Accepted Manuscript

Title: New Hybrid Adsorbent Based on Porphyrin

Functionalized Silica for Heavy Metals Removal: Synthesis,
Characterization, Isotherms, Kinetics and Thermodynamics
Studies

Authors: Smaail Radi, Chahrazad El Abiad, Nuno M.M.

Moura, Maria A.F. Faustino, M. Graça P.M.S. Neves

PII: S0304-3894(17)30814-2
DOI: https://doi.org/10.1016/j.jhazmat.2017.10.058
Reference: HAZMAT 18963

To appear in: Journal of Hazardous Materials

Received date: 28-7-2017

Revised date: 24-10-2017
Accepted date: 28-10-2017

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

Smaail Radi,1* Chahrazad El Abiad,1 Nuno M. M. Moura,2* Maria A. F. Faustino,2

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.

Corresponding authors emails: s.radi@ump.ac.ma; radi_smaail@yahoo.fr; nmoura@ua.pt

Graphical Abstract

Highlights

- A chelate porphyrin-silica particle was successfully prepared under mild conditions

- SiNTPP shows excellent adsorption ability towards Pb(II) compared to others sorbents

- Fast, spontaneous and homogeneous coordination was achieved after 25 min

- A low cost and high regenerable material was developed to remove toxic metal ions

- The new organic-inorganic hybrid proved to be efficient in aqueous solutions.

Abstract
The pollution of water resources due to the disposal of toxic heavy metals has been a
growing global concern for the last decades. For this purpose, the search for effective and
economic material based adsorbents is required, due to the efficiency of the process. In this
work, a novel inorganic-organic hybrid material based on silica chemically modified with a
porphyrin (SiNTPP), with a high metal removal efficiency, was developed. The new material
13
was characterized using a set of suitable techniques such as C NMR of the solid state,
elemental analysis, FTIR, nitrogen adsorption-desorption isotherm, BET surface area, BJH
pore sizes and scanning electron microscopy (SEM). The new material surface exhibits good
chemical and thermal stability based on the obtained thermogravimetric curves (TGA). An
adsorption study was accomplished to investigate the effect of porphyrin-silica hybrid on the
removal of Pb(II), Zn(II), Cd(II) and Cu(II) from aqueous solutions using a batch method. The
effect of various parameters, such as initial metal concentration, pH, temperature, as well as
the kinetics and thermodynamics for sorption on SiNTPP were investigated. The studies
demonstrate that adsorption is fast, as proved by the achievement of equilibrium within 25
min. The metals removal from aqueous solution are better adapted to the Langmuir isotherm
model than to the Freundlich model. The thermodynamic parameters (ΔG°, ΔH° and ΔS°)
disclose that the process was endothermic and spontaneous in nature, and the adsorption
process follows a pseudo-second order kinetics. The adsorbent can be regenerated
continuously without affecting its extraction percentage. Its effectiveness is highly justified
compared to previous described materials.

Keywords: Porphyrin; Adsorbent; Extraction; Heavy metal cations; Aqueous solution.

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].

2.2. Synthesis of 3-aminopropyl-silica (SiPn)

The first step in the preparation of the adsorbent was the reaction between the silylating
agent and the silanol groups presents on the silica surface. The previously activated silica gel
(30 g) was suspended in 200 mL of dried toluene and the reaction mixture was maintained
under stirring for 2 h at reflux under nitrogen atmosphere. Thereafter, 13 mL of 3-
aminopropyltrimethoxysilane was added dropwise and the mixture was kept under reflux for
24 h. After this period, the mixture was cooled and the solid was filtered, washed
successively with toluene, ethanol and dichloromethane and was then Soxhlet extracted with a
mixture of ethanol and dichloromethane (1/1) for 12 h to remove the residual silylating
reagent remaining. The obtained functionalized silica gel (SiPn), was dried in vacuum at
room temperature [17].

2.3. Preparation of porphyrin-silica material (SiNTPP)

The mixture of 3-aminopropyl-silica (SiPn) (2 g) and 2-formyl-5,10,15-20-
tetraphenylporphyrin (2-CHO-TPP) (150 mg) in 60 mL of dry toluene/ethanol (60/40) was
stirred and refluxed under nitrogen for 48 h. Thereafter, the mixture was cooled and the solid
product was filtered and transferred to the Soxhlet extraction apparatus for reflux-extraction
using toluene, ethanol and dichloromethane successively. The final material SiNTPP was
dried under vacuum at 40 °C over 1 h.

