Results in Chemistry 4 (2022) 100549

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Results in Chemistry
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Montmorillonite clay: Introduction and evaluation of its applications in

different organic syntheses as catalyst: A review
Nahid Yaghmaeiyan a, *, Mahdi Mirzaei a, Reza Delghavi b
a
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
b
Department of Chemistry, Ahar Branch, Islamic Azad University, Ahar, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: Microscopic crystals with soft phyllosilicate group of minerals which formed through precipitation of water
Montmorillonite solution, are called montmorillonite (MMT). It is concentrated and transformed by natural weathering in envi­
Clay ronment caves and left aluminosilicates which were contained in the bedrock. By the adding water, montmo­
Organic synthesis
rillonite swells and expanded considerably more than other clays. The amount of expansion is depended on the
Catalyst
Application
type of exchangeable cation contained in the sample. The presence of sodium as the predominant exchangeable
cation, is increased the swelling several times rather original volume. Hence, Na-MMT used as the major con­
stituent in nonexplosive agents for splitting rock in natural stone quarries. Advantageous properties of mont­
morillonite made it appropriate for many applications such as use in oil drilling industry as a component of
drilling mud, soil additive, component of foundry sand, desiccant to remove moisture from air and gases, catalyst
and various medicinal and pharmacological applications. This review article consists the various synthetic
methods for preparation of catalysts based on MMT for organic syntheses and assessing their catalytic activities.

Introduction 700 ◦ C for trans-vacant minerals and cis-vacant varieties, respectively.

1.1- Montmorillonite: definition and classification
Montmorillonite with chemical formula (Na,Ca)0.3(Al,
Mg)2Si4O10(OH)2n(H2O) is a very soft phyllosilicate group of minerals
was first described in 1847 for an occurrence in Montmorillon in the
department of Vienne, France, more than 50 years before the discovery
of bentonite in the US [1]. Its structure is well known nearly 7 decades
[2]. Several classification systems were proposed at the same time but
analysis of smectites is still difficult. MMT as a member of the smectite
group, is a 2:1 clay, with a central octahedral sheet of alumina sand­
wiched by two tetrahedral sheets of silica [3]. Dehydroxylation of clay
disregarded in classifications until now, so the structure of the octahe­
dral sheet in smectites remained unconsidered. Although, the cis- and
trans-vacant character of the dioctahedral smectites had been known for
a long time but a manageable proof was lacking. Determination of the
octahedral structure of the sheet for illites is possible by X-ray diffraction
but not for smectites because of their turbostratic disorder. Octahedral
sheet structure affected on dehydroxylation temperature of all dio­
ctahedral 2:1 clay minerals. Dehydroxylation temperature is 550 and
Mixed types with two dehydroxylation peaks also exist. Thus, simulta­
neous thermal analysis (STA) can be used for determination of the cis- or
trans-vacant character of MMTs [4] (Table 1).
In 1961, Grim and Kulbicki were classified MMTs based on phase
transformations and recrystallization products of the H+-exchanged at
high temperatures. Based on thermal behavior, they defined two
Wyoming and Cheto-type differing primarily in the distribution of the
calculated layer charge. Grim and Kulbicki neglected the dehydrox­
ylation although considered layer charge and octahedral cation popu­
lation and distribution. A low layer charge and low contents of Mg2+
substituting for Al3+, characterize the Wyoming-type in contrast to the
Cheto-type, which has high a content of Mg2+ and a higher layer charge.
There are also mixtures of Cheto- and Wyoming-type. These two types
differ in phase transformations above 1000 ◦ C. The Wyoming-type
transforms into cristobalite and mullite whereas the Cheto-type tran­
formed to β-quartz, β-cristobalite and cordierite at high temperatures
[5].
In 1969, a classification developed by Schultz based on the amount
and location of charge and the proportion of tetrahedral charge [6].
Dehydroxylation temperature and the amount of hydroxyl groups also

Abbreviations: MMT, Montmorillonite.

* Corresponding author.
E-mail address: nahidyaghma@yahoo.com (N. Yaghmaeiyan).

