J Inorg Organomet Polym
DOI 10.1007/s10904-016-0483-7
New Inorganic–Organic Hybrid Materials and Their Oxides
for Removal of Heavy Metal Ions: Response Surface Methodology
Approach
Elif Cerrahoğlu1 · Asgar Kayan1 · Deniz Bingöl1
Received: 14 October 2016 / Accepted: 8 December 2016
© Springer Science+Business Media New York 2016
Abstract In this paper, Cu(II), Fe(III), Pb(II), and Zn(II)
heavy metal ions were removed from their aqueous solu-
tions by using novel inorganic–organic hybrid materials,
Al-GPTS-H and Al-GPTS-NaOSiMe3-H (hybrid mate-
rial-1 and 2, respectively), and their oxides (calcined-1
and 2) as adsorbents. These ions removal by adsorption
was optimized by using response surface methodology
(RSM). Central composite design (CCD) method was used
in order to investigate the effects of initial pH, initial metal
concentration of solutions and adsorbent quantity on the
adsorption efficiency (R, %). As a result of the experiments
under optimum conditions, the maximum % R values were
obtained by hybrid material-1 for Fe(III) (99.89%) and by
calcined material-1 for Pb(II) (97.14%), respectively. These
quite high adsorption efficiency values have shown that
these hybrid materials and their oxides are suitable to use
for heavy metal ions removal from aqueous solutions.
Keywords Inorganic–organic hybrid materials · Heavy
metal ions · Adsorption · Response surface methodology
1 Introduction
Since the progressing of industrial activity, heavy metal
pollution in environmental water has been increased. Heavy
Electronic supplementary material The online version of this
article (doi:10.1007/s10904-016-0483-7) contains supplementary
material, which is available to authorized users.
* Deniz Bingöl
denizbingol1@gmail.com; deniz.bingol@kocaeli.edu.tr
1
Department of Chemistry, Kocaeli University, 41380 Izmit,
Kocaeli, Turkey
metals are not biodegradable and there are some interac-
tions between these metals and living organisms [1, 2]. In
addition to their effects on environment, heavy metals such
as copper, lead, zinc, and iron can harm mental and central
nervous system, reproductive system, lungs, liver, kidneys,
and other vital organs [1, 3, 4]. Therefore, their decontami-
nation has become a major topic for the water treatments.
There are many traditional methods to remove the heavy
metals from aqueous solutions like adsorption, solid phase
extraction, ion exchange, liquid–liquid extraction, chemi-
cal precipitation, electrochemical treatment, redox reaction,
and etc. [5–10]. Between these methods, due to its cheap,
easy and efficient application, adsorption is the most pre-
ferred method among the ones counted above. A number
of adsorbent materials such as activated carbon, silica, zeo-
lites and some waste materials were used for the removal
of heavy metal ions from wastewater [11–17]. In addition
to these, new adsorbents have been investigated by scien-
tists recently, and the sol-gel process has been an especially
interesting and important field of study [18, 19]. Applica-
tion of these kinds of materials as ion-exchange resins and
adsorbents for the removal of heavy metal ions from waste
water and oil have become increasingly popular because
of their mechanical attributes, thermal stability, and high
specificity to organic functional groups [20–22].
Response surface methodology, RSM, is a statistical
method based on the multivariate non-linear model that
consists of designing experiments to provide adequate and
reliable measurements of the response, developing a math-
ematical model having the best fit to the data obtained
from the experimental design, and determining the opti-
mal value of the independent variables that produces a
maximum or minimum response [23]. The techniques are
useful if a response is affected by various variables and
the objective is to optimize this response that is generally
13
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very economical. That is, they offer a large amount of use-
ful information from a small number of experiments. The
sequential single-factor-at-a-time approach requires all fac-
tors but one to be held constant while a univariate search
is carried out on the factor of interest [24, 25]. The weak-
ness of the single-factor-at-a-time approach is that it does
not include interactions between the various factors. This
means that the influence of both pH and temperature are
not independent. For example, the optimum pH at 40 °C is
different from that at 60 °C [26]. The least squares method
is used to estimate the parameters in the approximating
polynomials. Central composite design (CCD) is very use-
ful for obtaining data that can be used to fit the second-
order polynomial models. These designs can often be used
to rapidly optimize an analytical method, especially if the
number of factors is not large. The response surface analy-
sis is then performed using the fitted surface, if the fitted
surface is approximately equivalent to analysis of the actual
system [24, 25].
The main purpose of this paper is to remove Cu(II),
Fe(III), Pb(II), and Zn(II) ions from aqueous solution by
using novel inorganic–organic hybrid materials and their
oxides according to the statistically designed experiments.
CCD method was used to estimate the effects of initial pH,
initial metal concentration of solutions, and the adsorbent
quantity on the adsorption due to its advantages such as
