Microporous and Mesoporous Materials 266 (2018) 252–267

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Microporous and Mesoporous Materials

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

Silica-based mesoporous materials; emerging designer adsorbents for T

aqueous pollutants removal and water treatment
Paul N.E. Diagboya∗, Ezekiel D. Dikio
Department of Chemistry, Vaal University of Technology, Vanderbijlpark, Gauteng, South Africa

A R T I C LE I N FO A B S T R A C T

Keywords: This is a review of recent literature on pristine and specifically functionalized mesoporous silica-based materials
Silica or ‘designer silicates’ used as adsorbents for aqueous pollutants removal and water treatment. Ordered meso-
Adsorbents porous silicates, their synthesis, surfactants removal, and preparation of the designer silicates were briefly in-
Functionalization troduced before discussing their applications in the removal of inorganic and organic pollutants. Designer sili-
Water pollutants
cates, such as the nitrogen/thiol-containing, the magnetics, and the composites, are highlighted with their
Water treatment
various applications for the removal of toxic metal cations, anionic species, dyes, pesticides, industrial organics,
pharmaceuticals and other emerging pollutants. These applications were briefly discussed indicating salient
features and using illustrating figures where possible.

1. Introduction inertness, an abundant repertory of surface functional groups that can

Pollution of water sources by organic and inorganic chemical toxins
is a priority concern worldwide. The magnitude of this concern is en-
ormous, and remediation of contaminated water sources is seemingly
intractable because of the diverse nature of pollution sources [1–9].
Most current water treatment technologies are either expensive or lack
the effectiveness for complete toxins removal; hence, the search for
more efficient technologies is a continuing process.
Several techniques have been employed for pollutants removal from
water, such as filtration, chemical precipitation, ion exchange, reverse
osmosis, electrochemical treatment, membrane technology, evapora-
tion recovery, photocatalysis, solvent extraction, and adsorption.
However, most of these are limited by techno-economic and environ-
mental considerations [2–4,10–17]. Advances in materials science have
triggered large interests in specifically-designed adsorbents for water
treatments. The concept of a synergistic combination of two or more
molecules into a larger one has become a very successful approach in
materials science for achieving highly efficient and specific goals in
materials' property, such as adding new structural and functional
properties superior to those of the individual pure components
[1,2,8,14,18–24]. This kind of focus has resulted in the discovery of a
plethora of designer adsorbents such as the mesoporous silica-based
adsorbents [2,14,18,19,23].
Ordered mesoporous silica is eliciting a growing interest in water
treatment chemistry due to its various remarkable properties. These
properties include high specific surface area, large pore–size, chemical
be tailored for excellent selectivity towards specific pollutant, good
thermal stability and low cost of manufacture [18,25]. Highly porous
adsorbents, which are of particular demand in aqueous separations
involving large molecules, can be synthesized from ordered mesoporous
silica in other to include a wide variety of functionally active chemical
components by exploiting the structure-directing functions of electro-
static, hydrogen-bonding, and van-der-Waals interactions associated
with amphiphilic molecules [26–28]. Since mesoporous silica meet
most of the criteria for selection of adsorbents such as high specific
surface area, large pore–size, chemical inertness and easy addition of
abundant repertory of surface functional groups, pristine and functio-
nalized silica [26–28] have been successfully synthesized and studied
for adsorption of both organic and inorganic aqueous pollutants
[29–34] Many recent references demonstrate the versatility of ordered
mesoporous silica-based adsorbents.
The objectives here are to focus on the advances in ordered meso-
porous silica-based adsorbents used for aqueous inorganic and organic
pollutants removal. Brief highlights of the types, synthesis routes and
modifications/functionalization of the ordered mesoporous silica-based
adsorbents are given. This is followed by an overview of several studies
involved with the application of ordered mesoporous silica-based ad-
sorbents in the specific adsorption of inorganic and organic pollutants
from aqueous solutions. In summary, the review highlights the recent
reports (mainly from 2009 to 2017) on the use of ordered mesoporous
silica-based adsorbents for the removal of inorganic and organic pol-
lutants from aqueous solutions, and presents a brief description of these

∗
Corresponding author.
E-mail address: pauldn2@yahoo.com (P.N.E. Diagboya).

https://doi.org/10.1016/j.micromeso.2018.03.008
Received 20 November 2017; Received in revised form 3 March 2018; Accepted 10 March 2018
Available online 10 March 2018
1387-1811/ © 2018 Elsevier Inc. All rights reserved.
P.N.E. Diagboya, E.D. Dikio
Fig. 1. Morphologies of (a) MCM-41, (b) MCM-48, (c) MCM-50. Reproduced from Ref. [39] with permission from The Royal Society of Chemistry.
adsorbents, advantages, and limitations; and reports on regeneration
methods where available. To give insight into the adsorbents effec-
tiveness, reported adsorption capacities are noted.
2. Ordered mesoporous silicates
This class of mesoporous materials consists of extensive inorganic or
inorganic–organic hybrid arrays with the exceptional long-range order,
highly tunable textural and surface properties and controlled pore size
and geometry [35]. These properties, in addition to their usually large
surface areas, make them excellent adsorbent materials providing
higher possibilities for adsorbent–adsorbate interactions. It is worthy to
state here that silica framework is not crystalline but amorphous; it is
the mesopores that are arranged periodically within the structure.
Mesoporous silicates include the Mobile Composition of Matter (MCM)
family (such as the MCM-41, MCM-48, and MCM-50; Fig. 1), the Santa
Barbara Amorphous (SBA) family (such as the SBA-1, SBA-2, SBA-6,
SBA-8, SBA-11, SBA-12, SBA-15, and SBA-16), KIT-5 and KIT-6
[36–38]. The MCM, like most silicates, are classified according to the
order of the pores: hexagonal, cubic or mesolamellar phases for the
MCM-41, MCM-48, and MCM-50, respectively.
2.1. Synthesis of ordered mesoporous silicates
Mesoporous silicates can be synthesized under varying range of pH
conditions (from strongly acidic to highly basic – Fig. 2a) and tem-
peratures (from below room temperature to ≈150 °C) using different
templates or surfactants (cationic, anionic, neutral, zwitterionic, etc.)
[36]. Under appropriate synthesis condition, the silicate's surface area,
pore size, and volume can be controlled from the mesopore dimensions
to macropore. Typically, mesoporous silica synthesis comprises the
addition of a silicate source to the surface of ordered surfactant micelles
in an aqueous solution to produce the ‘as-synthesized’ mesoporous si-
lica. The discovery of template-assisted mesoporous silica synthesis
using surfactants has led to the synthesis of mesoporous silica with high
surface areas, tunable pore sizes, large pore volumes and a plethora of
different kinds of functionalization [36,40]. Mesoporous silica mate-
rials are synthesized under conditions where surfactant–silica assembly
occurs simultaneously with condensation of the inorganic species to
produce the composites (Fig. 2b). The dimensions and morphologies of
the resulting materials are dependent on the sol–gel chemistry condi-
tions such as temperature, water content, pH, characteristics of sur-
factants or copolymers, and the concentrations and the sources of silica
used. Hence, it is possible to design the silica size, mesostructure, and
morphology by controlling of these parameters [41]. Ideally, meso-
porous silica to be applied as an adsorbent for aqueous pollutant re-
moval should possess large surface area, large pore size, and pore vo-
lume. These external and internal properties provide large surfaces for
independent functionalization, as well as allow for a small amount of
the adsorbent to have contact with a large volume of the aqueous so-
lution and consequently a significant amount of the pollutant, resulting
in possibly high removal efficiency.
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Microporous and Mesoporous Materials 266 (2018) 252–267
Usually, a single surfactant (such as the Pluronic-type surfactant;
poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-
Pluronic P123 (EO20PO70EO20) or Pluronic F127, (EO106PO60EO106),
and cetyltrimethylammonium bromide (CTMAB)) is used as the organic
structure directing agent or template for the synthesis of surfactant-
templated silica materials [18,41–44]. However, binary surfactants of
different molecular weights has been used resulting in the formation of
dual-mesoporous silica materials [41].
2.2. Post-synthesis removal of surfactants
To access the pores within the ‘as-synthesized’ mesoporous silica
composites, it is necessary to remove the surfactants used in the self-
assembly. Mesoporous silica synthesized via the surfactant-templated
sol–gel reaction is carefully packed and shrink significantly and irre-
versibly when directly dried from solution thus losing its characteristics
[41]. Thus, it is necessary to be cautious of template removal methods.
Calcination is mostly used for the removal of surfactant from within the
pores [45–49] though in some cases solvent extraction is preferred to
calcination [18,42,50] and microwave digestion using UV [51]. The
typical calcination temperature range is 550–800 °C in flowing air or
nitrogen, while the optimized solvent extraction process is carried out
by refluxing for 24 h using a high ratio ethanol to water mixture.
Without high-temperature calcination, the extent of the silane mod-
ification can be relatively high, thus making the surface properties to be
easily adjusted.
2.3. Functionalization
Though remarkable properties of ordered mesoporous silicates are
highlighted for water treatment purposes, these properties are some-
times not accessible. A major challenge with mesoporous silicate upon
template removal is its hydrophilicity due to the high surface silanol
density (Fig. 3), consequently resulting in low adsorption for aqueous
pollutants especially the hydrophobic ones. Functionalization, or at-
tachment of highly active groups to the surface of the silicate material,
has become a highly successful method of accessing these remarkable
properties of ordered mesoporous silicates for water treatment pur-
poses. This has resulted in a plethora of functional designer silicates
with high efficiency and excellent selectivity towards specific aqueous
pollutants.
Typically, an organic functionality can be introduced post-synthesis
by grafting or chemical attachment onto the silanol groups in the me-
soporous silica or by co-condensation during the template-directed
synthesis of the mesoporous material. The chemical attachment of or-
ganic functionalities onto the silanol groups changes the silica wall
polarity and introduces the desired functionality which enhances the
surface adsorption properties (Fig. 3). One advantage of post-synthesis
chemical attachment is that the mesoporous structure is usually re-
tained, though this depends on the size and loading of organic func-
tionality added, as these could result in pore blockage. Post-synthesis
functionalization of the silicate surface may be achieved by the
P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267

