Journal of Colloid and Interface Science 283 (2005) 130138

www.elsevier.com/locate/jcis

Intercalation and functionalization of zinc hydroxide nitrate with monoand dicarboxylic acids
Fernando Wypych a, , Gregorio Guadalupe Carbajal Arzaga a ,
Jos Eduardo Ferreira da Costa Gardolinski b
a Universidade Federal do Paran, Departamento de Qumica, CP 19081, 81531-990 Curitiba, PR, Brazil
b Institut fr Anorganische Chemie, Christian-Albrechts-Universitt, Olshausenstrae 40, 24098 Kiel, Germany

Received 31 March 2004; accepted 13 August 2004

Available online 9 December 2004

Abstract
The intercalation of ions derived from succinic, glutaric, and adipic acid into layered zinc hydroxide nitrate by ionic exchange reaction
is reported. Different reaction conditions are investigated and the materials are characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermal analysis (simultaneous thermogravimetry and differential scanning calorimetry) and elemental analysis.
The dicarboxylic acids can be grafted to the matrix slab by one carboxylate group and the second hydrated carboxylate group is hanging
between the layers. Benzoate ions have also been intercalated by both ionic exchange reaction and stirring in acetonitrile. The two benzoateintercalated materials exchange the organic moiety by sulfate ions if stirred in magnesium sulfate solution, but the sample obtained by anion
exchange also allows the unusual incorporation of neutral magnesium sulfate in addition to free solvated sulfate ion. A schematic arrangement
of the intercalated species between the layers is presented.
2004 Elsevier Inc. All rights reserved.
Keywords: Zinc hydroxide nitrate; Intercalation; Carboxylic acid; Grafting

1. Introduction
Intercalation and functionalization processes involving
layered matrices and carboxylic acids are widely reported in
the specialized literature [113]. Functionalization processes
involve layered matrices of simple hydroxides [14], layered
double hydroxides [59], and hydroxide salts [1013]. The
capability of intercalation and grafting carboxylate groups to
the layers of a layered material can be described as follows:
In the simple hydroxides, due to the lack of exchangeable interlayer ions and the small distance between the
layers, only molecules with small dimensions are able
to access the interlayer space and react with the layer
surfaces [1,2].
* Corresponding author.

E-mail address: wypych@quimica.ufpr.br (F. Wypych).

0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.125

In the layered double hydroxides (LDH), due to preexpansion with the solvated ions and ionic exchange capability, possibilities are bigger. Nonetheless, only negative charged species could be exchanged, including the
solvent [5,6,9].
In the hydroxide salts, the situation is similar to that of
LDH, but due to the replacement of hydroxyl groups
by other ions, they become exchangeable and only one
metal is involved [1013].
The hydroxide salts structure can be considered as an
alteration of the hypothetical structure of zinc hydroxide,
CdI2 -type. One-fourth of the octahedrally coordinated zinc
atoms are removed from the layer and positioned at the bottom and top of the empty octahedral, with tetrahedral coordination. Three vertices of such tetrahedral coordination
are found to be occupied by hydroxide groups belonging to
the octahedral sheet, while the fourth, pointed to the inter-

F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

layer space, is occupied by a water molecule. Nitrate ions

are located between the layers and they are not directly coordinated with the zinc atoms [14].
Zinc hydroxide nitrate is ideal to subject to intercalation reactions because the nitrate ions have a bigger volume/charge rate in comparison with the ions such as sulfate
and carbonate. Therefore, the nitrate ions facilitate ionic exchange reactions [5].
Grafting or nongrafting of carboxylic acids into the layers
is not well defined in the case of LDH and for the hydroxide
salts and to the best of our understanding, there has been no
published work dealing with this phenomena. Similarly, use
of organic solvents for intercalation processes has not been
reported.
The objective of this work is therefore to evaluate
the intercalation process and the possibilities of covalent
bonding of the ions derived from dicarboxylic (succinate
( OOC(CH2 )2 COO ), glutarate ( OOC(CH2 )3 COO ),
adipate ( OOC(CH2 )4 COO ), and monocarboxylic acids
in the layers of zinc hydroxide nitrate. Experimental parameters such as temperature and different solvents used are
evaluated and discussed.

