Journal of Inorganic and Organometallic Polymers and Materials

https://doi.org/10.1007/s10904-019-01384-w

Application of Mesoporous Silica Nanoparticles Modified

with Dibenzoylmethane as a Novel Composite for Efficient Removal
of Cd(II), Hg(II), and Cu(II) Ions from Aqueous Media
Magdi E. Khalifa1 · Ehab A. Abdelrahman2 · Mohamed M. Hassanien3 · Wesam A. Ibrahim1

Received: 7 September 2019 / Accepted: 9 November 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
In this paper, a novel composite was synthesized through the modification of mesoporous silica nanoparticles with diben-
zoylmethane and used for the removal of Cu(II), Hg(II), and Cd(II) ions from aqueous media. The structure of the novel
composite was identified using FT-IR, XRD, CHN, and SEM techniques. Kinetic studies elucidated the relevance of the
pseudo-second-order model for the removal of Cd(II) ions while the pseudo-first-order controlled the removal of Cu(II) or
Hg(II) ions. Also, equilibrium studies elucidated that the removal of Cd(II), Hg(II), or Cu(II) ions followed the Langmuir
isotherm. The synthesized composite possesses maximum adsorption capacity equals 35.37, 25.17, and 31.76 mg g−1 in the
case of Cd(II), Hg(II), and Cu(II) ions, respectively. The removal processes were chemisorption in nature and the % desorp-
tion of Cd(II), Hg(II), and Cu(II) ions was 99.12, 99.07, and 98.37%, respectively using 0.5 V/V% HCl: water as eluting
media. The regeneration of the composite is judged by noticing the % removal of metal ions or the adsorption capacity which
remained almost constant after five regeneration cycles.

Keywords Composite · Dibenzoylmethane · Mesoporous silica · Metal ions · Adsorption

1 Introduction problems such as gastrointestinal disorders, genetic disor-

ders, skin rash, headache, spermatic atrophy, fetal abnor-
Water pollution by heavy metal ions such as copper, mer- malities, miscarriages, brain dysfunction, lung irritation, eye
cury, and cadmium ions causes many risks to humans and irritation, vomiting, and diarrhea [15–18]. Also, exposure
aquatic life organisms. These pollutants enter the water to cadmium leads to many risks such as kidney damage,
resources in several ways such as leakage in sewage, metal- diarrhea, severe vomiting, stomach pain, reproductive dis-
containing pesticides, and pumping of chemicals or food orders sometimes associated with infertility, cancer, and
products in water without treatment [1–13]. In 1932, leak- central nervous system atrophy [19–21]. Besides, exposure
age in sewage occurred in Minamata city, Japan making the to copper leads to many diseases such as metal fever, nasal
water of this city suffers from high mercury content. Hence, irritation, eye irritation, headache, stomach pain, vomiting,
mercury was bioaccumulated in marine organisms such as diarrhea, kidney atrophy, liver atrophy, and low-level psy-
fishes. Thus, mercury poisoning cases were spread strongly chic ability [22–24]. Several methods were utilized for the
in 1952 [14]. Exposure to mercury leads to many health removal of these pollutants such as adsorption, chemical
precipitation, electrolysis, and membrane filtration [25–33].
The adsorption technique has numerous points of interest
* Ehab A. Abdelrahman compared with other methods, for example, high availabil-
[email protected]; [email protected] ity, low cost, and easy operation. Recently, mesoporous
1
Chemistry Department, Faculty of Science, Mansoura silica nanoparticles modified by some organic substances
University, Mansoura 35516, Egypt such as thioglycolic acid were applied for the removal of
2
Chemistry Department, Faculty of Science, Benha some pollutants such as Hg(II), Pb(II), and Cd(II) ions [29,
University, Benha 13518, Egypt 34–36]. Functional groups of the loaded organic materials
3
Chemistry Department, Faculty of Industrial Education, such as hydroxide and thiol groups form chelates with the
Beni-Suef University, Beni Suef 62511, Egypt targeted metal ions. Consequently, the uptake efficiency was

