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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.
∗
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 Microporous and Mesoporous Materials 266 (2018) 252–267
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 Usually, a single surfactant (such as the Pluronic-type surfactant;
methods where available. To give insight into the adsorbents effec- poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-
tiveness, reported adsorption capacities are noted. Pluronic P123 (EO20PO70EO20) or Pluronic F127, (EO106PO60EO106),
and cetyltrimethylammonium bromide (CTMAB)) is used as the organic
2. Ordered mesoporous silicates structure directing agent or template for the synthesis of surfactant-
templated silica materials [18,41–44]. However, binary surfactants of
This class of mesoporous materials consists of extensive inorganic or different molecular weights has been used resulting in the formation of
inorganic–organic hybrid arrays with the exceptional long-range order, dual-mesoporous silica materials [41].
highly tunable textural and surface properties and controlled pore size
and geometry [35]. These properties, in addition to their usually large 2.2. Post-synthesis removal of surfactants
surface areas, make them excellent adsorbent materials providing
higher possibilities for adsorbent–adsorbate interactions. It is worthy to To access the pores within the ‘as-synthesized’ mesoporous silica
state here that silica framework is not crystalline but amorphous; it is composites, it is necessary to remove the surfactants used in the self-
the mesopores that are arranged periodically within the structure. assembly. Mesoporous silica synthesized via the surfactant-templated
Mesoporous silicates include the Mobile Composition of Matter (MCM) sol–gel reaction is carefully packed and shrink significantly and irre-
family (such as the MCM-41, MCM-48, and MCM-50; Fig. 1), the Santa versibly when directly dried from solution thus losing its characteristics
Barbara Amorphous (SBA) family (such as the SBA-1, SBA-2, SBA-6, [41]. Thus, it is necessary to be cautious of template removal methods.
SBA-8, SBA-11, SBA-12, SBA-15, and SBA-16), KIT-5 and KIT-6 Calcination is mostly used for the removal of surfactant from within the
[36–38]. The MCM, like most silicates, are classified according to the pores [45–49] though in some cases solvent extraction is preferred to
order of the pores: hexagonal, cubic or mesolamellar phases for the calcination [18,42,50] and microwave digestion using UV [51]. The
MCM-41, MCM-48, and MCM-50, respectively. typical calcination temperature range is 550–800 °C in flowing air or
nitrogen, while the optimized solvent extraction process is carried out
2.1. Synthesis of ordered mesoporous silicates by refluxing for 24 h using a high ratio ethanol to water mixture.
Without high-temperature calcination, the extent of the silane mod-
Mesoporous silicates can be synthesized under varying range of pH ification can be relatively high, thus making the surface properties to be
conditions (from strongly acidic to highly basic – Fig. 2a) and tem- easily adjusted.
peratures (from below room temperature to ≈150 °C) using different
templates or surfactants (cationic, anionic, neutral, zwitterionic, etc.) 2.3. Functionalization
[36]. Under appropriate synthesis condition, the silicate's surface area,
pore size, and volume can be controlled from the mesopore dimensions Though remarkable properties of ordered mesoporous silicates are
to macropore. Typically, mesoporous silica synthesis comprises the highlighted for water treatment purposes, these properties are some-
addition of a silicate source to the surface of ordered surfactant micelles times not accessible. A major challenge with mesoporous silicate upon
in an aqueous solution to produce the ‘as-synthesized’ mesoporous si- template removal is its hydrophilicity due to the high surface silanol
lica. The discovery of template-assisted mesoporous silica synthesis density (Fig. 3), consequently resulting in low adsorption for aqueous
using surfactants has led to the synthesis of mesoporous silica with high pollutants especially the hydrophobic ones. Functionalization, or at-
surface areas, tunable pore sizes, large pore volumes and a plethora of tachment of highly active groups to the surface of the silicate material,
different kinds of functionalization [36,40]. Mesoporous silica mate- has become a highly successful method of accessing these remarkable
rials are synthesized under conditions where surfactant–silica assembly properties of ordered mesoporous silicates for water treatment pur-
occurs simultaneously with condensation of the inorganic species to poses. This has resulted in a plethora of functional designer silicates
produce the composites (Fig. 2b). The dimensions and morphologies of with high efficiency and excellent selectivity towards specific aqueous
the resulting materials are dependent on the sol–gel chemistry condi- pollutants.
