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PII: S0304-3894(17)30814-2
DOI: https://doi.org/10.1016/j.jhazmat.2017.10.058
Reference: HAZMAT 18963
Please cite this article as: Smaail Radi, Chahrazad El Abiad, Nuno M.M.Moura,
Maria A.F.Faustino, M.Graça P.M.S.Neves, New Hybrid Adsorbent Based
on Porphyrin Functionalized Silica for Heavy Metals Removal: Synthesis,
Characterization, Isotherms, Kinetics and Thermodynamics Studies, Journal of
Hazardous Materials https://doi.org/10.1016/j.jhazmat.2017.10.058
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New Hybrid Adsorbent Based on Porphyrin Functionalized Silica
for Heavy Metals Removal: Synthesis, Characterization,
Isotherms, Kinetics and Thermodynamics Studies
M. Graça P. M. S. Neves2
1
Laboratory of Applied Chemistry and Environment (LCAE), Department of Chemistry,
Faculty of Sciences, University Mohamed Premier, Oujda, Morocco
2
QOPNA and Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
Graphical Abstract
Highlights
- SiNTPP shows excellent adsorption ability towards Pb(II) compared to others sorbents
- A low cost and high regenerable material was developed to remove toxic metal ions
1. Introduction
The presence of high concentrations of toxic heavy metal ions, such as Pb(II), Zn(II),
Cd(II) and Cu(II), in the environment represents a serious threat to human health, living
resources and ecological systems [1-3]. Toxic metals that arrive on the earth's surface
contaminate not only the earth's water (seas, lakes, ponds and reservoirs), but can also
contaminate groundwater in traces by fleeing from the ground after rain and snow [4].
Therefore, the elimination of heavy metals from natural waters and wastewater is attracting
increasing attention.
Traditionally, the elimination of these heavy metals is carried out using liquid-liquid
extraction [5], coprecipitation [6], ion exchange [7], membrane filtration [8], and resin
chelation [9]. However, these approaches have many disadvantages, such as the excessive
use of solvents, the non-selective elimination of metal ions, high reagent requirements, toxic
sludge production, time-consuming with laborious and expensive sample handling. These
difficulties are surmounted by solid-phase extraction (SPE) [10]. Indeed, the SPE technique
is considered a powerful procedure for the separation and enrichment of several inorganic
and organic analytes [11]. The benefits of SPE are related to its i) higher enrichment factor,
ii) sample operation, iii) minimal costs, due to low reagent consumption, iv) no organic
solvents required, v) high selectivity, vi) easiness of separation, and vii) its ability to be
combined with several modern detection techniques [12].
In this context, many ligands are immobilized on solid organic polymer matrices and have
been studied as chelating resins. However, the sorption capacities of these resins are generally
moderate due to their hydrophobicity [13]. Thus, silica gel has a great importance as a solid
support since it has specific advantages, such as: i) rapid sorption of metal ions, ii) no
swelling, iii) good selectivity, and iv) good mechanical stability [14-16].
For this reason, many chemically modified silica based materials has been developed.
Therefore, the use of silica-functionalized ligands for the extraction and preconcentration of
metal ions has recently been widely reported by our group [17-26] and others [27-29]. This
type of modified silicas has contributed for a rapid developing technology for solid-phase
extraction. In addition, these systems can be operated indefinitely without the loss of
expensive organic ligands. The efficiency of silica based materials is in general related with
the ability of the grafted ligands, containing donor atoms such as oxygen, nitrogen or sulphur,
to form complexes with several metal ions, resulting in some cases on their selective
extraction.
An important class of heterocyclic compounds with high potential to be used as ligands are
porphyrins due to their ability to coordinate with a wide range of metal ions affording stable
complexes [30,31]. Porphyrins reveal unique binding properties that are widely exploited in
nature to perform essential functions for life, like respiration and photosynthesis. Indeed, the
nitrogen atoms in the tetrapyrrolic core, due to their solid electron-donor properties, can act as
ligand sites to attract metal ions and consequently to allow their sensing or elimination with
high efficiency [32].