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 Journal of Inorganic and Organometallic Polymers and Materials

increased. Also, mesoporous silica nanoparticles are consid- with (3-aminopropyl)trimethoxysilane in 50 mL xylene for
ered good support for organic molecules because they have a 24 h. Finally, 2 g of the resulting product was refluxed for
remarkable higher surface area and uniform pore channels. 24 h with 25 mL ethanolic solution of dibenzoylmethane
In this paper, mesoporous silica nanoparticles modified by (0.36 mol ­L−1) in the presence of a few drops of sulfuric
dibenzoylmethane was synthesized as a novel composite for acid. After that, the product was filtered, washed with etha-
the removal of Cu(II), Hg(II), and Cd(II) ions from aqueous nol, and dried at 60 °C for 12 h.
media. Identification and elucidation of the structure of the
novel composite was ascertained based on the FT-IR, XRD, 2.3 General Procedure for the Removal of Cd(II),
CHN, and SEM measurements. Also, different impacts Hg(II), and Cu(II) Ions from Aqueous Media
affecting the removal efficiency such as contact time, pH,
concentration, amount of composite, temperature, desorp- In a polypropylene centrifuge tube, 100 mg of the synthe-
tion of the adsorbed ions, and reusability of the composite sized composite was added to 50 mL of 100 mg L ­ −1 Cd(II),
were studied. Besides, thermodynamic parameters (entropy, Hg(II), or Cu(II) metal solutions. The pH of the prepared
Gibbs free energy, and enthalpy), kinetic models (pseudo- solutions was adjusted during the experiments to 6.0 using
second-order and pseudo-first-order), and adsorption iso- 0.1 mol ­L−1 HCl or NaOH then the mixtures were shaken
therms (Freundlich and Langmuir) were investigated. at 300 rpm for 30 min at room temperature. The samples
were filtered to determine the concentration of Cd(II),
Hg(II) or Cu(II) ions which remained in the supernatant
2 Experimental by atomic absorption spectrophotometer. Alternatively,
desorption study was tested via stirring Cd(II), Hg(II),
2.1 Chemicals or Cu(II) loaded composite with 50 mL of 0.5 mol ­L−1
­Na4-EDTA or 0.5 (%V/V) different desorption media such as
The used chemicals are cetyltrimethylammonium bro- HCl:ethanol, HCl:methanol, HCl:chloroform, HCl:acetone,
mide (CTAB, C ­ 19H42BrN, Sigma-Aldrich), sodium silicate and HCl:water for 60 min. Reusability study was performed
nonahydrate ­(Na2SiO3·9H2O, Sigma-Aldrich), (3-amino- after using 0.5 V/V% HCl:water as desorption media each
propyl)trimethoxysilane (APTMS, C ­ 6H17NO3Si, Sigma- time as follows: 50 mL of 100 mg L ­ −1 Cd(II), Hg(II), or
Aldrich), ethanol (­ C2H6O, El-Gomhoria), dibenzoylmethane Cu(II) solutions optimized at pH equals 6 and 100 mg of
­(C15H12O2, Sigma-Aldrich), mercury(II) chloride ­(HgCl2, the regenerated composite was mixed together for 30 min.
Merck), copper(II) chloride dihydrate ­(CuCl2·2H2O, Merck), The adsorption efficiency was estimated up to five cycles of
cadmium(II) chloride ­(CdCl2, Sigma-Aldrich), hydrochlo- adsorption–desorption.
ric acid (HCl, EL-Nasr), ethylenediaminetetraacetic acid The % removal (% R) of Cd(II), Hg(II), or Cu(II) ions
tetrasodium salt dihydrate ­(Na4-EDTA, ­C10H16N2Na4O10, (%R) was estimated utilizing Eq. (1)
Sigma-Aldrich), sodium hydroxide (NaOH, El-Gomhoria),
potassium chloride (KCl, El-Gomhoria), cobalt(II) chlo- (1)
( )
%R = Ci − Ce 100∕Ci
ride hexahydrate (­ CoCl2.6H2O, Sigma-Aldrich), nickel(II)
chloride hexahydrate ­(NiCl2·6H2O, Sigma-Aldrich), zinc The adsorption capacity (Q, mg g−1) of the synthesized
(II) chloride ­(ZnCl2, Sigma-Aldrich), aluminum(III) chlo- composite was estimated utilizing Eq. (2).
ride hexahydrate (­AlCl3·6H2O, Sigma-Aldrich), lead(II)
(2)
( )
Q = Ci − Ce V∕m
chloride ­(PbCl2, Sigma-Aldrich), iron(III) chloride hexahy-
drate ­(FeCl3·6H2O, Sigma-Aldrich), sulfuric acid ­(H2SO4, The desorption ratio (% D) was estimated utilizing
EL-Nasr), methanol (­ CH3OH, El-Gomhoria), chloroform Eq. (3).
­(CHCl3, El-Gomhoria), and acetone (­ C3H6O, El-Gomhoria).