tions such as temperature, water content, pH, characteristics of sur- Typically, an organic functionality can be introduced post-synthesis
factants or copolymers, and the concentrations and the sources of silica by grafting or chemical attachment onto the silanol groups in the me-
used. Hence, it is possible to design the silica size, mesostructure, and soporous silica or by co-condensation during the template-directed
morphology by controlling of these parameters [41]. Ideally, meso- synthesis of the mesoporous material. The chemical attachment of or-
porous silica to be applied as an adsorbent for aqueous pollutant re- ganic functionalities onto the silanol groups changes the silica wall
moval should possess large surface area, large pore size, and pore vo- polarity and introduces the desired functionality which enhances the
lume. These external and internal properties provide large surfaces for surface adsorption properties (Fig. 3). One advantage of post-synthesis
independent functionalization, as well as allow for a small amount of chemical attachment is that the mesoporous structure is usually re-
the adsorbent to have contact with a large volume of the aqueous so- tained, though this depends on the size and loading of organic func-
lution and consequently a significant amount of the pollutant, resulting tionality added, as these could result in pore blockage. Post-synthesis
in possibly high removal efficiency. functionalization of the silicate surface may be achieved by the
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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.)
Fig. 3. Functionalization typical silicate (SBA–15) with 3–aminopropylethoxysilane 2.4. Characterization of silicates
group. Reprinted from Ref. [18], p. 44, Copyright (2014), with permission from Elsevier
Inc.
The aim of the routine characterization is to determine the physical
(morphology, structure, and texture) and chemical (functional groups,
following approaches [36]: nature of interactions between atoms and possibly their orientation)
properties of the final synthesized meso-structured silicate materials.
(a) Direct grafting (Primary modification) through reaction of suitable This implies that meso-structured silicates' characterization is classified
organosilane, in an appropriate solvent, with the silica surface into two groups: the physical and chemical characterizations.
under reflux [52,53]. The physical characterizations include determination of; (a) the
(b) Reacting a previously grafted functionality with another functional specific surface areas, pore volume and diameter, and porosimetry
species (Secondary modification) [47,54]. using gas physisorption method, (b) the organization of the silicate
(c) Transformation of the grafted functionalities by additional treat- morphology up to the three-dimensional order and nanoscale using
ments. electron (both scanning and transmission) microscopic techniques, and
(c) the types of meso-structures or any structural damage arising from
Co-condensation during the template-directed synthesis of the me- the functionalization process using the diffraction (X-ray and electron)
soporous material involves the simultaneous condensation of the de- techniques [38,55,56].
sired organic functionality (such as 3–aminopropyltriethoxysilane) The chemical characterizations include determination of; (a) the
alongside the primary silica source (usually the alkoxides such as tet- effectiveness of the desired functionalization, and possible nature and
ramethyl (or tetraethyl) orthosilicate) in the presence of a surfactant. form of the chemical constituents using spectroscopic techniques such
The desired organic functionality is covalently linked through a non- as the Infra-red, Raman and ultraviolet–visible spectroscopy, (b) the
hydrolysable SieC bond to a siloxane species, which then hydrolyzes to amounts of organic groups incorporated as well as their stability using
form a silica network. Most organic functionalities are usually hydro- thermogravimetry, (c) the quantities of some basic elements using
phobic and tend to align with the hydrophobic end of the surfactant; elemental chemical analysis, and (d) the effectiveness of covalent
hence, modifying the silica walls. Common organosilanes used in bonding of the organosilanes to the silica framework and the extent of
functionalization include the trialkoxy-organosilanes and chloro-orga- siloxane condensations using the nuclear magnetic resonance
nosilanes though the later is usually avoided because they give rise to [38,55–57].