https://doi.org/10.1016/j.rechem.2022.100549
Received 21 July 2022; Accepted 30 September 2022
Available online 5 October 2022
2211-7156/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
N. Yaghmaeiyan et al.
Table 1
Physicochemical properties of MMT [50].
Parameters Value
Color White
Density (g cm− 3) 2.3–3
Transparency Semi-transparent and opaque
Brightness Matt
Surface Area (m2 g− 1) 95.36
Reflective index 1–2
measured but only one temperature peak was recorded, even if there
were two peaks. Schultz defined seven types of MMTs and beidellites: 1)
ideal MMTs Wyoming-type, 2) Chambers-type (which corresponds to
the mixture of Cheto-and Wyoming-type of Grim and Kulbicki), 3)
Tatilla-type, 4) Otaytype (which corresponds to the Cheto-type of Grim
and Kulbicki), 5) ideal beidellite, 6) non-ideal beidellite and 7) non-ideal
MMT. Ideal and non-ideal types dehydroxylate at about 700 and 550 ◦ C,
respectively. Wyoming-types display a low layer charge and only bei­
dellite has a dominant tetrahedral charge. Differentiate between MMT
and beidellite have been determined via using Greene-Kelly test [7].
The ranges of composition for the different types gave by Brigatti [8]
and Poppi and Brigatti [9] based on the Schultz’ system [6]. Types of the
dioctahedral MMT series were characterized based on crystallochemical
data especially octahedral and tetrahedral distributions. Their classifi­
cation turned special interest to the content of iron in the octahedral
layer and 8 solid solution ranges were classified for smectites: 1)
Wyoming, 2) Tatilla, 3) Otay, and 4) Chambers-type, 5) non-ideal MMT,
6) nontronite, 7) beidellite and 8) Fe-rich beidellite. Fe-rich MMT and
beidellite correspond to non-ideal MMT and beidellite. The iron content
in the octahedral sheet of MMT and beidellite is less than 15 % of the
cations in the octahedral sheet and for non-ideal or Fe-rich MMTs and
beidellites 15–30 %.
Classification system was modified by new methods. In 1971, Lagaly
and Weiss gave a new insight into the cation density and charge distri­
bution of layer silicates through intercalation with alkylammonium
[10]. Structural formula calculations should be performed according to
Köster which means the measured layer charge has to be involved in the
calculation of the composition [11]. Tsipursky [12], Drits and Muller [4]
and Drits et al. [13] explained that the thermal behavior of dioctahedral
2:1 clay minerals is depended to the structure of the octahedral sheet,
directly. These two aspects are incorporated in the new classification
system.
There are samples in common classification cannot be classified as
any type proposed in the literature. Samples originating from other
places than Wyoming, Otay, Tatilla, etc. are difficult to characterize.
Although demand is increasing for industrial applications but the names
MMT/beidellite or even their trivial names Wyoming-type, etc. don’t
bear information of the minerals characteristics. Even in the smectite
Fig. 1. Layered structure of MMT [47] Physicochemical properties of MMT are summarized in Table 1 [50].
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Results in Chemistry 4 (2022) 100549
group, MMTs show distinct differences in chemistry, octahedral sheet
structure, Fe-content, layer charge and location of charge. To describe
these differences well defined adjectives are used. The adjective, that
gives information on the chemistry of the mineral and is not considered
to be part of the name [14,15]. It may precise the name and is not
connected to it which makes variations possible [16]. It should be
avoided to use the adjectives as hyphenated chemical prefix.
Montmorillonite: properties and applications
In oil drilling industry, MMT used as a component of drilling mud,
making the mud slurry viscous. It is kept the drill cool and removed the
drilled solids [17–21]. As a component of foundry sand and as a desic­
cant, it is also removed moisture from air and gases [18]. In drought-
prone soils, the clay also used as a soil additive to hold soil water. It is
used in the construction of earthen dams and levees to prevent the
leakage of fluids [22–26]. Swelling property of this clay makes MMT-
bentonite be useful also as a protective liner for landfills and as an
annular seal or plug for water wells [27]. Due to its adsorbent and
clumping properties, Na-MMT is also used as the base of some cat litter
products [28,29]. MMT has also been used in cosmetics [27,30,31]. In a
fine powder form, MMT can also be used as a coagulant in ponds [32]. As
it added into water, making the water “clouded”, attracts minute par­
ticles and then settles to the bottom. MMT is an effective absorbance for
heavy metals but to date, its effect on human health is not known [33].
It’s assumed that heavy metal adsorption is only applicable when the
clay has direct contact to it. Hence, it will not help when ingested
because almost doesn’t pass through the intestinal mucous membranes,
certainly. MMT has been used to treat contact dermatitis for external use
[34]. Because the clay may provide some resistance to environmental
toxins, it is added as an anti-caking agent to some animal’s foods [35].
MMT clays have been extensively used in catalytic processes [36]. For
over 60 years, MMT clays have been used as cracking catalysts [37–42].
Other acid-based catalysts use acid-treated MMT clays [43]. Other uses
include use in papermaking to minimize deposit formation [44,45] and
as a retention and drainage aid component [46].
Montmorillonite: structure and identification
As mentioned before, MMT is a phyllosilicate mineral with nano­
layered structure consists of stacked layers [47]. Thickness of layers is
about 1 nm. Each layer is composed of one O-Al(Mg)-O octahedral sheet
(about 100 nm × 100 nm, in width and length) sandwiched by two O-Si-
O tetrahedral sheets [48]. The layer is positively charged due to the
isomorphous substitution, so cations are existed in the interlayered
space of MMT. Van der Waals and electrostatic forces held neighboring
layers together to form the primary particles of clay [49]. Secondary
micrometer-scale to millimeter-scale particles are formed through
N. Yaghmaeiyan et al.
Fig. 2. IR spectrum of MMT [51].
Fig. 3. SEM micrograph of MMT [51].
aggregation of primary particles (Fig. 1) [47].
IR spectra of MMT recorded by Danková et al. presented in Fig. 2
[51]. As can be seen in this figure, an absorption band exist about 3626
cm− 1 attributed to the stretching vibrations of structural OH groups in
MMT [52]. The bands observed at 916 and 840 cm− 1 related to the Al-
Fig. 4. TEM micrographs of the MMT [59,60].
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Results in Chemistry 4 (2022) 100549
