Theng, B'K'G' 1974 The Chemistry of ClayOrganic Reactions,

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- Theng, B.K.G. (1974) The Chemistry of
Clay-Organic Reactions, London, Adam Hilger.
- Whittingham, M.S. and Jacobson, A.J., eds.
(1982) Intercalation Chemistry, New York,
Academic Press. - Bruce, D.W. and OHare, D.
(1996) Inorganic Materials 2nd ed., New York,
John Wiley Sons. - Alexandre, M. and Dubois, P.
(2000) Polymer-layered silicate nanocomposites
preparation, properties and uses of a new class
uses of a new class of materials, Mater. Sci.
Eng., 28, 1-63. - Schollhorn, R. (1996)
Intercalation system as nanostructured
functional materials, Chem. Mater., 8,
1747-1757. - Ogawa, M. and Kuroda, K. (1997)
Preparation of inorganic-organic nanocomposites
through intercalation of organoammonium ions
into layered silicated, Bull. Chem. Soc. Jpn.,
70, 2593-2618. - Ogawa, M. and Kuroda, K. (1995)
Photofunctions of intercalation compounds,
Chem. Rev., 95, 399-438.
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- A.D.600-700, the phenomenon of intercalation
have been discovered by the Chinese. They
produced porcelain from the intercalation of
alkali metal ion into natural materials such as
feldspar and kaolin. - The first intercalation
compound was reported in the scientific
literature in 1840. C. Schafhautl has reported
his observation on attempting to dissolve
graphite in sulfuric acid. - In 1926, Karl
Fredenhagen and Gustav Cadenbach described the
uptake of potassium vapour by graphite. Since
their report, the intercalation reactions
have fascinated inorganic, organic and
organometallic chemists.
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Layered host materials
Intercalation compounds
Intercalation is the reversible insertion of
guest species into an interlayer space of a
layered host material with maintaining the
structural features of the host.
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Framework (3-D)
Layer (2-D)
Linear chain (1-D)
Molecular (0-D)
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- The guest and host may lead the novel in their
geometrical, chemical and electronic
environment depending on the individual
characteristics of either the chosen host or
guest. - More importantly, these environments may
be subtly controlled and tailored to meet
specific requirements, such as catalytic
activity, battery technology.
The reaction of lithium with the layered metal
dichalcogenide, TiS2
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Why ?
layered host materials
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Layered structure of polysilicate
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Layered structure of LDH
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Layered structure of smectite
Layered structure of kaolinite
11 layered silicates
21 layered silicates
- Swelling behavior - Ion exchange properties -
Adsorptive properties - Large surface area
- No swelling - No cations and anions in the
interlayer space
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Ion
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Ion
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Neutral
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Neutral
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Intercalation compounds

Guest species
(Ref. Ogawa, M. and Kuroda, K., Bull. Chem. Soc.
Jpn., 1997, 70, 2593.)
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Staging
The original of this phenomenon is due to
structural or electronic reasons such as a
smaller loss of lattice energy at low guest
concentrations.
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• - Intercalation of potassium in graphite
• - hydrate phase Ax/nnMS2x-(H2O)
• (An alkali, alkaline earth, M Ti Nb and
  Tb) etc.

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- Smectites - V2O5 gel
- Exfoliated smectites in a nylon 6 polymer
matrix greatly improved the mechanical
properties of nanocomposite
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Surf./Si 0.2
FSM-16
Hexagonal
C16TMA
Kanemite
Surf./Si 2.0
(NaHSi2O5 3H2O)
TEM
Acid Treatment
KSW-2
Lamellar
- Kanemite reacts with alkylammonium ions give
a silicate-based mesoporous materials
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? Some guest species play a role of pillar in the
interlayer space of layered materials ?
Pillaring agent for smectites -
Alkylammonium ions - Bicyclic amine cations
- Metal chelate complexes - Polynuclear
hydroxyl metal cations
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Staging
- McKelvy et al. have observed staging processes
in Ag0.17TiS2 and HgxTiS2 using high
resolution TEM.
