Ultrasonics Sonochemistry 37 (2017) 71–82

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Rapid and high-capacity ultrasonic assisted adsorption of ternary toxic

anionic dyes onto MOF-5-activated carbon: Artificial neural networks,
partial least squares, desirability function and isotherm and kinetic
study
Hanieh Askari a, Mehrorang Ghaedi a,⇑, Kheibar Dashtian a, Mohammad Hossein Ahmadi Azghandi b
a
Department of Chemistry, Yasouj University, Yasouj 75918-74831, Iran
b
Department of Gas and Petroleum, Yasouj University, Gachsaran 75918-74831, Iran

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

Article history: The present paper focused on the ultrasonic assisted simultaneous removal of fast green (FG), eosin Y (EY)
Received 7 June 2016 and quinine yellow (QY) from aqueous media following using MOF-5 as a metal organic framework and
Received in revised form 28 October 2016 activated carbon hybrid (AC-MOF-5). The structure and morphology of AC-MOF-5 was identified by SEM,
Accepted 31 October 2016
FTIR and XRD analysis. The interactive and main effects of variables such as pH, initial dyes concentration
Available online 1 November 2016
(mg L
1), adsorbent dosage (mg) and sonication time (min) on removal percentage were studied by cen-
tral composite design (CCD), subsequent desirability function (DF) permit to achieved real variable exper-
Keywords:
imental condition. Optimized values were found 7.06, 5.68, 7.59 and 5.04 mg L
1, 0.02 g and 2.55 min for
Fast green
Eosin Y
pH, FG, EY and QY concentration, adsorbent dosage and sonication time, respectively. Under this condi-
Quinine yellow tions removal percentage were obtained 98.1%, 98.1% and 91.91% for FG, EY and QY, respectively. Two
MOF-5 models, namely partial least squares (PLS) and multi-layer artificial neural network (ANN) model were
Artificial neural network used for building up to construct an empirical model to predict the dyes under study removal behavior.
Ultrasonic assisted adsorption The obtained results show that ANN and PLS model is a powerful tool for prediction of under-study dyes
adsorption by AC-MOF-5. The evaluation and estimation of equilibrium data from traditional isotherm
models display that the Langmuir model indicated the best fit to the equilibrium data with maximum
adsorption capacity of 21.230, 20.242 and 18.621 mg g
1, for FG, EY and QY, respectively, while the
adsorption rate efficiently follows the pseudo-second-order model.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction bon nanotubes and graphene), porous material such as zeolites,

Toxic anionic organic dyes, as important industrial products,
have been widely used for the dyeing of silk, cotton and in the
paper-making industry [1,2]. These have many drawbacks, includ-
ing being toxic contaminants, and have generated much pollution
[3]. It is thus of vital importance to solve the problem of pollution
caused by anionic organic dyes. Therefore, several approaches such
as coagulation, membrane filtration, adsorption, photocatalysis
and advanced oxidation have been developed to remove of anionic
organic dyes from aqueous solutions. Among these, adsorption is
considered to be one of the best technologies due to its high effec-
tiveness and efficiency and low cost [4]. In this case, the good
adsorbents, such as carbon based materials (activated carbons, car-
⇑ Corresponding author.
E-mail address: m_ghaedi@mail.yu.ac.ir (M. Ghaedi).
MOFs, SBA-15, SBA-16, MCM-41, MCM-48 and polymeric materials
such as polysaccharide, cyclodextrin and molecularly imprinted
polymer have been utilized to remove organic dyes [5–8]. These
adsorbents can readily adsorb single organic dyes, while are gener-
ally poor in various mixed mode for removing the organic dyes.
Therefore, is necessary for this purpose to develop high capacity
adsorbent for the removal of them. Thus, intermixing porous car-
bon based materials with various nanostructures such as MOFs
lead to appearance of unique physical and chemical properties
viz. good disperse ability and high surface-to-volume ratio, which
is associated with increasing rapidity of adsorption and strong
change in kinetic of adsorption process by modification of proper-
ties of activated carbon which is composed of reactive centres like
COOH and amide groups [9–14]. So far, has not been reported from
MOF-5 and activated carbon hybrid for adsorption of organic dyes.
Moreover, the MOF-5-activated carbon as a neural charged hybrid

http://dx.doi.org/10.1016/j.ultsonch.2016.10.029
1350-4177/Ó 2016 Elsevier B.V. All rights reserved.
72 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82