Fig. 5. N2 adsorption–desorption isotherms and the corresponding pore size
distribution (insets) for MMT [60].
Fig. 6. XPS spectrum of MMT [60].
Al-OH and Al-Mg-OH bending vibrations, respectively [53,54]. A com­
plex band at 1040 cm− 1 corresponds to the stretching vibrations of Si–O
groups [53,54], whereas the Al-O-Si and Si-O-Si bending vibrations
recorded at 523 and 470 cm− 1 [55]. The band at 625 cm− 1 are assigned
to the out of plane vibrations of Al-O and Si-O [56]. A broad band at the
range of 3420–3450 cm− 1 correspond to the H2O-stretching vibrations.
The shoulder at about 3330 cm− 1 is an overtone of the bending vibration
of water at 1635 cm− 1 [57].
SEM micrograph of MMT is shown a dense aggregate formed through
N. Yaghmaeiyan et al.
Fig. 7. EDX spectrum of MMT [61].
Fig. 8. XRD pattern of MMT [50].
condensation of the sheet structure-leaf-like crystals (Fig. 3) [51]. The
layered structure of MMT is clear in this micrograph. The surface of clay
hasn’t homogenous dispersion. In addition, there are pores with
different sizes distributed, randomly [58].
In TEM image of natural sample of MMT from the Tagansoye deposit,
reported by Krupskaya et al. in 2017, there is a significant amount of
small and thin nano-sized particles among the laminar MMT particles
with a size of 1–2 µm, covered the specimen and produced grey back­
ground in micrographs (Fig. 4a) [59]. As can be seen in Fig. 4b which
recorded by Alamri et al. in 2021, the clay has a porous-like surface and
a nest-like form [60].
Nitrogen adsorption–desorption isotherms and Barrett-Joyner-
Halender (BJH) pore size distribution of MMT, obtained by Alamri
et al. in 2021, are shown in Fig. 5 [60]. Surface area, pore volume, and
particle size of MMT are 258.108 m2/g, 0.423 cm3/g, 8.092 nm,
respectively.
Alamri et al. were also prepared XPS spectrum of MMT, are shown in
Fig. 6 [60]. The spectrum indicates that Mg, O, C, Ca, Si, and Al existed
on the surface of MMT.
In 2018, M. Ahmadzadeh et al. prepared the EDX spectrum of MMT
clay (Fig. 7) [61]. In this spectrum, three sharp peaks are observed
which are related to Al, Si and O elements. Several weak peaks are also
observed which belong to Mg Fe, Na and K.
XRD pattern of the MMT is shown in Fig. 8 and the crystallographic
parameters are evaluated by measuring the (0 0 1) and (0 8 0) peaks. This
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Results in Chemistry 4 (2022) 100549
Table 2
Chemical composition of MMT [50].
Component Weight (%)
SiO2 49.40
Al2O3 19.70
MgO 0.27
CaO 1.50
Fe2O3 0.30
Na2O 1.50
H2O 25.67
Fig. 9. The pH variation of MMT suspension at different pHs [50].
pattern reported by Fil et al. in 2014 [50]. The peaks marked as MMT are
indicate 2:1 swelling clay and confirm the characteristics of the MMT
type clay and other peaks have been attributed to impurities corre­
sponding to quartz. A diffraction peak of the (0 0 1) plane at 2θ = 19.733
corresponds to its basal spacing of 4.99 Å. The (0 8 0) reflection at 2θ =
68.823 also indicates that MMT has a dioctahedral structure [62,63].
Fil et al. are also used from X-ray fluorescence (XRF) method to
identify the major minerals and chemical compounds present in the
MMT. Their results summarized in Table 2 [50].
They also gave the pH profiles of clay as a function of time in a 1.5 wt
% suspension at natural, acidic and basic conditions (Fig. 9) [50]. They
were shown that when distilled water (pH 5.45) is added to MMT, pH
raised to 8.15 in 45 min and to 7.7 after 75 min and then remained
almost constant upon reaching to the equilibrium pH of 7.7. Increasing
of pH in the first 45 minunes can be ascribed to the rapid adsorption of
H+ ions in water onto the negatively charged MMT surface and as po­
tential determining ions (pdi) in the electrical double layer (EDL) to
provide electroneutrality. In addition, the H+ ions exchanged with some
of the cations in the MMT lattice leading to the consumption of H+ ions.
All of the above data confirm the structure of MMT clay.
Montmorillonite: modification and functionalization
Hydrophilicity of MMT often causes the agglomeration of the
nanoclay in the polymer matrix so it is not compatible to most of
polymer matrixes [64–67]. Modification of the MMT surface, is the most
important method to achieve homogenous dispersion of clay platelets in
polymers. Nanoplatelets incorporated and distributed in polymeric
matrixes, homogeneously. The organic cations as a modifier decreased
the surface free energy of silicate layers and improve their compatibility
with hydrophobic polymers [68–78]. Ion exchange is a method can be
applied for MMT modification using cationic surfactants based on its
N. Yaghmaeiyan et al.
cationic exchange capacity (CEC) [79–81]. For example, cationic
smectites such as nontronite, laponite and MMT are the most common
clays are modified through replacement of their exchangeable ions
(Na+, Ca2+) with positively charged organic or biological molecules
[82]. Organomodification involves amino groups which results in
organic/inorganic hybrids with specific selectivity and reactivity
[82,83]. Functionalization generate selectivity in catalysts via spatial
constraints induction [84]. Generally, tremendous improvements in the
wide range of physical and engineering properties of nanoclays have
been observed, in recent years, [85–88].
Montmorillonite: application in different organic syntheses as
catalyst
MMT was first discovered in 1847, in France [1]. Many researchers
turned their attention to this clay due to its special properties, results
small size of the particles and their unique crystal structures. These
properties include cation catalytic abilities, exchange capabilities,
swelling behavior, plastic behavior when wet and low permeability
caused the clay be more applicable in many industries and processes
[89]. Several studies have been also reported on the antibacterial
properties of MMTs [90–100].
To date, many reports published in the field of MMTs and many re­
searchers prepared review papers about different aspects of these ma­
terials. We have referred to several of this reports in the following.
“Polypropylene/MMT nanocomposites, synthetic routes and mate­
rials properties” have been evaluated in a review published by Manias
et al. in 2001. According to this review, the nanocomposite is formed
either by using functionalized polypropylenes and common organo-
montmorillonites, or by using neat/ unmodified polypropylene and a
semi-fluorinated organic modification for the silicates. Hybrids can be
formed by solventless melt-intercalation or extrusion. The resulting
polymer/inorganic structures are characterized by a coexistence of