2.4. Batch experiments

The applicability of SiNTPP for elimination of Zn2+, Pb2+, Cu2+ and Cd2+ from aqueous
solutions was conducted by adding 10 mg of adsorbent in 10 mL of an aqueous solution of
metal ions with variable concentrations of 10–300 mg.L-1 at 25 °C. The pH effect was studied
in the range of 1–7. The effect of contact time was also checked in the range 5-35 min at 25
°C. After extraction, the solid phase was separated by filtration using the nylon 0.45 µm
membrane. The residual metal of the supernatant was determined by atomic absorption
measurements, and the amount of adsorbed metal was calculated using the following
equations [47]:

QM = (C0- Ce) x V/W (1)

QW = QM x M (2)
 Where QM is the quantity of adsorbed metal (mmol/g), QW is the quantity of adsorbed
metal (mg.g-1), V: the volume of the solution (L), C0 the initial concentration of metal ion
(mmol.L-1), Ce the equilibrium metal ion concentration in solution (mmol.L-1), W: the weight
of the adsorbent (g) and M: the atomic weight of the metal (g.mol-1). The analysis was
performed in duplicate for each sample and the mean data are reported.

3. Results and Discussion

3.1. Porphyrin-silica material preparation
The synthetic procedure for the preparation of new chelating material is summarized in
Scheme 1. The preparation involved the reaction of activated silica gel with 3-
aminopropyltrimethoxysilane in toluene to graft amino groups on the silica surface [48].
These NH2-groups on the surface of silica were then used to react with 2-formyl-5,10,15,20-
tetraphenylporphyrin under mild conditions (reflux temperature in an anhydrous mixture of
toluene/ethanol at atmospheric pressure) affording successfully after 48 h the new chelating
sorbent material SiNTPP (Scheme 1).
 Ph

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.

3.2. Material Characterization

3.2.1. Elemental Analysis
The detection carbon and nitrogen elements (not present in the activated starting silica) in
the prepared material SiPn by elemental analysis allowed to characterize and to demonstrate
the efficient attachment of 3-aminopropyltrimethoxysilane organic group on the surface of the
silica. The elemental analysis results of SiPn (% C = 5.03, % N = 1.63 and % H = 2.00)
confirmed that two methoxy groups were substituted by silanol. The final adsorbent
containing the porphyrinc unit (SiNTPP) showed also an increase in the percentage of C, N
and H (% C = 9.47, % N = 1.86 and % H = 1.61), what means that the second
functionalization step, where the porphyrin unit was immobilized on the amino-functionalized
silica gel surface (SiPn), was well-succeed.

3.2.2. FTIR Characterization

To confirm the presence of porphyrinic moieties in the prepared material (SiNTPP), FTIR
spectra were acquired for starting silica (Si), SiPn and SiNTPP, respectively (Figure 1). For
Si, the broad and intense band at around 3462 cm-1 is attributed to the O–H stretching
vibration of the silanol group [49]. The intense peak at around 1638 cm-1 is assigned to the
stretching vibration of Si–OH, the intense band at 1096 cm-1 is related to the Si–O–Si
stretching vibration and the band around 972 cm−1 is resulted from Si-O vibration [50]. In the
FTIR spectrum of SiPn, new peaks appeared at 2979 cm-1 and 1563 cm-1 corresponding to
(C–H) and (NH2) stretching vibrations, respectively [51]. These peaks indicate necessarily
the presence of 3-aminopropylsilane on the silica particle surface. After the reaction of SiPn
with 2-CHO-TPP, the band at 1563 cm-1, corresponding to (NH2), almost disappeared
indicating the reactivity of the amine function. We also notice the appearance of two new
characteristic bands at 1560 cm-1and 1472 cm-1 corresponding to the (C=N) and (C=C)
vibrations respectively. These results indicate the successful immobilization of porphyrin onto
the silica surface.

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).

3.2.4. Material Surface Properties

To show the surface and porosity changes of the porous silica, induced by the insertion of
porphyrin units in the silica surface, we measured the surface area SBET
(Brunauer−Emmett−Teller) and the pore diameter and pore volume of blank silica and its
material derivatives using nitrogen adsorption−desorption isotherms (Figure 3) and BJH
methods (Barrett−Joyner−Halenda) [52] (Figure 4) respectively. As shown in Table 1, it is
clear, that the density of pendant groups covalently bonded to the inorganic silica backbone
changes the original characteristics of the surface. Indeed, the decrease in SBET and in pore
volume, first for SiPn and second for SiNTPP, is mainly due to the presence in each stage of
additional organic units that can block the nitrogen adsorption–desorption. Moreover, the
nitrogen adsorption–desorption isotherms for SiPn and SiNTPP shown in Figure 3 are type
IV according to the I.U.P.A.C. classification and display a pronounced hysteresis for partial
pressures P/P0 > 0.
 Figure 3. Nitrogen adsorption–desorption isotherm plots of SiPn and SiNTPP.