that can completely separate mixed organic dyes through highly

selective adsorption and desirable was developed [15,16]. MOF-5
as one of the metal-organic-frameworks due to having features
such are the high specific surface area, elegant pore size, and large
pore volume was selected as a support in pompous adsorption pro-
cess [17,18].
Concern of simultaneous removal of dyes from aqueous solu-
tion is spectral overlap of them. Therefore, chemometric and
graphical calibration techniques in spectral analysis can be used
to solve this problem without any separation procedure before
the determination step of dyes concentration [19]. In this study,
due to the spectral overlap, the spectrophotometric derivative as
a chemometric calibration technique was applied to determine
the residual dyes amount in the solution [20].
The design of an adsorption process requires the expansion of a
model that can appropriately describe the adsorption process with
operating conditions. An empirical design of an adsorption process
tends to be expensive and time consuming. In recent years, many
researches in the adsorption process, predicting have resulted in
the development of several forecasting methods, which can gener-
ally be classified into two groups, linear and nonlinear methods
[21]. The most popular linear approaches include multiple linear
regression (MLR), partial least squares (PLS) regression, etc.
Recently, the nonlinear models have been paid much more atten-
tion for example, artificial neural network (ANN) [22,23]. These
approaches imitate the processes of the human neurological sys-
tem to process self-learning from the experimental data, especially
for nonlinear variations and now the ANN models have been
widely applied in adsorption forecasting [21–26]. Experimental
evidence indicates that the ANN models generally outperform
the linear approaches in the adsorption process. While, the
Fig. 1. Chemical structures of FG (a), EY (b) and QY (c) dyes.
approaches lack a systematic process for model constructing, thus,
achieving a reliable ANN model involves selecting a large number
of variables empirically through trial and error is important
[27,28–34].
2. Experimental
In this work, A Zn terephthalate (MOF-5) was hybrid with acti-
vated carbon (AC) by ultrasonically assisted hydrothermal method
2.1. Materials and apparatus
and successfully used for the simultaneous ultrasonic assisted
removal of three toxic dyes (fast green (FG) FCF, quinoline yellow
The chemical reagents used to include Zn(NO3)26H2O, ther-
(QY) WS and eosin Y (EY) chemical structures are shown in
phetalic acid, ethanol, activated carbon, HCl, FG, QY, EY and NaOH
Fig. 1) from contaminated water via adsorption process. These dyes
purchased from Merck (Darmstadt, Germany). Equipment’s were
has been selected, as it is inexpensive and widely used in textile,
used according to manufacture recommendation correspond to
pulp and paper industries [4]. Among hybrid systems for removal
previous publication [1,2,32,42–45]. An ultrasonic bath (Tecno-
of pollutants ultrasonic assisted adsorption which uses the combi-
GAZ SPA Ultra Sonic System, Parma, Italy) at 40 kHz of frequency
nation of ultrasonic waves and a adsorbent, is an alternative, low-
and 130 W of power was used for ultrasound-assisted adsorption
cost and effective technique for wastewater treatment [29–32].
procedure.
Combination of adsorption and ultrasound has showed synergistic
effects on the removal of many organic compounds [33–38]. Clean-
ing of adsorbents particles due to acoustic cavitation phenomenon
caused by ultrasound waves lead to mass transfer improvement 2.2. Synthesis of AC-MOF-5
between the solution phase and adsorbents surface by acoustic
cavitation [39]. The phenomenon of acoustic cavitation includes AC-MOF-5 was prepared by ultrasound-assisted solvothermal
the nucleation, growth, and sudden collapse of gas or vapor-filled method as follow: 0.10 g AC (5 wt% of the total solids) was soni-
microbubbles which is caused by the acoustical wave induced cated for 30 min in 20 mL ethanol, in parallel, 1,4-dicarboxylic
compression/rarefaction in a body of liquid [40,41]. The AC-MOF- acid (2.0 mmol) and zinc (II) nitrate hexahydrate (5.6 mmol) were
5 were characterized by powder XRD, SEM, FT-IR analysis. The sonicated for 30 min in 80 mL of solvent consist of 65 mL DMF
effects of various operating parameters, such as adsorbent mass, and 15 mL ethanol in a glass jar. Subsequently, the contents of
pH, sonication time and initial dyes concentration, on removal per- the two containers were added together and mixture dispersed
centage were investigated and optimized by central composite for 30 min. The suspension was kept for 1.0 h under sonication
design. Central composite design (CCD) is one of the most accepted that completely mixed and lead to fast mass transfer at the
designs under response surface methodology (RSM) was used to solid–liquid interface. Finally, the mixture was transferred into a
obtain optimum conditions and to consume fewer reagents with Teflon-lined autoclave, sealed and heated at 130 °C for 24 h.
less laboratory work [42,43]. ANN and PLS will be used for fore- Finally, the solvent was removed and heated in an oven at
casting adsorption of understudy dyes onto AC-MOF-5. Finally, 100 °C for 12 h to yield a AC-MOF-5. As compare, MOF-5 in lateral
the adsorption isotherms and kinetics of adsorption of dyes were stage evenly with the above steps without adding AC was
studied. prepared.
 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82 73

Table 1
CCD levels, matrix and response.

Factors Unit Surface factors

Levels Star point,
a = 2.38
(Low)
1 (Central) 0 (High) +1
a +a
(X1) Initial FG Concentration mg L
1 4 6 8 2 10
(X2) Initial EY Concentration mg L
1 4 6 8 2 10
(X3) Initial QY Concentration mg L
1 4 6 8 2 10
(X4) pH – 6 7 8 5 9
(X5) AC-MOF-5 mass g 0.015 0.02 0.025 0.01 0.03
(X6) Sonication time min 2 3 4 1 5
runs X1 X2 X3 X4 X5 X6 R% FG R% EY R% QY