the relative low cost, a reduced number of experiments,
increased possibilities to evaluate interactions among the
variables, and to provide more coverage [27].
2 Materials and Instruments
2.1 Materials
The metal ions solutions were prepared from their nitrate
salts (Merck). 0.1 or 0.01 M hydrochloric acid and sodium
hydroxide solutions were used to calibrate the pH value
of solutions. Aluminum sec-butoxide (97%, Alfa Aesar),
3-glycidyloxypropyltrimethoxysilane (97%, Alfa Aesar),
sodium trimethylsilanolate (95%, Aldrich), and n-butanol
(99%, Fluka) were used as received. All the chemicals were
in analytical grade.
2.2 Instruments
Concentrations of metal in the aqueous phase were deter-
mined by flame atomic absorption spectrometry (FAAS)
(Perkin Elmer AAnalyst 800 model) at the appropriate
wavelength for the tested metals, fitted with a deuterium
arc background corrector. The pH-measurements of begin-
ning and resulting metal ions solutions were measured
by Hanna pH 211 model pH meter and it was calibrated
13
J Inorg Organomet Polym
against standard buffer solutions of pH 4.0 and 7.0. Several
model magnetic stirrers were also used for adsorption pro-
cess. Protherm model ash furnace was used to calcine the
inorganic–organic hybrid materials.
2.3 Preparation of Inorganic–Organic Hybrid
Materials
Inorganic–organic hybrid materials Al(OBus)3-GPTS-
Hydrolyzate (Al-GPTS-H) and Al(OBus)3-GPTS-NaO-
SiMe3-Hydrolyzate (Al-GPTS-NaOSiMe3-H) were pre-
pared and characterized as in literature and their structure
shown at Fig. 1 [18]. These hybrid materials were cal-
cined at 1100 °C in a furnace and they were characterized
by XRD and FTIR spectroscopy. FTIR spectra of cal-
cined materials showed no organic groups remained after
calcinations.
2.4 Adsorption process
Stock metal ion solutions (1000 mg L−1) of Cu(II), Fe(III),
Pb(II), and Zn(II) were prepared in deionized water. Two
different synthesized inorganic–organic hybrid materi-
als and their oxides were used to determine the maximum
removals of Cu(II), Fe(III), Pb(II), and Zn(II) ions by basic
batch methods considering parameters of pH, contact time,
adsorbent mass, and initial metal concentration.
Batch conditions; a known amount of adsorbent was
stirred with 25 mL of the different metal ion concentra-
tions and different pH values of metal ions in 50 mL flask
at room temperature. After equilibrium time the adsorbent
was filtered with filter paper. Heavy metal ion concentra-
tions in the filtrate solution samples were determined by
FAAS.
Maximum adsorption capacity, qe (mg g−1), was calcu-
lated by using the following Eq. (1).
) V
(
qe = C0 − Ce × (1)
m
where, C0 and Ce are the initial and equilibrium concentra-
tions of adsorbed metal ions (mg L−1), V is the volume of
the metal ion solution (L), and m is the amount of adsor-
bent (g).
And removal percentage, R (%), was calculated by using
the following Eq. (2).
(C0 − Ce )
R(%) = × 100 (2)
C0
Firstly, the adsorption experiments were performed
to determine the effect of contact time in the range of
5–150 min. The initial pH of the metal ion solutions for
Cu(II) and Zn(II) were studied between 2.0 and 6.0; for
Pb(II) and Fe(III) were studied between 2.0 and 5.5. pH
J Inorg Organomet Polym
Fig. 1 Synthesis of inorganic–organic hybrid materials and their oxides
values were adjusted with 0.1 or 0.01 mol L−1 HCl and
NaOH solution before adding the adsorbents. The influence
of initial adsorbent amounts varying between 1.8 and 5.0 mg
and the influence of initial metal ion concentrations for each
metal ion were investigated between 28 and 100 mg L−1.
2.5 Response Surface Method
Response surface method (RSM) was applied in order to
determine the optimum experiment conditions of the adsorp-
tion process and experiments were performed by following
the determined plan by CDD. The effects of the experimental
parameters chosen as independent variables, including pH of
the solutions, initial concentration of solutions and quantity
of adsorbent, were investigated using CCD. Selection of these
factor levels were based on some preliminary experiments.
For the response surface methodology (RSM), a second-
order polynomial model, Eq. (3), is usually performed to
estimate the effects of various factors on a response based
on experimental results from experimental design.
k k k The effect of contact time on the adsorption is shown
∑ ∑ ∑
y = 𝛽o + 𝛽i xi + 𝛽ii xi2 + 𝛽ij xi xj + 𝜀
i=1 i=1 1≤i≤j
(3)
where y is the predicted response, xi and xj are coded vari-
ables, the βo is the constant, the βi is the linear coefficient,
the βii is the quadratic coefficient, and the βij is the interac-
tive coefficient, ε is a random error [22].
Central composite design was used to investigate the
factors affecting the adsorbed amount of Cu(II), Fe(III),
Pb(II) and Zn(II) ions on novel inorganic–organic hybrid
materials and their oxides.
In this work, the response surface analysis was employed
in order to achieve the highest amount of the metal ions
adsorbed by the four adsorbents. The experimental sets
were carried out according to Table 1 for all metal ions
given the coded and actual values of the three independent
factors.
3 Results and Discussions
3.1 Effect of Contact Time
in Fig. 2. All these experiments were performed for
each metal ion solution and for each adsorbent. In these
13
13
Table 1 Experimental data set for CCD
Factors Symbols Levels of factors