Fig. 2. (a) The inorganic silica species (tetraethoxysilanes) can hydrolyze under acidic or basic conditions producing triethoxysilanol which condenses as shown. Hydrolysis occurs by the
nucleophilic attack in water on the silicon atom on tetraethoxysilanes which produces alcohol (ROH), which is not shown in the reaction. (b) schematic diagram of surfactant-templated
mesoporous silica showing typical synthesis route for MCM-41 or SBA-15. Reproduced from Ref. [39] with permission from The Royal Society of Chemistry. (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article.)

undesired polymerization reactions. With co-condensation, the final

silica morphology can be controlled, and the above disadvantages of
post-synthesis by chemical attachment are eliminated. However, the
mesoporosity could be distorted if synthesis conditions are not carefully
controlled [35,36,41,55].

Fig. 3. Functionalization typical silicate (SBA–15) with 3–aminopropylethoxysilane
group. Reprinted from Ref. [18], p. 44, Copyright (2014), with permission from Elsevier
Inc.
following approaches [36]:
(a) Direct grafting (Primary modification) through reaction of suitable
organosilane, in an appropriate solvent, with the silica surface
under reflux [52,53].
(b) Reacting a previously grafted functionality with another functional
species (Secondary modification) [47,54].
(c) Transformation of the grafted functionalities by additional treat-
ments.
Co-condensation during the template-directed synthesis of the me-
soporous material involves the simultaneous condensation of the de-
sired organic functionality (such as 3–aminopropyltriethoxysilane)
alongside the primary silica source (usually the alkoxides such as tet-
ramethyl (or tetraethyl) orthosilicate) in the presence of a surfactant.
The desired organic functionality is covalently linked through a non-
hydrolysable SieC bond to a siloxane species, which then hydrolyzes to
form a silica network. Most organic functionalities are usually hydro-
phobic and tend to align with the hydrophobic end of the surfactant;
hence, modifying the silica walls. Common organosilanes used in
functionalization include the trialkoxy-organosilanes and chloro-orga-
nosilanes though the later is usually avoided because they give rise to
2.4. Characterization of silicates
The aim of the routine characterization is to determine the physical
(morphology, structure, and texture) and chemical (functional groups,
nature of interactions between atoms and possibly their orientation)
properties of the final synthesized meso-structured silicate materials.
This implies that meso-structured silicates' characterization is classified
into two groups: the physical and chemical characterizations.
The physical characterizations include determination of; (a) the
specific surface areas, pore volume and diameter, and porosimetry
using gas physisorption method, (b) the organization of the silicate
morphology up to the three-dimensional order and nanoscale using
electron (both scanning and transmission) microscopic techniques, and
(c) the types of meso-structures or any structural damage arising from
the functionalization process using the diffraction (X-ray and electron)
techniques [38,55,56].
The chemical characterizations include determination of; (a) the
effectiveness of the desired functionalization, and possible nature and
form of the chemical constituents using spectroscopic techniques such
as the Infra-red, Raman and ultraviolet–visible spectroscopy, (b) the
amounts of organic groups incorporated as well as their stability using
thermogravimetry, (c) the quantities of some basic elements using
elemental chemical analysis, and (d) the effectiveness of covalent
bonding of the organosilanes to the silica framework and the extent of
siloxane condensations using the nuclear magnetic resonance
[38,55–57].