1 4.00 4.00 4.00 6.00 0.01 2.00 91.28 69.56 82.36

2 4.00 8.00 8.00 6.00 0.03 4.00 100 100 95.2
3 8.00 4.00 8.00 8.00 0.03 2.00 98 100 94.19
4 4.00 8.00 8.00 8.00 0.01 4.00 99 94.5 94.12
5 4.00 8.00 4.00 8.00 0.01 2.00 90 86.3 90.2
6 6.00 10.00 6.00 7.00 0.02 3.00 99 98.63 96.7
7 8.00 4.00 4.00 6.00 0.01 4.00 98 100 93.19
8 6.00 6.00 6.00 7.00 0.02 3.00 98 97.3 91.7
9 6.00 6.00 6.00 7.00 0.02 3.00 96.7 97.25 91.45
10 2.00 6.00 6.00 7.00 0.02 3.00 98.36 94.25 94.7
11 6.00 6.00 6.00 7.00 0.03 3.00 99 105 100
12 6.00 6.00 10.00 7.00 0.02 3.00 94 95.5 94.12
13 8.00 8.00 8.00 6.00 0.03 2.00 97 95.39 92.1
14 8.00 8.00 4.00 6.00 0.03 4.00 99 100 92.5
15 6.00 6.00 6.00 5.00 0.02 3.00 97 88.7 89.2
16 4.00 4.00 8.00 8.00 0.03 4.00 100 97.63 93.26
17 6.00 6.00 6.00 7.00 0.02 5.00 91.25 100 100
18 10.00 6.00 6.00 7.00 0.02 3.00 95 99.4 91.36
19 6.00 6.00 6.00 9.00 0.02 3.00 99 100 94.7
20 4.00 8.00 4.00 6.00 0.03 2.00 100 100 88.51
21 6.00 6.00 6.00 7.00 0.02 3.00 96.58 97.01 91.6
22 6.00 6.00 6.00 7.00 0.01 3.00 91 68.2 72.25
23 6.00 6.00 6.00 7.00 0.02 3.00 96.9 97.15 91.2
24 6.00 6.00 6.00 7.00 0.02 1.00 98 95.36 84.7
25 8.00 4.00 4.00 8.00 0.03 4.00 100 100 91.7
26 6.00 2.00 6.00 7.00 0.02 3.00 96.58 93.25 71.25
27 8.00 4.00 8.00 6.00 0.01 2.00 83 90.7 83.12
28 6.00 6.00 6.00 7.00 0.02 3.00 96.58 97.08 91.12
29 6.00 6.00 2.00 7.00 0.02 3.00 100 100 95.17
30 4.00 4.00 8.00 6.00 0.01 4.00 100 100 94.12
31 8.00 8.00 4.00 8.00 0.01 4.00 99 86.5 85.189
32 4.00 4.00 4.00 8.00 0.03 2.00 99 95.63 91.7
33 8.00 8.00 8.00 8.00 0.01 2.00 85.69 84.36 77.2

2.3. Ultrasonic assisted removal procedure
In the adsorption experiment according to the all runs of CCD
matrix certain amount of the as-prepared AC-MOF-5 powder was
mixed with 50 mL of aqueous solution of FG, EY and QY with a cer-
tain concentration in an erlenmayer flask. The suspension was son-
icated in sonication bath at different time intervals at room
temperature. Then, 3.0 mL of the solution was pipetted and ana-
lyzed after centrifugation (4000 r/min, 5 min) by using a UV–Vis
spectrophotometer. For the adsorption capacity and isotherm
study, the initial concentrations of the ternary solution of FG, EY
and QY were scaled in the range of 5–30 mg L
1, and the dosage
of AC-MOF-5, sonication time and pH were kept at centre value
of CCD matrix. The concentration of FG, EY and QY was determined
using a linear calibration curve based on the absorbance value at
497, 222 and 555 nm, respectively, after first order derivative of
all spectrum. The removal percentage of each dye (R% FG, EY and
QY) and the capacities for the adsorption of each dye were calcu-
lated according to the our previous report [4,46]:
The adsorptions were found to proceed through a number of
different mechanisms such as electrostatic interactions, acid-base
sometimes, for a particular adsorption process, multiple interac-
tions might take place [48,49].
2.4. Principle of central composite design
CCD analysis (using STATICTICA 10.0 software) was used to give
detail about contribution of different variables on understudy dyes
removal percentages. The variables were EY, FG and QY (x1, x2 and
x3, respectively), pH (x4), AC-MOF-5 mass (x5) and sonication time
(x6) into five levels (low, central and high) with coded value (
1, 0,
1) and the staring points of +2 and
2 for +a and
a, respectively.
The design matrix corresponds the responses of three dyes are
shown in Table 1. The analysis of variance (ANOVA) related to
CCD is efficient to evaluate the significance levels of parameters,
multiple correlation coefficient R2, adjusted and predicted R2 val-
ues and F-value of model.
In general, the following full quadratic equation may be applied
to model a response versus the independent variables. It may
account for the possible interaction between the variables.
X
6 X
6 X
6 X
6

