Applied Clay Science 131 (2016) 107–112

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Applied Clay Science

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

Research paper

Reflections on the material science of clay minerals

Robert A. Schoonheydt
Department of Microbial and Molecular Systems, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Leuven, Belgium

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

Article history: Possible new applications of clay minerals are explored continuously. Three such areas are clay-polymer
Received 17 August 2015 nanocomposites, clay mineral films and clay mineral catalysts. Advances in these areas must come from
Received in revised form 7 December 2015 the increase of fundamental knowledge of the clay minerals, especially the expanding clay minerals or
Accepted 7 December 2015
smectites. Examples of fundamental research areas are: the mechanical properties of single clay layers
Available online 19 December 2015
and the change of these mechanical properties with the number of layers in a clay mineral particle; control
Keywords:
of the organization of clay mineral layers and of molecules in the interlayer space for the production of func-
Clay minerals tional films; and the distribution of pillars and of metal nanoparticles in the interlayer space for application
Clay–polymer nanocomposites as catalysts. Natural clay minerals suffer from several disadvantages, such as the presence of impurities and
Clay mineral films inhomogeneities in sizes and shapes of particles and in charge distribution. Synthesis of clay minerals with
Catalysis well-defined sizes and shapes of the particles and with homogeneous charge distribution is imperative to
obtain significant advancement of knowledge.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction 2. Clay–polymer nanocomposites

“The production of clay minerals for industrial and environmental
uses continues to grow annually and new applications of clays are an
exciting area of research and development. Sorbent clays, pillared
clays, swelling clays and surface modified clays all have applications in
the expanding environmental markets such as landfills, fluid barrier ap-
plications, selective ion sorption and others. The major industrial appli-
cations of clays are still expanding including uses in paper, paint,
plastics, ceramics, drilling fluids, foundry bondants, catalysts, agricul-
ture, construction materials, pet litters, sorbents for oil and water spills
and many others. The outlook for the future of applied clay science is in-
deed bright and hopefully we, the members of AIPEA, can cooperate to
make AIPEA the focus of international research and development of
clays and clay minerals for clay science” (Murray, 1994).
These words were written by H. Murray in 1993 as incoming presi-
dent of AIPEA. They are prophetic indeed and still valid today. At that
time the emphasis was clearly on the role of clays and clay minerals in
environmental science and technology. Now, 22 years later, the envi-
ronmental scope of clays and clay minerals is supplemented by in-
creased interest in research and development in at least 3 areas:
(1) clay–polymer nanocomposites (CPN), including clay–biopolymer
nanocomposites; (2) hybrid clay mineral films with special optical and
electrochemical properties; and (3) heterogeneous catalysis, including
bioreactive clay minerals.
E-mail address: Robert.schoonheydt@biw.kuleuven.be.
CPN's have been studied intensively for more than 20 years. The ear-
lier work has been reviewed extensively by Ray and Okamoto (2003).
More recently, several chapters in the handbook of Clay Science
(Bergaya et al., 2013; Detellier and Letaief, 2013; Lambert et al., 2013;
Ruiz-Hitzky et al., 2013) and a CMS workshop have also been devoted
to CPN's (Carrado and Bergaya, 2007).
CPN's are expected to have improved mechanical properties, im-
proved heat stability and improved gas barrier properties with respect
to those of the neat polymer. In many applications the transparency of
the CPN's is also an issue and one has to control the optical properties
of the CPN's too. In particular, the light scattering has to be minimized.
These improvements depend on (1) the dispersion of the clay mineral
layers and particles in the polymer matrix; (2) the nature and strength
of the clay mineral–polymer interactions; and (3) the properties of the
clay mineral itself such as the shape of the layers and particles, the
amount and location of the isomorphous substitution, and the number
and type of edge sites.
In the successful preparation of CPN's the hydrophobic/hydrophilic
properties of polymer and clay minerals have to be matched. This is
most easily done by exchange of the clay mineral with alkylammonium,
alkyl phosphonium and alkylpyridinium cations. Smectites are then the
preferred clay minerals. The d001 spacing increases upon exchange of
these alkylcations. This has two advantages: (1) polymer chains can
more easily diffuse in the interlayer space; and (2) as a consequence
the d001 spacing might increase to such an extent that exfoliation occurs.
The CPN's contain then individual smectite layers and clay mineral par-
ticles of various sizes i.e. composed of 2, 3 or more layers.