2. Experimental
2.1. Zinc hydroxide nitrate synthesis
The reagents used in the present work include
Zn(NO3 )2 6H2 O, 96103% (Synth), ZnO, P.A. (Merck), and

131

NH4 OH, 2830% analytical grade without further purification.

The synthesis of zinc hydroxide nitrate was carried out
following a procedure described elsewhere [15]. In short, it
is prepared by slow addition of NH4 OH, 30%, into 20 ml of
Zn(NO3 )2 , 0.5 mol L1 , under magnetic stirring and heated
to 4550 C for 1 h, with the pH adjusted to 7.
2.2. Preparation of the derivatives
Derivatives of zinc hydroxide nitrate are obtained mainly
by dispersing the solid in a solution under magnetic stirring.
In one case thermal treatment is also used. The different experimental conditions are listed in Table 1.
The samples treated in aqueous media are washed with
distilled water and those treated in organic solvents with
ethanol. For this purpose, materials are placed in a glass tube
and then centrifuged for 5 min at 4500 rpm and the liquid
phase is discarded. This procedure is repeated twice and finally the materials are dried at 5060 C for 24 h.
2.3. Instruments
Characterizations of all the materials in this study are
made by powder X-ray diffraction (XRD), Fourier transform
infrared spectroscopy (FTIR), thermal analysis (simultaneous thermogravimetry and differential scanning calorimetry
(TG/DSC)), and elemental analysis.
The powder X-ray diffraction study is conducted with a
Shimadzu XDR-6000 diffractometer with CuK radiation

Table 1
Conditions of the experiments done with zinc hydroxide nitrate
Experiment

Zinc hydroxide nitrate (g)

Acid (g)a

Molar rate hydroxide nitrate/acid

Medium (ml)

Temp. ( C)

Time (h)

1
2
3
4
5
6
7-B1
8-B2
9-S
10-G
11-A
12
13
14
15
16
17
18
19
20
21

0.2
0.2
0.2
0.3
0.3
0.3
0.2
1.50
1.50
1.50
1.50
0.15 S
0.15 S
0.15 G
0.15 G
0.15 G
0.15 A
0.15 A
0.15 B2
0.1 B1
0.1 B1

0.0379 Succ
0.0758 Succ
0.1517 Succ
0.0636 Glut
0.0636 Glut
0.0636 Glut
0.1568 Benzb
1.2200 Benzb
0.5905 Succb
0.6605 Glutb
0.7305 Adipb

1:1
1:2
1:4
1:1
1:1
1:1
1:4
1:4
1:2
1:2
1:2

30 i-butanol
30 i-butanol
30 i-butanol
30 i-butanol
30 toluene
30 acetone
15 acetonitrile
50 water
50 water
50 water
50 water
10 acetone
20 acetonec
10 acetone
10 toluene
10 i-butanol
10 acetone
10 acetonitrile
15d
25 water
15d

55
55
55
55
55
55
60
55
55
55
55
30
70
40
40
80
25
30
60
60
60

72
72
72
72
72
72
96
72
72
72
72
24
2
24
24
43
24
24
48
48
48

a
b
c
d

Succ = succinic, Glut = glutaric, Adip = adipic, Benz = benzoic acids.

Neutralized acids with NaOH 1 mol L1 .
Treated in a closed Teflon reactor.
Solution of MgSO4 0.1 mol L1 .

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F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

( = 1.5418 ) at 40 kV and 30 mA, using evaporated films

placed on a glass sampler holder. Simultaneous TG/DSC
studies are carried out using Netzsch equipment (Model STA
409 series EP) with 0.085 ml alumina crucibles in static
air atmosphere at a heating rate of 8 C min1 . FTIR spectroscopic studies are carried out in a Bio-Rad spectrometer, Model FTS 3500GX, using pellets prepared with KBr.
Elemental analysis is made in EUROVECTOR equipment,
Model EA 3000 CHNS.