interactions, hydrogen bonding, p–p stacking/interactions, and Y ¼ b0 þ bi X i þ bii X 2i þ bij X i X j j–i ð1Þ
i¼1 i¼1 j¼1 i¼1
hydrophobic interactions [47]. It has also been observed that
74 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82
Fig. 2. Structure of a back-propagation artificial neural network.
Desirability function approach consists of converting the
estimated response models (R %), which usually are second order
models, into individual desirability functions for each individual
response that are then aggregated into a composite function
Fig. 3. SEM image in tow magnification (a and b) and XRD pattern of AC-MOF-5 (c) and FT-IR of AC, MOF-5 and AC-MOF-5 (d).
[50–52]. This function is usually a geometric or an arithmetic aver-
age, which will be maximized or minimized, respectively. One or
two-sided functions are used, depending on whether each of the
number of responses has to be maximized or minimized, or has
an allotted target value. the response (R %) is converted into a par-
ticular desirability function in the range of 0.0 (undesirable) to 1.0
(very desirable), while, itis better that its value limited to one
[1,42,43,50,53].
2.5. Principle of artificial neural network model
In this study, MATLAB 2013a software was employed to forecast
the percentage of ternary mixture of FG, EY and QY dyes removal
from aqueous solution. A multilayer perceptron (MLP) based on
back propagation ANN was used to construct the predictive model
(Fig. 2). The network consists of an input layer, one or more hidden
layers and an output layer. The Inputs for the back propagation
ANNs are sonication time, AC-MOF-5 mass, pH and dyes concentra-
tion; output is percentage dyes removal. In this network, neuron
transfer input values to next layer in a forward direction. The
strength connections between inputs, hidden and out-put layers
determined by weights (w) and biases (b) that are known as
parameters of the ANNs. A three-layer back propagation (BP)
ANN with a 1 to 14 neurons in hidden layer, three neurons in out-
put layer, was built up to forecast and simulate AC-MOF-5 adsorp-
tion efficiency for understudy dyes removal.
Various back-propagation algorithms were considered to select
the best BP algorithm with a maximum the coefficient of determi-
nation (R2) and minimum mean squared error (MSE), shown by the
following equations [54,55]:
1 XN  2
MSE ¼ jyprd;i
yexp;i j ð2Þ
N i¼1
 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82
Fig. 4. Absorption spectra of FG, EY and QY in single and ternary solutions (a),
absorption spectrum of ternary solutions at different adsorbent dosage (0–0.02 g)
(b) and first order derivative spectra of FG, EY and QY in single and ternary solutions
(c).
PN  
yprd;i
yexp;i
R2 ¼ 1
Pi¼1
N   ð3Þ
i¼1 yprd;i
ym
where yprd,i the predicted value of the ANN model is, yexp,i is the
experimental value, N is the number of data, and ym is the average
of the experimental value.
Various variables may have different magnitudes, and some
could be unmerited, but favourable, influence on the monitored
quantity. In the present study, all inputs and output are normalized
within a uniform range of
1 and +1 according to the below equa-
tion [56]:
y ¼ 0:8  ðxi
xmin =xmax
xmin Þ þ 0:1
where y is the normalized value of xi. The xmax and xmin are the max-
imum and minimum value of xi, respectively. Also, the data were
randomly divided into two groups (75% training and 25% as testing).
2.6. Principle of partial least square model
Partial least square model (PLS) model (from MATLAB 2013a
software) is commonly applied in environmental studies in order
to model the change and dependency of numerous independent
variables to the dependent variable according to following mathe-
matical equation [57]:
Y ¼ b0 þ bi X i þ b2 X 2 þ . . . þ bn X n
75
Fig. 5. Calibration curve at select wavelength for determination of FG (a), EY (b) and
QY (c) dyes.
where Y was the predicted value of PLS model, bi (i = 0, . . . ,n) are the
regression coefficients, Xi (i = 1, . . . ,n) are the independent variables
(inputs). PLS model easily used in to determine the cumulative
influence of variables such as sonication time, AC-MOF-5 mass, dyes
concentration of dyes and pH on the removal percentage.
ð4Þ
3. Results and discussion
3.1. Characterization of samples
The morphology of AC-MOF-5 hybrid (Fig. 3a and b) strongly
identified the size of tetragonal cube MOF-5 in AC matrix in the
range of 2–3 lm with porous structure. That strongly confirm pos-
sibility of providing high surface area as good and strong recom-
mended requirement to design of efficient adsorbent for removal
of toxic organic dyes.
The XRD of crystal structure (Fig. 3c) show three sharp peaks at
ð5Þ 2h of 10, 17, 23 in XRD pattern match well to the (1 1 1), (2 0 0) and
(2 2 0) crystal planes of the pure MOF-5 (PDF card no, 04-0836),
76 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82

Table 2
ANOVA for the response surface quadratic model of R% FG, R% EY and R% QY.

Source R% FG R% EY R% QY
variation 1 2 3
DF SS MS F-value P-value SS MS F-value P-value SS MS F-value P-value
model 27 563.66 20.88 70.38 0.0001 2099.04 77.74 5038.02 <0.0001 1447.72 53.62 936.49 <0.0001
X1 1 2.93 2.93 9.87 0.0256 14.47 14.47 937.86 <0.0001 323.85 323.85 5656.25 <0.0001
X2 1 5.64 5.64 19.03 0.0073 13.26 13.26 859.38 <0.0001 5.58 5.58 97.42 0.0002
X3 1 18.00 18.00 60.68 0.0006 10.13 10.13 656.14 <0.0001 0.55 0.55 9.63 0.0268
X4 1 2.00 2.00 6.74 0.0484 63.85 63.85 4137.43 <0.0001 15.13 15.13 264.17 <0.0001
X5 1 32.00 32.00 107.88 0.0001 677.12 677.12 43880.23 <0.0001 385.03 385.03 6724.80 <0.0001
X6 1 22.78 22.78 76.80 0.0003 10.76 10.76 697.60 <0.0001 117.05 117.05 2044.26 <0.0001
X1X2 1 0.55 0.55 1.86 0.2310 112.52 112.52 7291.71 <0.0001 29.71 29.71 518.82 <0.0001
X1X3 1 0.059 0.059 0.20 0.6748 29.40 29.40 1905.47 <0.0001 0.77 0.77 13.52 0.0143
X1X4 1 4.71 4.71 15.87 0.0105 103.46 103.46 6704.56 <0.0001 106.03 106.03 1851.81 <0.0001
X1X5 1 0.65 0.65 2.19 0.1986 65.17 65.17 4223.30 <0.0001 13.59 13.59 237.37 <0.0001
X1X6 1 0.36 0.36 1.22 0.3190 44.86 44.86 2906.89 <0.0001 0.23 0.23 3.94 0.1038
X2X3 1 126.85 126.85 427.62 0.0001 30.29 30.29 1962.89 <0.0001 9.45 9.45 165.10 <0.0001
X2X4 1 5.03 5.03 16.95 0.0092 24.33 24.33 1576.66 <0.0001 29.49 29.49 515.02 <0.0001
X2X5 1 5.75 5.75 19.38 0.0070 5.14 5.14 333.19 <0.0001 35.76 35.76 624.63 <0.0001
X2X6 1 2.26 2.26 7.61 0.0399 37.79 37.79 2448.94 <0.0001 3.08 3.08 53.81 0.0007
X3X4 1 0.55 0.55 1.86 0.2310 4.48 4.48 290.57 <0.0001 4.00 4.00 69.84 0.0004
X3X5 1 3.60 3.60 12.14 0.0176 55.54 55.54 3599.21 <0.0001 10.11 10.11 176.59 <0.0001
X3X6 1 0.79 0.79 2.66 0.1641 1.10 1.10 71.36 0.0004 1.00 1.00 17.43 0.0087
X4X5 1 1.79 1.79 6.04 0.0575 16.32 16.32 1057.71 <0.0001 254.02 254.02 4436.55 <0.0001
X4X6 1 0.011 0.011 0.035 0.8581 64.04 64.04 4150.06 <0.0001 20.12 20.12 351.36 <0.0001
X5X6 1 105.22 105.22 354.70 0.0001 118.10 118.10 7653.54 <0.0001 47.54 47.54 830.27 <0.0001
X21 1 1.07 1.07 3.61 0.1160 2.53 2.53 163.92 <0.0001 101.98 101.98 1781.23 <0.0001
X22 1 0.24 0.24 0.80 0.4108 0.14 0.14 9.17 0.0291 5.40 5.40 94.38 0.0002
X23 1 2.4E
003 2.4E
003 8.2E
003 0.9311 0.80 0.80 51.66 0.0008 20.61 20.61 360.05 <0.0001
X24 1 1.75 1.75 5.90 0.0595 14.23 14.23 921.98 <0.0001 0.71 0.71 12.41 0.0169
X25 1 7.80 7.80 26.31 0.0037 207.50 207.50 13446.78 <0.0001 51.11 51.11 892.63 <0.0001
X26 1 10.94 10.94 36.89 0.0017 0.63 0.63 41.15 0.0014 1.94 1.94 33.83 0.0021
Residual 5 1.48 0.30 0.077 0.015 0.29 0.057
Lack of fit 4 0.042 0.042 0.12 0.7502 0.020 0.020 1.44 0.2956 0.036 0.036 0.58 0.4881
Pure Error 1 1.44 0.36 0.057 0.014 0.25 0.062
Cor Total 32 565.14 2099.12 1448.01
1
Degree freedom.
2
Sum of square.
3
Mean square.

