supra, model 55VP, Germany. Trans- adsorbent.
mission electron microscopy (TEM) imaging techniques were
performed using a Hitachi HT7700 microscope operated at 2.4. Adsorption kinetic studies
120.0 kV. A droplet of a diluted suspension of Ni(OH)2 in
ethanol, was deposited on a Cu grid covered with a thin carbon The effect of contact time in the 50 mL of MG solution concen-
film. trations in the range of 1.0–25 min in the presence of 0.035 g
of Ni(OH)2 -NPs-AC dispersed in solution by the agitation of
2.2.3. Infrared spectroscopy the solution at 400 rpm at room temperature. MG concentra-
Fourier transform Infrared spectroscopy equipped with an tion was quantified and the actual adsorbed MG at time t, qt
attenuated total reflectance accessory configured with a KSR-5 (mg g−1 ), was determined by the following equation:
crystal (ATR) (FT-IR (ATR)) Perkin Elmer, was used for recording
V
IR spectrum in the region 4000–400 cm−1 . qt = (C0 − Ct ) (3)
W
2.2.4. Light scattering where C0 (mg L−1 ) and Ct (mg L−1 ) are the concentration of dye
Particle size and size distribution of the Ni(OH)2 nanoplates at initial and any time t, respectively. V is the volume of the
were measured by laser light scattering (Zetasizer Nanoseries, solution (L), and W is the mass (g) of the adsorbent.
Malvern Instruments Co.). A diluted suspension of Ni(OH)2 in a
solution of NH4 Cl was used for characterization. The material 2.5. Antibacterial analysis
absorption unit was 0.001 w/v%.
Antibacterial activity of the sorbent was evaluated via disk
diffusion Agar (DDA) method. Three different types of bacte-
2.2.5. UV–vis spectroscopy
ria were examined, Escherichia coli (E266), Bacillus subtilis (B145),
A double beam spectrophotometer (UV-1800, Shimadzu,
and Staphylococcus aureus (S276). The test is carried out by pla-
Japan) was used for determination of MG concentration at
cing 6 mm diameter of paper disc containing antibiotic onto a
617 nm.
plate on which microbes are growing. The microbe culture is
standardized to 0.5 McFarland standards which are approxi-
2.2.6. Surface area analysis mately 10+8 cells. Not more than 6 discs should be placed on
Surface area and pore size distribution of the sorbent the same agar–agar plate. Streptomycin standard, bactericidal
was determined from the corresponding nitrogen adsorp- antibiotic, are used for each bacteria as reference. 5 l of solu-
tion desorption isotherms at 77 K using a Micromeritics tion pours on a filter paper plate then put it in the agar–agar
ASAP 2020 system. The surface area was determined by plate which bacteria dispersed on it at 37 ◦ C for 4 h. The plates
the Brunauer, Emmett and Teller (BET), Langmuir and are inverted and incubate for 18–24 h, 24–48 h or until sufficient
Barrett–Joyner–Halenda the (BJH) equations and pore size dis- growth has occurred. After incubation, each plate is examined.
tribution was calculated by using BET and BJH equations. The diameters of the zones of complete inhibition (as judged
by the unaided eye) are measured, including the diameter of
2.3. Measurements of dye uptake the disc. Zones are measured to the nearest whole millimeter,
using sliding a caliper or a ruler, which is held on the back of
Using the linear regression equation, obtained by plotting its the inverted Petri plate. The experiments were performed in
calibration curve, concentrations of MG were estimated. At duplicates.