Figure 4. BJH adsorption-desorption pore distribution of SiPn and SiNTPP.

Table 1. Physical properties of silica derivatives.

Silica Specific surface Pore volume
Derivatives SBET (m2.g−1) (cm3.g−1)
Si 434.6 ± 4.6 0.670 ± 0.002
SiPn 328.8 ± 5.6 0.480 ± 0.003
SiNTPP 242.3 ± 4.1 0.38 ± 0.01

3.2.5. TGA Analysis and Thermal Stability

The thermal stability of the prepared material was assessed by thermogravimetry and
allowed to confirm the presence of porphyrinic and aminopropyl groups attached into the
silica surface. The TGA curves were undertaken on both activated silica precursor (Si) and on
the modified silica materials (SiPn and SiNTPP). The curves are represented in Figure 5,
where the activated silica (Si) reveals the first mass loss up to 110 °C, which is attributed to
the release of water [53,54], followed by a second mass loss up to 800 °C due to the
condensation of free silanol groups on the surface of the silica gel [55]. Similarly, to the
activated silica (Si), SiPn and SiNTPP also show water loss followed by decomposition of
the organic groups anchored on the silica surface [56]. This result confirms the
immobilization of the organic counterparts on the silica.

Figure 5. Thermogravimetric curves of activated silica Si, SiPn, and SiNTPP.

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.

3.3. Adsorption Studies

3.3.1. Effect of pH
It is well-known that pH is one of the main variables affecting the sorption process. In fact,
it is an important factor governing the adsorption capabilities of the adsorbents for metal ions,
especially those containing functional groups such as amino groups. Such groups may be
easily protonated or deprotonated to form different surface charges in solutions at different
values of pH. The effect of pH on the adsorption of Pb(II), Zn(II), Cd(II) and Cu(II) was
investigated in the pH 1–7 range as shown in Figure 7. The results showed that, at lower pH
values, the retention is not significant, since the porphyrin receptor should be in the full
protonated form. With increasing pH, the protonation decreases which improves the
adsorption to reach its maximum at pH 5 to 7. At pH > 7, it was witnessed a decreased
adsorption due to the hydrolysis of metal ions (leading to M(OH)+ and M(OH)2 hydroxides),
this causes ambiguity between the M(II) hydrolysed or adsorbed. Therefore, the optimum pH
for a maximum adsorption of Pb(II) and Cd(II) was at pH ≥ 5, whereas for Zn(II) and Cu(II)
the maximum adsorption was at pH ≥ 6.
Figure 7. Effect of pH on the adsorption of studied metal ions on SiNTPP. Adsorption dose: V = 10 mL, m = 10
mg of SiNTPP at optimum concentration (53.17 ppm in each case), t = 35 min and 25°C. Lines just combine the
points.

3.3.2. Effect of Contact Time and Adsorption Kinetics

In order to establish an appropriate contact time required for the adsorption of the metal
ion by the modified silica, the achievement of the equilibrium conditions is of considerable
importance. The effect of contact time on the extraction of Pb(II), Zn(II), Cd(II), and Cu(II)
by SiNTPP was studied by the batch experiments. As can be seen from Figure 8, the kinetic
curves of metals under study showed that the adsorption was fast; most of the amount of the
studied metal ions was adsorbed after 5 min and the plateau was reached after about 25 min of
contact. The prompt adsorption of different metal ions suggests that the donor atoms of
tetrapyrrolic derivatives present on the modified silica gel surface, are so oriented that their
accessibility is not hindered and consequently, fast interaction with the free metal ions present
in aqueous solution is feasible. The variation of the adsorption abilities is likely a
consequence of metals and the cavity sizes. Thus, the great advantage of porphyrinic
macrocycles is the easily modulation of the macrocycle core to the metal ions size. It is
known that porphyrins can respond in several ways to a mismatch in size between the metal
ion (see table 2 for metal ionic radius) and the macrocycle cavity (2.03 ± 0.8 Å) [57]. Indeed,
the bonds are stretched or compressed depending on whether the metal ion is too small or too
large as previously described in literature for the metal ions under study [58].
It is known, that in general, in solution, the direct metalation of porphyrins with bivalent
metals proceeds via the initial formation of sitting-atop (SAT) complex in which the metal sits
above the porphyrin plane but with the two inner N-H protons still present. Depending on the
metal ion size and spin multiplicity a second step can occur involving its incorporation into
the macrocycle core accompanied by the loss of two N-H protons. The activation energy of
the rate-limiting step is dependent on the metal ions and can explain the different selectivity
with respect to the different metals [58,59].
On the other hand, it should be pointed out the relevance of the porphyrin receptor, grafted
onto silica surface (SiNTPP), on heavy metal adsorption. Indeed, native silica (Si) shows only
negligible adsorption (e.g. 0.0 mg.g-1 and 1.4 mg.g-1 for Pb(II) and Cd(II), respectively) as
already shown in our previous work [60]. For SiPn, it has been already pointed by other
authors that its adsorption capability toward for example Pb(II) is only 23.70 mg.g-1 [61],
while for SiNTPP it is 53.20 mg.g-1.