−α (−1.68) −1 0 +1 +α (+1.68)
pH X1 2 3 4 5 6
Co X2 10 28 55 82 100
(mg/L)
m (g) X3 0.0010 0.0018 0.0030 0.0042 0.0050
Run Actual and coded levels of vari- Removal (%)
ables
pH Co (mg/L) m (g) Hybrid material-1a Hybrid material-2 Calcined material-1 Calcined material-2
Cu Fe Pb Zn Cu Fe Pb Zn Cu Fe Pb Zn Cu Fe Pb Zn

1 −1 −1 −1 2.11 – – 7.86 31.36 12.29 27.40 42.50 27.82 42.71 55.07 15.36 38.60 20.82 36.32 40.92
2 +1 −1 −1 21.21 1.39 31.47 −20.4 69.06 98.71 95.84 81.92 69.93 96.29 88.53 47.57 59.07 98.56 77.32 79.78
3 −1 +1 −1 14.76 58.59 12.72 10.24 18.82 24.49 36.99 31.58 30.76 41.77 27.21 4.15 34.02 16.14 32.29 27.31
4 +1 +1 −1 21.76 57.52 21.04 24.02 42.08 86.14 69.96 58.84 47.21 92.96 73.51 25.98 43.45 96.61 73.75 51.82
5 −1 −1 +1 5.57 – – – 26.41 25.60 49.77 40.57 32.46 47.50 44.50 1.57 46.82 17.64 45.25 37.07
6 +1 −1 +1 14.34 – 36.69 – 80.32 97.25 98.58 66.46 70.04 95.58 88.12 43.71 64.14 95.29 78.40 60.46
7 −1 +1 +1 17.83 53.65 −7.07 0.73 27.85 27.85 43.64 34.15 30.37 41.59 32.39 6.34 31.80 16.68 39.21 25.36
8 +1 +1 +1 16.68 55.63 21.16 24.39 56.89 99.16 85.46 60.12 53.25 96.79 70.58 29.39 49.62 97.31 62.97 51.03
9 −1.68 0 0 20.11 – – – 3.48 22.73 11.71 34.04 6.53 37.94 7.63 2.90 6.41 61.51 12.07 15.61
10 +1.68 0 0 20.91 – 30.68 24.73 62.74 98.93 93.05 77.02 66.03 98.69 83.26 26.36 56.03 98.76 74.74 71.41
11 0 −1.68 0 17.90 8.27 15.78 47.4 67.18 87.84 99.57 89.77 87.10 98.78 89.84 46.10 79.99 98.53 76.12 84.76
12 0 +1.68 0 18.58 5.62 15.63 13.3 42.61 55.10 81.69 29.65 43.00 43.94 31.20 1.20 38.64 45.70 53.60 28.70
13 0 0 −1.68 11.82 5.16 7.53 – 50.21 38.31 83.05 64.13 45.98 55.05 72.43 18.55 44.80 48.56 72.16 57.54
14 0 0 +1.68 11.81 4.78 6.33 – 63.19 98.29 98.51 79.73 51.09 78.67 77.41 20.90 40.27 98.76 73.52 70.81
15 0 0 0 12.03 4.93 5.35 – 53.51 98.44 73.42 76.07 49.81 92.62 68.80 17.55 42.81 98.23 66.69 72.21
16 0 0 0 11.96 4.89 6.62 – 53.88 98.50 73.05 76.45 50.12 91.46 67.07 16.45 44.05 98.20 66.67 72.50
17 0 0 0 11.89 4.75 7.02 – 53.18 98.35 73.52 75.99 50.40 93.13 66.63 17.15 44.27 98.22 66.58 71.60
18 0 0 0 11.13 3.53 6.91 – 52.84 98.41 73.59 76.51 51.03 92.27 66.69 17.09 44.48 98.47 66.29 71.81
19 0 0 0 11.27 4.69 6.33 – 52.72 98.46 73.50 75.89 50.76 93.34 66.23 16.64 45.07 97.28 67.11 72.34
20 0 0 0 10.88 3.4 6.87 – 52.69 98.41 73.50 75.85 50.43 93.46 66.49 17.28 44.50 98.61 67.15 72.59
a
Hybrid material-1 was not evaluated since the meaningful results were not obtained
J Inorg Organomet Polym
J Inorg Organomet Polym