room temperature and time intervals in the range of 1–25 min,
the dye adsorption capacity of adsorbent was estimated and 3. Results and discussion
it was observed that the equilibrium was established after 15
and 20 min for 10 and 20 mg L−1 , respectively. The effect of 3.1. Characterization of Ni(OH)2 nanoplates
some variables affecting the adsorption removal of MG such
as pH, adsorbent dosage, initial dye concentration, tempera- 3.1.1. FT-IR-ATR characterization
ture, and contact time were evaluated by batch experiments. In order to evaluate characteristic of functional groups of the
50 mL of 10 and 20 mg L−1 of MG in 100 mL Erlenmeyer flasks synthesized nanoplates, FT-IR-ATR spectrum was used as a
was agitated on a stirrer at 400 rpm at room temperature and powerful identification tools. In fact, FT-IR spectrum gives
obtained experimental data at various times, temperatures information about the synthesis conditions of synthesized
and concentrations was fitted to different models. The per- compounds. According to Fig. 1, the sharp peak at
centage adsorption R was calculated as: 3638.18 cm−1 attributes to O H (disturbed hydroxyl) stretch-
ing mode of the free Ni OH groups. The broad absorption
C − C
0 t band observed at 3369.46 cm−1 corresponds to the O H (free
% Dye removal, R= × 100 (1)
C0 hydroxyl) stretching vibration which is the characteristic of
88 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97
Fig. 2 – (a and b) FESEM images of the Ni(OH)2 nanoplates. (c and d) TEM images of the Ni(OH)2 nanoplates.
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97 89
100
95
Removal (%)
90
10 ppm
85
20 ppm
80
0 2 4 6 8 10
pH
fact, the limiting factor for dye adsorption is the available site
on the adsorbent. Initial dye concentration at a fixed value
of adsorbent has reverse correlation with equilibrium time
(Nekouei et al., 2015; Bulai1 and Cioanca, 2011; Víctor-Ortega
et al., 2015, 2016).
Fig. 5 – Effect of contact time on the removal of MG Another important factor controlling the capacity of adsor-
[conditions: 0.035 g of Ni(OH)2 -NPs-AC in 50 mL, pH 6.5, bent is amount of adsorbent. In this work, the percent
room temperature, MG concentration of 10 and 20 mg L−1 ]. adsorption of MG dye on Ni(OH)2 -NPs-AC was studied using
different adsorbent dose in the range of 0.005–0.05 g at
rate was rapid at the initial stages probably due to high ratio of constant MG concentrations of 10 and 20 mg L−1 . It is evi-
vacant site to adsorbate molecule. This means that, the rapid dent in Fig. 7 that MG adsorption increases significantly
adsorption at the initial contact times can be attributed to the by rising amount of adsorbent. This phenomenon may be
availability of the reactive site of adsorbent, while at higher described by this fact that by rising amount of adsor-
time due to the slow pore diffusion or saturation of adsorbent bent because of being more available of the reactive sites
the removal rate did not alter remarkably (Ghaedi et al., 2012). with high tendency for interaction with various path-
ways are soft–soft interaction, – and hydrogen bonding
that notably improved by electrostatic interaction (Ghaedi
3.4. Effect of initial dye concentration
et al., 2013a). The removal efficiency was maximum when
the Ni(OH)2 -NPs-AC dose was 0.7 g L−1 , after that the
The effect of initial MG dye concentration in the range of
removal was not significantly increased. Hence, 0.7 g L−1 was
5–70 mg L−1 on its removal efficiency onto adsorbent was
chosen as the optimum adsorbent dose for further experi-
studied. Fig. 6 shows that the MG dye removal percentage
ments.
decreased with increase in its initial concentration. Rapid
increase in initial dye concentration led to decrease in mass
transport and finally removal efficiency because of lack of 3.6. Effect of temperature
available unoccupied sites. Fig. 6 also shows that increas-
ing concentration of MG dye from 10 to 50 mg L−1 results in In order to determine whether the ongoing adsorption process
decrease in removal percentage from nearly 99.8 to 89%. In is endothermic or exothermic naturally, it is essential to eval-
uate temperature effect on the removal of MG (Nekouei et al.,
2015). The experiments (MG adsorption onto (Ni(OH)2 -NPs-AC)
carried out under conditions of 10 and 20 mg L−1 of MG con-
centrations, pH 6.5, 0.7 g L−1 of Ni(OH)2 -NPs-AC and contact
times of 15 and 20 min. As shown in Fig. 8, the removal per-
centage of MG dye increases by increasing temperature and
maximum adsorption takes place at temperature of 323.15 K.