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):

qt = qe{1 - exp(-k1t)} (3)

t 1 1
= 2 +
t (4)
qt k2 qe qe
 Where qe and qt are the amounts of metal ions adsorbed (mg.g−1) at equilibrium and at time
t, respectively, and k1 and k2 are the rate constants of the first- and second-order adsorption,
respectively.
Results of pseudo-first-order and pseudo-second-order parameters are given in Table 2 and
Figure 9. It is evident that the values of regression coefficient obtained by the pseudo-second
order model are much higher for each metal under study. Furthermore, theoretical qe values
are close to the experimental values for pseudo-second-order kinetics indicating that the
pseudo-second-order model fitted well with the experimental adsorption data for Pb(II),
Zn(II), Cd(II), and Cu(II). It should be also noted that the results of Table 2 obviously show
the more selective of SiNTPP material towards Pb(II) in terms of mass quantity. However, in
terms of molar quantity the highest selectivity was found for Zn(II). In order to compare with
other studies reported in the literature and also thinking in practical applications, in this study
we decided to adopt mass quantity since we believe it is more traceable.

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.

3.3.3. Thermodynamic Modelling

A thermodynamic study, conducted by the Gibbs free energy change, was required to
conclude whether the adsorption process is spontaneous or not. The thermodynamics
parameters as enthalpy of adsorption (ΔH°), free energy of adsorption (ΔG°), and entropy of
adsorption (ΔS°) were studied by carrying out the adsorption experiments between 25 °C and
45 °C and using the following equations [62]:

C0  Ce V
Kd  (5)
Ce m
S 0 H 0
ln Kd   (6)
R RT
G°= H°- TS° (7)

Where C0 (mg.L-1) is the initial concentration of metal, Ce (mg.L-1) is the equilibrium

concentration, V (mL) is the volume of solution, m (g) is the mass of adsorbent, R is the
universal gas constant (8.314 J.mol.-1K-1), and T (K) is the temperature.
The values of ΔH° and ΔS° were determined from the slope and the intercept of the plots
of ln Kd versus 1/T. The ΔG° values were calculated using equation (5). The results are given
in Table 3 and Figure 10. It is clear that ΔH° values are positive due to the endothermic nature
of the adsorption. The positive values of entropy (ΔS°) show the increase in randomness at
the solid/solution interface during the sorption of Cu(II), Zn(II), Cd(II) and Pb(II). These
positive values are responsible for making the ΔG° < 0 [63], indicating the spontaneous nature
of adsorption which is more favourable at high temperature. The adsorption process of metal
ions suggests that a large amount of heat is consumed to transfer the Cu(II), Zn(II), Cd(II) and
Pb(II) metal ions from aqueous solution into the solid phase [64].

Table 3. Thermodynamic parameters for adsorption models used in this work.

Metal ΔH° (kJ.mol-1) ΔS° (J.k-1.mol-1) T (K) ΔG° (kJ.mol-1)

299.15 -0.19
Pb(II) 11.09 37.73 309.15 -0.57
319.15 -0.95
299.15 -0.83
Zn(II) 20.03 69.75 309.15 -1.53
319.15 -2.23
299.15 -0.97
Cd(II) 22.61 78.84 309.15 -1.76
319.15 -2.55
299.15 -1.10
Cu(II) 25.64 89.42 309.15 -2.00
319.15 -2.89

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.

Table 4. Adsorption isotherm parameters of heavy metals onto SiNTPP.