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3. Removal of aqueous pollutants (II), Pb(II), Ni(II) and Zn(II) ions that the co-condensed amino-func-
tionalization (they reported virtually no adsorption). However, the re-
3.1. Inorganic pollutants 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
In order to meet the evergrowing stricter water regulatory standards adsorption performance. Their co-condensed amino-functionalized
placed by governments and other regulatory bodies, numerous ad- SBA-15 was used to study removal of Cd(II), Co(II), Cu(II), Zn(II), Pb
vances in material science are emerging for enhancing water purifica- (II), Ni(II), Al(III) and Cr(III) from single and multi-metal aqueous so-
tion process. Functional designer silicates with high efficiency and ex- lutions. Amino-functionalized SBA-15 was able to adsorb the various
cellent selectivity towards specific aqueous pollutants are particularly metals to varying degrees with up to 95% adsorption observed at low
interesting due to the recorded successes of these materials for aqueous aqueous single metal solutions (10 mg/L) indicating high sensitivity
inorganic species adsorption. Nitrogen/thiol and magnetic silica-based except for Co(II) and Cr(III). The adsorbent capacity decreased for co-
designer materials have been at the forefront of these advances. existing metal cations in solution because of competition between ca-
tions for the amine groups. They also reported that application of their
3.1.1. Nitrogen and thiol designer silicates for inorganic pollutants adsorbent for removal of Cu(II) in tap water, river water, and electro-
Though pristine silicates have various remarkable properties which plating wastewater was a success.
may be beneficial in the water treatment process, they have been out- Bois et al. [67] grafted different functional (aminopropyl–, [amino-
classed by their designer derivatives. For instance, ordered mesoporous ethylamino]propyl–, (2-aminoethylamino)-ethylamino]propyl–, and
MCM-41 and MCM-48 silica were synthesized, amine functionalized mercaptopropyl– groups) materials to MCM-41 for aqueous heavy
with NeN dimethyl dodecyl amine and dodecyl amine, and used for metals adsorption. They observed that MCM-41 silica functionalized
adsorption of Cd(II), Co(II), Cu(II) and Pb(II) in aqueous solution [58]. with multiple nitrogens ([amino-ethylamino]propyl- and (2-ami-
The functionalized MCM-41 and MCM-48 silicates was over three-fold noethylamino)ethylamino]propyl-) groups exhibited higher loading
better than the pristine in the adsorption of these cations and were capacity for Cu(II), Ni(II), Co(II) and the anion Cr(VI), while the mer-
observed to be fast cationic adsorbents with higher affinity for Cu(II) capto functionalized silica exhibited higher loading capacity Cd(II).
and Pb(II) than for Cd(II) and Co(II) in single and mixed cations solu- Kang et al. [68] showed that imidazole (N-(3-triethoxysilylpropyl)-
tions, though adsorption capacity was reduced in the mixed solutions. 4,5-dihydroimidazole) functionalized SBA-15 could be used for pre-
These adsorbents exhibited a higher preference for Cu(II) in both single cious metal-chelating and recovery. They observed that the amino-rich
and mixed solutions while adsorption capacities in a single solution for functionalized SBA-15 silica exhibited excellent selectivity for Pt(II) and
amine-MCM-41 and amine-MCM-48 ranged from 227.9 to 279.6 mg/g Pd(II) ions over other metal ions such as Ni(II), Cu(II), and Cd(II), even
and 186.5–260.5 mg/g, respectively. The adsorption capacities in with an excess of the latter cations. Adsorbed precious metal ions could
mixed solutions were not significantly different for both the amine- be better recovered by simple HNO3 acid treatment compared to HCl or
MCM-48 and amine-MCM-48 and ranged from 62.2 to 101.7 mg/g. Lee NaOH treatments. They concluded that the ligand-functionalized me-
et al. [59] had earlier shown it is possible to incorporate different sostructured silica could be used not only in toxic heavy metal removal
functional groups into one silica material. They designed bi-functio- but also in the effective separation of precious metal ions. Tapaswi et al.