Increasing in the amount of adsorbed dyes with rising tem-
perature suggests endothermic nature of adsorption process
and great preliminary distinguished role of temperature for
removal (Ghaedi et al., 2013b). An increase in temperature is
known not only to increase the diffusion rate of the adsorbate
molecules across the external boundary layer and within the
Fig. 6 – Effect of initial dye concentration on the removal of pores but also to modify the equilibrium capacity of the adsor-
MG [conditions: 0.035 g of Ni(OH)2 -NPs-AC in 50 mL, pH 6.5, bent for a particular adsorbate by changing the temperature
room temperature]. (Nekouei et al., 2015).
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97 91
1
RL = (6)
1 + KL C0
Table 2 – Isotherm parameters correlation coefficients calculated by various adsorption models onto 0.035 g of
Ni(OH)2 -NPs-AC in 50 mL, pH 6.5, and room temperature.
Isotherm Equation Parameters Adsorbent
Fig. 9 – (a) Langmuir isotherm for adsorption of MG onto Ni(OH)2 -NPs-AC. (b) Freundlich isotherm for adsorption of MG onto
Ni(OH)2 -NPs-AC. (c) Temkin isotherm for adsorption of MG onto Ni(OH)2 -NPs-AC. (d) D–R isotherm for adsorption of MG onto
Ni(OH)2 -NPs-AC.
KT were calculated from the plot of qe against ln Ce (Table 2). D–R equation represents the poorer applicability of the exper-
As presented in Table 2 and Fig. 9(c), the low R2 value of this imental data than the other isotherm equations.
model shows its inapplicability for interpretation of experi-
mental data. 3.8. Adsorption kinetic modeling
3.7.4. The Dubinin–Radushkevich (D–R) isotherm Physical and chemical characteristics of the adsorbent sys-
D–R was another isotherm applied to evaluate the porosity, tem and the system conditions are the key factors in the
apparent free energy and characteristic of adsorption. The nature of the adsorption process. The experimental kinetic
equation of D–R isotherm is as follows (Dubinin, 1960): data of MG removal assessed by some conventional models
namely pseudo first and second-order, Elovich and intraparti-
ln qe = ln Qs − ˇε2 (9) cle diffusion to study the rate and mechanism of adsorption
process. Summarized properties and constants of each model
are presented in Table 3 at initial MG concentrations of 10 and
where qe is the amount of the dye adsorbed per unit weight of
20 mg L−1 using 0.035 g of adsorbent.
the adsorbent (mg g−1 ), Qs is the maximum sorption capacity
provided by the intercept (mol g−1 ), ˇ (mol2 J−2 ) is the activity
coefficient related to mean sorption energy, and ε (Eq. (10)) is 3.8.1. The pseudo-first-order model
Polanyi potential (Radushkevich, 1949). Pseudo-first-order (PFO) model, known as Lagergren (1898)
model, presented in Eq. (12) in its linear form, by plotting the
1
values of log (qe − qt ) versus t may give a linear relationship
ε = RT ln 1 + (10)
Ce that k1 and qe values can be determined from its slope and
intercept, respectively.
The slope of the plot of ln qe versus ε2 offers ˇ (mol2 (kJ2 )−1 )
and the intercept yields the adsorption capacity, Qs (mg g−1 ). k1 t
log (qe − qt ) = log (qe ) − (12)
In order to distinguish the physical and chemical adsorption 2.303
of dye on the adsorbent, its mean free energy, E per molecule
of adsorbate (for removing a molecule from its location in where qe and qt (mg g−1 ) are the amounts of MG adsorbed at
the sorption space to the infinity), can be computed by the equilibrium and at time t (min), respectively, and k1 (min−1 ) is
following equation (Dada et al., 2012): the rate constant of the PFO model.