fund in the AC-MOF-5 spectrum. However, this band interestingly

disappeared in the spectrum of the AC-MOF-5 and probably is
related to the oxygen binding to AC functional groups with the
open metal sites of MOF-5.

3.2. Analysis of ternary solutions by derivative spectrophotometry

Absorbance spectra of single solutions of FG, EY and QY as well

Fig. 6. The experimental data versus the predicted data for all dyes.
while, server overall of carbon were overlapped with MOF-5 that
shows strongly support successful preparation of AC-MOF-5
nanocomposites.
FTIR spectra of AC, MOF-5 and AC-MOF-5 in the range of 500–
3700 cm
1 (Fig. 3d) reveal the large broad band appeared over
the range of 3000–3400 cm
1 that is attributed to the O–H bond
stretching of surface active carbon, while the peaks around 1100
and 1600 cm
1 may be due to vibrational and bending modes of
H–O–H, respectively 48. In MOF-5 FTIR spectrum, the peaks at
1648, 1640 and 1481 cm
1 are correspond to the C@O symmetric
and asymmetric modes. In the spectra of AC-MOF-5, the bands
around 1100 cm
1 is assigned to C–O stretching vibrations and also
as their binary solution (Fig. 4a: all at 10.0 mg L
1) indicate the
spectra overlap between them, which makes it difficult to accu-
rately determine the concentration of dyes at their respective
wavelengths. This limitation can be simply resolved by derivative
spectrophotometry, while, the AC-MOF-5 as new adsorbent in dif-
ferent rang can be efficiency removal of these dyes in short time
(Fig. 4a).
First order derivative spectra of FG, EY and QY in single and
ternary solutions were obtained and shown in Fig. 4b. Then, for
each dye, the proper wavelength that which the first order deriva-
tive is zero was found. Thus, the first order derivative spectra of the
ternary solution at any of these wavelengths would correspond to
other dyes. The wavelength 620 nm, which the first order deriva-
tive of EY and QY spectra is zero (Fig. 4b), was typically used to
depict a calibration curve (Fig. 5a) for FG quantification. In this
case, the value of correlation coefficient (R2) is used to justify the
efficiency and suitability of each wavelength. Also, as shown in
Fig. 5b were found that at 483 nm the first order derivative of FG
and QY spectra is zero, that revealed at this wavelength, the
depicted calibration curve is usable for EY monitoring (Fig. 5b).
As seen, reveal that at 421 nm the first order derivative of FG
 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82 77

Train
10 0 Best

Mean Squared Error (mse)

10 -2

10 -4

10 -6

10 -8

10 -10

10 -12

0 5 10 15 20
Epochs

Fig. 7. The MSE versus epochs of the best neural network.

Fig. 8. A scatter plot of the ANN predicted versus experimental data of FG (a), EY (b) Fig. 9. the experimental data versus the predicted data of normalized removal
and QY (c) dyes. obtained with PLS models, (a) FG, EY (b) and QY (c).
78 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82

Table 3
Dependence among neuron number at hidden layer, MSE and R2.

