Solid State Ionics 98 (1997) 73–84

The intercalation of carboxylic acids into layered double

hydroxides: a critical evaluation and review of the different
methods
Simon Carlino*
Department of Chemistry, University of Reading, Whiteknights, P.O. Box 224, Reading, RG6 2 AD, UK
Received 13 August 1996; accepted 9 December 1996

Abstract

This review paper details the literature which is currently available concerning the intercalation of aliphatic and aromatic
mono- and dicarboxylic acids into layered double hydroxides (LDHs) and their calcined oxides (LDOs). We present a critical
overview of the major synthetic routes and detail, where possible, the main mechanisms of intercalation. The structure of the
intercalates formed in the various methods is also detailed. A discussion of the main techniques of analysis which may be
applied to these materials is also presented along with an empirical method for accurately determining 13 C chemical shifts.

Keywords: Layered double hydroxide (LDH); Layered double oxide (LDO); Carboxylic acids

1. Introduction (Mg 6 Al 2 (OH) 16 CO 3 ? 4H 2 O), the [Mg 6 Al 2 (OH) 16 ]

Layered double hydroxides, LDHs or the so-called
anionic clays, consist of layers of M II and M III
cations which are octahedrally co-ordinated by six
oxygen anions, as hydroxides [1]. These layers
(henceforth referred to as M II –M III –(OH) x ) exist
with a similar layered structure to that exhibited by
natural Mg(OH) 2 , also known as brucite. The substi-
tution of M III cations into the brucite-like hydroxide
layer imparts an overall positive charge on the
octahedral layer [2]. Thus, in the case of the
eponymous mineral of the group, hydrotalcite
*Present address: 23 Yorke Gardens, Reigate, Surrey, RH2
9HQ, UK.
layer has a charge of 1 2. Overall electrical neu-
trality is maintained by the presence of anions, which
are typically CO 322 or NO 32 [3], in the interlayer
region between the metal hydroxide layers. The
octahedral layers are able to form infinite 2-D sheets
via edge sharing [4] and can stack via hydrogen
bonding between the hydroxyl groups of adjacent
Mg–Al–(OH) x layers. A simplified view of the
interlayer of an Mg–Al–CO 3 hydrotalcite-like LDH
is shown in Fig. 1. The overall structure of the LDHs
are dependent upon the ratio of M II –M III –(OH) x
layers to interlayer anionic sheets present in the
structure.
The interlayer area between the adjacent M II –
III
M –(OH) x layers also contains water molecules
which are able to move randomly about their C 2 axes
[5]. The presence of this interlayer water was