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108 R.A. Schoonheydt / Applied Clay Science 131 (2016) 107–112
One might intuitively think that complete dispersion or complete
exfoliation i.e. up to individual layers is the ideal to be achieved. It max-
imizes the number of clay mineral layers in the polymer matrix and it
maximizes the contact and interaction between the clay mineral sur-
faces and the polymer molecules. However, the mechanical properties
of individual clay mineral layers, 0.96 nm thick, are unknown. Sato
et al. (2001) have performed a molecular dynamics (MD) simulation
on a single layer of beidellite with composition [Si31/3 Al2/3]IV[Al2]
O10(OH)2Na2/3. They found that a compression in the A direction by
3–40% leads to a curved layer, which breaks up once the compression
exceeds 40% (Fig. 1). This curving is mainly due to a change in Si–O–Si
bond angles and not to a change of bond lengths. This indicates that
under external forces in a polymer matrix single layers might easily
bend or curl. Measurement of the mechanical properties of single layers
of natural smectites to confirm these predictions are extremely difficult
to perform. The reasons are multifold: (1) presence of impurity particles
on the clay mineral layers; (2) ill-defined edges of the layers and parti-
cles; (3) heterogeneity of the charge distribution in the layers; (4) non-
uniform hydration of the layers in the clay mineral particles; (5) irregu-
lar stacking of the layers in the particles.
Kunz et al. (2009) measured the deformation of particles of a syn-
thetic Fluor-hectorite (F-hectorite) by atomic force microscopy (AFM).
F-hectorite is obtained by melt synthesis and consists of up to 10 μm
crystals. The individual layers are aligned perfectly parallel in the parti-
cles and have a uniform charge density. The particles have sharp edges
and a smooth well-defined morphology. The bending elasticity along
the c*-direction is measured to be C33 = 21 ± 9 Gpa, assuming that
the particle is clamped on both sides and 48 ± 20 GPa under the as-
sumption that the particle is free i.e. not clamped on both sides. These
numbers have to be compared with those of rectorite, 18.3 ± 4.6 GPa
and micas, 54.9–70.5 GPa. The differences in the numbers can be attrib-
uted to hydration, charge density and nature of the charge-compensat-
ing cation. F-hectorite is a one layer hydrate with d001 = 1.23 nm. In
rectorite half of the interlayers are one layer hydrates. In micas there
is no interlayer water. The charge compensating cation is K+ in micas,
Fig. 1. Schematic drawing of the basic cell structure of beiddelite: the A-type cell includes a
18 × 3× 1 A-bending layer; the B-type cell includes a 6 × 12 × 1 B-bending layer.
Adapted from Sato et al. (2001) with permission of ACS.
while it is Na+ for F-hectorite and the charge density of mica is twice
that of F-hectorite.
Particles with a thickness of less than 20 nm cannot yet be measured
with this AFM technique. Such thin particles tend to be sucked into the
gaps of the substrate (Fig. 2) and to be huddled against the wall of the
substrate. This is an indirect proof of the easy bending and curling of sin-
gle layers and of particles less than 20 nm thick or consisting of 2–15
layers.
The search for optimum dispersion of the clay mineral layers and
particles is a research topic of primary importance. This optimum dis-
persion will depend on the size, shape, charge density and hydration
of the clay mineral layers. It will be different for Laponite than for mont-
morillonite, saponite or hectorite. Recent studies on 1:1 clay minerals
such as kaolinite might also be inspirational.
Several strategies can be followed to prepare CPN's from kaolinite,
but they all start with a pre-intercalate (Detellier and Letaief, 2013;
Detellier and Schoonheydt, 2014). Exfoliation can be achieved, produc-
ing single layers of kaolinite in the form of nanorolls or nanotubes. This
is a very interesting observation. It shows that single layers of 1:1 clay
minerals curl into nanotubes. At the basis is the difference in bond
lengths between Si–O bonds in the tetrahedral sheet, typically
0.162 nm, and Al–O bonds in the octahedral sheets, typically
0.187 nm. Imogolite and halloysite are 1:1 nanotubes which exist in na-
ture. Single layers of 2:1 clay minerals such as smectites do not curl into
nanotubes. The same differences in bond lengths of Si–O bonds on one
hand and Al–O or Mg–O bonds on the other hand exist, but the octahe-
dral sheet is sandwiched between two tetrahedral sheets, preventing
curling up of single layers into nanotubes. The expectation is that the
single 2:1 layers do not spontaneously curl into nanotubes, but that
they are easily bent. When deposited on a surface they will adapt their
shape to the shape (roughness) of that surface. In a polymer matrix
the shape of the single layers of 2:1 clay minerals such as smectites is
determined by the interaction with the polymer chains. If the interac-
tion of the single layer–polymer chain is weak, the polymer acts as a sol-
vent. If the interaction of the single layer–polymer is strong, a smectite–
polymer complex is present in the CPN and the mechanical properties of
the CPN are expected to be different from those of the neat polymer and
the neat clay mineral.