nalized porous MCM-41 silica via the introduction of chelating ligands [69] also showed that SBA-15 functionalized with 1,4,7-triazacyclo-
(mercaptopropyl and aminopropyl groups) which was used for the re- nonane (another rich nitrogen compound), synthesized via post-synth-
moval of heavy metal ions (Hg(II), Cu(II), Ni(II), Cd(II), and Cr(III)) esis grafting, exhibited fast and selective Cu(II) adsorption from aqu-
from aqueous solutions [59]. These adsorbents showed improved effi- eous mixed metal ions solution containing Cu(II), Cr(III), Ni(II), Co(II)
ciency for Hg(II), Cd(II), and Cu(II) removal but not for Ca(II), Mg(II), and Li(I). The triaza-cyclononane functionalized SBA-15 had a max-
Ni(II), and Cr(III). The adsorption capacities of the mercapto- and imum Cu(II) adsorption capacity of 42.6 mg/g and can be readily re-
amino-functionalized adsorbents ranged from 76.2 to 302.9 mg/g with generated by HNO3eNH3 treatment.
a very high preference for Hg(II). Similarly, Burke et al. [60] showed Amino-functionalized mesoporous and nano-mesoporous MCM-41
that post-synthesis bi-functionalization, using aminopropyl and mer- silica have also been synthesized using 3-aminopropyltrimethoxisilane
captopropyl-silanes, can be achieved for mesoporous silica, and they and used for removal of Ni(II), Cd(II) and Pb(II) from aqueous solution
attempted the removal of Ni(II), Cr(VI), Pd(II), Fe(II) and Mn(II) from [48]. It was shown that the amino-functionalized MCM-41 silica ad-
water. The bi-functionalized mesoporous silica was highly effective in sorbents exhibited preference for the metals in the order Ni(II) < Cd
reducing a broad range of metal ions (from high concentration mixed (II) < Pb(II) with the highest adsorption capacity for Pb(II) of
metal ion solutions) to trace (> ppb) levels, while the mono-functio- 57.74 mg/g. Similarly, amino-functionalized SBA-15 (using N-3-tri-
nalized materials had specific responses to the metal ions. The max- methoxysilyl-propyldiethylenetriamine) of tailored pore sizes have
imum adsorption capacities were determined to be approximately equal been reported with good adsorption of 39 and 41 mg/g for Pb(II) and
(20 mg/g) for Cr(VI), Ni(II), Fe(II), Mn(II) and Pd(II) using the bi- Cd(II), respectively [53]. One observation about the reported adsorp-
functionalized mesoporous silica, and this was low in comparison to the tion capacities for Heidari et al. [48] and McManamon et al. [53] is that
report of Lee et al. [59]. they were low compared to others reported earlier.
Zhang et al. [61] have shown that in addition to aminopropyl- Aminopropyl (NH2) and melamine-based dendrimer amines (MDA)
triethoxysilane, multi-amines (such as N-[3-(triethoxysilyl)-propy- were separately used to functionalize SBA-15 mesoporous silica [46],
lethylene]diamine and triethoxysilyl propyl diethylenetriamine) can be and the resulting designer adsorbents were used to study the separate
grafted onto mesoporous SBA-15 silica. These multi-amine-SBA-15 ad- and ternary sorption of Pb(II), Cu(II) and Cd(II) ions onto SBA-15,
sorbents had excellent adsorption capacities for aqueous Hg(II) removal NH2–SBA-15 and MDA–SBA-15 (Fig. 4). The NH2–SBA-15 and
up to 726 mg/g. Interestingly, they also showed that the adsorbents MDA–SBA-15 exhibited enhanced adsorption of more than 150 and
could simultaneously remove Hg(II), Pb(II), Cd(II), Cu(II) and Zn(II) 400%, respectively, increase over the pristine SBA-15. The Langmuir
from wastewater. Liu et al. [62] had earlier reported high complexation maximum adsorption capacities of MDA–SBA-15 was 130, 126 and
affinity of Hg(II) by thiolated SBA-15 adsorbent while the aminated 98 mg/g for Pb(II), Cu(II) and Cd(II), respectively. These results were
analog exhibited exceptional binding ability for metal ions such as Cu remarkably high compared to others in the literature. Column experi-
(II), Zn(II), Cr(III) and Ni(II). Aguado et al. [63] suggested that the ments showed that metal ions removal percentage increased by 21.8%,
method of functionalization of the SBA-15 surface may affect the per- 10.4% and 11.6% for Pb(II), Cu(II) and Cd(II), respectively, but ad-
formance of the final adsorbent. Post-synthesis grafted amino-func- sorption efficiency was dependent on flow rate. The MDA–SBA-15 ad-
tional groups exhibited far better adsorption efficiency for Cu(II), Cd sorbent showed good potential for reuse though slight decreases in
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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.