3. Results and discussion

3.2. Experiments with organic solvents

A series of experiments were conducted (experiments
17) attempting the intercalation/grafting of carboxylates
using organic solvents. Dicarboxylic acids (succinic and glutaric) dissolved in isobutanol, toluene, and acetone have led
to partial formation of organic salts as detected by FTIR
spectrometry, without expansion of the basal spacing of zinc
hydroxide nitrate. Instead of anionic exchange reactions,
mixtures of the hydroxide nitrate and zinc succinate or glutarate are obtained.
For some experiments when the information can be presented in text form, the graphs are not presented.

3.1. Matrix

3.3. Experiments by anion exchange

Fig. 1a shows the XRD pattern for the matrix. In the

JCPDS database [16] it is identified as zinc hydroxide nitrate (Card 24-1460), with a basal distance of 9.9 . The
thermal analysis curve (Fig. 2) of the zinc hydroxide nitrate
has a complex profile with some endothermic peaks up to
300 C (72, 124, 153, 171 (shoulder), 235, and 277 C). Considering the loss of 25% of moisture (up to 237 C), then
17% mass loss related to hydroxide nitrate decomposition
[17] between 237 C and 684 C, and the final residue (58%)
as ZnO (confirmed by XRD), the formulation of the matrix obtained can be described as Zn5 (OH)8 (NO3 )2 10H2 O.
The compound, compared to that found in the literature, has
adsorbed/absorbed water in addition to crystallization water.

A successful procedure for the intercalation of organic

carboxylates into hydroxide through anionic exchange
[11,13] is followed to obtain the zinc hydroxide nitrate derivatives (experiments 811). Fig. 1 shows the XRD patterns
of these materials with basal spacing of 12.2, 13.2, 14.5,
and 19.0 for the materials treated with succinic, glutaric,
adipic, and benzoic acid neutralized with NaOH (in Table 1
they are identified as S, G, A, and B2 for their use in further
experiments). These spacings are found to be larger than the
length of the intercalated organic species. In order to account
for this additional space, the layer thickness is considered to
be that of brucite (4.8 ) [5]. The gap existing between the
zinc hydroxide nitrate layers and organic ions may be caused
by a layer of water and/or electrostatic interactions between
matrix and intercalated species (Table 2).
Fig. 3 shows the FTIR spectra, where it is possible to see
the sharp peak due to the stretching of the OH linked to the
matrix (3580 cm1 ), the broad band centered at 3400 cm1

Fig. 1. XRD patterns of zinc hydroxide nitrate (a) and products after anion
exchange reaction with succinate (b), glutarate (c), adipate (d), and benzoate (e) ions (identified in Table 1 as S, G, A, and B2, respectively).

Fig. 2. TG/DSC of zinc hydroxide nitrate.

F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

133

Table 2
Basal distances of the intercalated compounds and their relation with the
organic ions length
Zinc hydroxide
nitrate +

Organic ion length

()a

d = dL 4.8
()b

Gap
()

Succinate
Glutarate
Adipate
Benzoate

5.6
7.3
8.5
6.1

5.1
7.4
8.3
9.7
14.2

5.1
1.8
1.0
1.2
(2x) 2.0

a Distance between oxygen atoms in trans-conformation.

b d = basal distance () from the XRD patterns.
L

Fig. 4. Zoom of the FTIR spectra of product from experiment 11 showing

the splitting of the asymmetric (a) and (b) and symmetric (c) stretching
bands of the carboxylate ion.

Table 3
Splitting of the asymmetric band of COO and its distance from the
symmetric as presented in Fig. 6

Fig. 3. FTIR spectra of zinc hydroxide nitrate intercalated with benzoate (a),
succinate (b), glutarate (c), and adipate (d) ions.

is due to coordinated/adsorbed/absorbed water molecules.