2.2 Modification of Mesoporous Silica (3)

( ) (( ) )
%D = 100 Cd Vd ∕ Ci − Ce V
Nanoparticles by Dibenzoylmethane
where, m (g) is the weight of the synthesized composite, V
SiO2/(3-aminopropyl)trimethoxysilane composite was syn- (L) is the volume of metal ions (Cd(II), Hg(II), or Cu(II))
thesized according to the procedure described by Kenawy solutions, ­Ce (mg ­L−1) is the concentration of metal ions
et al. [34]. Shortly sodium silicate nonahydrate was added (Cd(II), Hg(II), or Cu(II)) solutions at equilibrium, C
­ i (mg
−1
to an aqueous solution of CTAB with vigorous stirring. The ­L ) is the primary concentration of metal ions (Cd(II),
formed gelatinous substance was filtered, washed with water, Hg(II), or Cu(II)) solutions, ­Cd (mg L­ −1) is the concentra-
and then dried at 50 °C for 6 h. Then, the sample was cal- tion of metal ions (Cd(II), Hg(II), or Cu(II)) in the desorp-
cined at 550 °C for 6 h. The calcined silica was refluxed tion media, and ­Vd (L) is the volume of desorption media.

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Journal of Inorganic and Organometallic Polymers and Materials

Point of zero charge (­ pHPZC) of the synthesized compos- of Cd(II), Hg(II), or Cu(II) solutions was measured using
ite was estimated as follows: 50 mL of 0.01 mol L ­ −1 KCl an atomic absorption spectrophotometer (Shimadzu, model
solutions have different pH values (­ pHi 2–12) and 0.25 g of AA-7000F). The Cd(II), Hg(II), or Cu(II) solutions and
the synthesized composite were mixed together. Then, the the synthesized adsorbent were shaken using a mechanical
mixtures were shaken at 300 rpm for 12 h using a mechani- shaker (Burrell Corporation) at 300 rpm.
cal shaker. The filtrates were separated at 2500 rpm using a
centrifuge then the final pH values ­(pHf) were measured and
plotted against pH initial. The p­ Hpzc is the p­ Hf level where 3 Results and Discussion
a typical plateau was gotten [37]. The effect of interference
between each of the Cd(II), Hg(II), or Cu(II) metals ions 3.1 Characterization of the Modified Mesoporous
and interference metal ions such as Co(II), Ni(II), Fe(III), Silica by Dibenzoylmethane
Zn(II), Pb(II), and Al(III) were studied as follows: 0.1 g of
the fabricated composite was mixed together with 50 mL of Figure 1 represents the FT-IR spectra of the modified
metal ions (Cd(II), Hg(II), or Cu(II)) solution which con- mesoporous silica nanoparticles by dibenzoylmethane. The
tains Co(II), Ni(II), Fe(III), Zn(II), Pb(II), or Al(III) with bands located at 465, 805, and 1097 cm−1 were assigned
different concentrations (50, 80, and 100 mg ­L−1). to Si–O–Si bending vibration, Si–O–Si symmetric stretch-
ing vibration, and Si–O–Si asymmetric stretching vibra-
tion, respectively. Also, the bands at 1641, 3208, 3000,
2.4 Instrumentation and 3035 cm−1 are attributed to C=N stretching vibration
and/or adsorbed water bending vibration, adsorbed water
XRD pattern of the synthesized composite was measured on stretching vibration, aliphatic CH stretching vibration, and
XRD diffractometer (D8 advance Bruker) using ­CuKα X-ray aromatic CH stretching vibration, respectively. Besides, the
radiation (λ = 1.54 Å) under working conditions of 40 mA presence of multiple bands in the region 1449–1596 cm−1
and 45 kV. An FT-IR spectrum of the synthesized composite confirmed the existence of aromatic C=C stretching vibra-
was recorded using KBr disk on a Nicolet i10 spectrometer tion. In addition, the presence of multiple bands in the region
in the 4000–400 cm−1 region. CHN percent of the synthe- 646–758 cm−1 is due to aromatic CH out of plane bending
sized composite was determined using Perkin Elmer 2400 vibration. Moreover, the peak present at 1346 cm−1 is due
CHN Elemental Analyzer. The morphology of the synthe- to CH bending vibration [34, 38–40]. Elemental analysis of
sized composite was obtained using an ultra-high resolution the synthesized composite for carbon, hydrogen, and nitro-
FE-SEM microscope (JSM5410 JEOL). The concentration gen showed that the %C, %H, and %N are 13.33, 3.13,

Fig. 1  FT-IR spectra of the synthesized composite

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 Journal of Inorganic and Organometallic Polymers and Materials

a cotton-like structure that demonstrates that the crystalline

structure of mesoporous silica overlapped or combined over
an amorphous background [34].