0167-2738 / 97 / $17.00  1997 Elsevier Science B.V. All rights reserved

PII S0167-2738( 96 )00619-4
74 S. Carlino / Solid State Ionics 98 (1997) 73 – 84

Table 1
Listing of the main literature on LDH–aliphatic mono- and
dicarboxylic acid intercalation reactions
Starting LDH Carboxylic acid Literature
M II –M III cations anion reference
Ca–Al citrate [47]
Ca–Al diglycolate [47]
Ca–Al maleate [47]
Ca–Al salicylate [47]
Ca–Al tartrate [47]
Fig. 1. A schematic view of the interlayer region of hydrotalcite
Li–Al citrate [47]
showing the carbonate, water molecules and hydrogen bonding Li–Al diglycolate [47]
between the Mg–Al–(OH) x layers. Li–Al laurate [15]
Li–Al maleate [47]
Li–Al myristate [15]
thought to be crucial to the preferential formation of Li–Al palmitate [15]
certain polytypes of LDHs over others in nature [6]. Li–Al salicylate [47]
Li–Al tartrate [47]
Although there have, as yet, been few studies cited Mg–Al acetate [29]
in the literature, there is current interest in layered Mg–Al adipate [29]
double hydroxides or their calcined oxides (hence- Mg–Al caprate [49]
Mg–Al citrate [47]
forth referred to as LDO or layered double oxides) Mg–Al diglycolate [47]
which are intercalated with organic acids. Interest in Mg–Al ethanoate [47]
these materials came about because it was thought Mg–Al glutarate [29]
Mg–Al laurate [15]
that they might form useful intermediates for the Mg–Al maleate [47]
preparation of LDHs which are ‘pillared’ with Mg–Al malonate [29]
macromolecules such as phthalocyanines, dyes or Mg–Al myristate [15]
Mg–Al oxalate [29]
polyoxometallates [7–10]. The scope of the current Mg–Al palmitate [15]
review article does not include details of the incorpo- Mg–Al propionate [29]
ration of photoactive anionic species (such as cinna- Mg–Al salicylate [47]
Mg–Al sebacate [17–19,47]
mate anions) into LDHs or their oxides or industrial Mg–Al succinate [29,47]
applications of alkylcarboxylate pillared LDHs. For Mg–Al tartrate [47]
details of these materials readers should consult Mg–Al n-valerate [29]
Ni–Al sebacate [18]
references ([11–14] respectively). Zn–Al acetate [32]
Zn–Al adipate [27]
Zn–Al citrate [47]
Zn–Al diglycolate [47]
2. Review of the current literature Zn–Al maleate [47]
Zn–Al malonate [27]
Zn–Al oxalate [27]
The more important LDH- / LDO-intercalated Zn–Al salicylate [47]
mono- and dicarboxylic aliphatic acids together with Zn–Al sebacate [27,47]
Zn–Al succinate [27,47]
their literature references are listed in Table 1. Zn–Al tartrate [47]
Similarly, the more important aromatic mono- and Zn–Cr acetate [32]
dicarboxylate intercalated LDHs or LDOs are given Zn–Cr citrate [47]
Zn–Cr diglycolate [47]
in Table 2. Zn–Cr ethanoate [47]
Zn–Cr maleate [47]
Zn–Cr salicylate [47]
2.1. Synthesis of carboxylic acid intercalated Zn–Cr sebacate [47]
LDHs Zn–Cr succinate [47]
Zn–Cr tartrate [47]

The five main experimental methods which may M II –M III refers to the starting LDH or LDO. For example: Mg–Al
is, in most cases, Mg–Al–CO 3 LDH or its calcined oxide.
be used in the preparation of carboxylic acid interca- Reference numbers refer to references cited at the end of this
lated LDHs or LDOs are summarised in Scheme 1. article.
 S. Carlino / Solid State Ionics 98 (1997) 73 – 84 75

Table 2
List of the main literature on LDH–aromatic mono- and dicarboxylic acid intercalation reactions
Starting LDH Carboxylic acid Literature
M II –M III cations anion reference
Ca–Al anthranilate [47]
Ca–Al benzoate [47]
Ca–Al phthalate [47]
Ca–Al terephthalate [47]
Li–Al anthranilate [47]
Li–Al benzoate [47]
Li–Al phthalate [47]
Li–Al terephthalate [47]
Mg–Al anthranilate [47]
Mg–Al benzoate [47,51,56]
Mg–Al benzenehexacarboxylate [56]
Mg–Al benzenepentacarboxylate [56]
Mg–Al 1,2,4,5-benzenetetracarboxylate [56]
Mg–Al 1,3,5-benzenetricarboxylate [56]
Mg–Al 1-naphthoate [51]
Mg–Al phthalate [47]
Mg–Al terephthalate [17,47,51,56]
Zn–Al anthranilate [47]
Zn–Al benzoate [32,47]
Zn–Al phthalate [47]
Zn–Al terephthalate [32,47]
Zn–Cr anthranilate [47]
Zn–Cr benzoate [47]
Zn–Cr phthalate [47]
Zn–Cr terephthalate [32,47]
M II –M III refers to the starting LDH or LDO as in Table 1.
Reference numbers refer to references cited at the end of this article.

Brief details of these synthetic methods are presented
below.
2.2. The direct ion exchange method
In the direct ion exchange method of intercalation,
the incorporation of carboxylic acid anions into the
LDH is achieved by shaking the LDH in a suitably
concentrated solution of the desired carboxylic acid
or its salt. A modified version of this method was
used more recently by Borja et al. [15] who success-
fully intercalated Mg–Al–Cl and Li–Al–Cl LDHs
by shaking them with aliquots of the desired acid in
alcoholic solution.
2.3. The coprecipitation method
The earliest suggestion of intercalating an organic
acid into an LDH (1,12-dodecanedicarboxylic acid
pillared Mg–Al LDH) was made by Reichle [16]
who used what is termed a ‘coprecipitation reaction’.
This method requires the addition of an M II / M III salt
solution to a base solution (or vice versa) containing
the carboxylic acid as the anion. The solution is then
crystallised using the same (hydrothermal) method
as employed in the preparation of the LDH host
material [2,16].
Since that time a number of authors have used
modified versions of this technique. Probably the
best known example of the use of the coprecipitation
technique is detailed in the paper by Drezdzon [17]
who termed the reaction a ‘digestion reaction’.
Drezdzon made use of the coprecipitation reaction to
synthesise a number of organic acid intercalated
LDHs, however, he states that this method could not
be used effectively to prepare a sebacic acid (seba-
cate) intercalated LDH.
76 S. Carlino / Solid State Ionics 98 (1997) 73 – 84

Scheme 1.