254
P.N.E. Diagboya, E.D. Dikio
3. Removal of aqueous pollutants
3.1. Inorganic pollutants
In order to meet the evergrowing stricter water regulatory standards
placed by governments and other regulatory bodies, numerous ad-
vances in material science are emerging for enhancing water purifica-
tion process. Functional designer silicates with high efficiency and ex-
cellent selectivity towards specific aqueous pollutants are particularly
interesting due to the recorded successes of these materials for aqueous
inorganic species adsorption. Nitrogen/thiol and magnetic silica-based
designer materials have been at the forefront of these advances.
3.1.1. Nitrogen and thiol designer silicates for inorganic pollutants
Though pristine silicates have various remarkable properties which
may be beneficial in the water treatment process, they have been out-
classed by their designer derivatives. For instance, ordered mesoporous
MCM-41 and MCM-48 silica were synthesized, amine functionalized
with NeN dimethyl dodecyl amine and dodecyl amine, and used for
adsorption of Cd(II), Co(II), Cu(II) and Pb(II) in aqueous solution [58].
The functionalized MCM-41 and MCM-48 silicates was over three-fold
better than the pristine in the adsorption of these cations and were
observed to be fast cationic adsorbents with higher affinity for Cu(II)
and Pb(II) than for Cd(II) and Co(II) in single and mixed cations solu-
tions, though adsorption capacity was reduced in the mixed solutions.
These adsorbents exhibited a higher preference for Cu(II) in both single
and mixed solutions while adsorption capacities in a single solution for
amine-MCM-41 and amine-MCM-48 ranged from 227.9 to 279.6 mg/g
and 186.5–260.5 mg/g, respectively. The adsorption capacities in
mixed solutions were not significantly different for both the amine-
MCM-48 and amine-MCM-48 and ranged from 62.2 to 101.7 mg/g. Lee
et al. [59] had earlier shown it is possible to incorporate different
functional groups into one silica material. They designed bi-functio-
nalized porous MCM-41 silica via the introduction of chelating ligands
(mercaptopropyl and aminopropyl groups) which was used for the re-
moval of heavy metal ions (Hg(II), Cu(II), Ni(II), Cd(II), and Cr(III))
from aqueous solutions [59]. These adsorbents showed improved effi-
ciency for Hg(II), Cd(II), and Cu(II) removal but not for Ca(II), Mg(II),
Ni(II), and Cr(III). The adsorption capacities of the mercapto- and
amino-functionalized adsorbents ranged from 76.2 to 302.9 mg/g with
a very high preference for Hg(II). Similarly, Burke et al. [60] showed
that post-synthesis bi-functionalization, using aminopropyl and mer-
captopropyl-silanes, can be achieved for mesoporous silica, and they
attempted the removal of Ni(II), Cr(VI), Pd(II), Fe(II) and Mn(II) from
water. The bi-functionalized mesoporous silica was highly effective in
reducing a broad range of metal ions (from high concentration mixed
metal ion solutions) to trace (> ppb) levels, while the mono-functio-
nalized materials had specific responses to the metal ions. The max-
imum adsorption capacities were determined to be approximately equal
(20 mg/g) for Cr(VI), Ni(II), Fe(II), Mn(II) and Pd(II) using the bi-
functionalized mesoporous silica, and this was low in comparison to the
report of Lee et al. [59].
Zhang et al. [61] have shown that in addition to aminopropyl-
triethoxysilane, multi-amines (such as N-[3-(triethoxysilyl)-propy-
lethylene]diamine and triethoxysilyl propyl diethylenetriamine) can be
grafted onto mesoporous SBA-15 silica. These multi-amine-SBA-15 ad-
sorbents had excellent adsorption capacities for aqueous Hg(II) removal
up to 726 mg/g. Interestingly, they also showed that the adsorbents
could simultaneously remove Hg(II), Pb(II), Cd(II), Cu(II) and Zn(II)
from wastewater. Liu et al. [62] had earlier reported high complexation
affinity of Hg(II) by thiolated SBA-15 adsorbent while the aminated
analog exhibited exceptional binding ability for metal ions such as Cu
(II), Zn(II), Cr(III) and Ni(II). Aguado et al. [63] suggested that the
method of functionalization of the SBA-15 surface may affect the per-
formance of the final adsorbent. Post-synthesis grafted amino-func-
tional groups exhibited far better adsorption efficiency for Cu(II), Cd
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Microporous and Mesoporous Materials 266 (2018) 252–267
(II), Pb(II), Ni(II) and Zn(II) ions that the co-condensed amino-func-
tionalization (they reported virtually no adsorption). However, the re-
port of Da'na et al. [64–66] contradicts Aguado et al. [63] regarding the
method of functionalization of SBA-15 surface and its effect on the
adsorption performance. Their co-condensed amino-functionalized
SBA-15 was used to study removal of Cd(II), Co(II), Cu(II), Zn(II), Pb
(II), Ni(II), Al(III) and Cr(III) from single and multi-metal aqueous so-
lutions. Amino-functionalized SBA-15 was able to adsorb the various
metals to varying degrees with up to 95% adsorption observed at low
aqueous single metal solutions (10 mg/L) indicating high sensitivity
except for Co(II) and Cr(III). The adsorbent capacity decreased for co-
existing metal cations in solution because of competition between ca-
tions for the amine groups. They also reported that application of their
adsorbent for removal of Cu(II) in tap water, river water, and electro-
plating wastewater was a success.
Bois et al. [67] grafted different functional (aminopropyl–, [amino-
ethylamino]propyl–, (2-aminoethylamino)-ethylamino]propyl–, and
mercaptopropyl– groups) materials to MCM-41 for aqueous heavy
metals adsorption. They observed that MCM-41 silica functionalized
with multiple nitrogens ([amino-ethylamino]propyl- and (2-ami-
noethylamino)ethylamino]propyl-) groups exhibited higher loading
capacity for Cu(II), Ni(II), Co(II) and the anion Cr(VI), while the mer-
capto functionalized silica exhibited higher loading capacity Cd(II).
Kang et al. [68] showed that imidazole (N-(3-triethoxysilylpropyl)-
4,5-dihydroimidazole) functionalized SBA-15 could be used for pre-
cious metal-chelating and recovery. They observed that the amino-rich
functionalized SBA-15 silica exhibited excellent selectivity for Pt(II) and
Pd(II) ions over other metal ions such as Ni(II), Cu(II), and Cd(II), even
with an excess of the latter cations. Adsorbed precious metal ions could
be better recovered by simple HNO3 acid treatment compared to HCl or
NaOH treatments. They concluded that the ligand-functionalized me-
sostructured silica could be used not only in toxic heavy metal removal
but also in the effective separation of precious metal ions. Tapaswi et al.
[69] also showed that SBA-15 functionalized with 1,4,7-triazacyclo-
nonane (another rich nitrogen compound), synthesized via post-synth-
esis grafting, exhibited fast and selective Cu(II) adsorption from aqu-
eous mixed metal ions solution containing Cu(II), Cr(III), Ni(II), Co(II)
and Li(I). The triaza-cyclononane functionalized SBA-15 had a max-
imum Cu(II) adsorption capacity of 42.6 mg/g and can be readily re-
generated by HNO3eNH3 treatment.
Amino-functionalized mesoporous and nano-mesoporous MCM-41
silica have also been synthesized using 3-aminopropyltrimethoxisilane
and used for removal of Ni(II), Cd(II) and Pb(II) from aqueous solution
[48]. It was shown that the amino-functionalized MCM-41 silica ad-
sorbents exhibited preference for the metals in the order Ni(II) < Cd
(II) < Pb(II) with the highest adsorption capacity for Pb(II) of
57.74 mg/g. Similarly, amino-functionalized SBA-15 (using N-3-tri-
methoxysilyl-propyldiethylenetriamine) of tailored pore sizes have
been reported with good adsorption of 39 and 41 mg/g for Pb(II) and
Cd(II), respectively [53]. One observation about the reported adsorp-
tion capacities for Heidari et al. [48] and McManamon et al. [53] is that
they were low compared to others reported earlier.
Aminopropyl (NH2) and melamine-based dendrimer amines (MDA)
were separately used to functionalize SBA-15 mesoporous silica [46],
and the resulting designer adsorbents were used to study the separate
and ternary sorption of Pb(II), Cu(II) and Cd(II) ions onto SBA-15,
NH2–SBA-15 and MDA–SBA-15 (Fig. 4). The NH2–SBA-15 and
MDA–SBA-15 exhibited enhanced adsorption of more than 150 and
400%, respectively, increase over the pristine SBA-15. The Langmuir
maximum adsorption capacities of MDA–SBA-15 was 130, 126 and
98 mg/g for Pb(II), Cu(II) and Cd(II), respectively. These results were
remarkably high compared to others in the literature. Column experi-
ments showed that metal ions removal percentage increased by 21.8%,
10.4% and 11.6% for Pb(II), Cu(II) and Cd(II), respectively, but ad-
sorption efficiency was dependent on flow rate. The MDA–SBA-15 ad-
sorbent showed good potential for reuse though slight decreases in
P.N.E. Diagboya, E.D. Dikio
Fig. 4. Structure of the MDA–SBA-15. Reprinted from Ref. [46], p. 507, Copyright (2011),
with permission from Elsevier Inc.
adsorption capacity were observed with subsequent cycles.
Comparable to melamine-based dendrimer amines [46], poly-
amidoamine (PAMAM) dendrimers, another high-density nitrogen li-
gand, have been explored for designer SBA-15 [70]. Polyamidoamine is
a unique chelating agent because of its high density of nitrogen ligands
and the possibility of attaching functionalities such as primary amines,
carboxylates, and hydroxymates, which can result in a substantial in-
crease in bonding capacity for a variety of toxic metal ions. The
PAMAM functionalized SBA-15 and EDTA-modified PAMAM-SBA-15
(Fig. 5) were used as adsorbents for the aqueous Ni(II), Pb(II), Cr(III),
Cu(II), and Zn(II) ions. Adsorption results of both adsorbents were as
high as 90% in most cases (using initial solution as high as 250 mg/L)
with fast rate (15 min). The regenerated and reused adsorbents showed
similar efficiency as the original.
Sayari et al. [40] expanded the pore size of MCM-41 silica post-
synthesis using NeN dimethyldecylamine. The material was found to be
a fast, sensitive and high-capacity recyclable adsorbent for metallic
cations and organic pollutants in aqueous solution. Adsorption capa-
cities of 61, 54 and 106 mg/g were recorded for Co(II), Ni(II) and Cu
(II), while 96 and 115 mg/g were observed for chloro-guaiacol and di-
nitrophenol, respectively. Recently, Sayari and co-workers [71] have
shown that polyethylenimine-functionalized mesocellular silica foam
could exhibit high Cd(II) adsorption capacity of up to 625 mg/g with
stable reusability after three uses. This Cd(II) adsorption capacity value
is fascinating considering several low values reported in literature.
Coupling of other active functional groups to already functionalized
silica materials has also been explored by coupling salicylaldehyde to
Fig. 5. Schematic preparation of (a) PAMAM-SBA-15 and (b) EDTA modified PAMAM-SBA-15. Reprinted from Ref. [70], p. 317, Copyright (2007), with permission from Elsevier Inc.
256
Microporous and Mesoporous Materials 266 (2018) 252–267
aminopropyl SBA-15 in the synthesis of N-Propylsalicylaldimino-func-
tionalized SBA-15 mesoporous silica (Fig. 6) [47]. This designer sili-
cates showed high adsorption capacity and selectivity for Cu(II) ions