3.2 Removal of Cd(II), Hg(II), and Cu(II) Ions from

Aqueous Media

3.2.1 Effect of Contact Time and Adsorption Kinetics

For studying the effect of contact time, 50 mL of 100 mg L­ −1

Scheme 1  Proposed structure of the synthesized composite
Cd(II), Hg(II), or Cu(II) solutions and 100 mg of the syn-
thesized composite were mixed together in polypropylene
centrifuge tubes. Then, the mixture was shaken at 300 rpm
for different time intervals (5–300 min) using a mechanical
shaker. Figure 4a represents the relation between contact
time and % removal (% R) of Cd(II), Hg(II), and Cu(II) ions
using the synthesized composite. % R of Cd(II), Hg(II), and
Cu(II) increased with increasing time until equals 69.97,
49.24, and 55.59% after 30 min, respectively. % R remains
almost constant perhaps because of the saturation of the syn-
thesized composite active centers. Figure 4b represents the
relation between contact time and adsorption capacity (Q) of
the synthesized composite toward Cd(II), Hg(II), and Cu(II)
ions. Q of the synthesized composite in the case of Cd(II),
Hg(II), and Cu(II) ions increased with increasing time until
equals 34.99, 24.62, and 27.79 mg g−1 after 30 min, respec-
Fig. 2  XRD of the synthesized composite tively. Q of the synthesized composite toward the aforemen-
tioned metal ions remained almost constant at higher times
due to the saturation of its active centers. Effect of contact
time on the removal of Cd(II), Hg(II), and Cu(II) ions can
be moreover evaluated utilizing pseudo-first-order (Eq. 4),
pseudo-second-order (Eq. 5), and intra-particle diffusion
(Eq. 6) kinetic models [37, 41, 42].

(4)
( )
log Qe − Qt = log Qe − KF t∕2.303

t∕Qt = 1∕KS Q2e + 1∕Qe t (5)

( ) ( )

Qt = KI t0.5 + C (6)
Fig. 3  FE-SEM image of the synthesized composite
where, ­KS (g mg−1 ­min−1) is the pseudo-second-order rate
constant, ­KF ­(min−1) is the pseudo-first-order rate con-
and 2.58%, respectively. These data along with the FT-IR stant, ­KI (mg g−1 ­min−0.5) is internal diffusion constant, ­Qt
of the synthesized composite assured the condensation (mg g−1) is the adsorption capacity at time t, Q ­ e (mg g−1)
reaction of dibenzoylmethane with the amino-silane deriva- is the adsorption capacity at equilibrium, and C (mg g−1) is
tive of silica and the structure of composite according to the thickness of boundary layer. Figure 5a–c represents the
Scheme 1. Figure 2 represents the XRD pattern of the modi- pseudo-first-order, pseudo-second-order, and intra-particle
fied mesoporous silica nanoparticles by dibenzoylmethane. diffusion kinetic models of the removal processes of Cd(II),
Broad band at about 22.9 demonstrated that the crystalline Hg(II), and Cu(II) ions using the synthesized composite,
structure of mesoporous silica overlapped or combined respectively. Taking into account the higher values of cor-
over an amorphous background. Figure 3 represents the relation coefficients, the removal of Cd(II) ions follows the
FE-SEM image of the modified mesoporous silica nanopar- pseudo-second-order while that of Cu(II) or Hg(II) ions
ticles by dibenzoylmethane. The synthesized composite has

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Journal of Inorganic and Organometallic Polymers and Materials

Fig. 4  The relation between contact time and % removal of metal ions (a). The relation between contact time and the adsorption capacity of the
synthesized composite (b)

Fig. 5  The pseudo-first-order (a), pseudo-second-order (b), and intra-particle diffusion (c) kinetic models

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 Journal of Inorganic and Organometallic Polymers and Materials

Table 1  Constants of the utilized kinetic models

Kinetic model Metal ion Constants
Qe (mg g−1) KF ­(min−1) R2

Pseudo first order Cd(II) 30.51 0.068 0.972

Hg(II) 27.82 0.091 0.974
Cu(II) 42.52 0.113 0.931
Metal ion Qe (mg g−1) KS (g mg−1 ­min−1) R2

Pseudo second order Cd(II) 41.41 2.454E−3 0.978

Hg(II) 48.52 8.533E−4 0.898
Cu(II) 112.36 1.257E−4 0.856
Metal ion C (mg g−1) KI (mg g−0.5 ­min−0.5) R2

Intra particle diffusion Cd(II) 0.766 6.154 0.982

Hg(II) 5.157 6.110 0.962
Cu(II) 10.415 7.811 0.988

follows the pseudo-first-order as shown in Table 1. Also, occupancy of the binding sites on the composite surface is
straight lines with high correlation coefficients and linear- in favor of (­ H+) leading to a relative decrease in values of %
ity were produced when Q ­ t was plotted versus t­0.5 but they R. On the contrary, as the pH increases higher than 3.2, more
do not go through the origin. Thus, the intra-particle diffu- negatively charged surface become available due to depro-
sion kinetic model is not the only mechanism that controls tonation, thus facilitating the approach of the metal ions to
the removal of Cd(II), Hg(II), or Cu(II) ions [37, 41–43]. the binding sites and metal uptake increases.