These features, associated to other unique porphyrin properties such as: i) light stability, ii)
high molar absorption coefficients in the visible region of the electromagnetic spectrum, iii)
fluorescence emission, iv) high Stokes shift, v) chemical reactions with specific fingerprints
that facilitate the analysis of receptor-analyte interactions, namely by UV-vis or fluorescence
spectroscopy, are being explored with high success in molecular recognition [32-34].
Additionally, the functionalization of this type derivatives to improve their receptor ability
have allowed the development of particularly sensitive systems for detection of analytes, like
cations, anions or neutral molecules [35,36].
In particular, the efficiency of meso-substituted porphyrins doped in silica platforms for
heavy metal ion sensing [37,38] and for gas sensing [39,40] have been widely reported.
However, a literature survey shows that the number of studies involving beta-functionalized
porphyrins as chemosensors is limited [41] and even more if these types of macrocycles are
supported in solid platforms [42]. A significant contribution for the development of these
beta-functionalized porphyrins as chemosensors was given by our group in the last years
namely by preparing polymethylmethacrylate (PMMA) films doped with a series of beta-
substituted porphyrins containing pyridine, pyrazole and chalcone type moieties. The results
showed that these types of systems are versatile and efficient to be used as metal ion
chemosensors [42-45], being able to discriminate in aqueous solutions Zn(II) and Hg(II) [43].
Considering our interest in finding new efficient adsorbents for metal ions removal and
new technological applications for porphyrinic macrocycles and analogues, in this paper we
describe the synthesis and the characterization of new adsorbent material made of a porphyrin
receptor immobilized on silica by a β-pyrrolic position and its use in heavy metal ions
removal.
2. Experimental
2.1. Materials and Methods
Scanning electron microscopy (SEM - Hitachi S4100 equipped with energy dispersion
spectroscopy) was used to characterize the silica particles. Brunauer, Emmett, Teller
(BET)/Barrett, Joyner, Halenda (BJH) determination of specific surface area and pore size
distribution were achieved by a Micromeritics Gemini 2380 surface area analyser with ca. 50
mg weight. 13C solid Nuclear Magnetic Resonance (NMR) spectra were recorded on a Bruker
Avance III 400 spectrometer. Elemental analyses were performed on a LECO CHNS-932
apparatus. Attenuated Total Reflectance Transmission Fourier Transform Infrared (ATR-
FTIR) spectra were registered on a FT Mattson 7000 galaxy series spectrophotometer. The
nitrogen adsorption–desorption was obtained by means of a Thermoquest Sorpsomatic 1990
analyzer. The mass loss determinations were performed in 90:10 oxygen/nitrogen
atmospheres on a TGA Q50 V6.7 Build 203 instrument, at a heating rate of 10 ◦C min−1.
Atomic absorption measurements were performed at the University of Oujda COSTE,
Morocco) by Spectra Varian A.A. 400 spectrophotometer. All the chemicals and solvents
were of analytical grade and were used without further purification. Silica gel (Merck; 70–230
mesh, 60 Å) was activated before use by heating it at 120 ºC for 24 h. 2-formyl-5,10,15,20-
tetraphenylporphyrin (2-CHO-TPP) was prepared according to literature procedures [46].
Ph N
HN
NH
N Ph
a) Ph
Ph O N
H2N
NH N
Ph Ph
Si OMe
Si OMe N HN
O O
O O
Ph
H2N
(2-CHO-TPP)
Silica
Silica Silica Particle
Particle + Particle Toluene/Ethanol,
Toluene, N2
MeO Si , N2
MeO OMe SiNTPP
Si SiPn
b) Porphyrin
Extraction
M2+
Silica
Scheme 1. a) Synthetic route to prepare the chelating material; b) metal binding to porphyrin grafted
silica.
Figure 1. FTIR spectra of activated silica (Si), 3-aminopropyl-silica (SiPn) and SiNTPP.
3.2.3. Scanning Electron Micrographs
Scanning electron micrographs (SEM) were obtained on the activated silica and chemically
modified silicas to detect differences in their surfaces. SEM of silica gel, SiPn and SiNTPP in
Figure 2 were obtained at 300× magnification. The micrographs were shown to clarify the
non-agglomeration of the silica gel particles after treatment to support the claim of even
distribution of the functional group over the entire surface. It was evident that the charged
functional groups were distributed over the entire surface, which made the surface of the final
product SiNTPP rough.