2.4. The rehydration method preparing carboxylic acid exchanged LDHs. The
method uses the calcined LDH (referred to as LDO)
This reaction route was pioneered in the late 1980s as its precursor. This LDO is added to solution
[18] and is by far the most common method of containing the carboxylic acid or its salt. The mix-
 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
ture is then either simply left to stir or refluxed for an
appropriate length of time. In order to obtain best
results the stirring and / or refluxing should be carried
out under a nitrogen atmosphere.
2.5. The thermal or ‘ melt’ reaction method
Recently an alternative reaction route by which
suitable organic acids may be intercalated into either
LDHs or LDOs has been developed [19]. This
reaction requires the intimate mixing of the organic
acid guest with either the LDH or LDO host prior to
heating at a ramp-rate not greater than 108C min 21
up to a temperature which is approximately 108C
above the melting point of the particular mono- or
dicarboxylic acid used. The mixture is then held at
this temperature for ca. 8 h in order to attain an
equilibrium and then cooled to room temperature at a
ramp-rate of 108C min 21 . The products are then
washed in hot ethanol and stored in a dessicator
under an inert atmosphere. (NOTE: readers should
note that no toxicological studies have been carried
out on thermal reactions and the author accepts no
responsibility, whatsoever, for the safety or effective-
ness of this reaction method.)
2.6. Glycerol effected exchange
Apart from the methods mentioned above, the
only other method listed in the literature for inter-
calating an organic acid into the interlayer of a
layered double hydroxide involves the use of gly-
cerol or other glycols 1 as exchange media. One of
the first reported uses of glycerol enhanced exchange
in LDHs was given by Hansen and Taylor [20] who
used this method to exchange the interlayer carbon-
ate present in samples of natural pyroaurite (the
Mg–Fe–CO 3 LDH) and synthetic hydrotalcite for
SO 422 , NO 32 or Cl 2 anions. Glycerol exchange may
be carried out via two different methods. Firstly, the
LDH may be heated in glycerol vapour in order to
preswell its interlayer region. The preswelled LDH is
then reacted with an appropriate solution of the
carboxylic acid to be exchanged.
The second method requires the LDH or LDO to
be stirred with a glycerolic solution of the desired
1
According to Ref. [20], glycerol is better than other glycols (for
example ethylene glycol) for preswelling treatments in LDHs.
77
carboxylic acid or its salt. This method was used by
Pinnavaia [21] who intercalated nonanoic and adipic
(hexanedioic) acids into a manasseite-like Mg–Al
LDH using a combination of rehydration to preswell
the LDO followed by glycerol intercalation of the
desired acid salt.
3. Mechanisms of intercalation and the
structure of the reaction products
3.1. The direct ion exchange mechanism
This mechanism relies upon the direct exchange of
the LDH’s interlayer anionic species with the desired
acid species. Our own experiments indicate that
carboxylic acids do not readily undergo intercalation
into the hydrotalcite-like Mg–Al–CO 3 LDH [6,19]
owing to the charge balancing carbonate anion which
is tenaciously held in the LDH interlamellar region.
These findings are confirmed by another author
[22] who noted that the exchange of the interlayer
carbonate anions was not greatly affected by the
direct exposure of uncalcined LDHs to aqueous
solutions of common anionic species. The following
sequence of exchange for both mono- and divalent
anions in LDHs has been derived [23–27]:
CO 22 22
3 4 SO 4 4
OH . F . Cl . Br 2 . NO 2
2 2 2 2
3 .I
(where the divalent anions are more strongly held in
the LDH interlayer than the monovalent anions;
carbonate is held most tenaciously of all).
The above shows the derived exchange sequence
of mono- and divalent anions into LDHs (from Refs.
[23–27]).
The direct ion exchange mechanism has more
recently been successfully modified by Dutta et al.
who reacted uncalcined LDHs with long-chain
monocarboxylic acids in alcoholic solution [15]. No
formal mechanism was proposed for this reaction;
however, the authors noted the presence of several
different species (as evidenced by FTIR spectros-