As can be seen in Table 3, both the distance of intercepts
1 from experimental qe value and low correlation coefficients
E= (11)
2ˇ show the unsuitability of this model to explain experimen-
tal data and rate of adsorption do not follow this equation.
The calculated values of D–R are given in Table 2. The Fig. 10(a) shows the PFO modeling on kinetic of the dye adsorp-
value of E calculated using Eq. (11) is 5.0 kJ mol−1 correspond- tion on Ni(OH)2 -NPs-AC.
ing to physisorption process playing an important role in the
adsorption of MG onto Ni(OH)2 -NP-AC. The value of correla- 3.8.2. The pseudo-second-order model
tion coefficient obtained from D–R model is lower than other The pseudo-second order (PSO) model based on the assump-
isotherms values mentioned above (Fig. 9(d)). In this case, the tion that the adsorption rate is linearly related to the square
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97 93
Table 3 – Adsorption kinetic parameters at different initial MG onto 0.035 g of Ni(OH)2 -NPs-AC in 50 mL at pH 6.5, room
temperature and MG concentration of 10 and 20 mg L−1 .
Model Equation Parameters C0 (mg L−1 )
10 20
PSO
(t/qt ) = 1/ k2 q2e + (1/qe ) t
k2 (g/(mg min)) 0.32 0.047
qe(calc) (mg g−1 ) 14.03 29.07
R2 0.9962 0.9985
SSE 0.163 0.54
ho,2 (mg (g min)−1 ) 62.99 39.72
of the number of unoccupied adsorption sites is expressed as conditions strongly confirm the applicability and suitabil-
(Hamoudi and Belkacemi, 2013): ity of this model to interpret experimental data. The initial
adsorption rates can be calculated from the PSO model by the
dqt following equation (Ghaedi and Mosallanejad, 2014):
= K2 (qe − qt )2 (13)
dt
t 1
1 ho,2 = K2 q2e (15)
= + t (14)
qt k2 q2e qe
and the results are presented in Table 3. It is evident that the
where k2 is the rate constant (g (mg min)−1 ). By plotting (t/qt ) initial adsorption rate decreases with intensifying the initial
versus t, the parameters qe and k2 can be estimated from MG concentration, at higher concentrations due to apparent
the slope and the intercept of the plot. Based on Table 3 and MG dimerization and difficult diffusion of large dimmers in
Fig. 10(b), the high R2 values of this model and good agree- small adsorbent pores that cause to aggravate kinetic param-
ment of calculated and experimental qe values under different eters (Nekouei et al., 2015).
Fig. 10 – (a) Plots of pseudo-first-order kinetic for MG concentrations of 10 and 20 mg L−1 . (b) Plots of pseudo-second-order
kinetic for MG concentrations of 10 and 20 mg L−1 . (c) Plots of Intraparticle diffusion model for MG concentrations of 10 and
20 mg L−1 . (d) Plots of Elovich model for MG concentrations of 10 and 20 mg L−1 .
94 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97
3.8.3. Test of kinetic models In the present study, the intercepts for both concentrations
Besides the value of R2 , in order to further quantitatively ver- are not zero but with high correlation coefficient values that
ify the accuracy of both kinetic methods, the sum of error indicate the contribution of two or more steps in the adsorp-
squares (SSE) was applied. The sum of error squares is given tion process. Therefore, there may be three stages in order of
as (Hameed et al., 2007): a fast step related to external surface adsorption, IPD step and
equilibrium, respectively.
2
qe,EXP − qe,Cal
SSE = (16) 3.8.5. Elovich model
N The Elovich equation is a kinetic equation related to the
chemisorption process. This equation is often validated for
where N is the number of data points. The higher value of systems where the surface of the adsorbent is heterogeneous.