3.2.3 Effect of Concentration and Adsorption Isotherms

3.2.2 Effect of pH
To 50 mL of Cd(II), Hg(II), or Cu(II) solutions having dif-
The effect of pH on the removal of Cd(II), Hg(II), and Cu(II) ferent concentrations (25–150 mg ­L−1) at pH 6, 100 mg of
ions using the synthesized composite was investigated in the the synthesized composite was added and the mixture was
range of 3–8, keeping other experimental conditions constant shaken at 300 rpm for 30 min. Figure 7a represents the rela-
(i.e. V = 50 mL, m = 100 mg, t = 30 min, and ­Ci = 100 mg tion between initial Cd(II), Hg(II), or Cu(II) concentration
­L−1). The pH values were adjusted using 0.1 mol ­L−1 HCl or and % R using the synthesized composite. % R of Cd(II),
NaOH solutions. Figure 6a represents the relation between Hg(II), and Cu(II) ions decreased with increasing metal
pH and % R of Cd(II), Hg(II), and Cu(II) ions using the ion concentration until equals 44.01, 32.03, and 39.58 at
synthesized composite. % R of Cd(II), Hg(II), and Cu(II) concentration equals 150 mg L ­ −1, respectively. Figure 7b
ions increased with increasing pH until equals 73.65, represents the relation between initial Cd(II), Hg(II), or
52.49, and 68.11% at pH equals 6, respectively. Also, % R Cu(II) concentration and capacity (Q) of the synthesized
remained almost unchanged when the pH increased from 6 composite. On using 100 mg L ­ −1 of the target metal ions,
to 8. Hence, the optimum pH was 6. Figure 6b represents Q of the synthesized composite toward Cd(II), Hg(II), and
the relation between the pH and adsorption capacity of the Cu(II) increased with increasing metal ion concentration
synthesized composite (Q) in the case of Cd(II), Hg(II), and until equals 36.83, 26.25, and 35.56 mg g−1, respectively. On
Cu(II) ions. Q of the synthesized composite in the case of using 150 mg ­L−1 of the target metal ions, Q of the synthe-
Cd(II), Hg(II), and Cu(II) ions increased with increasing the sized composite was slightly decreased until equals 33.01,
pH until equals 36.83, 26.25, and 34.06 mg g−1 at pH equals 24.03, and 29.69 mg g−1, respectively. Effect of metal ion
6, respectively. Also, Q remained almost unchanged when concentration on the removal of Cd(II), Hg(II), and Cu(II)
the pH increased from 6 to 8. Hence, the optimum pH was 6. ions can be moreover evaluated utilizing Langmuir (Eq. 7)
The point of zero charge of the synthesized composite was and Freundlich (Eq. 8) isotherms [37, 41, 42].
3.2 as shown in Fig. 6c. If the pH of the metal ion solution
(Cd(II), Hg(II), or Cu(II)) is less than 3.2, the surface of (7)
( ) ( )
Ce ∕Qe = 1∕KLang Qm + Ce ∕Qm
the synthesized composite is surrounded by positive hydro-
gen ions ­(H+). Hence, a proton-metal ion competition for

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Journal of Inorganic and Organometallic Polymers and Materials

Fig. 6  The relation between pH and % R (a). The relation between pH and adsorption capacity of the synthesized composite (b). Point of zero
charge (c)

Fig. 7  The relation between initial metal ion concentration and % R (a). The relation between initial metal ion concentration and adsorption
capacity of the synthesized composite (b)

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 Journal of Inorganic and Organometallic Polymers and Materials

Fig. 8  Langmuir (a) and Freundlich (b) adsorption isotherms

Table 2  Constants of the utilized adsorption isotherms

Adsorption model Metal ion Constants
Qm (mg g−1) KLang (L ­mg−1) R2

Langmuir Cd(II) 35.37 0.211 0.981

Hg(II) 25.17 0.359 0.992
Cu(II) 31.76 0.208 0.966
Metal ion Constants
Qm (mg g−1) KFre (mg g−1)(L ­mg−1)1/n R2