copy) in the reaction products which, in turn, sug-
gested that the reaction proceeded in a similar
manner to that of glycerol intercalation (vide supra)
– i.e. the alcohol molecules probably preswell the
LDH interlayer regions.
78 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
3.2. The coprecipitation reaction mechanism
The coprecipitation reaction relies upon the in situ
formation of the LDH M II –M III –(OH) x octahedral
layers around the ‘pillaring’ species in solution. The
LDH layers are thought to form in a similar manner
to those of the parent M II –M III –X LDH.
The method of coprecipitation has, more recently,
been used by Slade [28] in the synthesis of a
terephthalate pillared copper-LDH with the general
formula Cu 4 M 2III (OH) 12 [ 2 OOC–C 6 H 4 –COO 2 ]?
nH 2 O. This material gave a basal spacing of 15 A
and a gallery height of ca. 10.2 A. ˚ ated with conventional (solution) ion exchange re-
3.3. The rehydration reaction mechanism
The most commonly used method of intercalating
organic acids into LDHs relies upon the so-called
‘memory effect’ of the calcined LDH [29–31]. It
was found [12,18] that the LDO, when placed in an
aqueous solution containing 0.05 M sodium carbon-
ate, was able to rehydrate and revert back to a
structure which was similar to that of the parent
LDH. Using this principle, calcined LDHs have been
intercalated by rehydration in solutions of carboxylic
acids [18]. Following the intercalation of sebacic
acid by this method other groups have studied the
uptake of both mono- and dicarboxylic acids by
calcined LDHs in aqueous solution [29,32].
3.4. Thermal or ‘ melt’ reaction mechanism
The process of thermal intercalation has been
known for some time. For example, the use of
solid-state synthesis techniques for the preparation of
a wide variety of oxide-type materials is well
documented [33]. The selective solid-state intercala-
tion of cis- and trans-isomers of organic acids
(maleic, methylmaleic; fumaric and methylfumaric
acids) into montmorillonites was studied by Kato
[34]. The selectivity of the cis-form of the acids
(maleic and methylmaleic acids) was thought to
derive from the ability of the cis-isomers to form
chelate complexes with Al(III) of the montmorillo-
nite layers. The same authors also studied the
sorption of acrylamide [35], n-alkylamines [36] and
2,29-bipyridine [37] onto montmorillonites.
It is known that brucite, Mg(OH) 2 , is able to
expand in the direction of the c-axis (i.e. perpen-
dicular to the lamellae) from 4.75 A˚ at 208C to 4.81
˚A at 2028C when heated [38]. The difference be-
tween brucite and the Mg–Al–CO 3 LDH, aside from
aluminium substitution, is that the latter contains
tenaciously held interlayer carbonate anions together
with some mobile interlayer water molecules. The
thermal decomposition of LDHs has been well
documented [39–42]. It is known that the interlayer
space in hydrotalcite-like materials still provides a
˚ reactive environment upon the gentle heating associ-
actions [43]. Calcination studies on the LDH indi-
cated that the oxide material produced via a slow
heating process showed less of a deviation from the
original structure of the octahedral layers than that
produced by flash calcination [6,42]. The same study
also found (by using in situ variable temperature
27
Al MAS NMR) that the LDH starts to loose this
interlayer carbonate at a lower temperature than
traditionally expected. It was, therefore, decided to
try and exploit these two features and slowly heat the
Mg–Al–CO 3 LDH in order to try to expand the
weak bonding in the c-direction of the LDH layer
structure [43].
3.5. Mechanism of intercalation using glycerol as
an exchange medium
Several mechanisms have been postulated for the
intercalation of organic species following preswel-
ling treatment with glycerol or other glycols [20].
Probably the most plausible mechanism of those
suggested so far involves penetration of the glycerol
molecules into the metal hydroxide interlayers result
in a decrease in the hydrogen bonding of the
interlayer carbonate anions with the layer hydroxyl
groups. This decrease in hydrogen bonding enables
the CO 223 anions to be readily exchanged with the
anions outside the interlayer region (i.e. sebacate
etc.).
A second mechanism relies on the formation of
negatively charged glycerolate anions (CH 2 OH–