Number of neurons Testing set Training set

2
MSE R RMSE MSE R2 RMSE

12
1 0.1039 0.1878 0.0806 1.85  10 0.9045 1.53  10
07
2 0.1033 0.2129 0.0803 2.67  10
12 0.9078 1.84  10
07
3 0.1028 0.3120 0.0801 4.93  10
10 0.9012 2.50  10
06
4 0.1009 0.3800 0.0794 7.62  10
10 0.9345 3.11  10
06
5 0.0990 0.4920 0.0786 2.32  10
7 0.9345 5.42  10
05
6 0.0964 0.5278 0.0776 2.40  10
15 0.8902 5.51  10
9
7 0.0923 0.5398 0.0759 2.95  10
9 0.9225 6.11  10
06
8 0.0404 0.6118 0.0502 3.03  10
11 0.9423 6.20  10
07
9 0.0336 0.6974 0.0458 3.62  10
07 0.9427 6.77  10
05
10 0.0301 0.7806 0.0434 0.3235 0.9364 0.0640
11 0.0166 0.8901 0.0322 6.15  10
13 0.9780 8.82  10
08
12 0.0905 0.7625 0.0752 0.0394 0.9698 0.0223
13 0.0867 0.7602 0.0736 0.0142 0.9563 0.0134
14 0.0765 0.6253 0.0691 0.0097 0.9174 0.0111

⁄Bold show the best model

Table 4
Comparison of MSE and R2 obtained using the PLS and ANN models.

Model Testing set Training set

MSE R2 RMSE MSE R2 RMSE
ANN 0.0322 0.8901 0.0166 8.82E
08 0.9780 6.15E
13
PLS 0.946379 0.500324 0.11159 0.171318 0.588084 0.088245

and EY spectra is zero, therefore, at this wavelength, the depicted
calibration curve is usable for QY monitoring (Fig. 5c).
3.3. Analysis of CCD
To obtain the most important effects and interactions of vari-
ables, analysis of variance was calculated using a STATICTICA 10
(Table 2). The model F-value 70.38, 5038.02 and 936.49 and very
low of p-value (<0.0001) implied that the model for removal of
FG, EY and QY, respectively, shows the significance of model. More-
over, the p-value of terms were less than 0.05 indicating their sig-
nificance of terms in the polynomial equation within 95%
confidence interval. The lack of fit F-value 0.7502, 0.2956 and
0.4881 of this model for removal of FG, EY and QY, respectively,
implies the lack of fit is not significant relative to the pure error,
that not-significant lack of fit is good and model is a fit. Also, con-
firms the suitability of full quadratic model for predicting the real
behavior of preconcentration process with the values of 0.9974, 1.0
and 0.9998 for determination coefficient R2 of FG, EY and QY,
respectively indicates that this model is the most appropriate for
predicting the performance of FG, EY and QY adsorption on AC-
MOF-5. The Adeq precisions ratio of 33.886, 321.608 and 130.439
for FG, EY and QY, respectively, indicates that signal is sufficient
to model, data analysis gave a semi-empirical expression of follow-
ing equations for removal of dyes under study:
R%FG ¼ þ96:99 þ 0:61X1
0:84X2
1:50X3 þ 0:50X4
þ 2:00X5
1:69X6
0:94X1 X4
4:88X2 X3
þ 0:56X2 X4 þ 0:60X2 X5
0:65X2 X6 þ 0:47X3 X5

2:56X5 X6
0:51X25
0:60X26 ð6Þ

R%EY ¼ þ97:13 þ 1:34X1 þ 1:29X2
1:12X3 þ 2:83X4

þ 9:20X5 þ 1:16X6
2:65X1 X2
1:36X1 X3
þ 4:40X1 X4 þ 3:50X1 X5
1:67X1 X6
2:38X2 X3

1:23X2 X4
0:57X2 X5
2:66X2 X6
0:53X3 X4

1:86X3 X5 þ 0:45X3 X6 þ 1:75X4 X5
2:00X4 X6

2:72X5 X6
0:29X21 þ 0:069X22 þ 0:16X23
0:69X24

2:62X25 þ 0:15X26 ð7Þ
Fig. 10. Response surface plots.
 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82
R%QY ¼ þ91:38 þ 6:36X1
0:84X2
0:26X3 þ 1:38X4
þ 6:94X5 þ 3:82X6
1:36X1 X2
0:22X1 X3
þ 4:46X1 X4 þ 1:60X1 X5
0:12X1 X6 þ 1:33X2 X3

1:36X2 X4 þ 1:50X2 X5
0:76X2 X6
0:50X3 X4
þ 0:79X3 X5 þ 0:43X3 X6 þ 6:90X4 X5
1:12X4 X6