Symmetric and asymmetric stretching of CH2 are located
around 2960 cm1 . The band at 1630 cm1 is due to the
bending mode of the water molecule [18]. For the material treated in benzoate solution CC in-plane bending at
1594 cm1 is detected (denoted as ring in Fig. 3a) [19]. The
most important bands in the present work are those stretching bands of the COO functional groups at ca. 1559 cm1
( as COO ) and 1403 cm1 ( s COO ).
The wavenumber difference between the as and s
COO vibrational modes from the spectra provides information about coordination of the carboxylate ion and the
metal [20]. Careful observation of the as band of material
treated with adipate solution (A) from experiment 11 (Fig. 4)
near to 1550 cm1 reveals a splitting. This is also present in
materials treated with succinate (S) and glutarate (G) solutions (Figs. 3b and 3c), although in the latter the splitting
is not so clear. The phenomenon could be related to two
different environments for carboxylate anions, namely one

Intercalated
ion

Band positions
(cm1 )
a
b
c

Peak distances
(cm1 )
ac bc

Reference values
(cm1 )
 sodium salt

Adipate
Glutarate
Succinate
Benzoate

1559
1579
1559

157
175
162

122
150
145
136

1539
1559
1539
1559

1402
1404
1397
1403

137
155
142
156

forming the band (a) and the other the band (b), as shown
in Fig. 4. Near to the COO symmetric stretching band (c)
there is another sharp and intense peak (1384 cm1 ) due to
nitrate ions and not due to splitting. With these values, it is
possible to calculate  (Table 3). It may be noted that when
 is larger than the reference value (sodium salt of the respective acid), the carboxylate ion can be coordinated to the
metal with one oxygen atom [20].
The reference salts (sodium benzoate, succinate, glutarate, and adipate) have a  close to bc values of
the compounds obtained from experiment 811 and hence
one may expect a monodentade coordination; i.e., the carboxylate is bonded to the matrix layers through one oxygen
atom [20]. For the specific case of the dicarboxylate species,
where a splitting of the as COO is observed, the ac
values are larger than the reference value; thus the existence
of a carboxylate ion as a bridge is expected. The proposed
arrangement for dicarboxylates between layers is the grafting of one COO extreme to the zinc hydroxide nitrate
layer by one oxygen molecule and the other COO extreme
in contact with water molecules, forming hydrogen bonds
(Fig. 5). Some researchers have already considered the presence of water as an interface between carboxylate groups in
LDH [6,9] and gibbsite [4]. The existence of such an aqueous interface explains the gap between inorganic and organic

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F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

moieties calculated in Table 2, since the length of an isolated

molecule is not enough to account for the calculated interlayer spacing.
Table 4 shows the percentages of mass loss and their temperature range observed from the thermal analysis curves
(not shown), as well as carbon and nitrogen contents obtained from elemental analysis. This information lead to proposed compositions presented in Table 5.
In the formulations of Table 5 one may observe benzoate
anions reacting with some hydroxyl groups, in addition to
replacement of almost all nitrate ions. Dicarboxylate species
displace most of the nitrate ions; the larger the carbon chain,
the bigger is the amount of nitrate in the galleries. This may

be due to the fact that the gallery size depends on the length
of the organic salts and bigger galleries may let the small
ions be maintained or return into them.
Further, it is observed that material prepared in benzoate
solution (experiment 8) has the largest basal spacing and
does not contain nitrate, as seen in the elemental analysis
(Table 4). In this case the amount of organic species is higher
since the concentration of benzoate solution was doubled
with a view to comparing results with dicarboxylate salts.
Furthermore, benzoate ion has one half of the charge of dicarboxylate salts and thus is able to be diffused to deeper
interlayer regions and displace the nitrate ions.
The thermal analysis profiles (not shown) of the materials obtained by anion exchange present series of events
up to 300 C, where adsorbed/absorbed and coordinate water is removed (Table 4). After that the dehydroxylation of
the matrix and loss of nitrate ions [17] take place, followed
by the organic matter combustion, as evidenced by a sharp
exothermic peak in DSC curves, which appear at higher temperatures when carbon number of the chain increases. The
remainder of the material is identified by XRD as ZnO when
heated up to 1000 C.
3.4. Treatment after intercalation by ionic exchange

Fig. 5. Proposed arrangement for interlayer dicarboxylate ions. One extreme

grafted to the matrix and the other in contact with a water interface.

