Microporous and Mesoporous Materials 247 (2017) 145e157

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Review

Adsorption of heavy metals on functionalized-mesoporous silica:

A review
Enshirah Da'na
King Faisal University, Eastern Province, Saudi Arabia

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

Article history: This work is summarizing the main researcher's contributions in the development of heavy metals
Received 6 January 2017 adsorbent. Emphasis has been placed on the factors affecting the performance of the adsorbents such as
Received in revised form support structural properties, functional groups chemical properties, and properties of the combined
20 March 2017
inorganic-organic structure. The review includes adsorbents synthesized by two major synthesis routes
Accepted 27 March 2017
Available online 2 April 2017
namely (i) grafting and (ii) co-condensation. This literature review is aiming to trace the main
achievements toward the synthesis of an efficient heavy metals adsorbent.
© 2017 Elsevier Inc. All rights reserved.
Keywords:
Adsorption
Mesoporous silica
Grafting
Cocondensation
Heavy metals
Functionalization
Water treatment

1. Introduction environment friendly technologies. Adsorption is now considered

Heavy metal ions get into water system via several
manufacturing processes such as refining, fertilizer, and pesticides
and pose a severe risk to the environment [1]. Similar to other
pollutants, exceeding a threshold concentration in water, heavy
metals are harmful to human as well as other living organisms due
to their toxicity and bio-accumulation. Nonetheless, trace elements
are essential nutrients required by the human body, consumption
of high doses can lead to health complications such as irritation of
the central nervous system, and kidney and liver hurt [2]. Thus,
removing excess heavy metals from industrial effluents before
discharging is an important issue for health and environment
safety.
Many conventional approaches have been utilized for elimi-
nating these cations from water system such as coagulatione-
flocculation, chemical precipitation, flotation, reverse osmosis,
reverse osmosis, ion exchange, and ultra-filtration [3,4]. Never-
theless, these methods have their own restrictions such as low ef-
ficiency, sensitive working environments, and production of toxic
slurry [3]. Hence, there is an urgent need for more practical and
E-mail address: edana@kfu.edu.sa.
among the most effective, economic and selective methods for
water treatment and analysis purposes [4]. Activated carbon has
been extensively employed to purify contaminated water [5]
because it has very high surface area, chemically stable, and dura-
ble. Nevertheless, their random pore geometry restricts pollutant
species reaching to the adsorption sites, which in sequence, lowers
removal efficiency. Furthermore, activated carbon prices keeps
going up [4], which encouraged many researchers to focus on
developing cheaper and more effective adsorbents based on natu-
rally occurring materials such as agricultural waste materials. In
addition to being cost-effective and environment friendly, agri-
cultural waste is plentiful, renewable, and cheap. These agricultural
residuals can be used to adsorb metal cations directly without any
modification. However, Chemical or physical modifications were
recently reported to improve adsorption capacity [3,6e8]. Other
researchers have utilized bacteria, fungi, algae and yeast for
adsorbing heavy metals from aqueous solutions and reported sig-
nificant capacities [9].
Another approach was to utilize natural materials and residuals
for the development of new adsorbents. Among these adsorbents,
clays and soil constituents [10], red mud [11], chitosan [12], natural
zeolites [13] and fly ashes [14] have many advantages such as
availability in large quantities and low cost. In addition, they can be