Metal Langmuir isotherm model Freundlich isotherm model

q (mg.g-1) q (mmol.g-1) KL (L.mg-1) R2 KF (mg.g-1) n R2

Pb(II) 59.88 0.289 0.089 0.996 2.430 2.082 0.647

Zn(II) 37.03 0.566 0.061 0.998 4.224 2.224 0.928
Cd(II) 25.00 0.222 0.127 0.997 4.182 2.457 0. 913
Cu(II) 20.01 0.315 0.168 0.998 3.671 1.661 0.880
3.3.5. Selectivity adsorption of SiNTPP
Competitive adsorption experiments for SiNTPP were carried out from the mixed Pb(II)-
Zn(II)–Cu(II)–Cd(II) quaternary system using an aqueous solution containing optimum
concentration of each metal ion, required to reach a plateau shape, through the batch method.
Figure 13 shows the adsorption capacity of metal ions in the quaternary system. It is obvious
that SiNTPP displays an excellent adsorption for Pb(II) in this competitive mode. However,
the extraction seems to decrease with regard to the value obtained in the individual mode
experiments, indicating a competitive complexation with the four mixed metal ions.
Nevertheless, the remarkable selectivity toward Pb(II), in terms of mass quantity, suggests
that the new material could be used as a promising potential adsorbent, for the removal of
Pb(II) from aqueous solutions containing competing ions.

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).

3.3.6. Extraction of Heavy Metal in Natural Real Water Samples

Taking into account the final application of the prepared material, the extraction of heavy
metals in natural real water samples were performed. This study was performed to evaluate
the capability of SiNTPP for extraction of Pb(II), Zn(II), Cd(II), and Cu(II) in real condition
using natural water samples from Moulouya River (Morocco). All samples were collected,
using a polyethylene bottle, were filtered through a nylon 0.45 μm membrane and studied
without storage. The applicability of SiNTPP for retention of heavy metals was performed, in
a batch method, by mixing 10 mg of the adsorbent, 10 mL of the river water and 0.5 mL of
1% HNO3 at room temperature. Concentrations of metals ions were determined by atomic
absorption measurements. Assays were performed in duplicate for each sample and the
average data are reported in Table 5. Once more, the values show the efficiency and
selectivity results especially for Pb(II).

Table 5. Extraction of heavy metals in natural real water samples.

Water samples Metal ion Cfound  0.05 Capacity of SiNTPP

(mg.L-1) (mg.g-1)
Pb(II) 1.21 0.18
Cd(II) 1.52 0.12
Moulouya River
Cu(II) ND -
Zn(II) ND -
Cfound is the Initial metal contents in river water determined by atomic absorption measurements.
ND: Not detectable.

3.3.7. Regeneration of the Adsorbent Assessment

Desorption experiments showed that samples could be easily regenerated simply by
washing them with HCl solution for a few minutes. Indeed, SiNTPP was tested to repetitive
adsorption and desorption of Pb(II) for five cycles of adsorbent regeneration. The recovery
remained around 94-98% in each cycle suggesting no significant change in the percentages of
adsorption (Table 6). The stability of the organic groups onto the solid surface was also
confirmed by TGA, with no distinct changes in the sorbent material after five cycles of
utilisation.
Table 6. Adsorption / regeneration of hybrid material toward Pb(II).

Cycle number Pb(II) (mg.g-1)

1 52.13
2 50.54
3 51.07
4 51.61
5 50.05

3.3.8. Comparison with Alternative Materials

The adsorption efficiency of SiNTPP towards Pb(II), Zn(II), Cu(II) and Cd(II) was
compared with the one of other materials reported in the literature (Table 7). It is clear, from
the results summarized in Table 7, that the functionalized silica described in this work,
presents, in terms of mass quantity adsorbed, further improvement and shows better
adsorption capacity values and higher affinity for an effective adsorption of the metal cations
under study when compared to other adsorbents reported in the literature.

Table 7. Comparison of adsorption capacities of SiNTPP with some other reported sorbents.

Silica gel - ligand Reference Adsorption capacity (mg.g-1)

Pb(II) Zn(II) Cu(II) Cd(II)
Porphyrin (this work) - 55.17 34.62 19.08 26.46
3-Aminopropyltriethoxysilane (SiPn) [61] 23.70 - 19.20 14.10
p-toluenesulfonylamide [67] 33.20 12.60 5.00 -
Dithiocarbamate [68] 42.19 26.01 25.00 10.01
2-Hydroxy-3-methoxy benzaldehyde [69] 2.27 - 4.70 -
Gallic acid [70] 12.63 - 15.38 6.09
C,N-pyridylpyrazole [71] 9.50 0.0 1.8 1.4
Thiophene [72] 11.30 - 5.08 2.10
Calix[4]arene polymer [73] - - 5.08 -
Cetyltrimethylammonium bromide [74] - - 32.20 8.00
3-(2-aminoethylamino)propyl [75] 19.61 - - -
3-mercaptopropyl [76] 32.58 - - -

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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