R2 and the lower value of SSE shows the better goodness of The linear form of the Elovich equation is given as follows
fit (Hameed and El-Khaiary, 2008). The values of SSE for the (GuimarãesGusmão et al., 2013):
pseudo first and pseudo second kinetic models are given in
Table 3. It can be seen that the SSE values for second order 1 1
qt = ln (˛ˇ) + ln (t) (18)
kinetic model (0.163 and 0.54) are very lower than for the ˇ ˇ
pseudo first order model (6.17 and 9.18). Low values of SSE
as well as high R2 values for PSO strongly confirm the better where ˛ (mg g−1 min−1 ) is the initial adsorption rate and ˇ
applicability of the PSO model. (g mg−1 ) is the relationship between the degree of surface cov-
erage and the activation energy involved in the chemisorption.
3.8.4. Intra-particle diffusion model As shown in Table 3 and Fig. 10(d), the low R2 values of these
Another applied rate equation for the adsorption of solute models show their inapplicability for interpretation of exper-
from a liquid solution was intra particle diffusion (IPD) imental data.
model based on diffusive mass transfer that adsorption rate
expressed in terms of the square root of time (t) (Ozdes 3.9. Adsorption thermodynamics
et al., 2011). IPD is derived from Fick’s law and assumes that
the diffusion of the liquid film surrounding the adsorbent is To evaluate the thermodynamic feasibility and the sponta-
negligible, and intraparticle diffusion is the only rate con- neous nature of the adsorption, thermodynamic parameters
trolling step of the adsorption process. Eq. (17) shows the such as free energy change, enthalpy change, and entropy
mathematical expression used to study this phenomenon were calculated. Generally, thermodynamic constants can be
(GuimarãesGusmão et al., 2013). By plotting qt versus t1/2 may obtained from the following equations:
give a linear relationship that Kdiff and C values can be deter-
mined from its slope and intercept, respectively. C and Kdiff G◦ = −RT ln Ke (19)
values are related to the thickness of the boundary layer and
the IPD rate constant (mg g−1 min−1/2 ) were reported in Table 3. G◦ = H◦ − TS◦ (20)
qt = Kdiff t(1/2) + C (17) where G◦ , H◦ , S◦ , R, ke , T, are the Gibbs free energy
(kJ mol−1 ), enthalpy (kJ mol−1 ), entropy (kJ mol−1 K−1 ), the
Fig. 10(c) displays the diffusion modeling on kinetic of the universal gas constant (8.314 J mol−1 K−1 ), the thermody-
dye adsorption on Ni(OH)2 -NPs-AC. It was mentioned that the namic equilibrium constant, and the absolute temperature
intercept reflects the boundary layer effect. The greater value (K), respectively. Table 4 shows that the negative values of
of the intercept verifies the greater contribution of the sur- Gibbs free energy decreased with increasing the temperature.
face sorption in the rate-limiting step. As clearly evidenced This indicates the spontaneous nature and feasibility of the
in Fig. 10(c) and Table 3, high R2 values (≥0.99) confirm the adsorption via physical forces as well as high tendency of
adsorption mechanism also follows the IPD process. Addition- adsorbent to the adsorbate (Nekouei et al., 2015). Furthermore,
ally, if the plot of qt versus t1/2 is linear and passes through the Ke (L mol−1 ) is the Langmuir constant obtained from the plot
origin, it shows that IPD is the sole rate-limiting step. of Ce /qe versus Ce at different temperatures. The values of
Table 5 – Comparison of performance of proposed method with some previously reported MG dye adsorption systems.
Adsorbent Adsorption Contact time Adsorbent Reference
capacity (mg g−1 ) (min) dose (g)
4. Conclusion El-Bindary, A.A., Hussien, M.A., Diab, M.A., Eessa, A.M., 2014. J.
Mol. Liq. 197, 236–242.
Freundlich, H.M.F., 1906. J. Phys. Chem. 57, 385–470.