1:72X5 X6
1:84X21 þ 0:42X22 þ 0:83X23 þ 0:15X24

1:302X25 þ 0:25X26 ð8Þ
Another convenient expression of Eqs. (6)–(8) was also
expressed by comparing simultaneous removal of FG, EY and QY
on AC-MOF-5 between experiment and model predicted values
(Fig. 6). According to this plots experimental values of removal%
versus those calculated from equations indicated a good fit
3.4. Analysis of AAN
The number of neurons in hidden layer was considered by train-
ing various ANN topologies and selecting the optimal one based on
maximization of R2 and minimization of MSE of the topology. The
MSE, root of MSE and R2 for training and testing sets are summa-
rized and indicated in Table 3. The optimal topology of the ANN
model was including 6.0 inputs, one hidden layer with 11 neurons
and one output layer 3 neurons. It can be seen from the Table 3
that the best ANN model could predict the percentage of FG, EY
and QY dyes removal with MSE of 0.0166 and 6.15  10
13, RMSE
of 0.0322 and 8.82  10
08 and R2 of 0.8901and 0.9780 for testing
and training, respectively. Fig. 7 presents the assessment of the
MSE against the number of epochs for the optimal ANN model.
As seen, almost after 23 iterations, the MSE reached a minimum
level and increasing more epochs does not decrease the MSE.
Fig. 8 displays the goodness of fit between the forecasted values
of normalized removal of data in the testing data sets using the
ANN model against experimental data.
3.5. Analysis of PLS
PLS approach is used to study the presence of linear relationship
between normalized inputs and removal percentage of dyes under-
study. PLS of normalized removal values for 27 data in the training
set was achieved using of the six inputs and the following equa-
tions were obtained:
Y1 ¼ 0:5812 þ 0:0433X 1
0:2661X 2
0:2427X 3 þ 0:0710X 4
þ 0:3130X 5 þ 0:3761X 6 ð9Þ
Y2 ¼ 0:2164
0:0186X 1 þ 0:0827X 2
0:1228X 3
þ 0:1034X 4 þ 0:4145X 5 þ 0:3870X 6 ð10Þ
Y3 ¼ 0:1821 þ 0:2154X 1
0:1860X 2
0:0637X 3
þ 0:0730X 4 þ 0:2907X 5 þ 0:4384X 6 ð11Þ
where Y1, Y2, Y3 normalized removal (%) for R% FG, R% EY and R% QY
dye, X1, X2, X3 are concentration of FG, EY and QY dyes (mg/L) and
X4, X5, X6 are the pH, AC-MOF-5 dosage (g) and the sonication time
(min) respectively. Finally, the above models were applied to pre-
dict the actual removal percentage of experiments concern to test-
ing sets. Fig. 9a–c show the simulated values of normalized removal
of data in the testing sets using the PLS models and their plotting
versus normalized experimental data for FG, EY and QY respec-
tively. Table 4 compares the results acquired by the ANN and the
PLS models. The results illustrate that the ANN output is better than
the PLS model.
79
3.6. Analysis of CCD combined with desirability function
By STATISTICAL 10.0 software, the desirability function was
applied to optimize the variables including AC-MOF-5 mass, soni-
cation time, initial dyes concentration and pH value. The mini-
mum, middle and maximum values of desirability were
configured as 0.0, 0.5 and 1.0, respectively. The value closer to
1.0 means that the corresponding operating condition is optimum.
Optimized values were found 7.06, 5.68, 7.59 and 5.04 mg L
1,
0.02 g and 2.55 min for pH, FG, EY and QY concentration, adsorbent
dosage and sonication time, respectively. Under this conditions
removal percentage were obtained 98.1%, 98.1% and 91.91% for
FG, EY and QY, respectively.
3.7. Response surface plots
Typically, the effect of initial solution pH on R% FG was investi-
gated (Fig. 10a). As seen, at higher pH, the adsorbent surface will be
more negatively charged and thus electrostatic repulsion decreases
the migration of FG dye to the AC-MOF-5 surface. Also, this result
can be explained based on preliminary transfer of FG dyes mole-
cules to the external surface of AC-MOF-5. At lower pH, due to pro-
tonation of AC-MOF-5 the mass transfer increases for FG as anionic
dye and thus the R% FG was increases.
Typically, the effect of AC-MOF-5 mass on R% EY was investi-
gated (Fig. 10b). It was observed that the R% EY rapidly increased
with the increasing AC-MOF-5 mass until reaching an equilibrium
value after 0.025 g, which corresponds to 95% of the initial EY dye
adsorbed onto AC-MOF-5. An increase in R% EY may be concluded
due to the increase in availability of more adsorption sites of AC-
MOF-5. The slow slope in increasing of R% EY may be due to particle
aggregation, resulting from high adsorbent mass. This would lead
to a decrease in total surface area of the AC-MOF-5 and an increase
in diffusional path length.
Typically, the effect of initial concentration of EY on R% FG was
investigated (Fig. 10a). The R% FG at different concentrations is
rapid in the initial stages and gradually decreases with the pro-
gress of adsorption, until equilibrium. The R% FG was faster at the
beginning, due to the higher availability of active sites on the AC-
MOF-5. However, as time passes at higher concentration of EY
dye, these active sites were gradually occupied by the EY dye mole-
cules and a decrease in the adsorptive sites for the residual EY dye
molecules in the solution was observed.
Typically, the effect of sonication time on R% EY (Fig. 10b) show
that great amount of EY dye removal takes place in the first 3 min
and equilibrium reached within 4.0 min. Beyond equilibrium time,
the removal percentage do not change significantly. This is mainly
because of the fact that at the initial stage of adsorption the high
number of vacant surface sites is good and reactive sites for the
acceleration of EY dye onto the AC-MOF-5 following well disper-
sion of AC-MOF-5 into solution by ultrasonic power. Subsequently,
due to saturation of some reactive sites and possible repulsive
force between EY dye and bulk non-retained dye, the removal per-
centages significantly decrease or has slow enhance.
3.8. Kinetic study
The kinetic parameters are helpful for the prediction of adsorp-
tion rate and give important information for designing and model-
ing the adsorption processes. Thus, the kinetics of understudy dyes
adsorption onto AC-MOF-5 was studied by applying pseudo-first-
order, pseudo-second-order, Elovich and intraparticle diffusion
kinetic models (Table 5) [2,43]. The consistency between the
experimental and model predicted data was verified by the corre-
lation coefficients (R21). The values closer to 1 indicate more
applicability of the model to describe the kinetics of dyes under
80 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82

Table 5
Kinetic parameters.

Model Parameters Value of parameters

FG EY QY
pseudo-First-order kinetic k1(min
1) 65/1 867/1 411/0
qe (calc) (mg g
1) 230/42 425/38 711/30
R2 9234/0 9012/0 8976/0
pseudo-Second-order kinetic k2 (min
1) 0342/0 188/0 198/0
qe (calc) (mg g
1) 646/10 215/13 942/16
R2 999/0 999/0 999/0
Intraparticle diffusion Kdiff (mg g
1 min
1/2) 435/1 324/2 786/4
C (mg g
1) 423/8 234/12 654/8
R2 983/0 969/0 975/0
Elovich b (g mg
1) 432/0 728/0 678/0
a (mg g
1 min
1) 645/69 890/43 654/52
R2 9674/0 9326/0 9221/0
qe (exp) (mg g
1) 872/9 005/12 564/15

Table 6
Isotherm constant parameters and correlation coefficients calculated.