(up to 46 mg/g), but these were lower for Ni(II), Zn(II) and Co(II) ions
in both single and simultaneous adsorption and the adsorbent could be
regenerated by acid treatment without altering its properties. N-Pro-
pylsalicylaldimino-functionalized SBA-15 reported by Dindar et al. [72]
exhibited adsorption capacity of 64.2, 16.3 and 7.0 mg/g for Cr(VI), As
(V), and Hg(II), respectively, though this was slightly lower than their
aminopropyl-functionalized SBA-15 which had 79.6, 20.6 and 7.6 mg/g
for Cr(VI), As(V), and Hg(II), respectively. Similarly, aminopropyl-
functionalized manganese-loaded SBA-15 has been reported for Cu(II)
adsorption from aqueous solution [54]. The study showed that the
adsorbent could be regenerated and reused, exhibited high selectivity
for Cu(II), and had maximum adsorption capacity over twice (≈40 mg/
g) that of the unfunctionalized manganese-loaded SBA-15. Another
study using iminodiacetic acid for post-synthesis modification of me-
soporous SBA-15 showed the modified adsorbent had Cd(II) uptake of
36.4 mg/g [73].
The foregoing has shown that amino functionalizing of silica may be
essential for removal of aqueous pollutant cations. In that case, it may
also be possible to load a high amount of amino or nitrogen groups on
siliceous materials such as SBA-15 for higher cations removal. In line
with this logic, Zhao et al. [74] employed toluene diisocyanate as
‘bridge ’ molecule between SBA-15 and ethylenediamine. One NCO
group of the toluene diisocyanate was linked to the SBA-15 surface si-
lanols while the other was linked to ethylenediamine (Fig. 7). Appli-
cation of this high amino-load SBA-15 for removal toxic metal ions from
aqueous solution showed greater than 98% removal efficiency for Cu
(II), Zn(II), Cr(III), Ni(II) and Cd(II), and the authors attributed this to
the strong complexation reactions between the metal ions and the
grafted amine groups.
3.1.2. Magnetic silica-based adsorbents for inorganic pollutants
In order to ease the separation process of the silica adsorbents from
the aqueous solution after the pollutants adsorption, some workers have
magnetized the silicates. One major advantage of such designer silicates
is that they can be separated from aqueous solution after the adsorption
process by an external magnetic force (Fig. 8a). For instance, Wang
et al. [75] synthesized amino-functionalized core–shell magnetic me-
soporous SBA-15 silica composite which showed excellent adsorptive
capability (243.9 mg/g) toward Pb(II) ions. An interesting aspect of this
adsorbent was that it could be easily removed from solution by an ex-
ternal magnetic field and regenerated easily by acid treatment; since
most magnetic materials like magnetite dissolve in acidic media, pro-
tecting the magnetic material within the silica core-shell is an essential
P.N.E. Diagboya, E.D. Dikio
Fig. 6. Schematic of synthesis of N-Propylsalicylaldimino-functionalized SBA-15. Reprinted from Ref. [47], p. 1501, Copyright (2008), with permission from Elsevier Inc.
process. Similarly, Yuan et al. [76] synthesized large pore (≈10 nm)
amine-functionalized mesoporous silica shell with the Fe3O4 magnetic
core (Fig. 8b). In comparison to smaller pore size shells (< 4 nm), the
large pore size magnetic shell grafted far more amino functionalization
and consequently had higher heavy metals adsorption capacity for Pb
(II) (880 mg/g), Cu(II) (623 mg/g), and Cd(II) (492 mg/g). The ad-
sorbent was also easily regenerated using simple acid treatment. Li
et al. [77] had earlier synthesized and used thiol-functionalized mag-
netic spherical silica adsorbents for aqueous Hg(II) and Pb(II) adsorp-
tion. Though their adsorbent was not as efficient as that of Yuan et al.
[76], the reported adsorption capacity for Hg(II) (260 mg/g) was higher
than that of Pb(II) (91.5 mg/g), the adsorbent was reusable after re-
generation in acid solution and stable in water matrices from strong
acid and alkaline sources. Kumari et al. [78] have shown it is also
possible to synthesize magnetite nanospheres with hollow interiors in a
simple, one-pot, and template-free solvothermal method with ferric
chloride as the iron precursor. However, a major drawback of the
template-free solvothermal method is that it results in silicates with an
unusually small surface area, in this case, 11.3 m2/g. This led to an
extremely low aqueous metals adsorption capacity for Cr(VI) and Pb(II)
of ∼9 and ∼19 mg/g, respectively. Similarly, magnetic amino (NH2)
and melamine-based dendrimer amine (MDA) functionalized MCM-48
mesoporous silicates were used for the adsorption of aqueous Pb(II), Cu
(II), Cr(VI) and Cd(II) ions [79]. The MDA-magMCM-48 exhibited ad-
sorption capacity of 127.2, 125.8, 115.6 and 114.1 mg/g for the ions,
respectively, and was reusable for up to three times without significant
loss in adsorption capacity. Apart from the fact that incorporating
magnetic materials within or on mesoporous silicate adsorbents eases
the separation process of the adsorbent from the aqueous solution after
the pollutants adsorption, the report of El-Toni [80] indicated that the
incorporated magnetic materials enhanced the silicate adsorption
properties. They synthesized un-magnetized amino-functionalized
hollow core–mesoporous shell silica spheres using 3-aminopropyl-
trimethoxysilane. However, unlike other reports [75,76], their ad-
sorbent exhibited lower adsorption capacity notably for aqueous Pb(II)
and Cd(II) ions of 194 and 190 mg/g, respectively, the high surface area
(718 m2/g) notwithstanding.
Recently, cubic spinel crystallites of Zn−silica modified cobalt
ferrite magnetic nano-structured composite (CoFe2O4) was synthesized
and used for aqueous cationic pollutants from water [81]. The silica
modified CoFe2O4 exhibited better adsorption efficiency for removal of
both methylene blue and metal cations (Cr(III), Cu(II), and Pb(II)) over
the Zn(II) modified CoFe2O4, though the adsorption capacity was low
Fig. 7. Schematics of the high NH2 loading on the SBA-15. Reprinted from Ref. [74], p. 1046, Copyright (2011), with permission from Elsevier Inc.
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Microporous and Mesoporous Materials 266 (2018) 252–267
relative to those reported in literature here.
Some researchers have argued that it is vital to make the adsorbents'
preparation process eco-friendly by a substantial reduction of sec-
ondary pollutants. In line with this, Alotaibi et al. [82] synthesized iron
supported on bio-inspired green silica. The eco-friendly synthesis mi-
mics the bio-mineralization process and it is an easy process under mild
conditions with less toxic reagents. The process considerably reduces
the need for lengthy multistep procedures (≤72 h), high temperatures
(≤120 °C) and extreme pH conditions. The iron supported bio-inspired
green silica exhibited high arsenate ions removal capacity of 69 mg/g as
well as good reusability. Similarly, biodegradable nano-composite of
anionically modified guar gum with in-situ deposited silica nano-par-
ticles was synthesized through the sol-gel method [83]. The guar gum-
silica nano-composite exhibited remarkable adsorption capacity for
cationic dyes and metal cations of 781.3, 281.7, 645.2, and 709.2 mg/g
for malachite green dye, safranin dye, Pb(II), and Cd(II), respectively,
as well as good reusability. This adsorbent was also selective towards
cations as opposed to anions.
An attempt has been made at combing porous silica and graphene
nanosheets decorated with α-FeOOH and functionalized with thiol
groups (Fig. 9) [2]. Though the processes involved were quite cum-
bersome compared to other functionalized silicates discussed here, Hg
(II) ion adsorption performance was outstanding: > 800 mg/g at
400 mg/L Hg(II), and this significantly exceeded currently available
benchmark adsorbents. The adsorbent also exhibited efficient adsorp-
tion performance (∼100%) for removal of low (4 mg/L) and high
(120 mg/L) concentration of Hg in real water samples using this com-
posite in the form of membranes.
Wang et al. [84] have also advanced the concept of combining
multiple adsorbents by designing luminescent adsorbent that can be
visually monitored during the adsorption process instead of using the
usual instrumental methods to monitor pollutants concentration. Using
a simple microplasma-assisted method, they prepared luminescent
amino-functionalized ordered mesoporous silica-carbon dots composite
with high specific surface area, high adsorption efficiency and se-
lectivity for uranium even in the presence of various cations, as well as
the ability for simultaneous in situ monitoring of the adsorption pro-
cess. The combined individual properties of the pristine materials gave
rise to this composite. Adsorption using the luminescent adsorbent
could be monitored by monitoring the intensity of the composite's
fluorescence which decreased as the uranium uptake increased.
P.N.E. Diagboya, E.D. Dikio
3.1.3. Other designer silica-based adsorbents for inorganic pollutants
Inorganic functionalities have also been incorporated or imprinted
on silicate surfaces to improve the metals' adsorption process. For in-
stance, in order improve adsorption efficiency of Pb(II) from acidic
wastewater (pH 2.0), Pb(II) imprinted mesoporous silica functionalized
with iminodiacetic acid was fabricated [85]. The Pb(II) imprinted
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Microporous and Mesoporous Materials 266 (2018) 252–267
Fig. 8. (a) The separation of amino-functionalized magnetic SBA-15
particles by an external magnet. Reprinted from Ref. [75] p. 900,
Copyright (2015), with permission from Elsevier Inc.; (b) scheme
showing the synthesis of large pore amino-functionalized meso-
porous silica shell with Fe3O4 magnetic core and heavy metal ad-
sorption process. Reprinted from Ref. [76] p. 160, Copyright
(2013), with permission from Elsevier Inc.
mesoporous silica had high surface area was 762 m2/g with an ad-
sorption capacity up to 103 mg/g at pH 2.0 in 7 min; a better result than
that of the iminodiacetic acid-functionalized SBA-15 at pH 4.5. The
imprinted material also exhibited high selectivity among six competing
metal ions (Zn(II), Cd(II), Cu(II), Mg(II), Ca(II) and Fe(III)) with the
adsorption efficiency of above 93% after six regeneration cycles. The
Fig. 9. Schematics of synthesized graphene-DE-αFeOOH-
SH composite. (a) Natural graphite rock, (b) diatom silica
from diatomaceous earth (DE), (c) dispersed graphene
oxide sheets and 3-aminopropyltriethoxysilane modified
DE, (d) graphene-DE composite (GN-DE) decorated with
αFeOOH nanoparticles, (e) thiol-functionalized graphene-
DE-αFeOOH-SH composite obtained using chemical vapor
deposition from step e to step f. Reproduced from Ref. [2]
with permission from The Royal Society of Chemistry.
P.N.E. Diagboya, E.D. Dikio
Fig. 10. Schematics of phosphate-functionalized mesoporous SBA-15. Reprinted from
Ref. [87], p. 198, Copyright (2017), with permission from Elsevier Inc.
authors also showed that the imprinted silicate was effective for real
samples of strongly acidic wastewater.
Other organic molecules, such as the biologically active dopamine,
may be useful in the adsorption process. Uranium ions have been ad-