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P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267
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) relative to those reported in literature here.
amine-functionalized mesoporous silica shell with the Fe3O4 magnetic Some researchers have argued that it is vital to make the adsorbents'
core (Fig. 8b). In comparison to smaller pore size shells (< 4 nm), the preparation process eco-friendly by a substantial reduction of sec-
large pore size magnetic shell grafted far more amino functionalization ondary pollutants. In line with this, Alotaibi et al. [82] synthesized iron
and consequently had higher heavy metals adsorption capacity for Pb supported on bio-inspired green silica. The eco-friendly synthesis mi-
(II) (880 mg/g), Cu(II) (623 mg/g), and Cd(II) (492 mg/g). The ad- mics the bio-mineralization process and it is an easy process under mild
sorbent was also easily regenerated using simple acid treatment. Li conditions with less toxic reagents. The process considerably reduces
et al. [77] had earlier synthesized and used thiol-functionalized mag- the need for lengthy multistep procedures (≤72 h), high temperatures
netic spherical silica adsorbents for aqueous Hg(II) and Pb(II) adsorp- (≤120 °C) and extreme pH conditions. The iron supported bio-inspired
tion. Though their adsorbent was not as efficient as that of Yuan et al. green silica exhibited high arsenate ions removal capacity of 69 mg/g as
[76], the reported adsorption capacity for Hg(II) (260 mg/g) was higher well as good reusability. Similarly, biodegradable nano-composite of
than that of Pb(II) (91.5 mg/g), the adsorbent was reusable after re- anionically modified guar gum with in-situ deposited silica nano-par-
generation in acid solution and stable in water matrices from strong ticles was synthesized through the sol-gel method [83]. The guar gum-
acid and alkaline sources. Kumari et al. [78] have shown it is also silica nano-composite exhibited remarkable adsorption capacity for
possible to synthesize magnetite nanospheres with hollow interiors in a cationic dyes and metal cations of 781.3, 281.7, 645.2, and 709.2 mg/g
simple, one-pot, and template-free solvothermal method with ferric for malachite green dye, safranin dye, Pb(II), and Cd(II), respectively,
chloride as the iron precursor. However, a major drawback of the as well as good reusability. This adsorbent was also selective towards
template-free solvothermal method is that it results in silicates with an cations as opposed to anions.
unusually small surface area, in this case, 11.3 m2/g. This led to an An attempt has been made at combing porous silica and graphene
extremely low aqueous metals adsorption capacity for Cr(VI) and Pb(II) nanosheets decorated with α-FeOOH and functionalized with thiol
of ∼9 and ∼19 mg/g, respectively. Similarly, magnetic amino (NH2) groups (Fig. 9) [2]. Though the processes involved were quite cum-
and melamine-based dendrimer amine (MDA) functionalized MCM-48 bersome compared to other functionalized silicates discussed here, Hg
mesoporous silicates were used for the adsorption of aqueous Pb(II), Cu (II) ion adsorption performance was outstanding: > 800 mg/g at
(II), Cr(VI) and Cd(II) ions [79]. The MDA-magMCM-48 exhibited ad- 400 mg/L Hg(II), and this significantly exceeded currently available
sorption capacity of 127.2, 125.8, 115.6 and 114.1 mg/g for the ions, benchmark adsorbents. The adsorbent also exhibited efficient adsorp-
respectively, and was reusable for up to three times without significant tion performance (∼100%) for removal of low (4 mg/L) and high
loss in adsorption capacity. Apart from the fact that incorporating (120 mg/L) concentration of Hg in real water samples using this com-
magnetic materials within or on mesoporous silicate adsorbents eases posite in the form of membranes.