http://dx.doi.org/10.1016/j.micromeso.2017.03.050
1387-1811/© 2017 Elsevier Inc. All rights reserved.
146 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157
chemically modified to increase their binding capacity. However,
these adsorbents show many disadvantages because of their het-
erogeneous structure, irregular pore size distribution, low adsorp-
tion capacity and low metal selectivity. Thus, it is essential to
develop a new adsorbent that meet specific requirements,
including:
(i) Well-designed pore size and geometry with open pore
structure to achieve fast kinetics,
(ii) Accessible adsorption sites and suitable surface properties to
achieve high adsorption capacity,
(iii) High target metal selectivity in the existence of other ions
such as Naþ and Ca2þ,
(iv) Simple synthesis,
(v) Low cost, taking into consideration not only the material
synthesis cost, but also equipment cost, which depends on
adsorbent performance,
(vi) Regeneration ability under mild conditions,
(vii) Long term stability upon adsorption-desorption cycling.
Mesoporous silica for instance MCM-48, MCM-41, HMS, and
SBA-15 are considered superior in this type of applications due to
large surface area, narrow pore-size distributions and controlled
pore sizes [15]. Also, its affinity towards target metals can be
improved by introducing suitable functional groups to the surface
[16e18]. This review focus on latest developments in the synthesis
and evaluation of mesoporous silica as heavy metals adsorbent.
These materials will be divided into two categories based on the
functionalization route, the advantages and disadvantages of each
route in addition to the factors affecting the adsorbent efficiency
and selectivity will be discussed qualitatively in details.
2. General properties of mesoporous materials
Ordered structure mesoporous silica has attracted researchers
attention due to their important applications such as catalysis
[19e22], environmental protection via adsorption of CO2 [23e29],
adsorption of heavy metals from aqueous solutions [30e56],
adsorption of organic pollutants [57e60], adsorption of volatile
organic compounds [61], separation [62e67], medical applications
[68e75], and sensing applications [74e77]. The importance of
mesoporous materials came from their pore sizes, which allow
controlled accessibility for large molecules, depending on pore
geometry. Furthermore, the ordered mesoporous materials have
open pore structure, which allows improved access and transfer of
target molecules compared to bottleneck pores of amorphous
materials, which resist molecular diffusion to the adsorption sites
[78].
In 1990, Kuroda et al. [79] synthesized mesoporous silica with
uniform pore size distribution known as Folded Sheet Materials
(FSM-16). In 1992, scientists at Mobil developed a new mesoporous
silica labeled as M41S and reported MCM-41 and MCM-48 as new
members of this family [80,81]. In 1995, Tanev and Pinnavaia [82]
synthesized Hexagonal Mesoporous Silica (HMS) by means of
neutral templates. In 1998, Stucky et al. [83,84] described the
synthesis of Santa Barbara Amorphous (SBA-15), which is one of the
most promising mesoporous materials. This highly ordered mate-
rial has hexagonal structure with thick pore walls and tunable pore
diameter. Thus, it seems to be a good candidate for separation
processes such as adsorption.
Environmental applications of mesoporous silica for adsorption
of heavy metals require the material to have specific adsorption
sites for the target ions; however, silica does not have such sites.
Therefore, immobilization of appropriate chemical groups in the
mesopores has attracted much attention [16,17]. Generally,
mesoporous silica synthesis is performed by condensing a source of
silica in the existence of a suitable template agent followed by
template removal and eventually anchoring of special functional
groups onto the silica surface. Functional groups anchoring can be
achieved by three main routes: (i) using a functionalized silane, (ii)
co-condensation of silane with the silica, and (iii) post grafting of
the silica [33].
The earliest reports on adsorption applications of functional-
ized mesoporous materials are dedicated to heavy metals in
wastewater using propylthiol-modified MCM-41 [85] and HMS
[86] silica. Since then, adsorption of metal ions from wastewater
on functionalized mesoporous silica has attracted researcher's
attention. Among the many silica mesophases, SBA-15 attracted
much attention for many applications such as water treatment
[30e32,61e66], catalysis [93] adsorption of biomolecules [94] and
CO2 [95]. The strong interest in this material is related to its huge
surface area (600e1000 m2/g), narrow pore size distribution,
large and controlled pore diameter (5e30 nm), which facilitate
metal ions diffusion to the internal pore structure, resulting in fast
adsorption kinetics [87]. Furthermore, it is considered hydro-
thermally stable because of its thick walls, about 4 nm in com-
parison to 1 nm for MCM-41 [86]. In addition, enhancement of the
mechanical stability due to increased pore wall thickness is
important for some applications using compressed pellets [97]. All
these features make SBA-15 a promising support to introduce
many functionalities (-NH2, -SH, -S-, etc.) for developing suitable
adsorbents for the target application [39,44,48e50,53,55].
3. Functionalization of mesoporous silica
Co-condensation (one pot-synthesis) and grafting (post-syn-
thesis) are the two main routes that have been extensively studied
for adjusting the mesoporous materials via covalent bonding of the
organic functionality and the silica. In addition, mesoporous ma-
terials having functional groups within the framework, called pe-
riodic mesoporous organosilicates, have also been used for the
elimination of heavy metals [98,99].
The post-synthesis grafting methodology was used to integrate
a wide range of functional groups to the pre-synthesized meso-
porous silica's walls. The characteristics of the functionalized ma-
terials prepared by grafting are influenced by their structural
properties and chemical composition [40].
Another main route for introducing functionality is co-
condensation where the organosilane and silica precursor are
condensed together. Co-condensation shows many benefits such as
uniform spreading of the functional groups and faster synthesis.
Furthermore, it is very efficient in immobilizing huge amounts of
functional groups onto the mesoporous silica surface.
3.1. Adsorption of heavy metals on mesoporous silica prepared by
grafting
Development of heavy metals adsorbents depends on
combining the open pore structure of mesoporous silica with
suitable organic compounds that exhibit high reactivity toward the
target metal ions. Grafting route was used for mesoporous silica
modification by many different organic functionalities. One major
factor affecting the performance of grafted adsorbents is the
appropriate choice of the organic group. As an example, Liu et al.
[80] synthesized thiolated and aminated SBA-15 adsorbents and
tested their affinity for heavy metal cations. They found that the
thiolated SBA-15 have a negligible affinity for copper, while the
aminated ones have exceptional binding ability. Similarly, Lee et al.
[40] studied adsorption of heavy metal ions on aminated and
thiolated large-pores mesoporous silica and reported the same
 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157
results. In contrast, some researchers reported excellent Hg
removal efficiency on thiolated mesoporous silica compared to the
aminated ones [36,46]. Lee and Yi [81] grafted 3-(2-aminoethyl-
amino)propyltrimethoxysilane onto HMS mesoporous silica sur-
face. Their functionalized silica had copper removal capacity 10
times more than that of silica gel.
One main concern about grafting is that it reduces the pore size
of the modified-materials, especially when large size or large
amount of functional groups are introduced [32,102e111], resulting
in restricted diffusion to the adsorption sites. Mureseanu et al. [102]
reported a sharp decrease in pore volume and surface area of silica
after grafting (Table 1). For example, pore volume and surface area
of aminopropyl functionalized SBA-15 (NH2-SBA-15) with an
average of 3.1 aminopropyl molecules per nm2, decreased by 52%
and 53%, respectively, compared to the SBA-15 support [102].
Shiraishi et al. [112] studied adsorption of copper on many inor-
ganic adsorbents (MCM-41, silica gel, and aluminum oxide), func-
tionalized with ethylenediaminetetraacetic acid (EDTA) and
diethylenetriaminepentaacetic acid (DTPA). The EDTA loading on
the adsorbents surface was lower than DTPA loading. However, it
was found that the Cu2þ removal efficiency of DTPA-modified silica
was significantly lower than that for EDTA-modified material. This
suggests that the binding ability of DTPA attached to the silica is
lower than that of EDTA, despite the fact that copperDTPA com-
plex stability constant is reported to be higher than that of cop-
perEDTA complex in aqueous solution [112]. This is mainly
because DTPA molecule is bigger than that of EDTA, and since these
molecules are attached to the surface of the silica, adsorption of the
metals on DTPA is expected to be restricted. Furthermore, as more
DTPA ligand was anchored, more reduction of the pore size and
some pore blockage is expected.
Since grafted organic groups on mesoporous silica is often not
evenly distributed, the apparent density of functional groups on the
solid does not tell the real average space between such groups. This
difficulty in prediction of the real distribution resulted in a problem
in adsorption of metal ions, which required the linking with two or
more surface ligands. Manu et al. [113] investigated the impact of
amine surface loading of mesoporous silica gel. They prepared
propylamine-functionalized mesoporous silica gel with three
different loadings, namely GN1, GN2, and GN3. They reported a
nonlinear relation between the adsorption capacity and amine
groups loading on the silica gel surface. This is mainly related to
irregular distribution of functional groups obtained by grafting
since large silane molecules suffer diffusion limitations to penetrate
deep into the pores, and consequently, they may tend to react with
the hydroxyl groups near the pore mouth, leading to some pore
blockage, thus decreasing surface area, pore volume, and accessi-
bility of functional groups (Table 1). Walcarius et al. [114] reported
that a minimum pore volume of 0.5 cm3g-1 after grafting was
necessary to have good accessibility to the adsorption sites. Pin-
navaia and Mercier [115] tested accessibility of thiol groups grafted
on mesoporous silica via adsorption of Hg. Their results showed
improved accessibility of the active binding sites with well-defined
mesoporous channels, compared to disordered structure materials,
such as amorphous silica. Yuan et al. [54] grafted amino groups
onto large pore size (10.3 nm) and small pore size silica (2e4 nm).
Their results confirmed a great effect of the pore size on the
adsorbent performance. The large pore size one was grafted with
447 mg/g amino groups and showed high adsorption capacity
(Pb2þ: 880.6 mg/g, Cu2þ: 628.3 mg/g, Cd2þ: 492.4 mg/g) compared
to the small pore size samples [54].
Additional exploration of the effect of amine groups accessibility
on adsorption performance was performed by Zhang et al. [32].
They prepared mono-, di- and tri-amine-grafted on SBA-15 and
showed that these multi-amine grafted silica have nearly identical
147
affinity to Hg2þ, Pb2þ, Zn2þ, Cu2þ, Cd2þ in wastewater and can
efficiently remove them totally. The introduction of multi-amine
silane resulted in great density of N groups and great adsorption
ability showing the high accessibility of amine groups in the larger
pore channels of SBA-15 [116], thus the adsorption capacity was
improved. Using smaller pore MCM-41 silica, Yokoi et al. [116]
indicated that the aminosilane react with silane groups on the
surface located at the pore mouth and/or on the external surface.
Thus, the amine groups concentrated at the pores entrance would
hindered the diffusion of additional aminosilane into the pore,
resulting in a non-uniform distribution of amino groups within the
pores. Furthermore, the accumulation of the amine-organic moi-
eties at the pore entrance would reduce the effective pore size
(Table 1), reducing target molecules binding with amine groups
attached to the pores.
In addition to easy access, the rate at which cations reach the
active sites in the mesoporous material is also an important factor
affecting its efficiency. Walcarius et al. [114,117] studied the speed
at which copper ions reached active sites of aminopropyl-grafted
silica. They found that the size and the charge of the target spe-
cies to be adsorbed influence the kinetic of the process. Walcarius
et al. [117] compared between Cu2þ complexation with the amine-
grafted silica gel and the protonation process of the adsorbent using
HCl. The calculated Cu2þ diffusion coefficient was 3e4 times
smaller than that of Hþ, which is mainly due to the larger size of
Cu2þ compared to Hþ. Furthermore, adsorption of Cu2þ involves
diffusion of two positive charges, thus suffering more repulsive
force. The same group [114] studied the ability of metal ions to
reach the adsorption sites of APTESMCM-41 and APTESSBA-15
by protonation with HCl. They indicated that the extents of
consumed protons to reach the equivalent point for APTESMCM-
41and APTESSBA-15 corresponded to 79% and 85%, respectively of
the overall quantities of amine groups in each sample. The
incomplete protonation is due to some pore blocking in materials
with narrow openings. Furthermore, they evaluated the speed at
which copper ions reached the active sites of aminopropyl-grafted
silica having a pore diameter in the range 4 and 15 nm and organic
loads of 1.4e1.9 mmolg1. They found that the diffusion process
was very limited compared to those detected in homogeneous
solution, depending on a number of parameters such as adsorbent
pore size, target metal size, functional groups surface density, and
the structure of the silica used. The same group [114] grafted
aminopropyl on different ordered mesoporous silica with different
pore sizes and configurations (MCM-41 and MCM-48) and silica gel.
They studied copper accessibility to the adsorption sites and the
adsorption rate. They reported that both accessibility and rate of
adsorption were greater using ordered mesoporous silica with
average pore size of 6e7 nm, while the ordered mesoporous
structures of pore size (3.5 nm) showed similar efficiency as that of
large-pore silica gel. Furthermore, they demonstrated that the
benefit of ordered materials can be achieved by avoiding pore
blocking during the grafting procedure, otherwise there would be
no benefit of uniform pore structure in comparison to the disor-
dered materials.
The ordered structure of the adsorbent is expected to improve
its performance by improving accessibility to the adsorption sites
and/or speeding up transport processes within the pores. However,
this is not applicable under all conditions; Goubert-Renaudin [103]
found that binding sites accessibility of cyclam-functionalized silica
was not the most important factor affecting the maximum
adsorption efficiency and that ordered structure of the adsorbent
did not result in a faster kinetics of the copper adsorption. This is
mainly because the rate-limiting step was complex formation itself
and not diffusion. The rate of Cu2þ binding with cyclam groups in
aqueous solution was faster in basic medium because of functional
148 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157