Nacre is an extremely hard natural material composed of inorganic
nanoparticles cemented together by polymeric molecules. One would
like to prepare artificial nacre, which could eventually be used as a
bone implant. Clay minerals, in particular smectites, could be and have
been used to construct such artificial nacre-like implants. The composite
has a “brick-and-mortar” structure (Fig. 3), the bricks being the smectite
particles and the polymeric chains act as mortar. Such a brick-and-
mortar structure can be obtained by layer-by-layer (LbL) assemblage
in which layers and particles of Na-montmorillonite and of a cationic
polymer such as PDDA (PDDA = poly(diallyldimethylammonium))
are alternately deposited and held together by electrostatic and van de
Waals forces (Podsialdo et al., 2005). Such structures can absorb quite
a lot of energy. Upon deformation the layers of montmorillonite might
Fig. 2. AFM set-up to measure the mechanical properties of F-hectorite: The F-hectorite
particles are shown as hexagons lying over the 2 μm wide channels of the substrate.
Adapted from Kunz et al. (2009) with permission Of ACS.
 R.A. Schoonheydt / Applied Clay Science 131 (2016) 107–112
Fig. 3. Schematic drawing of the brick-and-mortar structure to mimic nacre: open laths are the clay mineral particles (bricks); curved thick lines represent the polymer molecules (mortar)
and the solid thick line at the bottom is the substrate.
slide over each other and the polymer undergoes conformational
changes. Thus, it is a strong and soft material. LbL assemblage is time-
consuming. Alternatives have been proposed. Walther et al. (2010)
self assembled clay mineral layers and particles with soft polymer coat-
ing into aligned nacre-mimetic films with a tensile modulus of 45 GPa
and a tensile strength of 250 MPa by techniques derived from the
paper-making industry. Liff et al. (2007) prepared nanocomposites
with Laponite in a solvent-exchange processing technique.
The considerations exposed in this section lead to the following
conclusions:
1. Carefully synthesized clay minerals with uniform charge density and
uniform size of layers and particles would be very useful for a funda-
mental study of the interaction between alkylcations and clay miner-
al surfaces, between polymeric molecules and organoclays. With this
knowledge factors determining the optimum dispersion of the
organoclays in the polymeric matrix could be qualitatively and quan-
titatively understood.
2. There is a need to know the mechanical properties of single layers of
clay minerals and their change upon adsorption of alkylcations and
polymers. With that knowledge one can apply a bottom–up ap-
proach and study the change of the mechanical properties of single
layers upon addition of layers, one at a time. An interesting question
is if free floating 1:1 and 2:1 clay minerals layers are flat or whether
they spontaneously curl into nanotubes. If the latter occurs, what is
the minimum number of layers in a clay mineral particle in order
to obtain a flat, two-dimensional particle?
3. Clay mineral films
Clay mineral films have been the subject of intensive research in the
last 20 years or so. This research has recently been reviewed (Zhou et al.,
2011; Suzuki et al., 2012; Schoonheydt, 2014). The ultimate goal of clay
Fig. 4. Schematic drawing of possible organizations of alkylammonium cations in the interlayer space.
109
mineral film preparation is to achieve a dual organization: (1) at the
level of the clay mineral layers; and (2) at the level of the molecules in
the interlayer spaces. The combination of a clay mineral layer and a
monolayer of molecules is called a bilayer. Ideal cases of this two-level
organization are shown in Fig. 4. Such ideal films require (1) complete
exfoliation of the clay mineral particles into individual layers; (2) depo-
sition of these clay mineral layers all oriented in the same direction and
not overlapping; (3) formation of monolayers of functional molecules in
the interlayer spaces; and (4) in multilayers all bilayers should be
identical.