Table 4
Thermal events, mass losses, and elemental analyses of intercalated zinc
hydroxide nitrate
Intercalated
ion

Water loss
range
(%)

Final Organic mater

temp. loss range
( C) (%)

Final
temp.
( C)

%C

%N

Succinate
Glutarate
Adipate
Benzoate

10076
10078
10070
10081

200
300
300
300

600
1000
1000
445

7.36
8.15
11.8
22.4

0.15
0.45
0.41
0.00

7657
7859
7046
8147

The intercalated materials from experiments 811 are

treated in some organic solvents, expecting covalent bonding
between the organic moieties and surface hydroxide species
(experiments 1218). The reaction would probably cause a
shift of the basal distances in the XRD patterns and in the
as and s COO bands in the FTIR spectra.
The FTIR and XRD results of assays involving succinateintercalated hydroxide nitrate (experiments 12 and 13) are
the same as those of compound S (experiment 9). It can be
deduced that the succinate ion stays in the interlayer gallery,
sharing one carboxylic oxygen atom with the matrix and the
other extreme in contact with a water molecule.
On the other hand, the intercalation product of the glutarate ion (G) has a basal spacing of 13.2 (experiment 10),
which decreased to 11.7 when was treated with acetone
(Fig. 6d, experiment 14), similar to the observation with
toluene treatment (Fig. 6c, experiment 15); but FTIR spectra
(Fig. 7) shows maintenance of the as and s COO bands
at the same positions. This shift of 1.5 of the basal spacing

Table 5
Minimal compositions of zinc hydroxide nitrate and its derivatives
Material

Compositions

Zinc hydroxide nitrate

Hydroxide nitrate + succinate
Hydroxide nitrate + glutarate
Hydroxide nitrate + adipate
Hydroxide nitrate + benzoatea
Hydroxide nitrate + benzoateb

Zn(OH)1.6 (NO3 )0.4 2H2 O

Zn(OH)1.5 (NO3 )0.02 (OOC(CH2 )2 COO)0.24 1.9H2 O
Zn(OH)1.56 (NO3 )0.04 (OOC(CH2 )3 COO)0.20 1.7H2 O
Zn(OH)1.35 (NO3 )0.05 (OOC(CH2 )4 COO)0.3 3H2 O
Zn(OH)1.5 (C6 H5 COO)0.50 1.8H2 O
Zn(OH)1.06 (NO3 )0.07 (C6 H5 COO)0.87 1.8H2 O

a Intercalated by anion exchange reaction.

b Intercalated by shacking in acetonitrile.

F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

Fig. 6. XRD patterns of zinc hydroxide nitrate intercalated with glutarate

(a) and products after stirring in i-butanol (b), toluene (c), and acetone (d).

Fig. 7. FTIR spectra of zinc hydroxide nitrate intercalated with glutarate (a)
and products after stirring in i-butanol (b), toluene (c), and acetone (d).

is not enough to be related to water loss (ca. 3 ) [6,21] but

maybe related to a change in the tilt angle of the glutarate
ion. The material subjected to isobutanol treatment (experiment 16) yields zinc glutarate, identified by the reflection of
6.9 in the X-ray diffraction pattern (Fig. 6b). The XRD
patterns of the products from experiments 1416 show three

135

Fig. 8. XRD patterns of product B1 (experiment 7) (a) and further stirring

in MgSO4 solution dried at 60 (b) and 110 C (c). Also stirred in water (d).
Product B2 (experiment 8) after stirring in MgSO4 solution (e).

Fig. 9. FTIR spectra of product B2 (experiment 8) (a) and after stirring in

MgSO4 solution (b); product B1 (experiment 7) (c) treated with MgSO4
solution (d) and water (e).

intense reflections between 31 and 37 (2 ), indicating formation of ZnO.

Further, neither X-ray analyses of products from experiments 17 and 18 nor FTIR spectra show differences from the

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F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