Table 1
Structural properties and functional group content.

Adsorbent Surface area (m2g1) Pore size (nm) Pore volume (cm3g1) Functional group Ref.
loading (mmolg1) or%

SBA-15 775 6.8 1.20 e [32]

N-SBA-15 373 6.0 0.76 1.41 [32]
NN-SBA-15 336 6.1 0.76 2.59 [32]
NNN-SBA-15 256 6.1 0.74 4.00 [32]
MSU-H 580.27 0.0689 [33]
MSU-H-AM 44.28 [33]
MSU-H-GM 4.77 [33]
MSU-H-MM 86.08 [33]
MSU-H-VM 36.86 [33]
MSU-H-pM 114.47 [33]
SBA-15-p 767 7.2 0.99 0% [40]
NH2-SBA-15-p 504 5.2 0.67 8.7% [40]
NH2-SBA-15-f 580 5.2 0.75 9.3% [40]
NH2-SBA-15-r 626 5.5 0.78 8.2% [40]
SH-SBA-15-p 504 5.6 0.67 9.6% [40]
SH-SBA-15-f 652 3.8 0.79 10.2% [40]
SH-SBA-15-r 637 3.4 0.84 7.3% [40]
APTS-SBA-15-AB 673 7.6 0.75 1.77 [92]
FSM-16 1000 2.9 1.26 e [99]
SBA-15 814 7.6 e [100]
SBA-15(SH) 416 e 0.66 e [100]
SBA-15(NH2) 279 e 0.45 e [100]
Commercial silica 294 14.7 1.16 e [101]
HMS (Soxhelt extracted-36 h) 1062 2.46 1.15 0.22a [101]
HMS (microwave extracted) 995 2.47 1.12 0.21a [101]
SBA-15 697 8.3 1.49 e [102]
NH2-SBA-15 368 7.8 0.77 3.1b [102]
SA-SBA-15 317 6.9 0.53 3.2b [102]
K60 457 e 0.81 e [103]
K60-mono 316 e 0.40 0.52 [103]
K60-di 380 e 0.46 0.37 [103]
K60-tetra 399 e 0.47 0.25 [103]
SBA-15 836 e 1.13 e [103]
SBA-15-mono 368 e 0.6 0.63 [103]
SBA-15-di 400 e 0.6 0.46 [103]
SBA-15-tetra 441 e 0.59 0.31 [103]
SBA-15 790 9.1 1.44 e [104]
SBA-15-N-C 345 7.2 0.58 1.9 [104]
SBA-15-N-C-H 178 6.4 0.28 2.8 [104]
SBA-15-N-E 565 9.0 1.02 3.1 [104]
C-SBA-15-N 572 8.2 0.87 0.9 [104]
C-SBA-15-NN 508 8.3 0.78 1.9 [104]
C-SBA-15-NNN 477 8.1 0.74 1.8 [104]
OSU-6-W 1283 5.11 1.24 e [105e107]
OSU-6-W-TCSPBr-1 1048 4.30 0.94 2.55b [105e107]
OSU-6-W-TCSPBr-2 719 3.65 0.76 4.53b [105e107]
MCM-41 1070 3.09 e e [104e110]
NH2-MCM-41 772 2.82 e 1.01 [104]
NH2-MCM-41 774 2.92 e 2.26 [108]
SH-MCM-41 990 3.02 e 1.00 [108]
COONa-MCM-41 679 2.85 e 1.46 [109]
NH2-MCM-41 750 2.92 e 2.53 [109,110]
MSM-e 672 2.9 1.05 e [111]
2N-MSM-e 513 2.0 0.35 5.66c [111]
GN1 575 4.72 0.61 e [113]
GN1 444 4.03 0.58 0.51 [113]
GN2 363 3.95 0.49 1.01 [113]
GN3 360 3.58 0.40 1.45 [113]
APS-MCM-41-A 87 e 0.16 3.3 [114]
APS-MCM-41-B 428 e 0.24 2.8 [114]
APS-MCM-41-C 411 e 0.76 2.6 [114]
APS-SBA-15 357 e 0.73 2.2 [114]
APS-MCM-48 662 e 0.31 3.0 [114]
MPS-MCM-41-A 162 e 0.19 2.8 [114]
MPS-MCM-41-B 818 e 0.52 1.55 [114]
MPS-MCM-41-C 706 e 1.24 1.0 [114]
MPS-SBA-15 467 e 0.79 1.0 [114]
MPS-MCM-48 390 e 0.23 2.7 [114]
MCM-41-AEDTC 632 4.16 0.54 32a [122]
MCM-41 1000 3.17 e e [123]
magMCM-41 800 3.2 e e [123]
NH2-magMCM-41 670 2.92 e 2.8 [123]
LDAPY-MCM-41 246 1.2 0.26 0.30 [125]
 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157 149

Table 1 (continued )

Adsorbent Surface area (m2g1) Pore size (nm) Pore volume (cm3g1) Functional group Ref.
loading (mmolg1) or%

NH2/SiO2/Fe3O4 73 e e [128]
SH-SBA-16-A 427 4.7 0.47 6.37 [128]
SH-SBA-16-B 320 4.1 0.38 6.99 [128]
SH-SBA-16-C 198 3.9 0.37 7.69 [128]
SH-SBA-16-D 188 3.7 0.29 8.23 [128]
SH-SBA-16-E 186 3.6 0.14 9.03 [128]
Na50 869 4.3 e 0.76c [128]
Na25 881 4.8 e 0.94c [129]
Na5 649 4.8 e 1.94c [129]
NH2-SBA-15 908 8 1.41 e [130]
TCPP/NH2-SBA-15 453 7.73 0.70 e [130]
GC1.5N 314 4.5 0.46 2.34 [131]
GC3N 360 4.7 0.50 2.10 [131]
GC4.5N 339 5.0 0.49 1.85 [131]
GC6N 347 4.2 0.49 1.65 [131]
DMDDA-41A 63 e 0.28 e [134]
DDA-41A 89 e 0.31 e [134]
DMDDA-48A 124 e 0.16 e [134]
DDA-48A 59 e 0.17 e [134]
NNN/SiO2 889 3.8 e 3.5 [141]
NH2/SiO2/A 336.3 4.6 0.488 e [142]
NH2/SiO2/B 128.4 2.4 0.279 e [142]
NH2/SiO2/C 421.9 6.1 0.556 e [142]
S 687e712 5.1 e 0 [143]
N-S 62e65 e e 1.8 [143]
NN-S 120e220 e e 1.6 [143]
NNN-S 245e314 e e 1.1 [143]
S-S 875e888 4.1 e 2.1 [143]
MNN 663 1.81 e 1.69 [145]
MGNN 614 1.53 e 1.62 [145]
a
Value given as wt %.
b
Value given as group/nm2.
c
Value given as N wt %.