The extremely small average size Ni(OH)2 nanoplates were
Garg, V.K., Gupta, R., Yadav, A.B., Kumar, R., 2003. Bioresour.
synthesized using a simple, fast and low cost method. Results
Technol. 89, 121–124.
obtained illustrated that Ni(OH)2 -NPs-AC is an efficient and Ghaedi, M., Mosallanejad, N., 2014. J. Ind. Eng. Chem. 20,
low cost adsorbent with satisfactory capacity adsorbent (76.92) 1085–1096.
for the removal of MG in liquid phase in a short time (≤20 min). Ghaedi, M., Heidarpour, S., NasiriKokhdan, S., Sahraie, R.,
In Table 5, the performance of the presented method has been Daneshfar, A., Brazesh, B., 2012. Powder Technol. 228, 18–25.
compared with some adsorbents reported for the removal of Ghaedi, M., Taghavimoghadam, N., Naderi, S., Sahraei, R.,
Daneshfar, A., 2013a. J. Ind. Eng. Chem. 19, 1493–1500.
some MG dye in literatures (Gupta et al., 1997; Tahir and Rauf,
Ghaedi, M., Ansari, M., Sahraei, R., 2013b. Spectrochim. Acta, A:
2006; Garg et al., 2003; Bekçi et al., 2008; Kumar and Sivanesan, Mol. Biomol. Spectrosc. 114, 687–694.
2007; Mittal, 2006; Shamsizadeh et al., 2014; Rahman et al., Ghaedi, M., Ansari, A., Habibi, M.H., Asghari, A.R., 2014. J. Ind.
2005; Önal et al., 2007; Zhang et al., 2008). Some analytical Eng. Chem. 20, 17–28.
influential parameters including pH, initial dye concentra- GuimarãesGusmão, K.A., Alves Gurgel, L.V., Sacramento Melo,
tion, temperature, contact time and amount of adsorbent on T.M., Gil, L.F., 2013. J. Environ. Manage. 118, 135–143.
Gupta, V.K., Srivastava, S.K., Mohan, D., 1997. Ind. Eng. Chem.
the MG removal percentage were well investigated and eluci-
Res. 36, 2207–2218.
dated. The equilibrium and kinetic studies were investigated
Gupta, V.K., Tyagi, I., Agarwal, S., Sadegh, H.,
for the adsorption process that Langmuir isotherm and PSO Shahryari-ghoshekandi, R., Yari, M., Yousefi-nejat, O., 2015. J.
along with IPD models were suitable to describe the adsorp- Mol. Liq. 206, 129–136.
tion process, respectively. After investigating thermodynamic Hajipour, M.J., Fromm, K.M., Ashkarran, A.A., de Aberasturi, D.J.,
parameters, it was found that the adsorption process was de Larramendi, I.R., Rojo, T., Serpooshan, V., Parak, W.J.,
endothermic because of positive amount of enthalpy. Fur- Mahmoudi, M., 2012. Trends Biotechnol. 30, 499–511.
Hameed, B.H., El-Khaiary, M.I., 2008. J. Hazard. Mater. 154,
thermore, negative amounts of Gibbs free energy showed the
237–244.
spontaneity of the adsorption process. Antibacterial studies
Hameed, B.H., Din, A.T.M., Ahmad, A.L., 2007. J. Hazard. Mater.
revealed that Ni(OH)2 nanoplates showed very good activity 141, 819–825.
against S. aureus, E. coli and specially B. subtilis bacteria. Hamoudi, S., Belkacemi, K., 2013. Fuel 110, 107–113.
Harish, K., Renu, R., Raj Kumar, S., 2011. J. Chem. Sci. 1,
42–48.
Acknowledgment Huang, G., Shi, J.X., Langrish, T.A.G., 2009. Chem. Eng. J. 152,
434–439.
The financial support from Young Researchers and Elite Club, Jiang, Y., Wang, H., Chen, X., Wang, X., Weib, H., Guob, Z., 2014.