sorbed in aqueous solution using post-synthesis dopamine grafted me-
soporous silica [86], and the results showed a spontaneously exo-
thermic process with fast adsorption rate (20 min), and a maximum
adsorption capacity of 196 mg/g at pH 6.0. The influences of K+ and
Na+ ions concentrations and solid-to-liquid ratio on the adsorption
process were negligible.
Coupling of inorganic phosphate to silicates is eliciting interest in
aqueous pollutants removal [18,87]. Gao et al. [87] synthesized phos-
phate modified SBA-15 by post-graft approach (Fig. 10) and used this
for adsorption of the rare earth ion Gd(III). The study showed that the
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Microporous and Mesoporous Materials 266 (2018) 252–267
phosphate-modified SBA-15 had high surface area (≈670 m2/g), large
pore size (9.1 nm), abundant surface phosphate groups, and the ad-
sorbent exhibited ultrafast adsorption rate (2 min) with adsorption ca-
pacity of up to 204.4 mg/g and could be reused multiple times without
significant loss in binding capacity.
3.2. Organic pollutants
Studies of adsorption of organic pollutants on pristine and meso-
porous silicates seem to be a less traveled part compared to adsorption
of inorganic pollutants like the toxic metals. Here, we shall discuss
some of the recent studies dealing with adsorption of organic pollutants
on silicates. One major drawback in using pristine silicates for organics
adsorption is that the surface silanol groups are hydrophilic and easily
forms hydrogen bonds with water thus limiting the adsorption process.
However, Huang et al. [88] have shown that this may not be the case
always because pristine ordered mesoporous SBA-15 molecular sieves
could be used for cationic dyes adsorption. The study suggested that
electrostatic attraction between the silanol groups and cationic dyes is
the primary removal process and SBA-15 exhibited excellent adsorptive
capability for cationic dyes (methylene blue and Janus Green B) but
almost no adsorption for anionic (Reactive black 5) and neutral dyes
(dimethyl phthalate). The SBA-15 adsorption capacity for methylene
blue and Janus Green B may reach 49.3 and 66.4 mg/g, respectively.
Aside from pristine silicates, designer silicates have been employed in
studies on aqueous organic pollutants removal. Here, we review recent
reports.
3.2.1. Nitrogen/thiol designer silicates for organic pollutants
In order to improve the efficiency of the silica-based materials,
several nitrogen-containing designer silicates have been synthesized
and studied. Aminopropyl- and tripolyphosphate-functionalized SBA-15
have been studied for pesticide (pentachlorophenol– PCP) removal
from aqueous solutions [18]. Fig. 11 depicts the scheme for the pre-
paration of the tripolyphosphate functionalized SBA-15. Compared to
pristine SBA-15, the functionalized derivatives exhibited higher PCP
removal following the trend SBA-15 (0.6 mg/g) < tripolyphosphate-
functionalized SBA-15 (2.5 mg/g) < aminopropyl-functionalized SBA-
Fig. 11. (a) cross section of ordered SBA–15 mesoporous
silica; schematics of the synthesis of SBA–15 materials
showing reactions with (b) 3–aminopropylethoxysilane and
(c) tripolyphosphate; (d) interaction of tripolyphosphate
with 3–aminopropylethoxysilane showing a flip electro-
static interaction/covalent bond between the phosphate
and amine group. Reprinted from Ref. [18], p. 44, Copy-
right (2014), with permission from Elsevier Inc.
P.N.E. Diagboya, E.D. Dikio
15 (3.3 mg/g). The study attributed ≥75% increase in sorption upon
functionalization to the electrostatic interaction between the PCP spe-
cies and amino group. Aminopropyl-functionalized SBA-15 adsorbents
with varied aminopropyl contents synthesized by co-condensation [89]
have also been studied as adsorbents for humic acid, an ubiquitous
pollutants in surface and groundwater. In contrast to humic acid ad-
sorption on SBA-15, substantially enhanced adsorption was observed
over the functionalized SBA-15 adsorbents with an increase in solution
pH resulting in decreased adsorption over the aminopropyl functiona-
lized SBA-15. Adsorption capacities of 8.5, 72.5 and 117.6 mg/g were
recorded for SBA-15, NH2-SBA-15-5% and NH2-SBA-15-10%, respec-
tively, where the percentage represents aminopropyl loading. Amino-
propyl-functionalized SBA-15 has also been shown to exhibit a good
capacity for removal of tannic acid from aqueous solution with ad-
sorption capacity of 272.4 mg/g [90].
Bi-functionalized SBA-15 based designer adsorbents have been
synthesized to target specific molecular features of pollutants [91].
While using any two of N-(2-aminoethyl)-3-aminopropyl-methyl-di-
methoxy-silane, 3-phenoxy-propyl-dimethylchloro-silane and n-hex-
adecyl-triethoxysilane as functionalizing organo-silane, diamine/
phenyl-SBA-15, diamine/cetyl-SBA-15 and phenyl/cetyl-SBA-15 were
specifically tailored for adsorption of eosin, 4-nonylphenol (4-NP) and
di-n-butyl-phthalate (DBP), respectively, from aqueous solutions.
Compared with the mono-functionalized adsorbents, bi-functionalized
SBA-15 adsorbents exhibited better adsorption efficiency for pollutants
at low concentration. The adsorption capacities for eosin, 4-NP, and
DBP were approximately 382.3, 207.3 and 434.2 mg/g on the ad-
sorbents, respectively. Considering the structural relationship between
the adsorbents and the adsorbates (Figs. 12 and 13), Zhang et al. [91]
attributed the success of pollutants removal to cooperative effects of
hydrogen bonding, electrostatic attractions, hydrophobic interactions,
and π–π stacking interactions. This cooperative effect could result from
two functional groups on the same solid surface leading to better
Fig. 12. Si solid-state NMR spectra of the three respective bi-functionalized adsorbents.
Reproduced from Ref. [91] with permission from The Royal Society of Chemistry.
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Microporous and Mesoporous Materials 266 (2018) 252–267
Fig. 13. Chemical structures of eosin, NP and DBP. Reproduced from Ref. [91] with
permission from The Royal Society of Chemistry.
adsorption performance. Recently, Fan et al. [92] showed that up to
40 mg/g adsorption capacity could be achieved from post-synthesis
prepared phenyl-functionalized SBA-15 in the adsorption of aqueous
DBP. Their result was lower than reported earlier [91] and it highlights
the effect of cooperative adsorption.
In line with the concept that cooperative effect [91] could result in
enhanced adsorption process, thiol-functionalized mesoporous poly-
vinyl alcohol/silica-based nano-fiber prepared by sol-gel and electro-
spinning methods was used for simultaneous but sequential adsorption
of Bisphenol A (BPA) and Cu(II) from their binary solutions [93]. It is
interesting to note here that the sequential adsorption of one pollutant
may lead to the enhanced synergistic adsorption of a second pollutant.
Adsorption of Cu(II) was attributed to chelating interaction by thiol
groups, while BPA was removed from solution due to intermolecular
attraction and hydrogen bonding. The BPA if adsorbed on the thiol
group first, could act as a molecular bridge for Cu(II) adsorption re-
sulting in the synergistic adsorption. However, the co-existence of both
pollutants resulted in decreased BPA uptake due to competition for the
thiol groups. The authors also showed that co-existence of Cl− and
NO3− ions enhanced Cu(II) adsorption but not BPA, and the adsorbent
was reusable after sequential desorption of BPA and Cu(II) using
ethanol and HCl solutions. Similarly, rhodamine 6G assisted adsorption
of metanil yellow over succinamic acid-functionalized MCM-41 has also
been reported [94]. Here, it was assumed that multilayer adsorption
between rhodamine 6G and metanil yellow might have resulted in this.
Another nitrogen-containing silicate is the polyacrylic acid-grafted
mono-disperse silica nanoparticles [95] which has been shown to be a
good adsorbent for methylene blue (≈305 mg/g). The polyacrylic acid-
grafted silica nanoparticles were synthesized through a combination of
mussel-inspired chemistry and Michael addition reaction. Firstly, the
silica nanoparticles were coated with poly-dopamine through self-
polymerization under mild conditions, and this was then conjugated
with amino-terminated polyacrylic acid (Fig. 14). The good adsorption
capacity of this adsorbent is worthy of note.
3.2.2. Magnetic silica-based adsorbents for organic pollutants
Various studies have reported that it is possible to magnetize de-
signer silicate adsorbents to be used for organics removal from aqueous
solution. However, unlike the adsorption of aqueous cations, less at-
tention has been given to designer magnetic-silicates for removal of
aqueous organic pollutants. Amino-functionalized magnetic meso-
porous MCM-41 silica (magMCM-41-NH2) was synthesized and used for
adsorption of tannic acid from aqueous solution [96]. The magMCM-
41-NH2 had an adsorption capacity of 510 mg/g, the adsorption was
favorable in the pH range of 4.5–7.0 indicating the adsorbent usability
over this pH range, and the process was enhanced by the presence of
aqueous coexisting cations (Na, K, and Ca). The magMCM-41-NH2
(surface area 668 m2/g; pore size 0.53 cm3/g) was a better adsorbent
for adsorption of tannic acid from aqueous solution when compared to
the un-magnetized amino-functionalized SBA-15 which showed an
P.N.E. Diagboya, E.D. Dikio
Fig. 14. Schematics of polyacrylic acid-grafted mono-disperse silica nanoparticles. Reprinted from Ref. [95], p. 287, Copyright (2016), with permission from Elsevier Inc.
adsorption capacity of 272.4 mg/g (surface area 246 m2/g; pore size
0.43 cm3/g) [90]. This, as well as the study of Teo et al. [97], showed
that magnetizing the adsorbent, in addition to easing adsorbent se-
paration from solution, enhances its adsorption capacity.
Magnetic core-shell silicates have also been recently used for re-
moval of Congo red dye from aqueous solution [98]. Congo red dye
adsorption on this magnetic silicate was mainly by electrostatic inter-
action and adsorption capacity was about 54.6 mg/g. Similarly, hybrid
shells of iron oxide nanoparticles coated with organic κ-carrageenan
and inorganic silica have also been used for the magnetically assisted
removal of methylene blue from aqueous solution [99]. The hybrid
shells exhibited good adsorption capacity (530 mg/g) which was at-
tributed to the sulphate-rich surface of the κ-carrageenan. The hybrid
shells were reusable with adsorption efficiency over six consecutive
adsorption/desorption cycles relatively stable (> 97%). Both studies
showed that in addition to magnetizing the silicate, functionalizing
significantly enhances adsorbent efficiency as well.
3.2.3. Other designer silica-based adsorbents for organic pollutants
In addition to the nitrogen-containing and magnetic functionalities
of designer silicates, others have been studied recently. For instance, a
comparison has been made of the effect of multiple roles of similar
organic functional groups in designer silicate adsorbents specifically
using mercapto- and sulphonic acid functionalization of SBA-15 for
adsorption of the antibiotics ciprofloxacin [3]. It was observed that the