group protonation under acidic conditions. At pH 3.2, Goubert-
Renaudin [103] reported no important differences between or-
dered and non-ordered adsorbents because the adsorption process
was controlled by the slow complexation step. The case was
completely different at pH 5.7, where adsorption on ordered SBA-
15 was much faster than that on amorphous silica. In this case,
mass transfer to the active sites was the rate-limiting step instead
of complexation step. Thus, the benefit from fast mass transfer in
uniform mesopore channels of ordered materials over the amor-
phous can be achieved only if the chemical reaction is fast.
The functional groups do not always have to be directly grafted
on mesoporous silica surfaces via a single step. Yantasee et al. [118]
first grafted MCM-41 with acetamide phosphonate silane (APH-
MCM-41) and propionamide phosphonate silane (PPH-MCM-41).
Then, they converted the ester forms of functionalized materials to
acid forms using trimethylsilyl iodide and water. They studied the
two functionalized adsorbent as potential heavy metals adsorbent.
Other two-steps grafting procedure was reported by Mureseanu
et al. [102]. They first grafted 3-aminopropyl-triethoxysilane (APTS)
followed by salicylaldehyde (SA). They investigated the efficiency of
heavy metal ions adsorption on grafted solids and reported high
selectivity and adsorption capacity for copper ions. They found also
that functionalized SBA-15 is more efficient than modified amor-
phous silica gel, due to higher surface area and ordered structure.
Furthermore, they found that at maximum Cu2þ loading
(0.92 mmolg1) the Cu/N molar ratio was 0.42, which is very close
to the theoretical ratio of 0.5.
Alothman and Apblett [105] prepared di-, tri-, or penta-amine
functionalized mesoporous silica via earlier treatment of a meso-
porous silica (OSU-6-W) with bromopropyl organic then displaced
bromine atoms with di-, tri-, or penta-amine, respectively. They
tested the efficiency of the adsorbents for heavy metal cations
adsorption from aqueous solutions and studied the effect of total
nitrogen content on the adsorption capacities.
Jiang et al. [119] used a multi steps process starting by grafting
propyl amine onto SBA-15 followed by reaction with methyl-
acrylate in the presence of methanol, then reaction with ethyl-
enediamine, resulting in the first generation NH2-SBA-15-G1. The
second, third and fourth generations were similarly synthesized by
repeating the same steps. Finally, they introduced EDTA function-
ality. The NH2-SBA-15-Gn-EDTA adsorbent showed high adsorption
efficiency (>94%) for Cu2þ. Furthermore, they found that samples
with EDTA were more efficient than the other samples. For
example, the copper removal efficiency using NH2-SBA-15-Gn did
not exceed 75% compared to more than 94% using NH2-SBA-15-Gn-
EDTA.
Alothman and Apblett [106,107] modified hexagonal meso-
porous silica (OSU-6-W) with 3-glycidoxypropyltrimethoxyesilane
(GPTMS) functional groups through one and two steps post-
synthesis procedures. First, they activated the material in the
presence of trimethylamine then, refluxed it with GPTMS leading to
(OSU-6-W-GPTMS). The final glycidoxypropyl functionalized mes-
oporous silica (OSU-6-W-GPTMS-2) was synthesized by repeating
the silylation step. They found that the functional group loading on
OSU-6-W-GPTMS-2 was higher than that of OSU-6-W-GPTMS with
a maximum copper uptake of 5.3 mmolg1, forming a 1.7 Cu2þ: 1
ligand complex.
Separation of ions mixture depends on choosing the proper
functional group with higher affinity towards one target ion than
others. As reported by Liu et al. [100], thiol-functionalized SBA-15
exhibited a negligible tendency to form complex with copper,
whereas the aminated ones showed exceptional binding ability.
According to hard and soft acids and bases (HSAB) theory [40], soft
metal ions are more likely to make stable complex with soft donor
150 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157

atoms. Hence, as sulfur is softer donor than nitrogen, the aminated

adsorbents have a higher tendency to complex with the harder
metal ion Cu2þ, whereas thiolated adsorbents display a higher
complexation affinity with the softer ion Pb2þ.
Lam et al. [108,109] applied this strategy for the separation of
silver and copper [108], and separation of Cr2O2 7 and copper [109]
using MCM-41 grafted with suitable functional groups. For copper-
silver separation [108], they compared thiolated (SHMCM-41) and
aminated (NH2MCM-41) mesoporous silica. They found that
SHMCM-41 selectively adsorbed silver ions while copper ions
remained in the solution. Similarly, NH2MCM-41showed higher
selectivity to adsorb copper from the same binary solution. How-
ever, the selectivity of NH2MCM-41 towards copper cations
strongly depended on solution pH. Adsorbents with amine groups
have the ability to adsorb specific cations or anions with different
solutions pH. Neutral amine groups are efficient cations adsorbent,
while protonated amine groups can adsorb anions via electrostatic
attraction [109,120]. Once the solution pH is lower than the pKb of
the grafted amine (The pKb value corresponding to the RNHþ 3 /RNH2
couple is about 4) [121], the protonated form of amine
Fig. 1. Effect of pH on the adsorption capacity.
(NHþ 3 MCM-41) loses its complexation ability for copper ions. Lam
et al. [109] utilized this property to separate copper ions from
Cr2O2 þ
7 . They found that the selectivity of NH3 MCM-41 for
2
adsorption Cr2O7 reach 100% at low pH (<3.5) with high adsorp-
tion capacity reaching the maximum value of two amines for one
Cr2O27 .
Solution pH does not only affect the RNHþ3 /RNH2 ratio, but it also
affects the charge distribution on the adsorbent surface. Since the
surface charge of functionalized-silica results from the protonation
or deprotonation of hydroxyl and active surface functional groups,
one expected effect of the point of zero charge (PZC), the solution
pH at which the surface is neutral, is the dependence of metal ions
adsorption on the solution pH. It is preferred to have low PZC since
it leads to an efficient cations adsorbent in a wide pH range as the
surface will be negatively charged at pH > PZC. Furthermore, the pH
value should be maintained lower than precipitation of metal hy-
droxide. Dimos et al. [122] reported the preparation of MCM-41
grafted with N-(2-aminoethyl)dithiocarbamate (AEDTC) with a
PZC of 3.2, which is one of the lowest PZC reported. This suggests
that in solution with pH value larger than 3.2, the ≡ХΟ species will
formed and thus, the MCM-41 surface will have a negative charge.
Chen et al. [123] reported a PZC of 3.5 for MCM-41 grafted with Fig. 2. Effect of pH on the removal efficiency.
aminopropyl and obtained a maximum copper uptake of
1.3 mmolg1 at pH of 5. Jung et al. [99] reported PZC of 5.44 for
FSM-16 whereas; Da'na and Sayari [100] obtained a PZC of 8.62 for for detection purposes. Ballesteros et al. [125] used a pyrimidine-
amine-functionalized SBA-15 with a maximum capacity of containing hybrid material (LDAPY-MCM-41) synthesized by
0.6 mmolg1 at pH of 6.5. Lam et al. [108] reported a PZC of 2.95 for reacting aminopropyl-grafted MCM-41 with 4-chloro-2,6-
NH2MCM-41 with maximum copper adsorption capacity of diaminepyrimidine. The pyrimidine-derivated material had high
0.3 mmolg1 at pH of 5. Solution pH effect on heavy metal ions selectivity toward copper, and the pre-concentration of copper
adsorption was explored by many other researchers from water was 100 folds. Similarly, Ganjali et al. [126] grafted
[31,35,37,40,41,43,100,103,105,108,125e130], and some of their re- MCM-41 with salophen and used it for pre-concentration of Cu2þ
sults are presented in Fig. 1 and Fig. 2. While generally an increase ions. They obtained a pre-concentration factor of 500 with a
in copper adsorption capacity with increasing pH was reported, detection limit of 34 ngL1, and a maximum capacity of 29 mgg1.
Shiraishi et al. [112] reported that EDTA ligands attached to silica In batch applications, it is difficult to recover functionalized
surface act effectively to form a complex with copper ions at lower mesoporous silica in its powder state. This problem can be solved
pH and this complexation ability decreases with increasing pH and by using adsorbent with magnetic properties. This method includes
vanishes at pH > 4. Despite the fact that the chelating ability be- integration of magnetic materials into the silica to allow these ag-
tween copper and free EDTA increases with increasing pH. This is glomerates to be magnetically separated [35,37,44,45,51,54]. Chen
mainly because increasing the solution pH increases the negative et al. [123] grafted propylamine on MCM-41 in the presence of
charge of the silica surface. Subsequently, the Hþ of the carboxylic 10 wt% iron oxide to introduce magnetic properties to the adsor-
group of the grafted EDTA attaches to the negatively charged bent. Similarly, Lin et al. [127] synthesized amine-grafted silica
adsorbent surface suppressing the complexation between copper magnetite (NH2/SiO2/Fe3O4) to use it for adsorbing anions or cat-
and EDTA. ions by controlling the aqueous solution pH. Kim et al. [111] grafted
Another important application of adsorption of copper on 3-(2-aminoethylamino)-propyltrimethoxysilane on the surface of
functionalized mesoporous silica is the pre-concentration of copper HMS shell containing magnetite-core structure. They indicated that
 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157 151