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- Schollhorn has studies the mechanism of
electrochemical intercalation of Na ions into
2H-NbS2 by in situ XRD measurements.
The initial stages
In recent year
1. host lattice 2. hydrated Na phases with
bilayers of water 3. hydrated Na phases with
monolayers of water 4. 3rd and 2nd stage compound
Recently, the reaction cell has been developed to
study intercalation reactions to be monitored in
situ using real-time XRD techniques.
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- Study on the kinetics of metallocene
intercalation into the layer metal
dichalcogenide hosts SnX2 (X S and Se) and ion
exchange intercalation involving the MnPS3
host lattices.
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Solid-gas reaction
Host lattice (solid)
Guest species (vapour)
Aqueous suspension of smectites
Guest species (solid)
Smectites (powder)
Guest species (solution, liquid)
grinding
heat
Product
stirring
Solid-solid reaction
Product
Advantages of solid-solid reaction - Ease of
operation - Possibility to prepare compounds
not accessible from solutions
Conventional ion- exchange reaction
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Products
( Ref. Ozin, G.A. and Gil, C., Chem. Rev., 1989,
89, 1749. Pinnavaia, T.J., Science,
1983, 220, 365.)
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The simplest and most widely used method for
preparing large amounts of an intercalation
compound is the direct reaction of the guest (G)
with a potential host lattice (MXn) as below.
Alkali metal intercalates of metal
dichalcogenides were prepared in this way by the
reaction of host lattice with metal vapour at
temperatures in the ranges 600-800 oC
metal vapour
metal dichalcogenides
600-800 oC
Solid-gas reaction
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The chemical reagent used extensively for alkali
metal intercalation was lithium dissolved in
liquid ammonia. While offering many advantages
over the direct reaction with alkali metals, it
is often accompanied by co- intercalation of
ammonia. Heating in vacuum to remove the
ammonia.
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Once an intercalation compound has formed the
intercalated guest ions can often be replaced by
immersing the material in concentrated solution
containing another potential guest ion.
Ion exchange reaction of Li ions in Na-TiS2
MCln.xH2O
Mn
Na
M(n)-montmorillonite
Na-montmorillonite
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Examples of intercalation compounds formed by
ion-exchange reactions
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Examples of intercalation compounds formed by
initially exfoliating
Ion exchange reactions of a layered structure to
accommodate guests can be largely overcome if
the host lattice can expanded by
pre-intercalation of a small molecule or ion.
Large cluster cations
Initially exfoliating
Intercalation compounds
Fe6S8(PET3)62/TaS2
Fe6S8(PET3)62
Na0.33TiS2 in N-methylformamide/ H2O solution
M13O4(OH)24(H2O)7 (M Al and Ga)/MoO3
M13O4(OH)24(H2O)7 (M Al and Ga)
NaxMoO3(H2O)y or LixMoO3(H2O)y in water
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Electrointercalation methods
Intercalation reactions can be performed
electrochemically. Host lattice serves as the
cathode of an electrochemical cell.
Formation of CuxTiS2 (Xmax 0.9) with the liquid
aprotic electrolyte.
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Rate enhancement methods
One of the major problems synthetic chemists face
when carrying out intercalation reactions is
that they are often lengthy (weeks or even
months) and require elevated temperatures.
Ultrasonic irradiation Microwave irradiation
Ultrasound irradiation
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- Generally, intercalation reaction proceeds by
stirring a layered host in a liquid phase of a
guest. - When a guest is in a vapour phase,
high pressure may promote the intercalation
reaction - When a guest is solid, it is
dissolved in a solvent and used as a liquid
phase or directly reacted with a host by a
solid-solid reaction - When intercalation
reaction do not proceed directly, a guest
displacement method may be effective.
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Intercalation of organoammonium ions into a
layered material by ion exchange reaction.
