American Mineralogist, Volume 87, pages 623–629, 2002

Infrared and Raman study of interlayer anions CO32–, NO3–, SO42– and ClO4– in Mg/Al-
hydrotalcite

J. THEO KLOPROGGE,* DAVID WHARTON, LEISEL HICKEY, AND RAY L. FROST

Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane Qld
4001, Australia

ABSTRACT
The difference in the local environment of CO32–, NO3–, SO42–, and ClO4– in Mg/Al-hydrotalcite
compared to the free anions was studied by infrared and Raman spectroscopy. In comparison to free
CO32– a shift toward lower wavenumbers was observed. A band around 3000–3200 cm–1 has been
attributed to the bridging mode H2O-CO32–. The IR spectrum of CO3– hydrotalcite clearly shows the
split n3 band around 1365 and 1400 cm–1 together with weak n2 and n4 modes around 870 and 667
cm–1. The n1 mode is activated and observed as a weak band around 1012 cm–1. The Raman spectrum
shows a strong n1 band at 1053 cm–1 plus weak n3 and n4 modes around 1403 and 695 cm–1. The
symmetry of the carbonate anions is lowered from D3h to C2s resulting in activation of the IR inactive
n1 mode around 1050–1060 cm–1. In addition, the n3 shows a splitting of 30–60 cm–1. Although NO3-
hydrotalcite has incorporated some CO32– the IR shows a strong n3 mode at 1360 cm–1 with a weak
band at 827 cm–1, and the n4 band is observed at 667 cm–1, although it is largely obscured by the
hydrotalcite lattice modes. The Raman spectrum shows a strong n1 mode at 1044 cm–1 with a weaker
n4 band at 712 cm–1. The n3 mode at 1355 cm–1 is obscured by a broad band due to the presence of
CO32–. The symmetry of NO3– did not change when incorporated in hydrotalcite. The IR spectrum of
SO4-hydrotalcite shows a strong n3 at 1126, n4 at 614 and a weak n1 mode at 981 cm–1. The Raman
spectrum is characterized by a strong n1 mode at 982 cm–1 plus medium n2 and n4 bands at 453 and
611 cm–1; n3 cannot be identified as a separate band, although a broad band can be seen around 1134
cm–1. The site symmetry of SO42– is lowered from Td to C2v. The distortion of ClO4– in the interlayer of
hydrotalcite is reflected in the IR spectrum with both n3 and n4 bands split around 1096 and 1145
cm–1 and 626 and 635 cm–1, respectively. A weak n1 band is observed at 935 cm–1. The Raman spec-
trum shows a strong n1 mode at 936 cm–1 plus n2 and n4 bands at 461 and 626 cm–1, respectively. A n3
mode cannot be clearly recognized, but a broad band is visible around 1110 cm–1. These data indica-
tive a lowering of symmetry from Td to Cs.

INTRODUCTION
Hydrotalcites or layered double hydroxides (LDHs) are also
described as anionic clays, due to their layered structure with a
charge opposite to that of cationic clays (like smectites) con-
sisting of negatively charged aluminosilicate layers with cat-
ions in the interlayer space to balance the negative charge. The
structure of hydrotalcite can be visualized as positively charged
OH-layers comparable to those in brucite [Mg(OH)2] in which
some of the Mg2+ is substituted by a trivalent metal like Al3+
separated by charge compensating, mostly hydrated, anions
between the OH-layers. In hydrotalcites a range of composi-
tions are possible of the type [M2+ 3+ n–
1–xM x(OH)2][A ] x/n.yH 2O,
where M2+ and M3+ are the di- and trivalent cations in the octa-
hedral sites within the OH-layers with x normally between 0.17
and 0.33. An– is an exchangeable anion. It is important that the
ionic radii of the M2+ and M3+ do not vary more than 30% in
* E-mail: t.kloprogge@qut.edu.au
size, e.g., 0.65 Å for Mg2+ and 0.45 Å for Al3+, and the solubil-
ity products S1 and S2 of M2+(OH)2 and M2+CO3 must satisfy 0 <
pS1 – pS2 < 10 where pS1 is the negative logarithm of the solu-
bility product of M2+(OH)2 and pS2 of M2+CO3 (Miyata and
Kumura 1973).
The number of counterbalancing anions or anionic com-
plexes in hydrotalcites is essentially unlimited provided that
the anion does not form a complex with the cations in the octa-
hedral sheets during formation; otherwise a hydrotalcite can-
not be formed (Vaccari 1998). Therefore, the variety possible
in both the cationic and anionic compositions of hydrotalcite
offers the possibility to prepare tailor-made materials for spe-
cific applications, such as basic catalysts, as a precursor for the
preparation of mixed metal oxidic catalysts, absorbents, and
for other specific powder properties such as filler, UV-radia-
tion stabilizer, chloride scavenger and, thermal stabilizer
(Titulaer 1993).
Infrared and rarely Raman spectroscopy have been used for
the study of hydrotalcites with different cations, the anionic
pillaring and thermal decomposition of hydrotalcites, mainly