Cu2þ adsorption on the developed adsorbent fits with the Langmuir
isotherm with qm value of 0.5 mmolg1 and Cu: NH2 molar ratio of
0.049 (Table 2).
Simonescu et al. [37] recently synthesized Fe3O4 magnetite with
o-Vanillin functionalized mesoporous silica and found it a prom-
ising adsorbent for retention of Pb(II) from polluted water. The
adsorbent reached 80e90% of the maximum adsorption capacity
(155.71 mg/g) in 60 min. .SimilarlyYuan et al. [54] developed
mesoporous silica with Fe3O4 magnetic core that exhibits large pore
size, high adsorption capacity and fast adsorption kinetics [54].
Not only the choice of the support and the active groups affect
the performance and the selectivity of the adsorbent prepared by
grafting, the type of the counter anions in the solution affected
metal ions adsorption on NH2MCM-41, with enhanced efficiency
in the presence of sulfate ions [106,107]. Lam et al. [110] investi-
gated the anion effect on copper adsorption on NH2-MCM-41 using
Cu(NO3)2 and CuSO4 solutions. They found that copper cations
adsorbed faster and more efficiently in the presence of SO2 4 anions
compared to NO 3 , with 70% of the adsorption sites accessible to
Cu2þ adsorption, while the remaining 30% of the functional groups
were accessible only in the presence of SO24 . These sites are either
energetically unfavorable or inaccessible, such as H-bonded amines
with the unreacted surface hydroxyls or insulated amine groups.
50% extra copper (i.e., 1.33 mmolg1) was adsorbed from the CuSO4
solution since SO2 4 may stabilize 1:1 amine: copper complexes.
They found that the Freundlich isotherm fits the Cu2þ adsorption
from Cu(NO3)2 and CuSO4 better than the Langmuir (Table 2). Jeong
et al. [130] grafted tetrakis (4-carboxyphenyl)porphyrin (TCPP) on
SBA-15 silica, and found it to have better adsorption performance
than NH2-SBA-15 silica with maximum adsorption capacity around
13 mmolg1.
Another limitation of introducing functional groups by grafting
is that packing is usually limited by the amount of Si-OH anchored
to the surface [131]. To illustrate these limitations, Aguado et al.
[104] followed different template removal procedures prior to the
modification of SBA-15 with APTES: calcination (C), extraction (E)
and calcination-hydration (C-H). The purpose of calcination-
hydration was to increase the amount of OH groups offered for
grafting, leading to higher loadings of functional groups. They
found that the amine content reduced according to the series: G-
SBA-15-N-E > G-SBA-15-N-C-H > G-SBA-15-N-C, due to surface
dehydration during calcination, leading to a lower amine loading
capacity. They also showed that the hydration step should be per-
formed carefully to prevent water accumulation on the surface,
which can support heterogeneous spreading of organic groups, and
thus pore blockage. Table 2 provides evidence that the highest
copper adsorption capacity on propyl amine-grafted SBA-15 is less
than the amine loading theoretical ratio, because two or more
amine groups are required to make stabilized Cu-amine complex.
Furthermore, Table 2 shows that the Cu2þ uptake on calcined G-
SBA-15-N-C is less than G-SBA-15-N-E and G-SBA-15-N-C-H
because silica prepared after extraction and calcination-hydration
exhibit higher amine loadings (around 3 against 1.9 mmolg1).
Nevertheless, monoamine-grafted SBA-15 adsorption capacities are
mostly less than capacities obtained for other mesoporous silica
[90,110,113,124,131]. They also showed that the copper adsorption
on sample functionalized with diamine (G-SBA-15-NN-E) is
significantly improved compared to silica functionalized with
monoamine, since the existence of two amine groups in the organic
molecule improves the metal uptake. Similarly, Manu et al. [131]
controlled the hydroxyl group surface density by controlling
calcination temperatures (150, 300, 450, and 600  C). Then they

Table 2
Freundlich and Langmuir constants for copper adsorption on different adsorbents.

Adsorbent Note Freundlich Langmuir Ref.

KF (Lmmol1) n R2 qm (mmolg1) KL (Lg1) R2

APTS-SBA-15-AB 293 K 0.43 4.7 0.98 0.54 10.62 0.96 [90]