previous materials. This suggests that there is no change in

the interactions of host and guest.
Reversibility of benzoate intercalation is tested (experiment 19), placing the material in a magnesium sulfate solution. Figs. 8 and 9 show the XRD pattern and FTIR spectra
respectively, obtained in this experiment. When benzoate intercalated product (experiment 8, B2) is reacted with MgSO4
solution, two phases with basal distances of 8.3 and 7.4 are
observed (Fig. 8e).
FTIR spectra of the product from experiment 19 (Fig. 9b)
shows the disappearance of the COO stretching bands at
1396 and 1600 cm1 present earlier in Fig. 9a, while a strong
band at 1100 cm1 ( 3 ) appears to be due to sulfate ions and
is followed by another at 605 cm1 ( 4 ). The presence of
3 and 4 bands is characteristic for the free sulfate ion with
Td symmetry [20]. Two weak shoulders appear centered at
1155 and 1014 cm1 , as splitting of the 3 band. Besides,
a low-intensity band at 962 cm1 ( 1 ) confirms that there
are also sulfate species with lower symmetry; i.e., the sulfate is bonded to a metal ion, but the amounts of these are
lower since the intensities are weaker than those of the Td
symmetry ions.
Considering that sulfate diameter is close to that nitrate
ion (2.5 vs 2.1 ) and water is removed from the matrix (located in the apical position of zinc tetrahedrals),
the basal distance would be 7.3 , close to the observed
value (7.4 ). Removal of water from the tetrahedrally
coordinated zinc does not exclude the existence of interlayer water, whose diameter is close to the sulfate dimensions (3 ) [6,21]. The 8.3- phase could be formed by
the presence of sulfate bonded to Mg2+ ions with a 1.32
diameter. The sample from Experiment 19 (Fig. 8e), after an extensive washing procedure, was submitted to EDS
analysis (Philips SEM-505), being the constituent element
detected (not shown). The semiquantitative determination
(at%) showed the ratio S/Mg = 8.7, confirming that sulfate
is the predominant counterion and neutral magnesium sulfate is also intercalated [22].
3.5. Intercalation of benzoic acid using acetonitrile
The thermal analysis (not shown) of the benzoate-intercalated matrix in acetonitrile (B1) indicates that water and
nitrate ions are removed up to 290 C (15% loss of material) and burning of the organic matter ends at 434 C (45%),
leaving behind ZnO (37%). Taking all these results along
with those of elemental analysis, the composition of this
material can be proposed as Zn(OH)1.06(NO3 )0.07(C6 H5 COO)0.87 1.8H2 O.
Fig. 8a shows the XRD pattern of product obtained from
experiment 7 (named B1), where the three phases shown
may correspond to different arrangements of benzoate ions
in the interlayer spaces (Fig. 10a). The most intense, 14.7
the is due to formation of a benzoate monolayer between
hydroxide nitrate layers and is in agreement with benzoate
intercalation in LDH [6,7]. The reflection of 13 would

represent an intermediate phase, when benzoate species are

introduced into the matrix. The biggest interlayer space of
19.3 , is due to a double layer arrangement of the benzoate
anions [12]. The amount of hydroxyl groups in the minimal
formulae of this material suggests that benzoic acid reacts
with more hydroxyl groups of the matrix when treated in
acetonitrile compared to the anion exchange reaction (see
Table 5).
In order to detect the behavior differences of zinc hydroxide nitrate modified with benzoate anion introduced by
stirring in acetonitrile (compound B1) and anion exchange
(compound B2), the compound B1 is also treated with
a magnesium sulfate solution. Another experiment (number 20) was made by stirring it in water to check possible
hydrolysis phenomenon. The product B1 (treated in acetonitrile) after shaking with water shows the carbon content as
23.41% in the elemental analysis compared to 35.23% in the
precursor (B1). The FTIR spectra of this shown in Fig. 9e
reveals the COO stretching bands at 1400 and 1550 cm1 ,
while the XRD pattern (Fig. 8d) indicates that it is formed as
one-phase product with a basal spacing of 19.2 .
The 19.3 reflection in Fig. 8a suggests a benzoate ions
arrangement in a double layer form (Fig. 10). The 14.7 and
13.0 phases are eliminated because larger reaction time
let the ions form such phase to achieve a more stable orientation so that the amount of benzoate ions lying in the
perpendicular direction to the surface of the matrix layer increase leading to a double layer arrangement.
In the FTIR spectra of product B1 stirred in magnesium
sulfate solution (experiment 21), the sulfate 1 (Fig. 9d) band
is weaker than the one in compound from experiment 19
(Fig. 9b). Probably the fraction of bidentade sulfate is also
smaller. It appears that these species do not have well defined splitting of 3 , and 4 and hence it may be assumed
that sulfate ions are mainly free in the layered material galleries.
X-ray diffraction pattern of B1 after treatment in sulfate
solution (Fig. 8b) dried at 60 C has a 14.7 basal distance, which coincides with dimension of a benzoate monolayer phase. However, the carbon content in this material
is 0.346% and there is no exothermic event in the thermal
analysis (not shown) related to organic matter combustion;
the product after heating at 650 C is ZnO confirmed by
X-ray diffraction analysis (not shown). A sample of the remainder oxide is analyzed by FTIR and strong signals of
sulfate are observed. It is therefore concluded that sulfate is
the main interlayer species besides water.
This can be explained further, by considering that the
basal distance in zinc hydroxide sulfate is 11 , and so the
distance formed by sulfate ion is 6.2 . It is known that space
formed by intercalated sulfate in other compounds is ca. 6
[21,22]. Thus, it can be concluded that a phase with a basal
plane of 14 spacing is formed by a free sulfate ion and two
layers of water. Further, when this material is dried at 110 C
for 5 h, the basal spacing collapses to 7.2 (Fig. 8c). A small
amount of sulfate ions could be close to zinc ions because in