the separation process of the adsorbent from the aqueous solution after Wang et al. [84] have also advanced the concept of combining
the pollutants adsorption, the report of El-Toni [80] indicated that the multiple adsorbents by designing luminescent adsorbent that can be
incorporated magnetic materials enhanced the silicate adsorption visually monitored during the adsorption process instead of using the
properties. They synthesized un-magnetized amino-functionalized usual instrumental methods to monitor pollutants concentration. Using
hollow core–mesoporous shell silica spheres using 3-aminopropyl- a simple microplasma-assisted method, they prepared luminescent
trimethoxysilane. However, unlike other reports [75,76], their ad- amino-functionalized ordered mesoporous silica-carbon dots composite
sorbent exhibited lower adsorption capacity notably for aqueous Pb(II) with high specific surface area, high adsorption efficiency and se-
and Cd(II) ions of 194 and 190 mg/g, respectively, the high surface area lectivity for uranium even in the presence of various cations, as well as
(718 m2/g) notwithstanding. the ability for simultaneous in situ monitoring of the adsorption pro-
Recently, cubic spinel crystallites of Zn−silica modified cobalt cess. The combined individual properties of the pristine materials gave
ferrite magnetic nano-structured composite (CoFe2O4) was synthesized rise to this composite. Adsorption using the luminescent adsorbent
and used for aqueous cationic pollutants from water [81]. The silica could be monitored by monitoring the intensity of the composite's
modified CoFe2O4 exhibited better adsorption efficiency for removal of fluorescence which decreased as the uranium uptake increased.
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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3.1.3. Other designer silica-based adsorbents for inorganic pollutants mesoporous silica had high surface area was 762 m2/g with an ad-
Inorganic functionalities have also been incorporated or imprinted sorption capacity up to 103 mg/g at pH 2.0 in 7 min; a better result than
on silicate surfaces to improve the metals' adsorption process. For in- that of the iminodiacetic acid-functionalized SBA-15 at pH 4.5. The
stance, in order improve adsorption efficiency of Pb(II) from acidic imprinted material also exhibited high selectivity among six competing
wastewater (pH 2.0), Pb(II) imprinted mesoporous silica functionalized metal ions (Zn(II), Cd(II), Cu(II), Mg(II), Ca(II) and Fe(III)) with the
with iminodiacetic acid was fabricated [85]. The Pb(II) imprinted adsorption efficiency of above 93% after six regeneration cycles. The
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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 ciprofloxacin; an indication that electrostatic interaction is more im-
0.43 cm3/g) [90]. This, as well as the study of Teo et al. [97], showed portant than hydrophobic interactions between sulfonic-SBA-15 and
that magnetizing the adsorbent, in addition to easing adsorbent se- aqueous ciprofloxacin species. The sulfonic-SBA-15 adsorbent could be
paration from solution, enhances its adsorption capacity. reused for thrice for adsorbing ciprofloxacin. The same research group
Magnetic core-shell silicates have also been recently used for re- also used azide-functionalized hollow silica nanospheres synthesized
moval of Congo red dye from aqueous solution [98]. Congo red dye from tetraethoxysilane and azidopropyltrimethoxysilane on F127 single
adsorption on this magnetic silicate was mainly by electrostatic inter- micelle template as an adsorbent for ciprofloxacin adsorption [100].
action and adsorption capacity was about 54.6 mg/g. Similarly, hybrid They concluded that functional groups such as phenyl-acetylene, pro-
shells of iron oxide nanoparticles coated with organic κ-carrageenan pargyl alcohol, 1-heptyne and 2-butyne-1,4-diol linked to these hollow
and inorganic silica have also been used for the magnetically assisted silica nanospheres played important roles in their adsorption proper-
removal of methylene blue from aqueous solution [99]. The hybrid ties. Gao et al. [101] have also shown that SBA-15 functionalized with
shells exhibited good adsorption capacity (530 mg/g) which was at- aminopropyl triethoxysilane, propyltrimethoxysilane, or phenyl-
tributed to the sulphate-rich surface of the κ-carrageenan. The hybrid trimethoxysilane may be used as an adsorbent for ciprofloxacin ad-
shells were reusable with adsorption efficiency over six consecutive sorption with possible adsorption capacities up to 2.2, 4.4, and
adsorption/desorption cycles relatively stable (> 97%). Both studies 11.2 mg/g at 0.1 mg/L of ciprofloxacin.