APTS-SBA-15-AB 313 K 0.73 5.14 0.97 0.88 17.10 0.96 [90]
APTS-SBA-15-AB 333 K 1.15 3.98 0.96 1.34 20.34 0.97 [90]
G-SBA-15-NN-E e e e e 0.83 e 0.99 [104]
G-SBA-15-N-C-E e e e e 0.39 e 0.99 [104]
G-SBA-15-N-E e e e e 0.35 e 0.99 [104]
G-SBA-15-N-C e e e e 0.24 e 0.99 [104]
SH-MCM-41 Cu2þ 0.0259 0.01 e e e e [108]
SH-MCM-41 Agþ 0.9694 0.12 e e e e [108]
NH2-MCM-41 Cu2þ 0.2453 0.05 e e e e [108]
NH2-MCM-41 Agþ 0.1077 0.06 e e e e [108]
NH2-MCM-41 Cu2þ/pH ¼ 2 0.00 0.00 e e e e [109]
NH2-MCM-41 Cr2O2
7 /pH ¼ 2 0.84 0.30 e e e e [109]
COONa-MCM-41 Cu2þ/pH ¼ 5 0.22 0.08 e e e e [109]
NH2-MCM-41 Cu(NO3)2 0.73 0.09 e 0.76 290 e [110]
NH2-MCM-41 CuSO4 1.27 0.16 e 1.33 120 e [110]
2N-MSM-e e e e e 0.50 1.1 e [111]
GN1 e 1.416 1.87 0.97 0.485 0.074 0.99 [113]
GN2 e 5.77 3.82 0.93 0.50 0.020 0.99 [113]
GN3 e 17.132 4.67 0.94 0.85 0.002 0.99 [113]
EDA-SAMMS e e e e 26.9a 26.6b e [124]
NH2/SiO2/Fe3O4 e 1.53 2.63 0.89 10.41a 0.037b 0.99 [127]
SH-SBA-16-C e 0.5237 6.24 0.86 36.42a 49.27 0.98 [128]
GC1.5N e e e e 1.53 0.0012 0.99 [131]
GC3N e e e e 1.43 0.0018 0.99 [131]
GC4.5N e e e e 1.14 0.0202 0.99 [131]
GC6N e e e e 0.9 0.041 0.99 [131]
DDA-41A e 1.06 1.90 0.97 3.93 0.38 0.99 [134]
DMDDA-48A e 0.95 1.81 0.96 4.08 0.35 0.99 [134]
DDA-48A e 0.99 1.88 0.96 3.51 0.39 0.99 [134]
DMDDA-41A e 1.08 1.85 0.98 4.39 0.31 0.99 [134]
a
Value given as mgg1.
b
Value given as Lmg1.
152 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157
functionalized these materials with APTES and used them for the
adsorption of Cu2þ ions. They indicated that the thermal treatment
of the silica gel affects the density of surface hydroxyl groups and
thus the NH2 density after grafting, which decreased from 2.34 to
1.65 mmolg1 when the temperature increased from 150 to 600  C
as shown in Table 1. They found that the Cu2þ adsorption capacity
calculated from Sips model decreased from 1.56 to 0.95 mmolg1,
with the reduction in amine surface density from 2.34 to
1.65 mmolg1. Kim et al. [111] removed the surfactant from hex-
agonal mesoporous silica by solvent extraction and by calcination.
They demonstrated that, template removal by calcination was more
efficient than solvent extraction, with surface area and pore volume
of the calcined samples (1003 m2g-1 and 1.05 cm3g-1) larger than
that of the extracted ones (672 m2g-1 and 0.75 cm3g-1). However,
surfactant removal at high calcination temperatures leads to severe
dehydration of surface hydroxyl groups on the pore walls, which
reduced the functional group density that could be grafted and
consequently, copper uptake capacity.
Immobilization of cyclic polyamines, which result in stable
complexes with a large number of metal ions [132], has also been
used to modify silica surfaces. Goubert-Renaudin et al. [103] grafted
silylated cyclam molecules with one, two, or four silyl groups onto
both ordered mesoporous silica (SBA-15) and amorphous silica gel
via one, two, or four arms and explored their stability and reactivity
towards copper ions. They always observed incomplete copper
uptake even in excess of functional groups compared to Cu2þ so-
lution concentration, suggesting that Cu2þ is more stable in
aqueous state than in a complex state. Furthermore, the number of
ligands attaching cyclam functunalities to the silica surface was
found to affect the copper adsorption on these adsorbents, with
much higher capacities obtained by minimizing the number of
arms. Similarly, multiarm binding resulted in better chemical
resistance toward degradation [121].
Some applications of mesoporous silica required large pore
sizes, which could be achieved by postsynthesis hydrothermal
treatment of silica in a solution containing suitable organic
expander. In addition to increasing the pore size, this treatment
introduces organic functionality to the inorganic framework. Sayari
et al. [133] considered adsorption of metal cations such as Cu2þ on
the pore-expanded and aminated mesoporous silica MCM-41. This
material exhibited high-capacity (1.67 mmol Cu2þ/g) and fast
adsorption, because of its open pore structure and suitable surface
properties. Similarly, Benhamou et al. [134] inspected the adsorp-
tion performance of the pore-expanded MCM-41 and MCM-48
toward Cu2þ. They expanded silica by post-synthesis treatment
with N-N dimethyldodecylamine (DMDDA) and dodecylamine
(DDA) and found the expanded materials to be fast adsorbents. As
shown in Table 2, they also found that the pore-expanded MCM-41
had higher adsorption capacity than the pore-expanded MCM-48
and that MCM-41 and MCM-48 pore-expanded with DMDDA were
more efficient than those pore-expanded with DDA indicating that
the adsorption capacity depends on both, support and kind of
amine used for pore expansion.
Although grafting route has been significantly developed, it is
known that homogeneous spreading of functional groups is not
frequently succeeded by this route [116,135]. Ordered mesoporous
silica offers three diverse areas for reaction: the external particle
surface, the internal pore surface, and the surface near the pore
mouth. Grafting results in accumulation of organic groups around
the pore opening leading to some pore blocking, which happens
more readily in small pores silica than in those with large pores. In
addition to pores blockage, grafting has the following drawbacks:
(i) reducing the pore size leading to enhanced diffusion resistance
within the pores. (ii) Concentration and distribution of organic
functionality is controlled by the surface hydroxyl group density
and by their accessibility, precursor reactivity, and diffusion limi-
tations, (iii) and most important, the complexity of the procedure
as it often requires several steps to achieve the final material [115].
3.2. Adsorption of heavy metal ions on mesoporous silica prepared
by co-condensation
In the co-condensation route, organic functionalities are
condensed together with silica source such as tetramethylorthosi-
licate (TMOS) and tetraethylorthosilicate (TEOS) [42]. Therefore,
organically functionalized mesoporous silica can be obtained
directly in one-step. Thus, reducing the number of synthesis steps
and time. It is assumed that direct synthesis of organically func-
tionalized mesoporous silica leads to homogeneously distributed
groups. While, grafting route forms silica with higher thermal
stability of the networks and more order structure than co-
condensation [135].
It is preferred to have homogeneous distribution of the organic
functionalities to achieve high surface coverage without altering
the diffusion of molecules within the pores. To investigate the
differences in distribution obtained by the two routes, Lim and
Stein [135] introduced vinyl-functionality to MCM-41 via co-
condensation and grafting. In co condensation of v-MCM-41,
higher vinyl density with uniform distribution was achieved, while
higher hydrothermal stability of v-MCM-41 was achieved via
grafting. Furthermore, they found that vinyl groups in a grafted
sample were mostly positioned on exterior surfaces and around
pores openings. They concluded a heterogeneous distribution of
the vinyl groups on the MCM-41 surface. On the contrary, uniform
distribution of vinyl groups within pores channels and on external
surface was detected in v-MCM-41 prepared by co-condensation.
Similar observations were reported by Yokoi et al. [92] for mono-
(N), di- (NN), and tri-amine (NNN) MCM-41 prepared by co-
condensation and grafting. Their results demonstrated that, the
adsorption capacities of (NNN) MCM-41 prepared by co-
condensation increased when the amount of amine groups inte-
grated to the surface increase. Conversely, for the (NNN) MCM-41
prepared by grafting increasing amine surface density resulted in
lower adsorption capacity suggesting that the amine groups dis-
tribution on the silica by the two methods are clearly different.
It is likely that increasing functional groups density while
maintaining open pore structure would result in a higher perfor-
mance. However, organic groups, which may interfere with the
silica condensation and disturb the micellar structure, have to be
avoided in the co-condensation process [136]. Furthermore, dete-
rioration of the periodic order may occur if the loading of functional
groups exceeds a certain limit. Chong et al. [137] investigated the
effect of the nature and the quantity of organosilanes initial con-
centration in the synthesis mixtures of TEOS and nonionic triblock
co-polymer P123 and acidic medium. They found that changing
synthesis conditions leads to different ranks of mesostructure
disorders after functionalization, depending on the organosilanes
used and its quantity in the reaction mixture. Organosilanes mo-
lecular size and shape and its chemical reactivity in acidic medium
affect the reaction of P123 with silica and P123 micellation and thus