Freundlich Cd(II) 42.45 9.051 0.766

Hg(II) 27.91 9.004 0.693
Cu(II) 36.68 8.771 0.678

3.2.4 Effect of Temperature and Thermodynamic

ln Qe = ln KFre + (1∕n) ln Ce (8)
Parameters
where, 1/n is the heterogeneity factor, ­KFre (mg g−1) is the
Freundlich constant, and ­KLang (L ­mg−1) is the Langmuir The effect of temperature on the removal of Cd(II), Hg(II),
constant. ­Qm of Freundlich isotherm can be calculated using and Cu(II) ions using the synthesized composite was inves-
Eq. (9). tigated in the range of 298–323 K, keeping other experi-
( )1∕n mental conditions constant (i.e. V = 50 mL, m = 100 mg,
Qm = KFre Ci (9) pH 6, t = 30 min, and ­C i = 100 mg ­L −1). Figure 9a rep-
resents the relation between temperature and % R of
Figure 8a, b represents the Langmuir and Freundlich Cd(II), Hg(II), or Cu(II) ions using the synthesized com-
isotherms of the removal processes of Cd(II), Hg(II), and posite. % R of Cd(II), Hg(II), and Cu(II) ions decreased
Cu(II) ions using the synthesized composite, respectively. with increasing temperature until equals 28.43, 9.43, and
The Langmuir isotherm controls the adsorption of Cd(II), 20.87% at 323 K, respectively. Figure 9b represents the
Hg(II), or Cu(II) because the correlation coefficient of the relation between temperature and capacity (Q) of the syn-
Langmuir isotherm is greater than that of Freundlich as thesized composite in the case of Cd(II), Hg(II), or Cu(II)
shown in Tables 2. ­Qm of the synthesized composite in the ions. Q of the synthesized composite in the case of Cd(II),
case of Cd(II), Hg(II), and Cu(II) ions equals 35.37, 25.17, Hg(II), and Cu(II) ions decreased with increasing tempera-
and 31.76 mg g−1, respectively. ture until equals 14.22, 4.72 and 10.43 mg g −1 at 323 K,
respectively. Thermodynamic parameters, for example,
change in free energy (ΔG°), change in the entropy (ΔS°),

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Journal of Inorganic and Organometallic Polymers and Materials

Fig. 9  The relation between temperature and % R (a). The relation between temperature and adsorption capacity of the synthesized composite
(b). The plot of lnKd versus 1/T (c)

Table 3  Thermodynamic T (K) ­ ol−1)

∆G° (KJ m ∆S° (KJ ­mol−1 ­K−1) ­ ol−1)
∆H° (KJ m
parameters
Cd(II) Hg(II) Cu(II) Cd(II) Hg(II) Cu(II) Cd(II) Hg(II) Cu(II)

298 − 121.78 − 151.24 − 129.48 0.203 0.256 0.217 − 61.29 − 74.95 − 64.81
303 − 122.79 − 152.52 − 130.57
308 − 123.81 − 153.79 − 131.65
313 − 124.83 − 155.08 − 132.73
318 − 125.84 − 156.36 − 133.82
323 − 126.86 − 157.64 − 134.90

and change in enthalpy (ΔH°) were determined utilizing where, T (K) is temperature, R (KJ ­mol−1 ­K−1) is gas con-
Eqs. (10) and (11) [37, 43]. ­ d (L g­ −1) is distribution co-efficient which is
stant, and K
calculated from Eqs. (12) or (13)
lnKd = (ΔS◦ ∕R) − (ΔH◦ ∕RT) (10)
(12)
[ ]
Kd = % R∕ (100 − % R) V∕m
ΔG◦ = ΔH◦ − TΔS◦ (11)

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 Journal of Inorganic and Organometallic Polymers and Materials

Fig. 10  The relation between the amount of composite and % R (a). The relation between the amount of composite and adsorption capacity of
the synthesized composite (b)

Kd = Qe ∕Ce (13)
Figure 9c represents the plots of l­nKd versus 1/T. Ther-
modynamic parameters were tabulated in Table 3. The
results showed that the adsorption process of Cd(II), Hg(II),
or Cu(II) ions using the synthesized composite is exothermic
and spontaneous (feasible) process due to the obtained nega-
tive ΔHo and ΔG° values, respectively. Besides, the adsorp-
tion processes are chemisorption because the calculated ΔH°
values are more than 40 kJ/mol [37, 43].