intercalated and exfoliated MMT layers. Tensile characteristics, higher
heat deflection temperature, retained optical clarity, high barrier
properties, better scratch resistance, and increased flame retardancy
improved by small additions of these nanoscale inorganic fillers [101].
In 2007, Leszczynska et al. were also reviewed polymer/MMT
nanocomposites with improved thermal properties and thermal stability
of MMT nanocomposites based on different polymeric matrixes, with the
aim to describe the basic changes in thermal behavior of different
polymeric matrixes upon addition of MMT. They also gave a brief
description of analysis of volatile and condensed products of degrada­
tion and the kinetics of the process decomposition in inert and oxidative
environment [102].
Leszczynska et al. prepared a review about “factors influencing
thermal stability and mechanisms of thermal stability improvement on
polymer/MMT nanocomposites” in 2007. This work presents a detailed
examination of factors influencing thermal stability, the role of chemical
constitution of organic modifier, composition and structure of nano­
composites and mechanisms of improvement of thermal stability in
polymer/MMT nanocomposites [103].
In 2008, a review article published by Bhattacharyya and Gupta. The
title was: “Adsorption of a few heavy metals on natural and modified
kaolinite and montmorillonite: A review”. This article is a unique
collection of vital information about the feasibility of using two
important and common clay minerals, kaolinite and montmorillonite, as
scavengers for removal of toxic heavy metals such as As, Cd, Cr, Co, Cu,
Fe, Pb, Mn, Ni, Zn in their ionic forms from aqueous medium. The au­
thors tried to incorporate how and why clays can be effectively used as a
liner in water treatment plants [33].
In 2009, Pagacz and Pielichowski provided a review article by this
title: “preparation and characterization of PVC/montmorillonite nano­
composites—a review”. In this review, preparation and characterization
of poly (vinyl chloride)/montmorillonite (PVC/MMT) nanocomposites
are being presented. Flammability of PVC/MMT nanomaterials are also
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Results in Chemistry 4 (2022) 100549
described. Finally, a future outlook is given [104].
“Montmorillonite supported metal nanoparticles: an update on syn­
theses and applications” is the title of a review article of Varadwaj and
Parida published in 2013 to cover numerous aspects of material syn­
theses and various fields of applications in which these materials show
their significant efficacies. They concluded this review with a positive
view for the future expansion of this field by the joint efforts of re­
searchers from various scientific and industrial areas [105].
An overview of the catalytic utility of MMT-K10 as solid acid, sup­
port for complex or metal nanoparticles in unimolecular and bimolec­
ular reactions have been presented by Kumar et al. in 2014. The main
part of this review is organized according to the role of clay in various
organic reactions and an emphasis is given in highlighting the greenness
of the processes. A fair comparison is also provided between clay cata­
lysts with respect to other homogeneous or heterogeneous catalysts.
Finally, the authors summarized their views in future trends and de­
velopments [106].
Adsorbents based on MMT for contaminant removal from water are
reviewed in a paper, published in 2016 by Zhu et al. The aim of this
review article is to help the readers in choosing proper and developing
novel clay mineral based adsorbents for target contaminants, and on the
other hand can give a proper example to systematically show the various
mechanisms for the uptake of contaminants on adsorbents. The mech­
anisms for uptake contaminants on adsorbents, various adsorbents
based on MMT and uptake of contaminants by them, comparison of the
adsorbents and disposal and reutilization of the spent adsorbents have
been reviewed in this article [107].
In 2018, a review paper published in the field of polymer nano­
composites based on silylated-montmorillonite by Bee et al. This paper
focus on silylation, to coat silane coupling agents on the clay which is a
type of covalent organic functionalization approach. Emphasis is placed
on possible factors such as the silane configuration, reaction conditions
and the nature of the solvent system, affected the degree of surface
modification during silylation. In this review, the effect of impregnation
of silylated-fillers in various macromolecular matrices is summarized
and compiled based on recent collected literatures and their processing,
morphologies, properties and future prospects are specifically detailed
and discussed. The authors believe that this review provides a compre­
hensive overview on the effect of silylated MMT on the structure and
properties of certain selected polymeric matrixes including polyamide,
vinyl polymer, biodegradable based polymer, elastomeric rubber ma­
trixes and epoxy resin [108].
“Exfoliation of montmorillonite and related properties of clay/
polymer nanocomposites” is the title of a review paper published in
2019 by Zhu et al. The literature survey suggests that future work should
place emphases on developing green and effective exfoliation methods,
deepening understanding of exfoliation mechanisms and the interfacial
interactions between the inorganic MMT nanolayers and organic
monomers/polymers. It is suggested that future research assembling
exfoliated MMT nanolayers with functional polymeric molecules or
other nano-scale building blocks to produce functional hierarchical
nanomaterials with practical applications [49].
In 2019, Dlaminia et al. were published a review is titled “Critical
review of montmorillonite/polymer mixed-matrix filtration membranes:
possibilities and challenges”. They were reviewed the articles focused on
clay/polymer (CP) based mixed-matrix membranes (MMM) for water
treatment. Fabrication and the structure of clay/polymer nanoparticles
(CPNs), CPN membranes for water filtration, and inconvenience of
layered platelets to mass transport, are the subjects explained in this
paper. They conclude that it is possible to achieve significant improve­
ments in water flux without compromising solute rejection [109].
In order to increase the activity of MMT in different applications, the
surface of MMT has been modified and functionalized by different
methods [110–120]. In recent years, a great attention has been attracted
to MMTs as the heterogeneous catalyst due to their unique properties.
These solid catalysts have advantages such as high yield and simple
N. Yaghmaeiyan et al. Results in Chemistry 4 (2022) 100549