Such ideal films have not been obtained yet. One comes closest to it
with layer-by-layer (LbL) assemblage and the Langmuir–Blodgett (LB)
technique. Multilayered LbL films have rough surfaces and overlapping
clay mineral layers, although the average amount of deposited clay min-
eral layers and deposited molecules is identical in each bilayer of the
multilayered film (Van Duffel et al., 1999; Szabo et al., 2007). With the
LB technique a bilayer is formed at the air–water interface of the LB
trough. These bilayers can be deposited on a substrate and multilayers
are formed by repetition of this process. Also these LB films show sur-
face roughness. This is due to (1) incomplete coverage of the substrate
by the bilayer; (2) the presence of clay mineral layers and particles i.e.
incomplete exfoliation; (3) overlapping clay mineral layers; and
(4) slow diffusion of clay mineral layers into the aqueous dispersion
due to gravitational forces during the bilayer preparation process
(Szabo et al., 2009).
If functional films have to be prepared, the functionality (e.g. dipole
moment) is carried by the molecules in the interlayer spaces. These
molecules must then be organized in the interlayer space in such a
way that the desired macroscopic property (functionality) is generated
in the film. In the case of dyes aggregation must be avoided and – gen-
erally speaking – interaction between the adsorbed molecules and clay
mineral surfaces must be maximized and interaction between the
adsorbed functional molecules themselves must be minimized. Several
110 R.A. Schoonheydt / Applied Clay Science 131 (2016) 107–112
strategies are offered in the literature: (1) dilution of amphiphilic opti-
cally active Ru(II) complexes with alkylammonium cations (Umemura
et al., 2002); (2) matching of the distances between positive charges
on porphyrins and the average distance between the negative charges
in the clay minerals (Takagi et al., 2006); and (3) improvement of the
planarity of the π-electron system of the adsorbed dyes upon adsorption
on the clay mineral surfaces (Suzuki et al., 2012).
The two-dimensional organization of functional molecules in the in-
terlayer space is more demanding than the one-dimensional organiza-
tion in the channels of zeolites, such as zeolite L (Calzaferri et al.,
2010; Calzaferri, 2012; Fois et al., 2013; Devaux et al., 2013) In zeolite
l the molecules are designed to be 0.72–0.75 nm thick, which is also
the free diameter of the channels. With these sizes the molecules cannot
pass each other in the channels and a well organized system can be
built. This is shown in Fig. 5 with donor (D) and acceptor
(A) molecules, necessary to build fluorescence resonance energy trans-
fer (FRET) systems. In the interlayer space of clay minerals there is in
principle no limit on the size of the molecules, because of the swelling.
However, the molecules can diffuse in the interlayer space and rear-
range. It will therefore be more difficult to build organized systems.
Optimal (ideal) clay mineral films are difficult to prepare with natu-
ral smectites. This is mainly due to the heterogeneity of natural clay
minerals, heterogeneity in sizes and shapes of the particles and layers,
in organization of the layers in the particles, in charge distribution,
and in the presence of impurities. Synthetic clay minerals offer an alter-
native. Some are commercially available: Laponite, Smecton, Kunipia F,
Kunipia P, F-hectorite. Careful synthesis in the lab is however required
(Breu et al., 2001) to obtain homogeneous materials which can be sub-
jected to fundamental studies. An additional advantage is that synthetic
smectites can be prepared with transition metal ions in the octahedral
sheets. Thus, electron transfer and energy (photon) transfer from the
transition metal ions in the octahedral sheets to adsorbed functional
molecules and vice versa can be studied.
Finally, the films, once prepared, must be mechanically stable; stable
in environmental conditions such as humidity and – in the case of films
in optical devices – the light scattering must be minimized and ulti-
mately eliminated. LbL films acting as oxygen barriers and with flame
retardant properties have been prepared and studied (Priolo et al.,
2010; Li et al., 2010; Jang et al., 2008). The group of Kawamata obtained
films with very low light scattering by optimization of the size of the
clay mineral particles, the mass% of clay mineral in the dispersion, and
dissolution of dyes in an organic solvent (Suzuki et al., 2012).