affect the structural properties. Walcarius and Delaco ^ te [138] pre-
pared a wide range of mercaptopropyl-functionalized MCM-41
(MPTMS-MCM-41) adsorbents by changing the ratio of MPTMS/
TEOS. They compared between three categories of adsorbents: (i)
MCM-41 with an ordered structure obtained by using MPTMS
concentration < 10%. All functional groups in this sample were
accessible however; there was some mass transfer limitations to
diffusing deep in the mesopore channels to reach the active sites
located there. (ii) Wormhole-like with cylindrical mesopores and
less-ordered structures, 100% accessibility of the binding sites was
 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157
possible by using less than 30% MPTMS. Using higher MPTMS
concentration resulted in higher surface loading leading to lower
accessibility because of pore blockage and increasing surface hy-
drophobicity (iii) Amorphous materials with maximum functional
group loadings and very high resistance to mass transfer rates and
limited binding sites accessibility.
Aguado et al. [87,88] prepared thiolated mesoporous silica via
co-condensing MPTMS and TEOS with P123 as a template. They
studied the effect of changing MPTMS/(MPTMS þ TEOS) ratio in
the range 5e50% on both the textural properties and metal ions
adsorption capacity. To maintain the order mesoporous structure
in the synthesized material with high propylthiol loading it was
necessary to minimize the amount of TEOS. When MPTMS molar
ratios up to 10% were used, samples with a good structural order
were obtained, while materials obtained with larger MPTMS
amounts showed less order. Similarly, Xue and Li [128] synthe-
sized thiol-functionalized SBA-16 mesoporous silica using one-
pot method by changing the TEOS/MPTMS molar ratio. Their
results (Table 1) showed that maintaining TEOS/MPTMS molar
ratio between 3 and 4 was a factor to get high structural order
and high Cu2þ uptake with a maximum of 36.38 mgg1 in the pH
range of 5e6.
Markowitz et al. [139] synthesized functionalized-SBA-15 mes-
oporous silicates via co-condensing TEOS and ethyl-(ETES),
carboxylate-(CTES), and ethylenediamine-triacetic acid (EDTA).
They showed that, preparing samples with a maximum of 5% silane
resulted in ordered mesoporous materials. However, when silane
quantity reach 20% a significant structural disorder of the silica was
observed. High adsorption capacity of Cu2þ was observed only for
the EDTA-SBA-15, with Cu/N around 0.15, which is less than the 1:1
theoretical ratio for Cu2þ and EDTA, suggesting incomplete EDTA
groups binding with Cu2þ. Burleigh et al. [140] synthesized ordered
mesoporous organosilicas by co-condensation of bis(triethoxysilyl)
ethane and N-(2-aminoethyl)-3-aminopropyl-trimethoxy silane
(AAPTS). They found that by increasing AAPTS, both surface area
and the pore volumes decrease, without significant change in the
pore diameter (Table 1). Thus, more than 70% of the AAPTS were
available for copper adsorption. Furthermore, as the amount of
functional silane increases from 0.17 to 0.87 mmolg1, the
adsorption sites accessibility decreases from 80 to 70%. Algarra et al.
[129] investigated the efficiency of metal ions adsorption on
aminopropyl-functionalized MCM-41 synthesized by co-
condensing TEOS and APTES with different TEOS/APTES molar ra-
tios of 5, 25 and 50. They showed that the copper adsorption ca-
pacity could be increased by decreasing the TEOS: APTES ratio with
maximum copper adsorption capacities of 1.28, 0.75 and
0.54 mmolg1, respectively. Dey et al. [141] synthesized adsorbent
by co-condensation of TEOS and the organosilane N-[3-(trime-
thoxysilyl)propyl]diethylenetriamine and evaluated its adsorption
performance. They obtained a maximum copper adsorption ca-
pacity of 2.2 mmolg1 with copper/ligand molar ratio of 1:2,
considering 1.2 mmol of functional groups per gram adsorbent.
Yang et al. [142] used CTAB and TMAOH as a template and
ethanol as a solvent for synthesis of mesoporous adsorbents. When
a mixture of CTAB and TMAOH was used as a structure directing
agent, the resulted sample denoted in Table 1 as (C) indicated an
increase in pore size, pore volume, and surface area. This is mainly
because TMAOH has accelerated the silica condensation and thus,
reinforced the physical structure. On the other hand, when only
CTAB was used as a template, the resulted sample (B) showed
smaller pore size, pore volume and surface area compared to the
sample prepared with P123 (A). This is mainly because P123 has a
longer chain than CTAB. The three samples were used to adsorb
metal cations and the best adsorbent among the three was sample
(C), with maximum copper uptake of 0.39 mmolg1.
153
Bois et al. [143] synthesized functionalized mesoporous silica
with aminopropyl (N-S), amino-ethylamino]propyl (NN-S), (2-
aminoethylamino)-ethylamino]propyl (NNN-S), and mercapto-
propyl (S-S) groups using dodecylamine as a template. As shown
in Table 1, specific surface area of N-S sample was lower than that of
NN-S and NNN-S. In contrast, thiolated sample (S-S) showed an
increase in the specific surface area. They also indicated that the
aminated silica was less ordered and less porous than the thiolated
samples. They related that to the development of hydrogen
bonding between amine and silanol groups. According to Bois et al.
[143] aminopropyl is expected to strongly interact with silica sur-
face, SiO … þNH3-, creating a cyclic structure that occupy more
space within the pores. Possibility of forming this cyclic structures
decreased when longer amine chains (NN- and NNN-S) is used. On
the other hand, thiolated materials, do not form hydrogen bonds
between thiol and silica surface and thus, silica structure is
conserved. Maximum copper ion uptake by NN-S and NNN-S
samples were 0.5 mmolg1 with Cu/N ratios of 0.3 and of 0.4
respectively, indicating that copper ions were not able to reach all
amine groups.
Adsorbent morphology is another important factor affecting
adsorption. In this area, Nasreen et al. [33] studied the effect of
functional groups introduced to MSU-H silica by co-condensation
on adsorption performance and surface morphology. The surface
morphology and textural properties of these functionalized MSU-H
(AM, GM, MM, VM, and PM) were different according to the func-
tional groups in the channels. Thus, affected the adsorption effi-
ciency of the adsorbent with removal efficiency within the range of
62e96%, 38e99%, 68e99%, 79e93%, and 67e98% on AM, GM, MM,
VM, and PM, respectively. Lee et al. [40] prepared aminated and
thiolated SBA-15 with different pore channel lengths and different
morphologies. Their results showed that initial adsorption rate was
rapid, and then started to slow down. Furthermore, they found that
the platelet morphology rate was faster than that of fiber-like and
rod-like morphologies, and that the Pb2þ equilibrium adsorption
capacity on platelet morphology was greater than that of the other
morphologies and its pore size was the largest among all as shown
in Table 1. This is mainly because platelet morphology has shorter
channel length than those of rod-like and fibrous SBA-15. Conse-
quently, the diffusion distance and the time ions need to diffuse
from bulk solution to the internal functional groups were reduced.
In addition, the larger pore size minimize pore blockage by func-
tional groups attached to the pore walls.
Fakhfakh et al. [144] prepared ethylenediamine functionalized
mesoporous silica with groups via co-condensation, and studied
the influence of (i) presence or absence of structure directing agent
(template), (ii) the synthesis temperature, and (iii) the acid used
(HCl, CH3COOH, or C2H5COOH). The best textural properties were
obtained in the absence of surfactant and using carboxylic acids
dissolved in propanol. The copper adsorption capacity was
0.53e0.90 mmolg1 for silica prepared with HCl or acetic acid as
catalysts, while the silica prepared with propionic acid showed a
lower uptake of 0.41 and 0.13 mmolg1 for the solid prepared at 35
and 60  C, respectively. Sales et al. [145] synthesized ethylenedi-
amine modified mesoporous silica via co-condensation of TEOS
with N-[3-(trimethoxysilyl)-propyl]-ethylenediamine and ethyl-
enediamine incorporated into 3-glycidoxypropyltrimethoxysilane
to produce MNN and MGNN with structural properties shown in
Table 1. They found that MGNN and MNN had similar maximum
copper adsorption capacity of 1.4 mmolg1.
Aguado et al. [104] synthesized SBA-15 functionalized with
mono- (C-SBA-15-N), di- (C-SBA-15-NN) or tri- (C-SBA-15-NNN)
amine functional groups by co-condensation. Their materials
showed negligible metal adsorption capacity even with the high
nitrogen content and suitable textural properties as shown in
154 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157