F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

137

Fig. 10. Arrangements of benzoate anions between hydroxynitrate layers in product B1 (a) and after treatment in water (b) and magnesium sulfate solution
dried at 60 (c) and 110 C (d); sulfate ions after treatment of B2 in magnesium sulfate solution (e).

the FTIR spectra the 1 band and two weak shoulders of 3

appear. If they are to be caused by magnesium, the basal
spacing would be larger than 8 . In the X-ray diffraction
pattern of the material dried at 60 C, there is a second basal
reflection of the 14 that coincides with the first one when
dried at 110 C (Figs. 8b and 8c), and hence the 7.2 phase
is probably present in the former material.
3.6. Benzoate-intercalated zinc hydroxide nitrate in
acetonitrile (B2) vs benzoate intercalated by ionic
exchange (B1)
Zinc hydroxide intercalated with benzoate ions in acetonitrile (B1) and ionic exchange (B2) does not exhibit the
same behavior when treated in magnesium sulfate solution.
The former intercalates free sulfate ions as expected and the
later has two clear phases where one contains neutral magnesium sulfate, this unexpected result can lead to future studies
of incorporation of interlamelar cations in positively charged
layered matrices. These phenomena can be related to dif-

ferent interactions of organic/inorganic moieties influenced

by the preparation route. Further studies in this are required
to get more information about differences between zinc hydroxide nitrate modified in organic and aqueous media.

4. Conclusions
The interlayer space increment after insertion of the carboxylate anions is bigger than the length of the carboxylate.
The detected increase can be related to the presence of a water molecule layer, which solvates one extreme of the dicarboxylate anion while the other extreme of the dicarboxylate
is grafted to the matrix through one oxygen atom (monodentade coordination).
Interlayer spaces depend upon the length of dicarboxylate
anions. Intercalation of benzoate ion into the matrix occurs
in a double-layer arrangement, producing bigger expansions
than the dicarboxylate anions.

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F. Wypych et al. / Journal of Colloid and Interface Science 283 (2005) 130138

The zinc hydroxide nitrate modified with benzoate anions

by ion exchange reaction and stirred in a magnesium sulfate
solution, intercalates mainly free sulfate ions besides magnesium sulfate, both characterized by two basal spacing.
The compounds obtained when benzoate is intercalated
using acetonitrile as solvent (basal distances of 19.3, 14.7,
and 13.0 ) can be attributed to the arrangement of benzoate
ions in the form of double layers, single layer and an intermediate arrangement, respectively.
Water does not hydrolyze this material; nevertheless, it
favors a double layer arrangement (19 ). A aqueous solution of magnesium sulfate promotes the displacement of
benzoate anions by sulfate ones forming a one-phase material with a 14.7 basal spacing due to intercalation of
hydrated sulfate ions. When this material is heated at 110 C
the space is reduced to 7.2 .

Acknowledgments
The authors thank Dr. Kestur Gundappa Satyanarayana
for the revision of the paper. G.G.C.A. thanks PEC/PG of
CAPES/CNPq, IEL Nacional, Brazil.

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