showed that in addition to magnetizing the silicate, functionalizing A comparative adsorption study of Boldine (2,9-dihydroxy-1,10-di-
significantly enhances adsorbent efficiency as well. 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
3.2.3. Other designer silica-based adsorbents for organic pollutants SBA-15 and its functionalized propyl-sulfonic derivative showed higher
In addition to the nitrogen-containing and magnetic functionalities adsorption than SBA-16 and MCF, though no reason was proffered for
of designer silicates, others have been studied recently. For instance, a this trend.
comparison has been made of the effect of multiple roles of similar Apart from incorporation of organic functionalities on the silica
organic functional groups in designer silicate adsorbents specifically surface, inclusion of transition metal (such as Co(II), Ni(II) and Cu(II))
using mercapto- and sulphonic acid functionalization of SBA-15 for functionality onto the surface of MCM-41 [103] and SBA-15 [104] via
adsorption of the antibiotics ciprofloxacin [3]. It was observed that the an already attached organic amino-moiety enhanced the silica
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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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 volume (0.85 cm3/g) in comparison to Al-MCM-41. Suraja et al. [110]
grafting technique [104] on the silicates were similar (Fig. 15), and the also showed that nanosized cobalt oxide (Co3O4) particles incorporated
authors concluded that similar strategies might hold promise for re- (maximum at 10%) onto SBA-15 mesoporous silica showed adsorption
moval Pharmaceutical and Personal Care Products (PPCPs) from aqu- potential (16 mg/g) for aqueous methylene blue. However, this was far
eous solution, especially those present at ppm levels. less efficient when compared with Al-MCM-41 obtained from coal fly
Recently inorganically modified spherical mesoporous MCM-41 si- ash source [108]. Recently, Zhang et al. [111] showed that porous
lica using CuO exhibited better adsorption capacity for the cationic metal silicates could also be obtained from other waste sources. They
dyes– crystal violet and methylene blue (52.9 and 87.8 mg/g, respec- prepared various three-dimensional metal (magnesium, zinc, nickel,
tively) compared to the pristine spherical mesoporous MCM-41 (46.2 and cobalt) silicates from waste rice husks and the magnesium silicate
and 65.7 mg/g, respectively) [105]. The same research group also exhibited high aqueous adsorption capacities of 557.9, 381.3 and
showed that similarly, iron oxide-modified MCM-41 exhibited en- 482.8 mg/g for Pb(II), tetracycline, and UO22+, respectively. The rice
hanced adsorption for aqueous aniline [106]. The enhancements in husk porous silica doped with Ni nanoparticles also exhibited high
adsorption were attributed to electrostatic interactions between the catalytic activity as well as good stability for reduction of aqueous 4-
mesoporous MCM-41 loaded metals (Cu and Fe) and the aqueous ca- nitrophenol.