3.2.5 Effect of Amount of Composite

The effect of amount of composite on the removal of

Cd(II), Hg(II), and Cu(II) ions was investigated in the Fig. 11  The relation between desorption media and % desorption
range of 0.05-0.15 g, keeping other experimental con-
ditions constant (i.e. V = 50 mL, T = 298 K, pH 6, and D of Cd(II), Hg(II), and Cu(II) ions equals 95.04, 95.26,
­C i = 100 mg ­L −1 ). Figure 10a represents the relation and 95.43% using 0.5 M N ­ a4-EDTA as desorption media,
between the amount of composite and % R of Cd(II), respectively. % D of Cd(II), Hg(II), and Cu(II) ions equals
Hg(II), or Cu(II) ions. % R of Cd(II), Hg(II), and Cu(II) 99.12, 99.07, and 98.37% using 0.5 V/V% HCl: water as
ions increased with increasing the amount of composite desorption media, respectively. % D of Cd(II), Hg(II), and
until equals 79.18, 55.54, and 71.09% using 0.15 g, respec- Cu(II) ions equals 40.73, 57.15, and 44.05% using 0.5 V/V%
tively. Figure 10b represents the relation between the HCl: Acetone as desorption media, respectively. % D of
amount of composite and capacity (Q) of the synthesized Cd(II), Hg(II), and Cu(II) ions equals 47.52, 66.68, and
composite in the case of Cd(II), Hg(II), or Cu(II) ions. Q 51.39% using 0.5 V/V% HCl:ethanol as desorption media,
of the synthesized composite in the case of Cd(II), Hg(II), respectively. % D of Cd(II), Hg(II), and Cu(II) ions equals
and Cu(II) ions decreased with increasing the amount of 74.68, 76.20, and 80.75% using 0.5 V/V% HCl: methanol as
composite until equals 26.39, 18.51, and 23.69 mg g −1 desorption media, respectively. % D of Cd(II), Hg(II), and
using 0.15, respectively. Cu(II) ions equals 81.47, 85.73, and 88.09% using 0.5 V/V%
HCl: chloroform as desorption media, respectively. The
results confirmed that 0.5 M ­Na4-EDTA and 0.5 V/V% HCl:
3.2.6 Desorption Studies water are the best media for the desorption of Cd(II), Hg(II),
and Cu(II) ions from composite. EDTA is the head member
Figure 11 represents the relation between different desorp- of the family of ligands. EDTA is a hexadentate ligand form-
tion media and % D of Cd(II), Hg(II), or Cu(II) ions. % ing highly stable complexes with Hg(II), Pb(II), and Cd(II)

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Journal of Inorganic and Organometallic Polymers and Materials

Fig. 12  The relation between the regeneration cycle and % R of Cd(II) (a), Hg(II) (b), and Cu(II) (c) ions

ions in aqueous solution. So, it has the affinity to uptake reuse in the removal of Cd(II), Hg(II), and Cu(II) ions from
these metal ions from the composite surface. Besides, the aqueous media.
use of 0.5 V/V% HCl: water media increases remarkably
the concentration of ­H+ leading to desorption of metal ions 3.2.8 Study of Interference
from the composite active centers due to the instability of
their complexes at highly acidic solutions. Table 4 represents the impact of the concentration of con-
comitants ions on Q of fabricated composite and % R of
3.2.7 Regeneration and Reuse of Composite studied metals ions. The interfering ions were Co(II), Ni(II),
Fe(III), Zn(II), Pb(II), and Al(III). The obtained results indi-
Figure 12a–c represents the relation between the regener- cate that there is a slight decrease in the values of Q or % R
ation cycles and % R of Cd(II), Hg(II), and Cu(II) ions, of metal ions in the presence of 50 fold excess of the inter-
respectively. Also, Fig. 13a–c represents the relation fering metal ion concentration. Also, there is a significant
between the regeneration cycles and adsorption capacity decrease in the values of Q or % R of metal ions when the
of the synthesized composite in the case of Cd(II), Hg(II), concentration of the interfering metal ion equals 80 or 100
and Cu(II) ions, respectively. The results proved that % R fold excess.
or the adsorption capacity of the synthesized composite in
the case of the aforementioned metal ions remained almost
constant for five regeneration cycles. Hence, the synthesized
composite can be considered a promising and efficient for

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 Journal of Inorganic and Organometallic Polymers and Materials

Fig. 13  The relation between the regeneration cycle and adsorption capacity of the synthesized composite in the case of Cd(II) (a), Hg(II) (b),
and Cu(II) (c) ions

3.2.9 Comparison Between the Adsorption Capacity 3.2.10 Removal of Cd(II), Hg(II), and Cu(II) Ions from Real
of the Synthesized Composite and Other Adsorbents Water Samples