introduced sulfonic functionality enhanced the adsorption of
Fig. 15. Modification of SBA-15 using the grafting technique. Reprinted from Ref. [104], p. 472, Copyright (2010), with permission from Elsevier Inc.
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Microporous and Mesoporous Materials 266 (2018) 252–267
ciprofloxacin; an indication that electrostatic interaction is more im-
portant than hydrophobic interactions between sulfonic-SBA-15 and
aqueous ciprofloxacin species. The sulfonic-SBA-15 adsorbent could be
reused for thrice for adsorbing ciprofloxacin. The same research group
also used azide-functionalized hollow silica nanospheres synthesized
from tetraethoxysilane and azidopropyltrimethoxysilane on F127 single
micelle template as an adsorbent for ciprofloxacin adsorption [100].
They concluded that functional groups such as phenyl-acetylene, pro-
pargyl alcohol, 1-heptyne and 2-butyne-1,4-diol linked to these hollow
silica nanospheres played important roles in their adsorption proper-
ties. Gao et al. [101] have also shown that SBA-15 functionalized with
aminopropyl triethoxysilane, propyltrimethoxysilane, or phenyl-
trimethoxysilane may be used as an adsorbent for ciprofloxacin ad-
sorption with possible adsorption capacities up to 2.2, 4.4, and
11.2 mg/g at 0.1 mg/L of ciprofloxacin.
A comparative adsorption study of Boldine (2,9-dihydroxy-1,10-di-
methoxyaporphine) was carried out using pristine and propyl-sulfonic
acid-functionalized SBA-15, SBA-16, and mesocellular foam (MCF)
[102]. Like other reports, functionalization enhanced adsorption while
SBA-15 and its functionalized propyl-sulfonic derivative showed higher
adsorption than SBA-16 and MCF, though no reason was proffered for
this trend.
Apart from incorporation of organic functionalities on the silica
surface, inclusion of transition metal (such as Co(II), Ni(II) and Cu(II))
functionality onto the surface of MCM-41 [103] and SBA-15 [104] via
an already attached organic amino-moiety enhanced the silica
P.N.E. Diagboya, E.D. Dikio
Fig. 16. Suggested adsorptive mechanism for naturally obtained silicates. Reprinted from Ref. [114], p. 324, Copyright (2016), with permission from Elsevier Inc.
adsorption of Naproxen from aqueous medium. These transition metals
grafting technique [104] on the silicates were similar (Fig. 15), and the
authors concluded that similar strategies might hold promise for re-
moval Pharmaceutical and Personal Care Products (PPCPs) from aqu-
eous solution, especially those present at ppm levels.
Recently inorganically modified spherical mesoporous MCM-41 si-
lica using CuO exhibited better adsorption capacity for the cationic
dyes– crystal violet and methylene blue (52.9 and 87.8 mg/g, respec-
tively) compared to the pristine spherical mesoporous MCM-41 (46.2
and 65.7 mg/g, respectively) [105]. The same research group also
showed that similarly, iron oxide-modified MCM-41 exhibited en-
hanced adsorption for aqueous aniline [106]. The enhancements in
adsorption were attributed to electrostatic interactions between the
mesoporous MCM-41 loaded metals (Cu and Fe) and the aqueous ca-
tions (pollutants: dyes and aniline), as well as, to a less degree, the
enhanced pore structure of the adsorbent.
Similar to the inclusion of transition metal functionality onto the
silicate surface, coal fly ash (containing primarily Si, Al, and Fe at
concentrations of 239.5, 108.0 and 60.3 mg/g, respectively) was used
to modify 3-aminopropyltriethoxysilane functionalized mesoporous
MCM-41 [107]. The synthesized material exhibited high affinity for
aqueous Cu(II) ions with up to 95% removal at 45 mg/L. However,
using coal fly ash as the source of amorphous SiO2 and Al2O3 compo-
nents rather than as modifying agents, Zhou et al. [108] synthesized
spherical Al-MCM-41. This was quite interesting taking into con-
sideration that (i) the primary raw material source of the Al-MCM-41
was a supposed waste material-coal fly ash, (ii) the final BET surface
area was up to 525 m2/g with a pore volume of 0.71 cm3/g, and (iii)
methylene blue adsorption capacity of 277 mg/g. Their study suggested
that Al-MCM-41 obtained from industrial solid waste of coal fly ash
could be an economic adsorbent for treatment of methylene blue in
aqueous solution. This has been supported by another study showing
that fly ash Al-MCM-41 [108] is better than Al-SBA-15 [109] for aqu-
eous methylene blue adsorption. The Al-SBA-15 [109] synthesized by
the conventional method [18] exhibited a maximum adsorption capa-
city of 83 mg/g even with a larger surface area (693 m2/g) and pore
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Microporous and Mesoporous Materials 266 (2018) 252–267
volume (0.85 cm3/g) in comparison to Al-MCM-41. Suraja et al. [110]
also showed that nanosized cobalt oxide (Co3O4) particles incorporated
(maximum at 10%) onto SBA-15 mesoporous silica showed adsorption
potential (16 mg/g) for aqueous methylene blue. However, this was far
less efficient when compared with Al-MCM-41 obtained from coal fly
ash source [108]. Recently, Zhang et al. [111] showed that porous
metal silicates could also be obtained from other waste sources. They
prepared various three-dimensional metal (magnesium, zinc, nickel,
and cobalt) silicates from waste rice husks and the magnesium silicate
exhibited high aqueous adsorption capacities of 557.9, 381.3 and
482.8 mg/g for Pb(II), tetracycline, and UO22+, respectively. The rice
husk porous silica doped with Ni nanoparticles also exhibited high
catalytic activity as well as good stability for reduction of aqueous 4-
nitrophenol.
In the same vein, Wang and co-workers have shown that metal ion-
modified mesoporous silicates obtained from naturally occurring paly-
gorskite or Illite clay may be used for efficient removal of both organic
pollutants and metals cations [57,112–115]. Their reports were quite
interesting because it highlighted that mesoporous silicates can be ob-
tained from relatively abundant clay sources. Their Mg-modified paly-
gorskite clay exhibited 218.9 and 107.9% increase in adsorption of the
antibiotics chlortetracycline (329.84 mg/g) and oxytetracycline
(207.47 mg/g), respectively, compared to the pure palygorskite clay
[112]. The same adsorbent exhibited adsorption capacity of 527.2 and
210.6 mg/g for methylene blue and Cu(II) ions, respectively [57]. Si-
milarly, Mg-modified mesoporous silicate obtained from illite clay
showed higher chlortetracycline adsorption capacity of 408 mg/g
compared with the pure Illite clay (159.7 mg/g) [115]. However, Zn-
modified red palygorskite clay was slightly less effective for removal of
aureomycin and tetracycline with adsorption capacity of 384 and
337 mg/g, respectively, in contrast with the 154 and 140 mg/g of the
pure red palygorskite clay [114]. The large specific surface areas, as
well as large pore structures of these naturally obtained silicates, are
noteworthy. The proposed mechanism for the removal of these pollu-
tants from solution involves monolayer electrostatic interaction with
charged surfaces, hydrogen bonding as well as complex formation
P.N.E. Diagboya, E.D. Dikio
Fig. 17. Schematics of the aerogel synthesis. Reproduced from Ref. [117] with permission from The Royal Society of Chemistry.
(Fig. 16) and possibly pore filling.
The combination of adsorbents has also been studied as a method of
increasing pollutants adsorption capacity. In this regard, mesoporous
silica has been coated on micrometer-sized and nanometer sized zeolite
A and these were compared with the pristine zeolite A for adsorption of
butyraldehyde [116]. Adsorption on both composite materials almost
doubled those of the pristine zeolites A (nano and micro; 151 and
146 mg/g, respectively); while the nano-zeolite A composite (314 mg/
g) exhibited better adsorption than micro-zeolite A composite (266 mg/
g).
Lately, silica aerogels [117] reinforced with polyacrylonitrile fibers
(Fig. 17) have been synthesized for use in adsorbing diesel oil from
water and oil mixtures. This adsorbent exhibits high porosity and sur-
face area, low density, and three-dimensional reticular structures with
excellent adsorption capacity (Fig. 18) for oil (9.56 g/g). Interestingly,
authors stated the adsorbent could be reused up to 100 times without
Fig. 18. Demonstration of diesel oil adsorption by the aerogel with 0.3% fibers.
Reproduced from Ref. [117] with permission from The Royal Society of Chemistry.
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Microporous and Mesoporous Materials 266 (2018) 252–267
diminished property. This type of designer adsorbent is quite fasci-
nating considering the very high adsorption capacity, and its benign,
straightforward, and economic preparation.
Another recently attempted synthesis of designer silicate with the
simultaneous ability for fast removal of organic, inorganic, and mi-
crobial contaminants from aqueous solution [118]. Herrmann et al.
[118] synthesized a polyoxometalate-ionic liquid (POM-IL) complex
immobilized on porous silica (POM-SILP). Each component of this
complex has its specific contribution which targets a particular type of
contaminant resulting in the water-insoluble POM-IL composed of an-
timicrobial alkyl-ammonium cations and lacunary polyoxometalate
anions with heavy-metal binding sites. The silica support also has
radionuclides binding capacity, and this, in addition to the complex's
lipophilicity enables adsorption of organic contaminants (Fig. 19). The
use of POM-SILP in filtration columns could result in one-step multi-
contaminant portable water purification.
Though various mesoporous silica materials have recently been in-
vestigated for pollutants removal from aqueous solution, SBA-15 and
MCM-41 have received the greatest attention. Comparison of some re-
cent designer silicates and pollutants adsorbed from aqueous solutions
are shown in Tables 1 and 2. Several of these designer silicates have
shown promising adsorption capacity for both organic and inorganic
pollutants.
3.3. Some other environmental remediation applications
Apart from the use of these silicates for direct adsorption of aqueous
pollutants from water, designer mesoporous silica and its functionalized
derivatives have been applied in areas such as photocatalysis. Titanium
substituted SBA-15 has been prepared by several methods and used as
support for TiO2 [49,121,122]. The photocatalytic activity of this ma-
terial increased proportionally as the Ti content and TiO2 loading.
Dou et al. [123] and Qin et al. [124] have also shown differently
that mesoporous silica can be useful for removal of volatile organic
compounds (VOCs). Dou et al. [123] functionalized SBA-15, MCM-41,
MCM-48 and KIT-6 (Fig. 20) with phenyltriethoxysilane and in-
vestigated the static adsorption of benzene. The adsorption perfor-
mance was observed to be related to the pore diameter: the larger the
pore diameter, the better the adsorption performance. Hence, phenyl-
grafted KIT-6 offered the best adsorption performance while phenyl-
grafted MCM-41 exhibited the lowest adsorption efficiency than the
other functionalized materials owing to the restricted size of the
P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267