Fig. 2 Effect of contact time on the adsorption of metal ions on a Al-GPTS-H, b Al-GPTS-NaOSiMe3-H

Fig. 3 XRD pattern of calcined

Al-GPTS-NaOSiMe3-H

experiments, 2.5 mg adsorbent and metal ion solutions of
50 mg L−1 were mixed in 250 mL volume in actual pH val-
ues. Equilibrium adsorption time was indicated 120 min for
each metal ion and each adsorbent. According to results,
subsequent experiments were performed within 60 min.
3.2 Characterization of Calcined Materials
It was reported in the previous paper that hydrolyzed
materials Al-GPTS-H and Al-GPTS-NaOSiMe3-H were
amorphous [18]. These hybrid materials were calcined
at 1100 °C and they were used for the removal of heavy
metal ions from aqueous solutions. Therefore it is impor-
tant to elucidate the crystal structures of these calcined
materials. The X-ray analysis results have yielded qualita-
tive information about the formation of phase Al2O3.SiO2
and NaAlSiO4 obtained from calcined Al-GPTS-H and
Al-GPTS-NaOSiMe3-H, respectively. Figure 3 shows the
XRD diffraction patterns of NaAlSiO4. All the diffraction
peaks of the calcined material Al-GPTS-NaOSiMe3-H can
be assigned to pure hexagonal phase of NaAlSiO4. This
hexagonal phase of NaAlSiO4 seems to be identical with