Scheme 1. Intra and intermolecular clay-catalyzed generation of 2,2-dimethylbenzopyrans (3) [123].

Scheme 2. Acetylation of sugars (7) using MMT-K10 [127].

isolation of product, simple and clean work up and reusability of the
catalyst [121,122]. In this review article, we have provided an overview
of using the MMTs as catalysts. We have been also evaluated the
structure of some modified and functionalized MMTs and explained
their catalytic application in the organic syntheses. In the following of
our review research, several reports in the field of organic synthesis by
non-modified MMT have been presented.
Dintzner et al. generated 2,2-dimethylbenzopyran derivatives (3) via
a one-pot condensation of substituted phenols (1) with phenyl bromide
(2), catalyzed by MMT-K10 [123]. They reported that phenol could be
directly condensed with phenyl bromide while in previously work which
was originally observed by Dauben et al. in 1990, the major product was
o-phenyl phenol (4) with minor amounts of p-phenyl phenol (5) and
benzopyran (3) also generated under optimal conditions (Scheme 1)
[124]. A detailed study of the intramolecular clay-catalyzed [1,3] shift
reaction of 3-methyl-2- butenyl phenyl ether (6) also presented by
Dintzner et al. in 2004 [125].
In 1997, Li et al. used the MMT-K10 clay as a remarkable acetylation
catalyst for acetylation of primary and secondary alcohols, thiols,
amines and phenols with acetic anhydride in excellent yield. Mild con­
ditions, high yield, easy separation and inexpensive and environmen­
tally friendly catalyst are some advantages reported for these reactions
[126].
Bhaskar and Loganathan have developed an efficient, convenient
and environment-friendly method for the acetylation of sugars (7) using
the inexpensive MMT-K10 as the heterogeneous catalyst, in 1998
(Scheme 2) [127]. The authors believe that MMT-K10 as an inexpensive
solid acid is shown to be an efficient catalyst for the per-O-acetylation of
several mono-, di- and trisaccharides. The pyranose forms (8) accounted
for 75–100 % of the acetylatedproducts.
In 2002, Yadav et al. reported that aryl amines (9) react smoothly
with cyclic enol ethers (10) on the surface of MMT-KSF under mild re­
action conditions to afford the corresponding pyrano- and furano[3,2-
c]- quinolines (11 and 12) in high yields with high diastereoselectivity
(Scheme 3) [128]. The authors described the notable features of this
procedure which are greater selectivity, mild reaction conditions,
cleaner reaction profiles, high yields of products and ready availability
of the reagents at low cost.
In 2006, different bismaleimides (16) and bisphthalimides (17) were
synthesized by Habibi and Marvi through the condensation reaction of
maleic (13) and phthalic (14) anhydrides with different diamines (15)
on MMT-K10 clay as catalyst under microwave irradiations and solvent-
free conditions (Scheme 4) [129]. Solvent-free reaction conditions,
simple experimental and product isolation procedures, easy recovery

Scheme 3. Synthesis of pyrano- and furano[3,2-c]- quinolones (11 and 12) in the presence of MMT-KSF [128].