Table 3
Copper adsorbents regeneration conditions.

Adsorbent Stripping agent Cycles Functionality loss % Capacity loss % Ref.

APTS-SBA-15-AB 0.1 M EDTA 10 <10 10 [90]

APTS-SBA-15-AB 0.1 M HCl/0.1 M NaHCO3 10 <10 40 [90]
SBA-15(SH) HCl 3 e 40 [100]
SBA-15(NH2) HCl 3 e 40 [100]
MCM-41(SH) HCl 3 e 65 [100]
MCM-41 (NH2) HCl 3 e 65 [100]
SA-SBA-15 0.3 M HCl/0.3 M NaHCO3 4 e 3.3 [102]
OSU-6-W-TCSPBr-1 2.0 M HCl 4 e 30 [105e107]
NH2-MCM-41 5.2 M HCl 1 e 0 [109]
COONa-MCM-41 5.2 M HCl/NaHCO3 1 e 0 [109]
2N-MSM-e 0.1 M HCl 1 5.4 e [111]
Silica ED 1 M HCl 1 0 0 [112]
OSU-6-W-TCSPBr-1 2.0 M HCl 3 e 24 [106,108]
APH-MCM-41 20 wt% HCl 10 e 0 [118]
EDTA-G4-PAMAM-SBA-15 0.1 M EDTA 1 e 5e7 [119]
LDAPY-MCM-41 1 M HCl 3 e 0 [125]
NH2/SiO2/Fe3O4 0.1 M HNO3 e e e [127]
SH-SBA-16-C 1 M HCl 7 11.6 9.9 [128]
TCPP -SBA-15 0.2 M HCl 3 e 2.3 [130]
NH2/SiO2/C 1 M HCl 8 e 9.1 [142]

Table 1. Later on, Da'na and Sayari [90,91] suggested several reasons
for the negligible adsorption capacity of this material including: (i)
Poor extraction of P123 template from the pores. (ii) Since SBA-15 is
prepared in acidic conditions, this caused amine groups proton-
ation [146], thus diminishing their availability for adsorption, and
therefore, basic treatment is needed to recover neutral amine
groups. (iii) Zero point charge (ZPC) of the aminated SBA-15 syn-
thesized via co-condensation was reported around 8.62 implying
that as the solution pH get lower than 8.62, the surface hydroxyl
groups will be protonated (^SiOHþ 2 ) and the aminated SBA-15-AB
surface will be positively charged. This implies that in a wide range
of pH (pH < 8.62) the material will not adsorb copper effectively.
They found that changing solution pH from 4 to 6.5 resulted in
gradual increase in Cu2þ adsorption efficiency with zero Cu/N ratio
at pH of 4.0. Generally alkylamines pKb value is about 4 [147].
Therefore, at this pH, most of the amine groups will be protonated
with no ability to complex with cations. In addition, the surface
becomes positively charged at low pH leading to high repulsion
between cations and the binding sites. Therefore, the approach of
copper cations to the active adsorption sites will be inhibited. (iv) It
is possible that there is some hydrogen bonding between amine
groups and hydroxyl groups on the surface reducing their adsorp-
tion efficiency [86].
4. Adsorbents regeneration
For commercial applications of an adsorption system it is
important for the adsorbent to be structurally stable with steady
metal adsorption capacity over a multi adsorptionedesorption
cycles. In addition to adsorbents recycling, desorption gives
important information about the reversibility of the adsorption
process. Many researchers reported recycling of the adsorbents
they used mainly by washing with HCl solution
[89,90,100,102,105e109,111,112,118,125,128,130,142], HNO3 solution
[103,127] or treatment with complexing agent such as EDTA [64,95]
to elute the metal ions and their results are summarized in Table 3.
After metal desorption with acids, the neutral amine should be
recovered using NaHCO3 solution [90,102,109]. Da'na and Sayari
[90] showed that EDTA was more powerful than HCl/NaHCO3 for
regeneration of amine loaded silica since it reacts with Cu2þ
forming a very stable octahedral complex [148]. Acid treatment
results in the protonation of the adsorbent surface, which increased
positive surface charge density [90,99,123]. This might result in re-
adsorption of negative-ligand enclosed Cu2þ species as reported by
Wambu et al. [149]. They showed that such re-adsorption may be
followed by surface precipitation that would immobilize re-
adsorbed copper on the adsorbent.
Another possible reason for loss of adsorption capacity is
structural instability of the adsorbent, which upon regeneration
treatment may lose its structural order and adsorption sites
accessibility within the pores. Nitrogen adsorption data obtained
by Liu et al. [100] are in good agreement with this argument. They
indicated that the surface area and pore volume for SBA-15(SH) and
SBA-15(NH2) adsorbents decreased only slightly (5%), however the
pore size did not change. While a huge reduction in surface area
and pore volume of MCM-41(SH) and MCM-41(NH2) adsorbents
were observed, the surface area and pore volume of the regener-
ated MCM-41(SH) are 465 (665) m2g1 and 0.41 (0.61) cm3g1; for
MCM-41(NH2), 282 (460) m2g1 and 0.26 (0.41) cm3g1. This result
agreed perfectly with the previously reported results that SBA-15 is
more stable than MCM-41 [96] and may explain the lower regen-
eration performance of MCM-41 based adsorbent compared to
SBA-15 as presented in Table 3.
In some circumstances, the adsorption capacity increases after
the first regeneration cycle especially for samples with high load-
ings of functional groups. This is mainly because of high steric
hindrance effect and the lower accessibility of adsorption sites
[102,112]. After regeneration, the functional groups content may
decrease. Therefore, the adsorption sites become more accessible to
target ions than in the starting samples. Thus, the adsorption ca-
pacity increases as reported by Zhang et al. [32].
5. Conclusions
Organically-modified mesoporous silica is considered very
promising adsorbent for the retention of heavy metal ions. This is
primarily related to the attractive features such as structure order,
large surface area, and open porous structure to facilitate access to
the functional groups. Thus, it has attracted researcher's attention
to be examined for heavy metal ions adsorption. Depending on the
target ions to be adsorbed, modifications of organic-inorganic
hybrid materials were performed to ensure strong binding and
high selectivity toward target pollutant.
Despite the numerous investigations and interesting results
presented earlier, mesoporous silica functionalization is still not
applicable in real environments. In fact, after years of research in
 E. Da'na / Microporous and Mesoporous Materials 247 (2017) 145e157
this field, still there is no any commercial application of these
materials. Surely, it is not possible to expect what the future will be,
however the two main challenges are to design suitable meso-
porous materials with high adsorption capacity to be applied for
large volumes of discharges (e.g., continuous process column) and
the synthesis of high selectivity adsorbents with high stability and
effective recyclability. For the first challenge, efforts are required to
control the particle size of mesoporous adsorbents since it is
difficult to efficiently pack adsorption column with powdered
materials. Furthermore, if batch process used for adsorption, it is
difficult to recover this powder by filtration. The second challenge
stems from the limited availability of commercial organosilane
reagents. Thus, efforts are required for the design of such reagents
with suitable functionality to increase the adsorbent selectivity,
which is a very significant factor in operating real process. Another
serious fact that seems challenging is improving the durable sta-
bility of the developed adsorbent to prevent their structural
collapse during adsorption or regeneration steps. If all these issues
have been met and the mesoporous adsorbents performance has
been enhanced, one should ask if these mesoporous adsorbents
could compete with commercial adsorbents in cost and stability.
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