Table 2 The second-order

polynomial models (as coded
values)
Calcined material-1
2
Cu (%) = 49.070 + 16.040 pH − 8.482 C0 + 1.388 m − 5.811 pH2 + 4.545 C20 − 5.203 pH m
Fe (%) = 92.702 + 22.715 pH − 7.410 C0 + 3.475 m − 8.222 pH2 − 7.145 C0 − 8.736 m2
2
Pb (%) = 65.186 + 21.144 pH − 12.532 C0 − 0.026 m − 7.394 pH
2
+ 3.027 m2
Zn (%) = 17.619 + 11.619 pH − 8.630 C0 − 0.593 m + 2.801 C0 − 3.684 pH C0
Hybrid material-2
Cu (%) = 53.453 + 17.836 pH − 528 C0 + 3.807 m − 7.913 pH2 − 4.912 pH C02+ 2.747 pH m + 2.192 C0 m
Fe (%) = 98.621 + 30.693 pH − 3.753 C0 + 9.454 m − 14.563 pH2 − 10.801 C 2
0 − 11.922 m
2
2 C 2
Pb (%) = 73.907 + 24.078 pH − 4.803 C0 + 5.364 m − 10.556 pH + 2.967 02+ 3.021 m − 5.307 pH C0
Zn (%) = 76.433 + 13.972 pH − 10.829 C0 + 0.928 m − 9.295 pH2 − 7.816 C0 − 3.497 m2
Calcined material-2
2
Cu (%) = 43.788 + 10.873 pH − 8.734 C0 + 0.704 m − 4.167 pH22 + 5.766 C0
Fe (%) = 90.664 + 27.762 pH − 6.914 C0 + 5.800 m − 11.736 C0 − 11.190 m2
Pb (%) = 66.578 + 17.923 pH − 4.902 C0 + 0.618 m − 9.092 pH2 − 3.194 pH m2
Zn (%) = 72.079 + 15.104 pH − 11.495 C0 − 0.263 m − 11.509 pH2 − 6.834 C0 − 4.202 m2

13
 J Inorg Organomet Polym

literature data [ICDD # 035–0424] [28]. No peaks of any

77.70 ± 2.49
81.90 ± 1.32

76.57 ± 2.72
76.70 ± 2.10
other phases or impurities were observed from the XRD
diffraction pattern of NaAlSiO4, indicating that pure NaAl-

98.11

98.13
Zn
SiO4 crystalline phase could be obtained using the present
synthesis route.

92.91 ± 10.07
89.81 ± 2.27
90.36 ± 0.85

90.43 ± 0.17
XRD diffraction pattern of the other material calcined
from Al-GPTS-H has shown an excellent match to the
99.50

88.38
report published for Al2O3.SiO2 spinel phase [29].
Fe

99.89 ± 0.03

83.50 ± 2.65
86.24 ± 0.58
3.3 Experimental Design
110 ± 0.99
99.83

97.82 The adsorption experiments were carried out in solutions

Pb

containing Cu(II), Fe(III), Pb(II), and Zn(II) ions using

CCD. The regression models for metal ions removal by
83.41 ± 0.48
86.71 ± 0.48

80.93 ± 1.43
82.97 ± 1.19
Material-2

Al-GPTS-H, Al-GPTS-NaOSiMe3-H and their oxides are

99.93

98.89

respectively given in the following equations in Table 2.

Cu

To evaluation of fitted mathematical model, the analysis of

variance (ANOVA) in the confidence interval of 95% was
55.34 ± 2.92
52.50 ± 2.30

used. The statistical significance of models have presented

significant effect (p value <0.05). Then, a quadratic model
94.95
Zn

was fitted to data to describe the experimental region [30].

–
–
–

From ANOVA analysis, the effects that significantly affect

98.39 ± 0.49
97.14 ± 0.20

the response are pH, initial metal concentration, and adsor-

bent mass had a p value less than 0.05.
99.96

To analyze the experiment, we used a second-order

Fe

–
–
–

polynomial models for the data (Table 2). pH was found to

98.96 ± 2.74
96.80 ± 0.90

be an important factor in hybrid and calcined materials for

nearly all metal. The sense of the effect was always posi-
98.48

tive, meaning that higher pH favored higher metal removal.