tions (pollutants: dyes and aniline), as well as, to a less degree, the In the same vein, Wang and co-workers have shown that metal ion-
enhanced pore structure of the adsorbent. modified mesoporous silicates obtained from naturally occurring paly-
Similar to the inclusion of transition metal functionality onto the gorskite or Illite clay may be used for efficient removal of both organic
silicate surface, coal fly ash (containing primarily Si, Al, and Fe at pollutants and metals cations [57,112–115]. Their reports were quite
concentrations of 239.5, 108.0 and 60.3 mg/g, respectively) was used interesting because it highlighted that mesoporous silicates can be ob-
to modify 3-aminopropyltriethoxysilane functionalized mesoporous tained from relatively abundant clay sources. Their Mg-modified paly-
MCM-41 [107]. The synthesized material exhibited high affinity for gorskite clay exhibited 218.9 and 107.9% increase in adsorption of the
aqueous Cu(II) ions with up to 95% removal at 45 mg/L. However, antibiotics chlortetracycline (329.84 mg/g) and oxytetracycline
using coal fly ash as the source of amorphous SiO2 and Al2O3 compo- (207.47 mg/g), respectively, compared to the pure palygorskite clay
nents rather than as modifying agents, Zhou et al. [108] synthesized [112]. The same adsorbent exhibited adsorption capacity of 527.2 and
spherical Al-MCM-41. This was quite interesting taking into con- 210.6 mg/g for methylene blue and Cu(II) ions, respectively [57]. Si-
sideration that (i) the primary raw material source of the Al-MCM-41 milarly, Mg-modified mesoporous silicate obtained from illite clay
was a supposed waste material-coal fly ash, (ii) the final BET surface showed higher chlortetracycline adsorption capacity of 408 mg/g
area was up to 525 m2/g with a pore volume of 0.71 cm3/g, and (iii) compared with the pure Illite clay (159.7 mg/g) [115]. However, Zn-
methylene blue adsorption capacity of 277 mg/g. Their study suggested modified red palygorskite clay was slightly less effective for removal of
that Al-MCM-41 obtained from industrial solid waste of coal fly ash aureomycin and tetracycline with adsorption capacity of 384 and
could be an economic adsorbent for treatment of methylene blue in 337 mg/g, respectively, in contrast with the 154 and 140 mg/g of the
aqueous solution. This has been supported by another study showing pure red palygorskite clay [114]. The large specific surface areas, as
that fly ash Al-MCM-41 [108] is better than Al-SBA-15 [109] for aqu- well as large pore structures of these naturally obtained silicates, are
eous methylene blue adsorption. The Al-SBA-15 [109] synthesized by noteworthy. The proposed mechanism for the removal of these pollu-
the conventional method [18] exhibited a maximum adsorption capa- tants from solution involves monolayer electrostatic interaction with
city of 83 mg/g even with a larger surface area (693 m2/g) and pore charged surfaces, hydrogen bonding as well as complex formation
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P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267
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. diminished property. This type of designer adsorbent is quite fasci-
The combination of adsorbents has also been studied as a method of nating considering the very high adsorption capacity, and its benign,
increasing pollutants adsorption capacity. In this regard, mesoporous straightforward, and economic preparation.
silica has been coated on micrometer-sized and nanometer sized zeolite Another recently attempted synthesis of designer silicate with the
A and these were compared with the pristine zeolite A for adsorption of simultaneous ability for fast removal of organic, inorganic, and mi-
butyraldehyde [116]. Adsorption on both composite materials almost crobial contaminants from aqueous solution [118]. Herrmann et al.
doubled those of the pristine zeolites A (nano and micro; 151 and [118] synthesized a polyoxometalate-ionic liquid (POM-IL) complex
146 mg/g, respectively); while the nano-zeolite A composite (314 mg/ immobilized on porous silica (POM-SILP). Each component of this
g) exhibited better adsorption than micro-zeolite A composite (266 mg/ complex has its specific contribution which targets a particular type of
g). contaminant resulting in the water-insoluble POM-IL composed of an-
Lately, silica aerogels [117] reinforced with polyacrylonitrile fibers timicrobial alkyl-ammonium cations and lacunary polyoxometalate
(Fig. 17) have been synthesized for use in adsorbing diesel oil from anions with heavy-metal binding sites. The silica support also has
water and oil mixtures. This adsorbent exhibits high porosity and sur- radionuclides binding capacity, and this, in addition to the complex's
face area, low density, and three-dimensional reticular structures with lipophilicity enables adsorption of organic contaminants (Fig. 19). The
excellent adsorption capacity (Fig. 18) for oil (9.56 g/g). Interestingly, use of POM-SILP in filtration columns could result in one-step multi-
authors stated the adsorbent could be reused up to 100 times without 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.
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-
Fig. 18. Demonstration of diesel oil adsorption by the aerogel with 0.3% fibers. grafted MCM-41 exhibited the lowest adsorption efficiency than the
Reproduced from Ref. [117] with permission from The Royal Society of Chemistry.
other functionalized materials owing to the restricted size of the
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P.N.E. Diagboya, E.D. Dikio Microporous and Mesoporous Materials 266 (2018) 252–267
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.
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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.
*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.
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