4. Clay mineral catalysts
There are 3 important parameters for heterogeneous catalysts:
(1) surface areas, pore volumes and pore sizes; (2) number, distribution
and strength of active sites; and (3) stability and ability to regenerate
the catalysts. Zeolites are considered as ideal catalysts. They are crystal-
line, three-dimensional solids with crystallographically defined micro-
porosity. The active sites are also crystallogaphically defined: the
acidic bridging OH group (Si–OH–Al), transition metal ions and their
oligomeric clusters. To match these properties of zeolites with clay
Fig. 5. Schematic drawing of possible arrangements of donor (D) and acceptor
(A) molecules in the interlayer space of clay minerals (left) and in the channels of zeolite
L (right).
minerals is not an easy task. Clay minerals are layered materials,
which collapse, when the reaction temperature exceeds 100 °C. For
acid catalysis two strategies have been developed to achieve this goal:
acid activation and pillaring.
Acid activation partially dissolves the clay mineral lattice, creates
Brönsted and Lewis acid sites and increases the pore volumes and sur-
face areas of the catalysts into the domain of zeolites, typically to
0.10–0.20 cm3/g and 200–300 m2/g respectively. Acid activated clays
are commercially available (K10, KSF) and have been investigated at
the laboratory scale in a variety of organic reactions (Adams and
McCabe, 2006). The downside of acid activation is that the activated
clay mineral catalyst is very complex. It consists of partially disrupted
clay mineral structures and some amorphous silica, alumina and/or sil-
ica–alumina. The acid sites are Brönsted acid sites and Lewis acid sites of
various nature and strength. As a consequence acid activated clay min-
eral catalysts are susceptible to unwanted side reactions and coke
formation.
Pillaring is the introduction of metal oxide pillars in the interlayer
space of smectites. The best known examples are the aluminium oxide
pillars. The clay mineral is exchanged with a partially hydrolyzed solu-
tion of Al3+, containing predominantly [Al13O4(OH)24(H2O)12]7+ with
Keggin ion structure. After washing, drying and calcination the Keggin
ions in the interlayer space are transformed into Al2O3 pillars. Surface
areas and pore volumes are significantly increased in comparison with
those of the parent smectite (Table 1). The pores are mainly micropores,
indicating that a micropore system has been created in the interlayer
space. These Al-pillared clays or Al-PILC's can be used as acid catalysts
in hydrocarbon conversions. They contain Brönsted and Lewis acid
sites, covering a wide range of acid strengths. Pillaring has gone far be-
yond Al. Fe, Ga, Ti and other metal ions have been used for pillaring
often in combination with Al. The catalysis is not only restricted to hy-
drocarbon conversions, but photocatalytic reactions and reactions for
environmental clean-up have been extensively studied (Schoonheydt
and Jacobs, 2006; Gil et al., 2000, 2010).
Clay minerals are also redox catalysts. An example is the complete
mineralization of organic pollutants through catalytic ozonation
(Shahidi et al., 2015). This catalysis requires Fe, which is one of the
most intensively studied elements in clay minerals. Structural Fe3+ in
the octahedral sheets can be reduced to Fe2 +. This reduction affects
the hydration of the clay mineral surfaces, the Si–O bond strengths
and the surface acidity (Stucki, 2006). Reduction of Fe increases the neg-
ative charge density of the clay mineral lattice. As a consequence the
structural oxygens become more basic. Reduced Fe containing clay min-
erals are more active than oxidized clay minerals in degradation of pes-
ticides, dechlorination of chlorinated hydrocarbons, and reduction of
nitroaromatics. A plausible mechanism is that the chlorinated hydrocar-
bons interact with the lattice oxygens via the adsorbed water molecules.
The protons of water are strongly attracted to the more basic oxygens of
the surface of the clay mineral layers. The oxygen atom of the water
molecules carries excess negative charge and interacts with the H
atom of the chlorinated hydrocarbon, thus producing adsorbed H3O+
cations. The negative side of the reduction of structural Fe is that the re-
duction causes partial collapse of clay mineral layers, thus reducing the
accessibility of the surface for reagents.
Table 1
Typical surface areas and pore volumes of pillared montmorillonite.
Pillaring cation BET surface areas Pore volumes
m2/g cm3/g
Al 250–340 0.091–0.132
Ti 280 0.154
Zr 270 0.094
Fe 200–270 0.082–0.148
Cr 240–286 0.015–0.090
 R.A. Schoonheydt / Applied Clay Science 131 (2016) 107–112
Table 2
Coupling reactions between azides and alkynes catalyzed by Cu nanoparticles on mont-
morillonite. Adapted from Dutta et al. (2015) with permission of Taylor & Francis.