Pb

–
–
–

In other words, changing levels of factors pH and adsorbent

94.04 ± 0.36

mass from their low levels to the corresponding high lev-

93.1 ± 1.73
Material-1

els, leads to an increased metal ions removal. The adsor-

98.98

bent mass had a relatively minor effect upon metal ions

Cu

–
–
–

removal. Important square interactions of factors were

Experimental removal (%) ± s (N = 3)

Experimental removal (%) ± s (N = 3)

also identified and quantified. Note that, pH and adsorbent

mass (hybrid material) have generally the largest positive
main effect (i.e., used alone) in the increasing of the metal
ions removal. However, because C0 is negative, it produces
Predicted removal (%) ± s

Predicted removal (%) ± s

Table 3 Results of some optimum adsorption condition

lower metal ions removal than would be expected by using

any of the components alone. This means that the influ-
ence of both pH and adsorbent mass are not independent
[31]. These models are a very good representation of metal
removal response. The adjusted R2 values (Table 3) show
that the model has a good fit for the data [30].
The shape of the fitted overall response can be best
summarized in graphs and can generate response sur-
Co: 10 mg/L

Co: 10 mg/L
m: 0.0030 g

m: 0.0030 g
R2(adj) (%)

R2(adj) (%)

face plots for the fitted model (Figs. 4, 5, 6, 7). The sur-
pH: 5

pH: 5

face plots of the response (%) versus pH, initial metal

ions concentration (C0) and adsorbent mass (m) for the
optimization of metal ions adsorption on adsorbents are
CALCINED

shown in Figs. 4, 5, 6 and 7. For all metal ions in adsor-

HYBRID

bents, the results show that the ideal adsorbent mass

was approximately center point (~3.0 mg) and the ideal

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Fig. 4 The surface plots of Hybrid material-2 for Cu(II)

hybrid material-2 for Cu(II)

100 100
R (%) 70 R (%) 70
40 40
100 0.005
0 50 Co (mg/L) 0 0.003
2 2 m (g)
4 6 0 4 6 0.001
pH pH

Hold Values
100
pH 4
R (%) 70
40 Co (mg/L) 55
0.005
0 0.003 m (g) 0.003
0 m (g)
50 0.001
Co (mg/L) 100

Fig. 5 The surface plots of Hybrid material-2 for Fe(III)

hybrid material-2 for Fe(III)

100 100
70
R (%) 40 70
R (%) 40
0 100 0 0.005
50 Co (mg/L) 0.003
2 2 m (g)
4 6 0 4 6 0.001
pH pH

Hold Values
100
R (%) 70 pH 4
40 Co (mg/L) 55
0.005
0 0.003 m (g) 0.003
0 m (g)
50 0.001
Co (mg/L) 100

pH was 5.0 for adsorption of Cu(II), Fe(III), and Pb(II),
and pH 6.0 for Zn(II). This justifies that low adsorbent
mass led to the highest metal removal. The metal ions
concentration that led to the highest metal ions removal
was at least 1.0 mg L−1; therefore the results were com-
promised because some of them were carried out at pH
5–6. In addition, it can be seen that the hybrid material-2
presented a higher metal ions removal for Cu(II), Pb(II),
Fe(III) and Zn(II) when compared with hybrid mate-
rial-1 adsorbent.
When response surface 3D plots were analyzed, it
appeared that there were differences in the removal effi-
ciency of metal ions. The differences in the removal
efficiency possibly resulted from the differences in the
radius, the charges of Cu(II), Zn(II), Pb(II), and Fe(III)
ions and the different porous structures of adsorbents
(BJH adsorption average pore with 35.196–42.874 nm)
[18]. For example, the heavy metal ions removal effi-
ciency appeared in the following order: Pb(II) > Fe(III)
> Cu(II) > Zn(II) for hybrid material-2. Since the ionic
radius of Zn(II) (0.74 Å) and Cu(II) (0.73 Å) are notice-
ably smaller than of Pb(II) (1.19 Å), they hydrate easier
than Pb(II) ion in the aqueous solutions. As a result,
Zn(II) and Cu(II) ions were more mobile in the bulk
solution and had a lesser tendency to adsorb on hybrid
material-2 [28]. The iron ion had higher tendency to
adsorb on hybrid material-2 because of its high charge
(3+) causing higher electro-static interactions between