CHOH–CH 2 O 2) which react with the interlayer
carbonate of the LDH and are then exchanged out by
the pillaring species in solution outside the interlayer
region.
 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
Other mechanisms suggest a decrease in the
positive layer charge. Certainly, in the case of
phosphonic acids [44] heated with the Mg–Al–CO 3
LDH there is some evidence to suggest that the
octahedral layers of the LDH may not be as stable as
expected. This may also apply to heating with
glycerol.
In reality, a combination of these postulated
mechanisms is most probably responsible for the
anion exchange phenomenon with glycerol. It is
known that the temperature of glycerol treatment is
important [20]. For example, treatment of Mg–Al–
CO 3 LDH with liquid glycerol gives a d 003 of 9.7 A˚
(an increase in interlayer spacing of ca. 2 A). ˚ variety of phases (including regions of unintercalated
Corresponding treatment with glycerol vapour gives
an increase in interlayer spacing of 6.7 A˚ (d 003 of
˚
14.4 A). These correspond to one or two layers of
glycerol intercalate respectively.
4. Methods of analysis of intercalation reaction
products
4.1. Powder X-ray diffraction studies
4.1.1. Interpretation of PXRDs: assumptions and
models
Overall, the process of intercalation of carboxylic
acids into LDHs or LDOs may be summarised by
Fig. 2. The unintercalated host LDH has (in most
cases) a basal spacing of ca. 7.6 A ˚ and a corre-
2 ˚
sponding interlayer distance of 2.9 A. Upon interca-
lation each of these parameters (in the direction of
the c-axis) increases to some new value designated y
and x respectively in Fig. 2.
It may be assumed from the observed PXRD data
that the reflection with the greatest d-spacing value
˚
(in angstrom) is the basal spacing of the intercalated
material. In reality this reflection may or may not
correspond to the reflection with the greatest observ-
able percentage intensity in the powder pattern as
2
The interlayer height of either the host LDH or intercalation
reaction products is simply found by subtracting a value of 4.77 A ˚
˚ is the
from the observed basal spacing (d L ). Where 4.77 A
thickness of one layer of brucite (natural Mg(OH) 2 ) [45]. This is a
good approximation of the thickness of a single Mg–Al–(OH) x
layer.
79
Fig. 2. A schematic view of the simple intercalation of a
carboxylate into an LDH – typically via direct ion exchange. (See
main text for details of the parameters ‘x’ and ‘y’.)
these materials are, almost without exception, X-ray
amorphous microcrystalline solids and, therefore, a
host LDH) may co-exist in the reaction products.
Typically, the PXRD pattern of a carboxylate inter-
calated LDH will have as its three major reflections:
(i) the large basal spacing (d 003 ); (ii) the half-height
harmonic (d 006 ) (where d 006 ¯ ]12 d 003 ) and (iii) the
d 009 reflection (where d 009 ¯ ]13 d 003 ). The remaining
reflections can be indexed as either lesser reflections
of the intercalated phase or from areas of uninterca-
lated LDH.
The results of the studies by Lagaly et al. [46–48]
show that monocarboxylate intercalated LDHs have
a more complex structure than that of their corre-
sponding dicarboxylate intercalates. This is probably
because the dicarboxylates with two terminal carbox-
yl functional groups, have a limited number of
orientations between contiguous LDH layers. Where-
as, in the case of the monocarboxylates, bonding
through the carboxyl group to an M II –M III –(OH) x
layer only fixes one end of the molecule, allowing
the terminal methyl group to exhibit a hydrophobic
interaction with the protons in the LDH Mg–Al–
(OH) x layers [19,49].
A total of three situations may exist for LDH or
LDO carboxylate intercalates. (i) they may form ‘flat
stacks’ in the LDH / LDO interlayer region; (ii) they
may form monolayers of carboxylate anions in the
LDH / LDO interlayer and (iii) they may form a
bilayer of carboxylate anions in the interlayer. The
exact nature of these structures also depends upon
the functionality of the carboxylate; i.e. if it is a
mono- or dicarboxylate. It is also known that aro-
matic anions such as the terephthalate salt ( 2 OOC–
C 6 H 4 –COO 2), will not form flat stacks, but will
form pendant groups from the layers which abut in
80 S. Carlino / Solid State Ionics 98 (1997) 73 – 84