The adsorption capacity of the synthesized composite Samples of groundwater and Nile water were collected from
exceeds that of many other substances such as cellulose- El Senbellawein City-Egypt. Besides, seawater and tap water
g-poly(acrylonitrile), cellulose-g-poly(acrylic acid), NaA were collected from Port Said-Egypt and Faculty of Science-
zeolite coated magnetic nanoparticles, polydopamine coated Mansoura University-Egypt, respectively. All water samples
natural zeolite, natural zeolite, maifanite/MgAl-LDHs, were filtered before measuring the elements under investiga-
EDTA-LDH/PVA, modified steel-making slag, rice straw, tion using the atomic absorption spectrophotometer. Table 6
α-Fe2O3, thiol-functional magnetic nanoparticles, and PEI- shows the concentrations of Cd(II), Cu(II), and Hg(II) ions
AC composite [41, 44–49] as shown in Table 5. The syn- in the real samples. Also, data presented in Table 6 indi-
thesized composite possesses an adsorption capacity equals cated that the % removal of the studied metal ions was 100%
35.37, 25.17, and 31.76 mg g−1 in the case of Cd(II), Hg(II), under the following conditions; (V = 50 mL, m = 100 mg,
and Cu(II) ions, respectively. The arrangement of (C=N) t = 30 min, T = 298 K, and pH 6).
functional groups around the methylene C ­ H2 group enables
the formation of stable five-member ring chelates with the
targeted metal ions. Consequently, the uptake efficiency was
increased compared to other adsorbents in Table 5.

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Journal of Inorganic and Organometallic Polymers and Materials

Table 4  The impact of Interference metal ion %R Q (mg g−1)

interference ions on the
adsorption capacity and % Type Concentration Cd(II) Hg(II) Cu(II) Cd(II) Hg(II) Cu(II)
removal of metals ions (mg ­L−1)

Co(II) 0 73.65 52.49 68.11 36.83 26.25 34.06

50 73.53 53.44 66.92 36.77 26.71 33.46
80 67.20 43.32 57.08 33.60 21.66 28.54
100 61.45 36.64 53.80 30.72 18.32 26.90
Ni(II) 0 73.65 52.49 68.11 36.83 26.25 34.06
50 73.99 53.82 66.47 36.99 26.91 33.23
80 68.01 45.61 57.82 34.00 22.91 28.91
100 59.95 34.16 54.09 29.98 22.80 27.05
Fe(III) 0 73.65 52.49 68.11 36.83 26.25 34.06
50 68.69 48.28 64.08 34.35 24.14 32.04
80 65.02 45.04 60.66 32.51 22.52 30.33
100 54.20 36.45 47.09 27.10 18.23 23.55
Zn(II) 0 73.65 52.49 68.11 36.83 26.25 34.06
50 69.04 54.19 57.53 34.52 27.01 28.76
80 64.21 43.51 55.29 32.11 21.76 27.65
100 56.50 34.92 47.69 28.25 17.46 23.85
Pb(II) 0 73.65 52.49 68.11 36.83 26.25 34.06
50 74.57 54.96 67.51 37.28 27.48 33.76
80 67.43 45.80 56.63 33.72 22.90 28.32
100 57.54 37.21 48.58 28.77 18.61 24.29
Al(III) 0 73.65 52.49 68.11 36.83 26.25 34.06
50 73.76 54.58 66.32 36.88 27.29 33.16
80 66.05 44.08 55.44 33.03 22.04 27.72
100 57.65 37.21 50.67 28.83 18.61 25.72

Table 5  Comparison between Metal ion Adsorbent Adsorption Refs.

the adsorption capacity of the capacity
synthesized composite and (mg g−1)
other adsorbents
Cu(II) Cellulose-g-poly(acrylonitrile) 12.96 [41]
Cu(II) Cellulose-g-poly(acrylic acid) 14.24 [41]
Cu(II) NaA zeolite coated magnetic nanoparticles 13.80 [44]
Cu(II) Polydopamine coated natural zeolite 13.60 [44]
Cu(II) Mesoporous silica nanoparticles modified by dibenzoylmethane 31.76 This study
Cd(II) Natural zeolite 0.54 [45]
Cd(II) Maifanite/MgAl-LDHs 3.77 [45]
Cd(II) EDTA-LDH/PVA 8.18 [45]
Cd(II) Modified steel-making slag 10.16 [45]
Cd(II) Mesoporous silica nanoparticles modified by dibenzoylmethane 35.37 This study
Hg(II) Rice straw 22.00 [46]
Hg(II) α-Fe2O3 11.20 [47]
Hg(II) Thiol-functional magnetic nanoparticles 9.50 [48]
Hg(II) PEI-AC composite 16.39 [49]
Hg(II) Mesoporous silica nanoparticles modified by dibenzoylmethane 25.17 This study

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 Journal of Inorganic and Organometallic Polymers and Materials

Table 6  Removal of Cd(II), Sample Concentration (mg ­L−1) %R

Cu(II), and Hg(II) ions from
real samples Cd(II) Hg(II) Cu(II) Cd(II) Hg(II) Cu(II)

Ground water from El Senbellawein city-Egypt 1.905 – 1.765 100 – 100

Nile water from El Senbellawein City-Egypt 0.144 – 0.499 100 – 100
Seawater from Port Said-Egypt 8.513 – 1.425 100 – 100
Tap water from Faculty of Science-Mansoura 0.370 – 2.057 100 – 100
University-Egypt

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