Science and Research Branch, Islamic Azad University is grate- Appl. Surf. Sci. 316, 66–71.
fully acknowledged (2015). Kamath, P.V., Subbanna, G.N., 1992. J. Appl. Electrochem. 22,
478–482.
Khattri, S.D., Singh, M.K., 1999. Indian J. Chem. Technol. 6,
Appendix A. Supplementary data 112–116.
Koch, M., Yediler, A., Lienert, D., Insel, G., Kettrup, A., 2002.
Chemosphere 46, 109–113.
Supplementary data associated with this article can be found, Kumar, K.V., Sivanesan, S., 2007. Dyes Pigm. 72, 124–129.
in the online version, at http://dx.doi.org/10.1016/j.psep. Lagergren, S., 1898. Handlingar 24, 1–39.
2016.02.011. Langmuir, I., 1916. J. Am. Chem. Soc. 38, 2221–2295.
Malik, P.K., Saha, S.K., 2003. Sep. Purif. Technol. 31, 241–250.
Mittal, A., 2006. J. Hazard. Mater. 133, 196–202.
References Mohammadi, N., Khani, H., Gupta, V.K., Amereh, A., Agarwal, S.,
2011. J. Colloid Interface Sci. 362, 457–462.
Asfaram, A., Ghaedi, M., Agarwal, S., Tyagi, I., 2015. RSC Adv. 5, Morones, J.R., Elechigierra, J.L., Caacho, A., Holt, K., Kouri, J.B.,
18438–18450. Ramirez, J.T., Yacaman, M.J., 2005. J. Nanotechnol. 16,
Aziz, A., Ouali, M.S., Elandaloussi, E.H., Menorval, L.C.D., 2346–2353.
Lindheimer, M., 2009. J. Hazard. Mater. 163, 441–447. Motlagh, M.M.K., Youzbashi, A.A., Sabaghzadeh, L., 2011. Int. J.
Baker, C., Pradhan, A., Pakstis, L., Pochan, D.J., Shah, S.I., 2005. J. Phys. Sci. 6, 1471–1476.
Nanosci. Nanotechnol. 5, 244–249. Nair, M.G., Nirmala, M., Rekha, K., Anukaliani, A., 2011. Mater.
Bekçi, Z., Coşan, Ö., Seki, Y., Yurdakoç, K., 2008. J. Hazard. Mater. Lett. 65, 1797–1800.
154, 254–261. Nekouei, F., Nekouei, S., Tyagi, I., Gupta, V.K., 2015. J. Mol. Liq. 201,
Boisseau, P., Loubaton, B., 2011. C.R. Phys. 12, 620–636. 124–133.
Bulai1, P., Cioanca, E.-R., 2011. Tehnomus J. 18, 64–67. Ni, X., Zhao, Q., Li, B., Cheng, J., Zheng, H., 2006. Solid State
Cheng, B., Le, Y., Cai, W., Yu, J., 2011. J. Hazard. Mater. 185, 889–897. Commun. 137, 585–588.
Chong, M.N., Jin, B., Chow, C.W.K., Saint, C., 2010. Water Res. 44, Önal, Y., Akmil-Başar, C., Sarıcı-Özdemir, C., 2007. J. Hazard.
2997–3027. Mater. 146, 194–203.
Ciardelli, G., Corsi, L., Marcucci, M., 2000. Resour. Conserv. Recycl. Ozdes, D., Duran, C., Senturk, H.B., 2011. J. Environ. Manage. 92,
31, 189–197. 3082–3090.
Crini, G., 2006. Bioresour. Technol. 97, 1061–1085. Panswed, J., Wongchaisuwan, S., 1986. Water Sci. Technol. 18,
Culp, S.J., Beland, F.A., 1996. J. Am. Coll. Toxicol. 15, 219–238. 139–144.
Dada, A.O., Olalekan, A.P., Olatunya, A.M., Dada, O., 2012. J. Appl. Radushkevich, L.V., 1949. Zh. Fiz. Khim. 23, 1410–1420.