the interlayer region (see, for example, Ref. [44] on

phenylphosphonic acid).

4.1.2. Observed PXRD patterns

Typical PXRD patterns for the coprecipitation,
rehydration and thermal methods of intercalation for
an Mg–Al LDH system are shown in Fig. 3(a)–(c)
respectively. Although it is correct to talk of the d 003
(basal spacing) a typical PXRD pattern obtained
from any of the different synthetic methods will
typically show a broad spread of reflections which
make up this main reflection. This indicates that, in
reality, there are several intercalating species at
slightly varying orientations or environments. The
observed maximum d-spacings may also vary slight-
ly from method to method owing to the degree of
hydration of each sample.
An example of a PXRD pattern observed for the
coprecipitation reaction is shown in Fig. 3(a). This
pattern of the Mg–Al–[Sebacate] intercalate shows a
large d 003 of 17.6 A ˚ which corresponds to an
˚ This may be compared
interlayer spacing of 12.8 A.
with a typical pattern for Mg–Al–[Sebacate] ob-
tained by the rehydration method (Fig. 3(b)). This
PXRD pattern has a d 003 of 16.3 A ˚ which corre-
sponds to an interlayer spacing of 11.5 A. ˚ The
˚
half-height harmonic (d 006 ) of 8.1 A is also present
˚ (i.e. ]1 (d 003 )). The
along with the d 009 value of 5.4 A 3
difference between the observed d-spacings of these
two methods is probably accounted for by the
structure of the LDO which may have areas which
are ill-defined or varying degrees of hydration (see
also Section 3.4). The coprecipitated product is also
known to contain no carbonate in the interlayer
region [18] which may explain the difference in
spacing.
A typical example of a PXRD for the Mg–Al– Fig. 3. Powder X-ray diffraction patterns for Mg–Al–[Sebacate]
[Sebacate] system obtained using the thermal or obtained by (a) rehydration method, (b) coprecipitation method
‘melt’ reaction is shown in Fig. 3(c). The maximum and (c) the thermal or ‘melt’ method. All patterns are indexed
using JCPDS Card No. 22-700 (Synthetic Hydrotalcite) and Refs.
spacing obtained for this material compares well [18,19]. Note that pattern (c) contains reflections from a phase
with those of the two previous methods indicating corresponding to a region of unintercalated host LDH (marked as
that the products are the same (i.e. a d 003 of 19.3 A). ˚ ‘*’).
The main differences between this and other methods
are (i) that there is, in this case, no reflection
corresponding to the half-height harmonic (d 006 ) and materials which are truly X-ray amorphous. There
that (ii) there are also some areas of unintercalated was thought to be an interaction between the carbon-
LDH as evidenced by the d 003 of 7.7 A ˚ of the host ate in the LDH interlayer and the carboxylate anions.
LDH. The thermal reaction method, therefore, gives This may explain the relatively large observed basal
 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
Fig. 4. Schematic view of the proposed structure of the LDH–
[carboxylate] reaction products with a ‘flat stack’ of carboxylate
anions in the LDH interlayer region.
spacing of this material compared to those obtained
for the coprecipitation and rehydration methods (vide
infra).
4.1.3. Low loading of the LDH or LDO with
carboxylic acids
When the intercalation reaction takes place with a
low percentage of intercalate present in the reaction
mixture the product may not contain a phase corre-
sponding to a monolayer or bilayer (vide supra) of
intercalated acid. In the case of the thermal reaction
mechanism (q.v.), when the reaction takes place with
a low initial acid:LDH (LDO) concentration the
observed PXRD patterns suggest that the mono-
Fig. 5. Schematic view of the proposed structure of the LDH–
[carboxylate] reaction products with mololayer of carboxylate: (a)
hydrated phase with a monolayer of water and (b) dehydrated
phase. (See main text for details of the parameters d L and d 1 .)
81
carboxylate anions are, in fact, parallel to the layers
of the LDH (or LDO) as ‘flat stacks’ (see Fig. 4).
In the case of the coprecipitation and rehydration
methods (vide infra) the reaction products are always
monolayers (Fig. 5(a) and (b)) or bilayers (Fig. 6) of
carboxylate anions.
4.1.4. Monolayer structures
Using the terminology of Lagaly [46–48] the
following equation may be used to derive the