Fig. 19. Purification of water using POM-SILPs: the POM-

SILP column filter removes toxic heavy metals (e.g. Ni(II),
Pb(II), UO2(II)), aromatic organic pollutants (e.g. trityl
dyes), and microbes (E.coli) due to the presence of anti-
microbial tetra-alkyl ammonium cations and lacunary
polyoxometalate anions with specific metal binding sites
(orange arrow). Reproduced from Ref. [118], p. 1668, ©
2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 1 mesopores. Qin et al. [124] reported a similar result. The success of
Comparison of some designer silicates and some inorganic pollutants adsorbed from using methyl and phenyl functionalized SBA-15 for removal VOCs has
aqueous solutions. also been reported [125].
Designer Silicate Pollutant qe (mg/g) Solution Reference
4. Conclusion and outlook
Bio-inspired Fe-supported on silica As(V) 69.6 Single [82]
a
APTS-SBA-15 As(V) 20.6 Mixed [72] In order to meet the evergrowing stricter water regulatory standards
N-propylsalicylaldimine-SBA-15 As(V) 16.3 Mixed [72]
Magnetic melamine-MCM-48 Cd(II) 114.1 Mixed [79]
placed by governments and other regulatory bodies, numerous ad-
a
NH2-HCMSSs Cd(II) 190.5 Mixed [80] vances in material science are emerging for enhancing the water pur-
Large pore magnetic amino-silica Cd(II) 492.4 Single [76] ification process. One such advance includes the functionalized ordered
Imino-di-acetic acid- SBA-15 Cd(II) 36.4 Single [73] mesoporous silica or designer silicates. In the last eight years, designer
Magnetic core-shell APTS-silica Cd(II) 22.5 Single [119]
silicates have gained wide interest as adsorbents for aqueous pollutants
Guar gum-Silica composite Cd(II) 709.2 Single [83]
Polyethylenimine silica foam Cd(II) 625 Single [71] due to the plethora of designer opportunities available. The nitrogen/
Co(II) ion-imprinted triglycine Co(II) 181.7 Mixed [120] thiol-containing silicates and the magnetized derivatives or magnetics
SBA-15 (surface or core-shell) have been extensively explored for the removal
a
SBA-TACN Co(II) 0.9 Mixed [69] of toxic cationic and anionic species, dyes, pesticides, industrial or-
a
SBA-TACN Cr(III) 3.6 Mixed [69]
Magnetic melamine-MCM-48 Cr(VI) 115.6 Mixed [79]
ganics, pharmaceuticals and other emerging pollutants. Recently,
APTS-SBA-15 Cr(VI) 79.6 Mixed [72] higher definition designer silicates, comprising of functionalized me-
N-propylsalicylaldimine-SBA-15 Cr(VI) 64.2 Mixed [72] soporous silicates and other adsorbents synergistically combined, are
Magnetic melamine-MCM-48 Cu(II) 125.8 Mixed [79] proving far more successful materials than the lone functionalized si-
a
SBA-TACN Cu(II) 42.4 Mixed [69]
licates.
Large pore magnetic amino-silica Cu(II) 628.3 Single [76]
Mn-loaded APTS-SBA-15 Cu(II) 40.7 Mixed [54] In conclusion, the present review emphasizes the following:
Mn-loaded-SBA-15 Cu(II) 19.9 Mixed [54]
Magnetic core-shell APTS-silica Cu(II) 29.9 Single [119] i. Though pristine silicates have various remarkable properties which
Phosphorous acid-SBA-15 Gd(III) 204.4 Single [87] may be beneficial in the water treatment process, they have been
a
Magnetic MPTS-silica Hg(II) 1.31 Mixed [77]
APTS-SBA-15 Hg(II) 7.6 Mixed [72]
outclassed by their designer derivatives.
N-propylsalicylaldimine-SBA-15 Hg(II) 7.0 Mixed [72] ii. It is possible to synthesize designer silicates having single or multi-
SBA-TACN Ni(II) 6.7 Mixed [69] functionalizations, by co-condensation or post-synthesis grafting,
a
Magnetic APTS-SBA-15 Pb(II) 243.8 Single [75] using various molecules ranging from organic, inorganic to biolo-
(microspheres)
gical molecules. Inclusions of transition metals functionality onto
Magnetic melamine-MCM-48 Pb(II) 127.2 Mixed [79]
a
NH2-HCMSSs Pb(II) 194.4 Mixed [80] the silicate surface via an already attached organic-moiety resulting
MPTS-silica Pb(II) 0.44 Mixed [77] in enhanced adsorption have also been achieved. Coupling of other
Large pore magnetic amino-silica Pb(II) 880.6 Single [76] active functional groups to already functionalized silica materials is
Magnetic core-shell APTS-silica Pb(II) 76.7 Single [119] an emerging trend that is proving successful for enhanced adsorp-
Iminodiacetic acid-SBA-15 Pb(II) ≈20 Mixed [85]
tion efficiency.
Pb(II)-imprinted iminodiacetic Pb(II) ≈144 Mixed [85]
acid-SBA-15 iii. Recent studies have shown that some ‘supposed waste materials’,
Cobalt Ferrite Magnetic Zn(II)- Pb(II) ≈20 Single [81] such as fly ash and rice husk, could be used as major raw material
Silica sources for designer silicates instead of the commercially-available
Mg-Silicate Pb(II) 557.9 Single [111]
organosilanes. This could drastically reduce the cost of designer
Guar gum-Silica composite Pb(II) 645.2 Single [83]
Dopamine-SBA-15 U(VI) 196 Single [86]
silicates production. It is also possible to synthesize eco-friendly
APTS-SBA-15 U(VI) ≈90 Single [84] designer silicates which exclude the extreme conditions of the
APTS-SBA-15-Carbon dot U(VI) ≈170 Single [84] popular classical method of preparation such as extreme pH, high
composite temperature and toxic chemicals.
Mg-Silicate UO22+ 482.8 Single [111]
iv. Co-condensation or post-synthesis grafting of functional groups
NH2-HCMSSs Zn(II) 193.0 Mixed [80]
does not significantly affect adsorption efficiency, but the type and
a
Modifying agents – APTS: Aminopropyltriethoxysilane; TACN: 1,4,7-triazacyclono- density of the functionality. For instance, multi-nitrogen-functio-
nane; NH2-HCMSSs: APTS hollow core-mesoporous shell silica sphere; MPTS: 3-mercap- nalized silicates exhibit higher pollutant loading capacity than the
topropyl)-trimethoxysilane.