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Scheme 4. Condensation reaction of maleic (13) and phthalic (14) anhydrides with different diamines (15) on MMT-K10 clay as catalyst [129].

Scheme 5. Preparation of amidoalkyl naphthols (22) in the presence of MMT-K10 [130].

Scheme 6. MMT-KSF-promoted synthesis of chalcones (24) [131].

Scheme 7. Synthesis of 1,2-bisubstituted (26) and 2-substituted (27) benzimidazoles in the catalyzed by MMT-K10 [133].

and reuse of the natural clays, cleaner reaction profiles and availability
of the reagents at low cost, high yields of products and enhanced rates
are the notable features of this procedure.
An efficient green protocol for the preparation of amidoalkyl naph­
thols (22), employing a three-component one-pot condensation reaction
of 2-naphthol (18), aromatic aldehydes (19), amides (20) or urea (21) in
the presence of MMT-K10 clay under solvent free conditions reported by
Kantevari et al. in 2007 (Scheme 5) [130]. Recovery and reusability of
catalyst, short reaction time, excellent yields and simple workup are the
advantages of this method.
In 2014, Rocchi et al. developed a solvent-free, inexpensive and fast
microwave-assisted method for cross aldol condensations of aromatic
aldehydes (19) and ketones (23) for synthesis of aryl and heteroaryl
trans-chalcones (24) under microwave irradiation and solvent-free
conditions in the presence of MMT-KSF (Scheme 6) [131]. They
explained that in comparison to their previously reported methods, this
protocol constitutes a user- and environment-friendly alternative that
proceeds normally in good to excellent yields [132].
In 2020, Iriti et al. developed a fast, cheap, simple and environ­
mentally sustainable method for the synthesis of 1,2-bisubstituted
benzimidazoles (26) and 2-substituted benzimidazoles (27) from orto­
phenylnediamine (25) and aldehyde derivatives (19) catalyzed by
MMT-K10 under microwave assistance (Scheme 7) [133]. The reactions
were carried out in a short reaction time under solvent-free conditions
by using an inexpensive and environmentally friendly heterogeneous
catalyst. The authors shown that the reaction process is applicable in the
industrial fields. They also compared this procedure to their previous
work [134] and found that the proposed method does not require a
previous treatment for the preparation of deep eutectic solvents (DESs)
as eco-friendly and sustainable solvent and catalytic systems.

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Scheme 8. Reaction of benzylation of arenes (28 and 29) in the presence of different types of Fe-K10/MMT as catalyst [135].

Scheme 9. Preparation of SANM [137].

(28 and 29) in the presence of different types of Fe-K10/MMT as catalyst

Scheme 10. Methoxymethylation of alcohols (32) catalyzed by SANM [137].
In addition to the above reports, there are many other reports related
to the use of modified MMTs in the organic synthesis, which shows the
high potential of this clay as the catalyst. In the continuation of this
review article, some of these reports are mentioned.
In 2000, Pai et al. were designed the reaction of benzylation of arenes
(Scheme 8). Fe3+-K10, K10-FeOO, K10-FeOA and K10-FeAA were syn­
thesized. Each catalyst was activated at 120, 280 and 550 ◦ C for a period
of 5 h. For example, K10-FeOO was activated at 120, 280 and 550 ◦ C to
obtain K10-FeOO120, K10-FeOO280 and K10-FeOO550 catalysts,
respectively. K10-FeOO120 was the best. It was found that in the reac­
tion monobenzylated product (30) was formed as the main product
(<93 %) and the three isomers of dibenzylated product (31) were pro­
duced as byproducts [135].
They prepared Fe3+-K10 catalyst by the reported procedure [136].
For K10-FeOO preparation, they dissolved FeCl3 in dry acetonitrile and
added MMT-K10. They stirred resulting slurry at room temperature for
5 h and then filtered and washed the clay with acetonitrile and then with

Scheme 11. Preparation of SO3H-APTES@K10-MMT [138].