interlayer spacing and physical constants such as
slant angle, a, of the carboxylic chains from the
normal:
d L 5 d 0 1 1.27n sin a 1 d 1 (1)
where d L 5observed basal spacing in the PXRD
experiment; d 0 5distance between the terminal ion-
ised carboxyl group and the centre of the Mg–Al–
(OH) x layer; d 1 5distance between the terminal
methyl group and the centre of the LDH Mg–Al–
(OH) x layer; a 5the slant angle of the carboxylate
carbon chains from the normal of the LDH / LDO
M II –M III –(OH) x layers.
The relationship between the number of carbon
atoms in the aliphatic carbon chain of the mono-
carboxylic acid, n, and the slant angle, a, is ac-
counted for by the 1.27 and 2.54 constant terms in
Eq. (1) and Eq. (2). This relationship is accepted and
Fig. 6. Schematic view of the proposed structure of the LDH–
[carboxylate] reaction products with a full bilayer of carboxylate
in the LDH interlayer region. (See main text for details of the
parameters d L , d 0 , d 2 , a and n.)
82 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
documented for other systems including zirconium
phosphates [50].
Monocarboxylic acids are able to form two differ-
ent types of monolayer. Firstly, they may be hy-
drated monolayers; i.e. with a minimum of one layer
of water molecules between the hydrophobic termi-
nal methyl group of the carboxylic acid and the
adjacent LDH M II –M III –(OH) x layer (Fig. 5(a)).
Secondly, they may be dehydrated monolayers; i.e.
without any water molecules between the terminal
methyl group and the M II –M III –(OH) x layer (Fig.
5(b)).
4.1.5. Bilayer structures
Bilayer structures may be accurately described by
the following equation [49]:
d L 5 d 0 1 2.54n sin a 1 d 2 (2)
where d L , d 0 and a are the same as for Eq. (1). The
value of d 2 corresponds to the distance between the
two facing terminal methyl groups in the bilayer
structure. This is always taken as 3 A.˚
4.2. Solid-state MAS NMR studies on the reaction
products
4.2.1. 27 Al MAS NMR spectroscopic studies
Both one- and two-dimensional 27 Al MAS NMR
spectroscopic studies on the common hydrotalcite-
like Mg–Al–CO 3 LDH are detailed in the literature
[42]. In this LDH all of the aluminium is present as
octahedrally co-ordinated species; i.e. as Al(OH) 6
with possibly some Al(O) 6 [6,42]. In the case of the
monocarboxylate anion intercalated reaction products
the thermal intercalation reaction show a single
resonance at (typically) 18.8 ppm from TMS. This
indicated that the LDH layers were unchanged from
their original (octahedral) structure.
In contrast, the coprecipitation reaction product
showed a complex 1-D 27 Al MAS NMR spectrum
with resonances which could be assigned to both
octahedrally and tetrahedrally co-ordinated alumin-
ium species [51]. The rehydration method showed
tetrahedral, octahedral aluminium resonances for
terephthalate, benzoate and naphthoate. Some evi-
dence was also found for 5-fold co-ordinated alu-
minium species [51].
4.2.2. Interpretation of 13 C MAS NMR spectra
The 13 C MAS NMR spectra of the hydrotalcite-
like Mg–Al–CO 3 LDH host material is detailed in
the literature [19]. This material shows a single
resonance at ca. 1170.6 ppm which has been
assigned to the interlayer charge balancing carbonate
anions of the LDH [6,19]. The 13 C MAS NMR
spectra of the reaction products will, in most cases,
contain a signal corresponding to this interlayer
carbonate. The exact intensity of this resonance will
depend upon the method of intercalation used and
prevalent reaction conditions.
It is possible to assign observed resonances in the
13
C NMR spectra to the carbons in a carboxylic acid
skeleton using an empirical ‘additive-shift’ method
of chemical shift calculation [52–54]. The Lin-
deman–Adams Equation used for these calculations
was of the form [55]:
d(i) 5 2 2.5 1 na 1 nb 1 ng 1 nd 1 ne 1 n . . . (3)
where d(i) is the calculated chemical shift (in ppm
from TMS) of the ith carbon atom in the acid chain.
The value of 22.5 is the value for the chemical shift
of methane. The a, b, g, d and e terms refer to the
chemical shift parameters of the carbon atoms one,
two, three, four and five bonds removed from the ith
carbon in question. The values used for these car-
bons (from reference [55]) are: a, 19.1 ppm; b,
19.4 ppm; g, 22.5 ppm; d, 10.3 ppm and e, 10.1
ppm. The term n is simply the number of a, b, g, d