Figure 2. SEM images of activated silica (Si) (a), SiPn (b) and SiNTPP (c).
13
3.2.6. C NMR characterization
13
The final material (SiNTPP) was characterized by solid state C NMR and the
corresponding spectrum is shown in Figure 6, where two main signal groups can be clearly.
Identified. The signals due to the 3-aminopropyl resonances appear in part (a) at 9.5, 22.3
and 42.4 ppm that have been assigned to the propyl carbon, Si–CH2, –CH2– and N–CH2,
respectively; the signal at 51.3 ppm was assigned to the non-substituted methoxy group (–
OCH3). This data is in accordance with elemental analysis obtained were the presence of
13
nitrogen and carbon was detected in the SiPn material. In the (b) part of the C NMR
spectrum additional signals appeared at 120.4–172.2 ppm corresponding to the resonance of
the porphyrinic carbons.
172.1658
141.8038
127.2413
120.3709
51.2694
42.4184
22.2823
9.5239
Figure 6. Solid 13C NMR spectrum of SiNTPP.
Figure 8. Effect of shaking time on the adsorption capacity of Pb(II), Zn(II), Cd(II), and Cu(II). Adsorption
dose: V = 10 mL, m = 10 mg of SiNTPP, at optimum pH (pH = 6), 25°C and optimum concentration (53.17
ppm in each case). Lines just combine the points.
Kinetic modelling was performed to find the rate of metal ions adsorbed onto the SiNTPP
material. The study was investigated using the pseudo-first-order (Eq. 3), given by Lagergren
and the pseudo-second-order models (Eq. 4):
Figure 9. Pseudo-second-order model fit for the adsorption of Pb(II), Zn(II), Cd(II), and Cu(II) by SiNTPP.
Adsorption dose: V = 10 mL, m = 10 mg of SiNTPP using optimum pH (pH = 6), optimum concentration (53.17
ppm in each case), and 25°C. Lines just combine the points.
Table 2. Kinetics of heavy metals removal onto SiNTPP.
Metal
Parameters
(Ionic radius)
Pb(II) Zn(II) Cd(II) Cu(II)
(1.19 Å) (0.74 Å) (0.95 Å) (0.73 Å)
qe exp a(mg.g-1) 53.20 32.16 23.26 19.07
qe exp a (mmol.g-1) 0.257 0.492 0.207 0.300
Pseudo-First-Order b
-1
qe (mg.g ) 52.21 31.57 22.91 18.68
qe (mmol.g-1) 0.252 0.483 0.204 0.294
K1 (min-1) 0.362 0.238 0.236 0.358
R² 0.994 0.991 0.991 0.990
Pseudo-Second-Order
qe (mg.g-1) 54.64 33.67 24.27 19.53
qe (mmol.g-1) 0.264 0.515 0.216 0.307
K2 (min-1) 34.27x10−3 21.30x10 −3
33.95x10−3 64.25x10−3
R² 0.999 0.995 0.996 0.998
a - Experimental data obtained when the plateau was reached (after 25 min of contact). b - The pseudo-
first order data were determined by least-squares method.
C0 Ce V
Kd (5)
Ce m
S 0 H 0
ln Kd (6)
R RT
G°= H°- TS° (7)
Pb(II)
1,2
Zn(II)
Cd(II)
1,0
Cu(II)
0,8
ln Kd
0,6
0,4
0,2
0,0
0,00310 0,00315 0,00320 0,00325 0,00330
1/T(K)
Figure 10. Effect of temperature for the sorption of metal ions onto SiNTPP (shaking time = 35 min; pH = 6,
Adsorption dose: V = 10 mL, m = 10 mg of SiNTPP at optimum concentration). Lines just combine the points.
3.3.4. Effect of Initial Concentration and Isotherm Modelling
The effect of initial concentration on metal ions removal was studied using the
concentration range (10 mg.L−1 to 300 mg.L−1 at 25 °C and optimum pH) (Figure 11). The
curves show the increase of adsorption with increasing of initial concentration of metals until
reaching the plateau shape.