Isotherm Equation Parameters Value of parameters

FG EY QY
Langmuir qe = qmbCe/(1 + bCe) Qm (mg g
1) 230/21 242/20 621/18
Ka (L mg
1) 770/2 430/3 159/3
R2 9970/0 9875/0 989/0
Freundlich ln qe = ln KF + (1/n) ln Ce 1/n 511/0 4593/0 3488/0
KF (L mg
1) 317/3 312/3 276/3
R2 9655/0 9019/0 7643/0
Temkin qe = B1 ln KT + B1 ln Ce B1 600/4 223/4 327/3
KT (L mg
1) 12/28 438/38 329/3
R2 9917/0 9713/0 8957/0
Dubinin-Radushkevich (DR) ln qe = ln Qs–Be2 Qs (mg g
1) 566/16 803/9 674/15
B  10
7 33/3 03/3 88/1
E 873/3 890/3 157/5
R2 9825/0 9467/0 7269/0

Table 7
Comparison of the removal of FG, EY and QY dyes by other method and adsorbents.

Adsorbent Dye Sonication time (min) Adsorption capacity (mg g
1) References
Cu containing ionic liquid based nanoporous organosilica EY 14 286 [58]
Ag nanoparticles loaded AC EY 14 250 [58]
Ethylenediamine modified chitosan EY 500 294.1 [59]
Chitosan hydro beads EY 800 100 [60]
Chitosan nanoparticles EY 100 3.33 [61]
Polypyrrole-wood sawdust EY 30 3.148 [62]
Polyaniline-wood sawdust EY 30 3.186 [62]
AC-MOF-5 EY 2.55 20.24 Our work
Bottom Ash FG 1962.50 – [63]
De-Oiled Soya FG 10104.00 – [63]
AC-MOF-5 FG 2.55 21.23 Our work
Quinoline yellow–molqulary imprinted polymer QY 120 20.538 [64]
Quinoline yellow–non imprinted polymer QY 10 9.316 [64]
AC-MOF-5 QY 2.55 18.62 Our work

study adsorption onto AC-MOF-5. The judgment about the suitabil-
ity of these models is also based on relative difference between the
experimental and theoretical adsorption capacities [43]. The
pseudo-second-order kinetic model (Table 6) was shows correla-
tion coefficient of 0.999 that can efficiently predict experimental
data.
3.9. Isotherm study
tal data suggests that the dyes under study adsorption is limited to
monolayer coverage and the surface is relatively homogenous in
terms of functional groups with significant interaction with FG,
EY and QY molecules. Maximum adsorption capacity of AC-MOF-
5 were obtained to be 21.230, 20.242 and 18.621 mg g
1, for FG,
EY and QY, respectively, while, the Langmuir model was investi-
gated for adsorption of FG, EY and QY on MOF-5 and maximum
capacities were obtained to be 8.5, 5.7 and 4.8 mg g
1, respectively.

The experimental equilibrium data of adsorption of dyes under
study were fitted to conventional isotherms such as Langmuir, Fre-
undlich, Temkin and Dubinin–Radushkevich (D-R) with assump-
tions presented in Table 6 [54]. According to this table, the
suitability of Langmuir model for the interpretation of experimen-
3.10. Comparison of this method and adsorbent with other literature
A comparison of performance of previous adsorption capacities
of dyes under study adsorbed onto various adsorbents is presented
in Table 7. As seen, content (sonication) time for proposed method
 H. Askari et al. / Ultrasonics Sonochemistry 37 (2017) 71–82
in comparison with all of the method are preferable and superior
and shows satisfactory removal performance for dyes under study.
This observation indicates efficiency of ultrasound power in simul-
taneus removal of dyes under study is rapid uptake and quick
establishment of equilibrium. Also, observed that adsorption
capacity for AC-MOF-5 in comparison with all of the adsorbents
due to its high surface area and availability of more active adsorp-
tion sites are preferable and superior and shows satisfactory simul-
taneous removal performance 48–54.
4. Conclusion
In the present study, high-performance adsorbent activated
carbon-MOF-5 hybrid was successfully synthesized, characterized
using XRD, FT-IR and SEM and utilized for the ultrasonic assisted
removal of fast green, eosin Y and quinoline yellow dyes from
aqueous solution. Central composite design combined with desir-
ability of function shows the maximum uptake efficiency for com-
bination of ultrasound with adsorbent activated carbon-MOF-5
hybrid. A three layer ANN model with 1 to 14 neurons at hidden
layer and 3 neurons at output layer were employed and the results
indicated a network with 11 neurons in the hidden layer was the
best topology of the ANN during the training using Levenberg Mar-
quardt algorithm. The best ANN model could predict the percent-
age of FG, EY and QY dyes removal with MSE of 0.0166 and
6.15  10
13, RMSE of 0.0322 and 8.82  10
08 and R2 of
0.8901and 0.9780 for training and testing, respectively. And also
multivariate linear regression (PLS) model exhibit a coefficient of
determination (R2) of 0.588084 and MSE of 0.171318 for their
training, while the PLS model was also evaluated on the testing
set, the results show R2 of 0.500324, and MSE of 0.946379for FG,
EY and QY, respectively. The isotherm equilibrium data were best
described by the Langmuir model. In addition, the kinetics models
to describe experimental data points at various initial concentra-
tions of adsorbate shows that can be successfully fitted to the
pseudo-second-order kinetic model.
Acknowledgements
The authors thanks of the Research Council of the Yasouj
University and Iran National Science Foundation for financial sup-
porting this work.
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