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Fig. 6 The surface plots of Hybrid material-2 for Pb(II)

hybrid material-2 for Pb(II)

100 100
R (%) 70 R (%) 70
40 40
100 0.005
0 50 Co (mg/L) 0 0.003
2 2 m (g)
4 6 0 4 6 0.001
pH pH

Hold Values
100
R (%) 70 pH 4
40 0.005 Co (mg/L) 55
0 0.003 m (g) 0.003
0 m (g)
50 0.001
Co (mg/L) 100

Fig. 7 The surface plots of Hybrid material-2 for Zn(II)

hybrid material-2 for Zn(II)

100 100
R (%) 70 R (%) 70
40 40
0 100 0.005
50 Co (mg/L) 0 0.003
2 2 m (g)
4 6 0 4 6 0.001
pH pH

Hold Values
100 pH 4
R (%) 70 Co (mg/L) 55
40
0.005
0 0.003
m (g) 0.003
0 m (g)
50 0.001
Co (mg/L) 100

iron ions and surface of hybrid material-2. The other
adsorbents; hybrid material-1, calcined-1, and cal-
cined-2 had also similar behaviors.
By fitting the empirical models, optimum adsorption
conditions of Cu(II), Fe(III), Pb(II), and Zn(II) metal
ions as predicted-experimental removal values can be
achieved under these conditions (Table 4).
4 Conclusion
In this study, statistically significant mathematical models
describing the effects of pH, initial metal concentrations,
and the adsorbent quantity in the metal ions removal
using novel inorganic–organic hybrid materials and their
oxides were derived. RSM was applied for each metal ion
to optimize metal ions removal properties of these mate-
rials. RSM enables to estimate all linear and quadratic
effects and 2-factor interactions, and requires less runs
compared to conventional time-consuming experimen-
tal methods. Novel inorganic–organic hybrid materials
and their oxides were found to be potential adsorbents.
Since the experimental values and predicted values from
the model were quite compatible, CCD can be consid-
ered as a proven model for the removal of Cu(II), Fe(III),
Pb(II), and Zn(II) ions from aqueous solutions by novel

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Table 4 Results of some adsorption conditions as predicted and experimental metal ions removal values

Conditions Materials Metal ions R2(adj) Predicted removal (%) ± s Experimental removal
−1 (%) (%) ± s (N = 3)
pH C0 (mg L ) m (g)

6 30 0.0020 Calcined-1 Cu(II) 98.98 78.58 ± 1.74 80.45 ± 0.47

5.5 30 0.0010 Calcined-1 Pb(II) 98.48 100.44 ± 2.74 92.55 ± 0.34
5 10 0.0020 Calcined-1 Fe(III) 99.96 89.33 ± 0.49 87.79 ± 0.11
6 10 0.0010 Calcined-1 Zn(II) 94.95 71.01 ± 2.92 72.45 ± 0.25
6 10 0.0050 Hybrid-2 Cu(II) 99.96 95.60 ± 0.48 93.84 ± 1.50
6 10 0.0050 Hybrid-2 Pb(II) 99.83 97.90 ± 0.99 96.23 ± 0.32
5 50 0.0020 Hybrid-2 Fe(III) 99.50 98.59 ± 2.27 97.14 ± 0.44
5 35.5 0.0030 Hybrid-2 Zn(II) 98.11 85.24 ± 2.49 73.14 ± 0.66
6 10 0.0030 Calcined-2 Cu(II) 98.89 81.29 ± 1.43 83.20 ± 0.74
5.6 10 0.0010 Calcined-2 Pb(II) 99.83 88.67 ± 0.99 86.15 ± 1.09
5 10 0.0010 Calcined-2 Fe(III) 88.38 50.86 ± 10.06 51.69 ± 2.37
4.83 30 0.0027 Calcined-2 Zn(II) 98.11 81.62 ± 2.72 74.83 ± 0.53

inorganic–organic hybrid materials and their oxides
using batch adsorption method in a limited number of
experiments.
Acknowledgements This study was supported by the research foun-
dation of Kocaeli University, (Project No: 2014/17).
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