Organoammonium-exchanged layered material
immobilizes organophilic species in its
interlayer region.
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Montmorillonite
Mx(Al4-xMgx)Si8O20(OH)4
Saponite
MxMg6(Si8-xAlx)O20(OH)4
where M monovalent cation x
0.5-1.3
Layered structure of smectite
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Na
Na-montmorillonite
0.85 nm
Co2
Co(II)-montmorillonite
(Ref. Ogawa, M., Hashizume, T., Kuroda, K. and
Kato, C., Inorg. Chem., 1991, 30, 584.)
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Example of layered host susceptible to
intercalation by a polymer
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- Exfoliation-adsorption - In situ intercalative
polymerization - Melt intercalation - Template
synthesis
Ordered Exfoliation Nanocomposite
Disordered Exfoliation Nanocomposite
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The layered silicate is exfoliated into single
layers using a solvent in which the polymer (or
prepolymer) is soluble.
Exfoliation-adsorption
- Exfoliation-adsorption from polymers in
solution
used with water-soluble polymers to produce
intercalated nanocomposites
poly(vinyl alcohol), PVOH poly(ethylene oxide),
PEO poly(vinylpyrrolidone), PVPyr poly(acylic
acid), PAA
polymeric aqueous solutions are added to
dispersions of fully delaminated sodium layered
silicates
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Exfoliation-adsorption
- Exfoliation-adsorption from prepolymers in
solution
poly(imides) some conjugated polymers have the
particular property of being insoluble in organic
solvents
the only possible route to produce nanocomposites
with the polymer
using soluble polymeric precursors that can be
intercalated in the layered silicate
thermally or chemically converted in the desired
polymer
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Exfoliation-adsorption
- Exfoliation-adsorption by emulsion
polymerization
poly(methyl methacrylate), PMMA poly(styrene), PS
intercalation of insoluble water polymers within
Na-montmorillonite that is delaminated in water
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In situ intercalative polymerization
The layered silicate is swollen within the liquid
monomer (or a monomer solution). Polymerization
can be initiated either by heat or radiation, by
the diffusion of a suitable initiator or by an
organic initiator.
- Thermoplastic nanocomposites
- Thermoset nanocomposites
- Elastomeric nanocomposites
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Melt intercalation
The layered silicate is mixed with the polymer
matrix in the molten state. No solvent is
required.
A model polymer poly(styrene)
nylon-6
polypropylene
ethylene-vinyl acetate copolymers
poly(styrene-b-butadiene) copolymer (SBS)
elastomer
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The silicates are formed in situ in an aqueous
solution containing the polymer. For example
Template synthesis
in situ hydrothermal crystallization of the clay
layers (hectorite) in aqueous polymer gel medium
polymers often act as template for the layers
formation
this method is particularly adapted to water
soluble polymers
poly(vinylpyrrolidone), PVPyr hydroxypropylmethylc
ellulose, HPMC poly(acrylonitrile),
PAN poly(dimethyldiallyammonium),
PDDA poly(aniline), PANI
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Properties
- Mechanical properties
effect on tensile properties stress at
break elongation at break impact
properties dynamic mechanical analysis
- Thermal stability and flame retardant properties
- Gas barrier properties
- Miscellaneous
ionic conductivity thermal expansion coefficient
Tunneling electron microscope
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- Some guest species play a role of pillar in the
interlayer space of layered materials.
- alkylammonium ions - bicyclic amine cations -
metal chelate complexes - polynuclear hydroxyl
metal cations
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Organosilicon species such as tetraethyl
orthosilicate (TEOS) and 3-aminopropyltriethoxysi
lane (APTES) are successfully applied for
pillared layered materials.
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octahedral
trigonal prismatic
close-packed MX2 layer
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TaS2(NH3)
TaS2(Py)0.5
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Lamellar host lattices and their intercalates
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Layered structure of smectite
Layered structure of kaolinite
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Characterization
Property
- UV - FL - Catalytic Reaction