8
N. Yaghmaeiyan et al.
Scheme 12. One-pot deacetalization–nitroaldol (Henry reaction) in the presence of SO3H-APTES@K10-MMT [138].
Scheme 13. Synthesis of pyrano[2,3-c]pyrazoles (44 and 45) using MMT-ZSA under solvent-free conditions [139].
benzene. If the clay washed with deionised water instead of acetonitrile
and benzene, K10-FeOA and K10-FeAA are prepared depending on the
reaction conditions [135].
Sulfonic acid functionalized ordered nanoporous Na-MMT (SANM)
was easily prepared by the reaction of Na-MMT with chlorosulfonic acid
(Scheme 9) by Shirini et al. in 2012 [137]. The modified catalyst used for
methoxymethylation reaction of alcohols (32) with formaldehyde
dimethyl acetal (33, FDMA) in chloroform under reflux conditions in
good to excellent yields (Scheme 10). Short reaction times, heteroge­
neous nature of reaction conditions, use of relatively small amounts of
FDMA, ease of preparation, stability of the reagent, recyclability, and
easy workup procedure are important features of the reported method.
In 2014, a multi-functionalized catalyst has been synthesized by
Varadwaj et al. through supporting 3-aminopropyltriethoxysilane (35)
and mercaptopropyl trimethoxysilane (36) on the surface of K10-MMT
which possesses the ability to act as either base or acid. At first, they
prepared SO3H@K10-MMT by adding MPTMS into K10-MMT. Then,
APTES was added to the SO3H@K10-MMT and the prepared SO3H-
APTES@K10-MMT was obtained (Scheme 11) [138].
The catalytic activity of the prepared SO3H-APTES@K10-MMT was
evaluated as a heterogeneous catalyst for one-pot deacetaliza­
tion–nitroaldol (Henry reaction) giving a 99.2 % product (38) from
benzaldehydedimethylacetal (37), yield in just 2 h (Scheme 12). The
authors reported that this material has also been shown outstanding
capacity for the heavy metal cations adsorption and can be utilized as a
potential candidate for the remediation of contaminated water. This
Scheme 14. Synthesis of zwitterionic sulfamic acid modified MMT [139].
9
Results in Chemistry 4 (2022) 100549
material is also potent enough to carry out the Henry reaction without
any significant loss of its activity [138].
In 2017, Safari and Ahmadzadeh reported that an equimolar
amounts of carbonyl compound (39 and 40), hydrazine hydrate (41),
β-keto ester (42) and malononitrile (43), in the presence of zwitterionic
sulfamic acid functionalized MMT nanoclay MMT-ZSA nanoclay at 90 ◦ C
under solvent free conditions formed pyrano[2,3-c]pyrazoles (44 and
45) (Scheme 13) in 84–95 % yields. Short reaction times, heterogeneous
reaction conditions, a much mild procedure, a wide range of functional
group tolerance, high reaction rates, absence of any tedious workup or
purification, avoid of hazardous reagents/solvents and reusability of the
catalyst are some advantages of this work. [139].
For preparation of MMT-ZSA, at first, the MMT-NH2 nanoclay was
prepared by silane condensation [140]. Then, for the synthesis of sul­
fonated MMT, chlorosulfunic acid added to MMT-NH2 (Scheme 14)
[139].
In 2017, Zarnegar et al. used NH2-MMT nanoclayas as an eco-
friendly, nontoxic, inexpensive, and chemically highly stable nano­
catalyst for the synthesis of azine (47) and 2-aminothiazole (50) de­
rivatives in excellent yields at room temperature. (Scheme 15 and 16)
[141]. Simplicity of performance, easier work-up procedure, short re­
action times and high yields of the products are some advantages fea­
tures that authors have been mentioned for this report.
In order to preparation of NH2-MMT, the grafting of MMT with
organic moieties containing amine was performed with APTES via
silanization procedure (Scheme 17) [140,141]. NH2-MMT have been
N. Yaghmaeiyan et al. Results in Chemistry 4 (2022) 100549

Scheme 15. Synthesis of azines (47) using NH2-MMT [141].

Scheme 16. Synthesis of 2-aminothiazoles (50) using NH2-MMT [141].

Scheme 17. Preparation of NH2-MMT nanocatalyst [141].

Scheme 18. Synthesis of 4H-pyran derivaties (53) with ethyl acetoacetate (51) in the presence of K2CO3 supported on acidic MMT [147].

Scheme 19. Synthesis of 4H-pyran derivaties (53) with 5,5-dimethylcyclohexane-1,3-dione (52) in the presence of K2CO3 supported on acidic MMT [147].

10
N. Yaghmaeiyan et al. Results in Chemistry 4 (2022) 100549

Scheme 20. Sonochemical synthesis of isoxazoles (55) using Sn-MMT-K10 [61].

Scheme 21. Preparation of 2,3-dihydroquinazolin-4(1H)-ones (57) catalyzed by H3BO3/MMT K10 [149].