This fascinating chemistry of Fe-containing clay minerals opens per-
spectives for synthetic clay minerals with other transition metal ions in
the octahedral or tetrahedral sheets. Cobalt is the most obvious choice
because it has two oxidation states, +2 and +3, such as Fe, and Co2+
likes to coordinate both in tetrahedral and octahedral symmetry. Mn,
Cr and V are other candidates, but these cations have more than 2 stable
oxidation states.
Transition metal ions can of course be exchanged in the interlayer
space of clay minerals. Such transition metal ion (TMI) exchanged clay
minerals are also redox catalysts. The best known examples are the Fe-
and Cu- exchanged clay minerals which polymerize pyrrole to polypyr-
role, a reaction which has been observed and studied a long time ago by
Pinnavaia and Mortland (1971). To prevent collapse of the clay mineral
layers low temperatures reactions with transition metal ion complexes
must be realized. Clay minerals have an advantage over zeolites in that
there is in principle no limit to the size of the complexes. Bulky complexes
can be adsorbed which are too big to enter the micropores of the zeolites.
Thus heterogenization of enzymes is an area worthwhile to be investigat-
ed in detail in order to develop heterogenized biocatalysts.
Clay minerals can also be used as supports of metal nanoparticles,
which are catalysts in synthesis of fine chemicals. Metal ions are intro-
duced by ion exchange or impregnation and reduced by a variety of
methods. A high surface area is required to stabilize the metal nanopar-
ticles and thus acid activated clay minerals are the first choice, although
PILC's have also been used. A variety of reduction methods is reported
(Dutta et al., 2015), but the metal nanoparticles must be prevented
from sintering into large particles. The catalytic reactions studied in-
clude oxidations of pollutants, hydrogenations, such as the reduction
of the nitro group to NH2. Quite interesting is the potential of metal
nanoparticles/montmorillonite catalysts in coupling reactions and syn-
thesis of fine chemicals in general (Dutta et al., 2015). The potential is
illustrated by the data of Tables 2 and 3.
In summary, clay minerals certainly have potential as supports of
catalytically active species such as metal (nano)particles and transition
metal ion complexes or homogeneous catalysts. The conditions for suc-
cess are (1) both interlayer surfaces and edge surfaces of the clay min-
eral particles must be available; (2) the reactions must be truly
heterogeneous i.e. the active species must be strongly adsorbed; (3) re-
action products and catalysts particles must be easily separated; and
(4) impurities, inherently present in natural clay minerals, may not
hamper the catalysis and should be avoided. Hence there is a need for
carefully synthesized clay minerals to be used in catalysis.
Such well-defined synthetic clay minerals have the advantage that
fundamental studies can be performed. Examples are: (1) formation of
111
Table 3
Heck reactions catalyzed by Pd on montmorillonite. Adapted from Dutta et al. (2015) with
permission of Taylor & Francis.
pillars and their distribution in the interlayer space. Is it a single Al13
Keggin ion which is transformed into a Al2nO3n pillar or two or more?
(2) Is it possible to control the distribution of active sites in the interlay-
er space so as to make them all available for reaction? (3) Is it possible to
prepare shape-selective catalysts from clay minerals? Intercalation and
ordering of molecules in the interlayer space of synthetic F-hectorite has
been shown (Stöter et al., 2013). The synthesis of clay minerals with
transition metal ions in the octahedral and/or tetrahedral sheets is an-
other advantage. The example of Fe (Stucki, 2006) illustrates the poten-
tial of these materials as catalysts.
5. Conclusions
For the 3 research areas briefly discussed in this paper, carefully syn-
thesized clay minerals are an advantage. They allow a fundamental
study of clay mineral–polymer interactions, of intercalation and organi-
zation of adsorbed molecules in the interlayer space, of pillaring and
acid activation. This fundamental knowledge is necessary for making
significant progress towards application of clay minerals in industry.
Special attention should be given to “new” clay minerals or synthetic
clay minerals which do not have a natural counterpart, such as transi-
tion metal ion containing clay minerals with prospects in catalysis. In
the area of clay mineral–polymer composites special attention should
be given to immobilized enzymes and their conformation in the
adsorbed state. This determines whether the catalytically active sites
of the enzyme are accessible by reactants and thus whether reaction
can occur.
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