Chem. 3, 38–45. Rahman, I.A., Saad, B., Shaidan, S., Sya Rizal, E.S., 2005. Bioresour.
De Moura, A.P., Lima, R.C., Paris, E.C., Li, M.S., Varela, J.A., Longo, Technol. 96, 1578–1583.
E., 2011. J. Solid State Chem. 184, 2818–2823. Roosta, M., Ghaedi, M., Daneshfar, A., Sahraei, R., Asghari, A.,
DoganUluozlu, O., Sari, A., Tuzen, M., Soylak, M., 2008. Bioresour. 2014. Ultrason. Sonochem. 21, 242–252.
Technol. 99, 2972–3298. Sadegh, H., Shahryari-ghoshekandi, R., Agarwal, S., Tyagi, I., Asif,
Dubinin, M.M., 1960. Chem. Rev. 60, 235–241. M., Gupta, V.K., 2015a. J. Mol. Liq. 206, 151–158.
Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 85–97 97
Sadegh, H., Shahryari-ghoshekandi, R., Tyagi, I., Agarwal, S., Temkin, M.J., Pyzhev, V., 1940. Acta Physiochim. URSS 12,
Gupta, V.K., 2015b. J. Mol. Liq. 207, 21–27. 327–356.
Shamsizadeh, A., Ghaedi, M., Ansari, A., Azizian, S., Purkait, M.K., Víctor-Ortega, M.D., Ochando-Pulido, J.M., Martínez-Férez, A.,
2014. J. Mol. Liq. 195, 212–218. 2015. Ecol. Eng. 77, 18–25.
Soler-Illia, G.J.D.A., Jobbagy, M., Regazzoni, A.E., Blesa, M.A., 1999. Víctor-Ortega, M.D., Ochando-Pulido, J.M., Martínez-Férez, A.,
Chem. Mater. 11, 3140–3146. 2016. Ecol. Eng. 86, 53–59.
Song, X., Gao, L., 2008. J. Am. Ceram. Soc. 91, 4105–4108. Vitela-Rodriguez, A.V., Rangel-Mendez, J.R., 2013. J. Environ.
Srivastava, S., Rangana, S., Roy, D., 2004. Aquat. Toxicol. 66, Manage. 114, 225–231.
319–329. Wei, J., Zhang, X., Liu, Q., Li, Z., Liu, L., Wang, J., 2014. Chem. Eng.
Stoimenov, P.K., Klinger, R.L., Marchin, G.L., Klabunde, K., 2002. J. 241, 228–234.
Langmiur 18, 6679–6686. White, B., Yin, M., Hall, A., Le, D., Stolbov, S., Rahman, T., Turro,
Sun, Y.K., Ma, M., Zhang, Y., Gu, N., 2004. Colloids Surf., A: N., O’Brien, S., 2006. Nano Lett. 6, 2095–2098.
Physicochem. Eng. Aspects 245, 15–19. Ye, H., Zhu, Q., Du, D., 2010. Bioresour. Technol. 101,
Taghizadeh, F., Ghaedi, M., Kamali, K., Sharifpour, E., Sahraie, R., 5175–5179.
Purkait, M.K., 2013. Powder Technol. 245, 217–226. Zhang, J., Yan, L.I., Zhang, C., Jing, Y., 2008. J. Hazard. Mater. 150,
Tahir, S.S., Rauf, N., 2006. Chemosphere 63, 1842–1848. 774–782.
Taylor, R., Otanicar, T., Herukerrupu, Y., Bremond, F., Zhang, F., Liu, Y.J., Liu, Q.H., Li, Q., Li, H., Cai, X.Y., Wang, Y.D.,
Rosengarten, G., Hawkes, E., Jiang, X., Coulombe, S., 2013. 2013. Mater. Technol. 28, 310–315.
Appl. Opt. 52, 1413–1422.