also used as nanocatalyst in a variety of chemical reactions and as a good
support for heterogeneous catalytic processes, such as Ullmann coupling
reaction [142], synthesis of heterocyclic compounds [143], Henry re­
action [138], C–S coupling reaction [140], Knoevenagel reaction
[144], carbonylative sonogashira reaction [145] and synthesis of iso­
xazoles [146].
In 2017, Pham et al. introduced an efficient and green synthesis of
4H-pyran derivatives (53) via one-pot, three-component condensation
of aromatic aldehyde (19), ethyl acetoacetate (51) (or 5,5-dimethylcy­
clohexane-1,3-dione (52)) and malononitrile (43) under ultrasound
irradiation in the presence of K2CO3 supported on acidic MMT at 50 ◦ C
in 50 % EtOH:H2O as solvent (Scheme 18 and 19) [147]. K2CO3 sup­
ported on the surface of acid treated MMT was changed to KHCO3 due to
ions H+ presenting in the inter lamellar space react with K2CO3 during
this procedure.
In 2018, Ahmadzadeh et al. were synthesized isoxazole derivatives
(55) in 87–96 % yields via one-pot multicomponent cyclocondensation
of hydroxylamine hydrochloride (54), ethylacetoacetate (51) and
benzaldehyde derivatives (19) in water under ultrasound irradiations in
the presence of sn-MMT-K10 as catalyst (Scheme 20). This reaction is
significant due to low-cost and eco-friendliness catalyst, rapid comple­
tion of the reactions, avoidance of using organic solvents, excellent yield
and mild conditions [61].
They prepared sn-MMT-K10 by ion exchange between SnCl2 ac­
cording to the reported procedure in the literature [148].
In 2019, Kancherla et al. used boric acid supported on MMT (H3BO3/
MMT-K10) as an efficient reusable and eco-friendly heterogeneous
nanocatalyst for the synthesis of 2,3-dihydroquinazolin-4(1H)-one de­
rivatives (57) via condensation of anthranilamide (56) and benzalde­
hyde (19) (Scheme 21) [149]. This method is simple, requires cheaper
reagents, the products are easy to separate from reaction mixture and
the catalyst is reusable at least three times with negligible loss of

Scheme 22. Preparation of copper(II) anchored on modified MMT K10 [150].

11
N. Yaghmaeiyan et al.
Scheme 23. One-pot synthesis of bispyrano[2,3-c]pyrazoles (60) in the presence of copper (II) anchored modified MMT [150].
Scheme 24. Proposed mechanism for synthesis of 3-methyl-4-arylmethylene isoxazole-5-(4H)-ones by nano-MMT-Sn.
activity. The authors believe that These catalysts can be used for many
acid-catalyzed organic transformations wherein mild acidity is required.
In 2021, another heterogeneous catalyst was also synthesized by
Ahmadzadeh et al. named copper(II) anchored on amine-functionalized
MMT (MMT-[(CH2)3-NH– – CHPy]-Cu(II)) [150]. In order to synthesize
this catalyst, they first added MMT K10 to 3-aminopropyltrimethoxysi­
lane (35) according to their previously reported method [146] to pre­
pare MMT-(CH2)3-NH2. Then, MMT-[(CH2)3-NH– – CHPy] synthesized by
adding 2-pyridine carboxaldehyde (58) and finally, MMT-[(CH2)3-
NH– – CHPy]-Cu(II) prepared by adding copper acetate (Scheme 22).
This modified MMT is behaved as a highly efficient catalytic system
for the four-component condensation reaction of hydrazine hydrate
(41), β-ketoester (42), malononitrile (43) and terephthalaldehyde (59)
toward the synthesis of multisubstituted bispyrano[2,3-c]pyrazole de­
rivatives (60). In aqueous media (H2O-EtOH) under reflux conditions
(Scheme 23) [150]. The authors reported that the catalyst is environ­
mentally friendly, has a simple synthesis and workup procedure and
high synthesis yield, and has a short reaction time which has been
recycled and reused five times for the reaction without losing its activity.
We conclude this review with a brief explanation of acid treated and
cation exchanged MMTs. These are high potential catalysts for organic
reactions [151]. Oligomerization of alkenes [152–154], dehydration of
alcohols [155–157], addition reactions [158–164], alkane isomerization
and rearrangements [165,166], Friedel crafts reaction [167–172],
miscellaneous (Diels alder, Suzuki and Heck) reactions [173–175],
12
Results in Chemistry 4 (2022) 100549
aromatic alkylation [176,177], Michael reaction [178–183] and
Sakurai–Hosomi reaction [184–186] are examples of these reactions.
Montmorillonite: mechanisms of some typical reactions over
modified/functionalized MMT
Before the modification or functionalization of the clay structure, it is
acted through the sites which have Lewis and Bronsted activity.
Depending on the function, the modified clay act as an acid (Scheme 24)
or base (Scheme 25) via the functions.
Comparison of MMT catalytic role with other contemporary clay
based catalyst
Clays such as kaolinite [187–190], smectite [191], illite [192],
chlorite [193], vermiculite [194], talc [195] and pyrophyllite [196]
have been used as a catalyst in organic reactions. These clays act similar
to each other. The reactions are used of the acidic nature of acid-treated
or cation-exchanged clay minerals. Both Lewis and Bronsted activity are
common. Free acid (in acid activated clay minerals) or dissociation of
interlayer water molecules coordinated to polarizing interlayer cations
caused the Bronsted activity [197].
[ ]m+ [ ](m− 1)+
M(OH)n + B→ M(OH2 )n− 1 OH + BH +
Where B is water or an organic species in interlayer space [198].
N. Yaghmaeiyan et al. Results in Chemistry 4 (2022) 100549

Scheme 25. Proposed mechanism for synthesis of 4-arylmrthylene isoxazole-5(4H)-ones by NH2-MMT.

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