264
P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267

Table 2
Comparison of some designer silicates and organic pollutants adsorbed from aqueous solutions.

Designer Silicate Pollutant qe (mg/g) Solution Reference

α-Fe2O3-MCM-41 acetylsalicylic acid ≈6.5 Single [97]

SBA-15 Ciprofloxain ≈100 Single [3]
Mercaptopropyltrimethoxysilane-SBA-15 Ciprofloxain ≈125 Single [3]
Sulfonic acid-SBA-15 Ciprofloxain ≈250 Single [3]
Silica coated magnetic nanospheres Congo red 54.6 Single [98]
MCM-41 Crystal violet 46.2 Single [105]
CuO/MCM-41 Crystal violet 52.9 Single [105]
Phenyl-SBA-15 di-n-butyl phthalate ≈39 Single [92]
SBA-15 Humic acid 8.5 Single [89]
APTS-SBA-15 Humic acid 117.6 Single [89]
Guar gum-Silica composite Malachite green 781.3 Single [83]
Co3O4 doped SBA 15 Methylene blue 16.7 Single [110]
Al-MCM-41 (spherical) Methylene blue 277.8 Single [108]
Cobalt Ferrite Magnetic Zn(II)-Silica Methylene blue ≈24 Single [81]
MCM-41 Methylene blue 65.7 Single [105]
CuO/MCM-41 Methylene blue 87.8 Single [105]
Magnetic carrageenan-silica hybrid shells Methylene blue 530 Single [99]
SBA-15 Methylene blue 45.1 Single [109]
Al-SBA-15 Methylene blue 79.8 Single [109]
CH3-MCM -41 Methylene blue 375.5 Single [8]
MCM -41 Nitrobenzene 25.8 Single [8]
Silica aerogel Oil 9560 Single [117]
SBA-15 Pentachlorophenol 2.1 Single [18]
APTS eSBA-15 Pentachlorophenol 4.2 Single [18]
Tripolyphosphate APTS eSBA-15 Pentachlorophenol 3.5 Single [18]
Guar gum-Silica composite Safranin 281.7 Single [83]
Magnetic APTS-MCM-41 Tannic acid 510.2 Mixed [96]
APTS eSBA-15 Tannic acid 272.4 Single [90]
Mg-Silicate Tetracycline 381.3 Single [111]
Zn-Silicate Tetracycline 337 Single [114]
Zn-Silicate Aureomycin 384 Single [114]
Mg-Silicate Methylene blue 408.0 Single [113]
Mg-Silicate Crystal violet 397.2 Single [113]

*Modifying agents – APTS: Aminopropyltriethoxysilane; TACN: 1,4,7-triazacyclononane; NH2-HCMSSs: APTS hollow core-mesoporous shell silica sphere; MPTS: 3-mercaptopropyl)-
trimethoxysilane.

Fig. 20. Schematics of the surface functionalization of SBA-15, MCM-41, MCM-48 and KIT-6. Reprinted from Ref. [123], p. 1617, Copyright (2011), with permission from Elsevier Inc.

265
P.N.E. Diagboya, E.D. Dikio
sparse analogues– mono-nitrogen-functionalized silicates.
v. The magnetics, apart from easing the adsorbent separation process
by using an external magnetic force, enhances adsorption capacity.
vi. Higher definition designer silicates have been synthesized by cou-
pling ordered mesoporous silicates with other adsorbents. These
kind of materials have resulted in
a. Extra-ordinary adsorption capacity,
b. Luminescent adsorbent that can be used to visually monitor the
adsorption process instead of using the usual instrumental
methods, and
c. Designer adsorbents with the simultaneous ability for fast re-
moval of organic, inorganic, and microbial contaminants from
aqueous solution.
vii. Designer silicates have shown high adsorption and excellent se-
lectivity towards specific pollutant, as well as the capacity for si-
multaneous removal of aqueous pollutants. It is worthy to note that
these materials exhibited excellent reusability.
vii. The success of aqueous pollutants removal by designer silicates
could be attributed to hydrogen bonding, electrostatic attractions,
hydrophobic interactions, or π–π stacking interactions between the
silicates and pollutant. In some cases, it has been attributed to the
cooperative effects among these, or even sequential adsorption of
one pollutant may lead to the enhanced synergistic adsorption of a
second pollutant.
With the large literature available and still being published on de-
signer silicates, perhaps some of the biggest challenges to overcome
now are: actual field trials, synthesis of greener designer silicates, and
their large-scale production.
(a) Available literature are mostly idealized laboratory studies and
cannot be used to predict the usefulness of designer silicates in
actual field situations due to the presence of interfering agents. The
applicability of these materials might be another challenge since
most laboratory studies are batch processes while the column or
fixed bed is usually preferred in the industries.
(b) The byproducts of the sol-gel synthesis methods are not en-
vironmentally friendly; greener synthesis methods for designer si-
licates is of high necessity so as not to cause a bigger environmental
challenge will endeavoring to solve another.
(c) Despite the promising potential of designer silicates, difficulty in
large-scale production is still a stumbling block for their industrial
applications because the currents synthesis methods are compli-
cated, difficult to control, not eco-friendly, and results in small
yields. It is envisaged that with the rapid development of new and
facile synthesis methods, the listed challenges will result in exciting
research outcomes, and designer silicates are bound to play a vital
role in water treatment technologies.
Acknowledgements
We acknowledge the supports of Vaal University of Technology
Research Directorate, the World Academy of Sciences (TWAS) Trieste
Italy and the Chinese Academy of Sciences (CAS) China, for the award
of CAS-TWAS Postgraduate Fellowship (FR number: 3240255024) to
PNE Diagboya.
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