The experimental data are applied here in two isotherm models; the first one is Langmuir
isotherm model [65] (Eq. (8)), which described the monolayer coverage of the sorption
surfaces and assumes that sorption sites are energetically identical. The second one is
Freundlich isotherm model [66] (Eq. (9)), describing the multilayer adsorption on
heterogeneous solid surfaces.
Ce Ce 1 (8)
qe q qK L
ln Ce
ln qe ln KF (9)
n
Where Ce is the equilibrium ion concentration in the solution (mg.L-1), qe is the amount of
solute sorbed (mg.g-1), q is the saturated adsorption capacity (mg.g-1), KL is the Langmuir
adsorption constant (L.mg-1). n is Freundlich constant and KF is the binding energy constant
(mg.g-1).
The data of the fitted models are presented in Figure 12 and Table 4, where it can be
concluded that the adsorption of Pb(II), Zn(II), Cd(II), and Cu(II) onto SiNTPP was better
described by Langmuir model than when applied the Freundlich model. This statement is also
supported by the higher values of the correlation coefficient (R2) found by the Langmuir
isotherm model.
It is well known that the Langmuir equation is applicable to the homogeneous adsorption,
where the adsorption onto the surface had equal adsorption activation energy. The results of
maximum adsorption capacity of SiNTPP for Pb(II), Zn(II), Cd(II) and Cu(II) in accordance
with the Langmuir model show, in terms of mass quantity, 59.88 mg.g-1, 37.03 mg.g-1, 25.00
mg.g-1 and 20.01 mg.g-1, respectively (Table 4).
Figure 11. Effect of concentration on metal ions adsorption onto SiNTPP (adsorption dose: 10 mg, V = 10 mL,
25 °C and pH = 6). Lines just combine the points.
Figure 12. Langmuir adsorption model fit of Pb(II), Zn(II), Cd(II) and Cu(II) on SiNTPP.
Figure13. Effect of foreign metal ions on the extraction of Pb(II) with SiNTPP (shaking time: 25 min, pH = 6, T
= 25 °C. Adsorption dose: V = 10 mL, m = 10 mg of SiNTPP at optimum concentrations: 53.17 ppm of each
studied metal, Pb(II), Cu(II), Zn(II), and Cd(II).
Table 7. Comparison of adsorption capacities of SiNTPP with some other reported sorbents.
4. Conclusion
Based on the experimental results, it can be concluded that a new adsorbent material based
on silica chemically modified with the highly chelate 2-formylporphyrin derivative (2-CHO-
TPP) has been successfully prepared, via a simple heterogeneous procedure, and the material
surface was fully characterized. The functionalized material displays an excellent adsorption
capacity towards Pb(II), Zn(II), Cd(II), and Cu(II) when compared to several reported
sorbents. The maximum values for adsorption were reached in only 25 min, suggesting a fast
coordination. The adsorption kinetics fit into the pseudo-second-order model, which reveals a
homogeneous character. The thermodynamic parameters are in agreement with an
endothermic and spontaneous process. The competitive adsorption proves the efficiency of
this new organic-inorganic hybrid material for removing heavy metal cations from aqueous
solutions. It can be concluded that SiNTPP seems to be an effective, alternative, and low cost
sorbent for the efficient removal of toxic heavy metals from aqueous solutions. So, this work
shows that the development of adsorbent materials bearing β-functionalized porphyrins merits
a special attention and further improvements can be achieved by appropriate functionalization
of this type of templates.
Acknowledgement
Thanks are due to the University of Aveiro and FCT (Fundação para a Ciência e aTecnologia)
for the financial support to the QOPNA research project (FCT UID/QUI/ 00062/2013)
through national funds and when applicable cofinanced by FEDER under the PT2020
Partnership Agreement, and also to the Portuguese NMR Network. NMM Moura thanks FCT
for his postdoctoral grant (SFRH/BPD/84216/2012)). The authors extend their appreciation to
the PPR2-MESRSFC-CNRST-P10 project (Morocco) for the financial support.
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