or e carbon atoms joined to the ith carbon. This
equation does not utilise the so-called ‘corrective
term’ of Grant and Paul [53] for the various steric
hindrances associated with branched paraffins.
Overall, this method permits the accurate calcula-
tion of chemical shifts and has been found to be
diagnostic for both C 2 and C 3 methylene carbons of
the dicarboxylic acid carbon skeleton. In particular, it
enables a distinction to be made between dissociated
and undissociated (i.e. intercalated and ‘free’ acid)
carboxylate groups. Assignment of other chemical
shifts (i.e. as C 4 or C 5 ) was found to be tentative.
From our results on mono- and dicarboxylic acids
it was found that the adjacent carbon to a dissociated
(i.e. intercalated) carboxyl group showed a chemical
shift of ca. 138 ppm in the 13 C spectrum [6,19,49].
A value of ca. 28 to 29 ppm was obtained for C 3
 S. Carlino / Solid State Ionics 98 (1997) 73 – 84
methylene carbons in the dissociated acid chain.
Similarly, it was found that the carbon of the ionised
carboxyl group itself appeared at a chemical shift of
ca. 182 ppm.
5. FTIR spectroscopic studies
Our own results suggest that FTIR studies on the
reaction products are inconclusive. This was thought
to be because of the fact that, in each case, several
environments of carboxylates were noted which
added to the complexity of the FTIR spectra. For
example, we noted that there may be a difference in
spectra obtained for mono- and dicarboxylates re-
lated to the orientation (i.e. the ‘fixed’ end) of the
molecule to the LDH layers which resulted in the
absence of characteristic group vibrations (i.e.
[nasym (CO)]. This anomaly may possibly be ex-
plained by the change in the structure of the LDH
metal hydroxide layers resulting in a change in the
FTIR extinction coefficient. Details of the FTIR
analyses of carboxylate intercalated LDHs are pre-
sented in the paper by El Malki et al. [32].
6. Conclusions
This review shows that there are five main types
of reaction routes which may be used to intercalate
both mono- and dicarboxylic acids into layered
double hydroxides or their oxides. From the com-
parison of the various methods (principally by
PXRD and NMR studies) it was found that the
coprecipitation and rehydration methods were the
most effective. These two methods gave, on the
whole, single phase reaction products as indicated by
PXRD. It has also been demonstrated that both 1-
and 2-D 27 Al solid-state MAS NMR techniques have
their role to play in structure elucidation of the
intercalates. Such studies indicated that there were
many different environments or orientations taken up
by the acid even in environments which PXRD
studies suggested had only contained a single phase
of reaction product. The direct ion exchange method
was found to be the least effective owing to the
carbonate anion which is present in the interlamellar
region of most synthesised LDHs. This method is,
83
therefore, best applied to non-carbonate LDHs and
has been found to be effective if carried out in
alcoholic solution. The thermal reaction method
produces PXRD amorphous materials which include
some areas of non-intercalated LDH or LDO host
material. This route leads to a variety of products
which are dependant upon the initial ratio of acid to
LDH / LDO host material.
Glycerol effected exchange has been found to be
effective in the exchange of carboxylic acids into
LDHs. The method depends upon the exact heating
conditions employed and is thought to depend upon a
combination of several mechanisms including the
formation of glycerolate anions.
Powder X-ray diffraction is still the principal
technique for discerning the structure of the interca-
lates. The technique of 13 C MAS NMR was also
found to be effective at determining the presence of,
for example, the interlayer carbonate anions of the
LDH. Finally, the use of the ‘additive-shift’ method
of 13 C chemical shift calculation was found to be a
useful and diagnostic tool for ionised and unreacted
intercalating carboxylate groups.
Acknowledgments
The author would like to thank Dr W. Jones of the
Department of Chemistry, University of Cambridge
for his permission to reproduce the PXRD pattern of
the Mg–Al–[Sebacate] LDH prepared via the rehy-
dration method shown in Fig. 3(b).
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