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624 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS

for showing the presence of various exchangeable anions, such
as CO32–, Cl–, ClO4–, NO3–, SO42–, and CrO42– (Evana et al. 1992;
Miyata 1975; Miyata and Okada 1977; Reichle et al. 1986),
larger groups such as anionic silica SiO(OH)3– (Schutz and
Biloen 1987) and larger polyoxometalate ions or Fe(CN)6n–
(Hansen and Koch 1994; Idemura et al. 1989; Wang et al. 1991).
Each of these anions shows specific infrared or Raman bands;
e.g., CO2– is characterized by a double peak around 1360 and
1400 cm–1 and peaks at 880 and 680 cm–1 (Hernandez-Moreno
et al. 1985). However, most of these papers do not present any
details about the exact site group symmetries of the anions in
the interlayer of hydrotalcite and the consequences this has on
the infrared and Raman spectra. Therefore, this paper aims at
describing the infrared and Raman spectra of some of these
most abundant interlayer anions in hydrotalcite and the corre-
sponding site symmetry of the anions.
THEORETICAL ANALYSIS OF FREE ANIONS
In order to understand the spectra of interlayer anions in the
hydrotalcite structure it is important to examine the spectral
behavior of the free anions and how this changes upon con-
finement within the crystal structure. An overview of the se-
lection rules for the free anions is presented in Table 1.
When CO32– is present as a free ion it will exhibit a molecu-
lar point group of D3h. Group theoretical analysis of the car-
bonate molecule (although it does not exist as a free anion
except in solution) predicts four normal modes. As a result the
bending non-planar mode n2(A''2), the antisymmetrical stretch-
ing mode n3(E ') and the bending angular mode n4(E '), will be
observed in the IR spectrum at 880, 1415, and 680 cm–1, while
the symmetric stretching mode n1(A'1) is IR inactive (Ross
1972). In the Raman spectrum one will observe n1(A'1), n3(E '),
and n4(E') modes (Farmer 1974; Ross 1972). Similarly, free
nitrate NO3– will exhibit a molecular point group of D3h with A1'
Raman actively only, A2'' IR active only, and 2E ' both Raman
and IR active. This means that the out-of-plane symmetric de-
formation mode n2, antisymmetric stretching mode n3, and an-
tisymmetric deformation mode n4 will be observed in the IR
spectrum around 830, 1350, and 680 cm–1, while the symmet-
ric stretching mode n1 together with the aforementioned n3 and
n4 will be observed in the Raman spectrum around 1049, 1355,
and 690 cm–1 (Ross 1972).
The free SO42– anion has a Td symmetry corresponding to a
molecular point group of O7h with the stretching and bending
modes n3(F2) and n4(F2) modes both Raman and IR active, while
the symmetric stretching mode n1(A1) and the bending mode
n2(E) are only Raman active with n1 at 981, n2 at 451, n3 at
1104, and n4 at 613 cm–1 (Ross 1972). The free ClO4– anion is,
in terms of structure and symmetry, quite similar to SO42– and
also has symmetry Td. This means that n1 and n2 are only Raman
active with bands at 928 and 460 cm–1, whereas n3 and n4 are
both IR and Raman active with bands at 1128 and 645 cm–1.
However, the ClO4 tetrahedron is very easily distorted result-
ing in the activation of the n1 mode in the IR spectrum, while
n3 and n4 are often split (Ross 1972). The correlation table for
both D3h and Td symmetry groups and their subgroups is pre-
sented in Table 2.
EXPERIMENTAL METHODS
Hydrotalcite with theoretical composition Mg6Al2(OH)16CO3◊
nH2O was synthesized according to the method described by
Kloprogge and Frost (1999a, 1999b, 1999c). This method com-
prises the slow simultaneous addition of a mixed aluminum
nitrate (0.25 M)-magnesium nitrate (0.75 M) and a mixed NaOH
(2.00 M)-Na2CO3 (0.125 M) solution under vigorous stirring
while buffering the pH at approximately 10. The product was
washed to eliminate excess salt and dried at 60 ∞C.
The incorporation of carbonate during the synthesis of the
hydrotalcites containing the other anions was as much as pos-
sible prevented by boiling the deionised water before use, by
rinsing the NaOH pellets before use, and by executing the syn-
thesis under a nitrogen atmosphere. As sources for the sulfate
and perchlorate anions in solution the corresponding magne-
sium and aluminum salts were used instead of the magnesium

TABLE 1. Correlation table and selection rules for the free anions used in this study
Point group Mode and symmetry class Activity
n1 n2 n3 n4 Raman only IR only IR + Raman
CO32–/NO3– D 3h A' 1 A" 1 E' E' A'1 A''1 2E '
SO42–/ClO4– Td A1 E T2 T2 A1, E 2 T2

TABLE 2. Correlation table for tetratomic molecules in D3h and pentatomic molecules in Td
shÆsv(zy) sh sv
D3h C3h D3 C3v C2v C3 C2 Cs Cs
A' 1 A' A1 A1 A1 A A A' A'
A' 2 A' A2 A2 B2 A B A' A"
E' E' E E A 1+ B 2 E A+ B 2 A' A'+A"
A" 1 A" A1 A2 A2 A A A" A"
A" 2 A" A2 A1 B1 A B A" A'
E" E" E E A 2+ B 1 E A+ B 2 A" A'+A"

Td T D2d C3v S4 D2 C2v C3 C2 Cs

A1 A A1 A A A A1 A A A'
A2 A B1 A2 B A A2 A A A"
E E A 1+ B 1 E A+ B 2A A 1+ A 2 E 2A A'+A"
T1 T A 2+ E A 2+ E A+ E B 1 + B 2+ B 3 A 2 + B 1+ B 2 A+ E A+2B A'+2A"
T2 T B 2+ E A 1+ E B+ E B 1 + B 2+ B 3 A 1 + B 1+ B 2 A+ E A+2B 2A'+A"
 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS
and aluminum nitrates discussed above.
The crystalline nature of the resulting materials was checked
by X-ray powder diffraction (XRD). The XRD analyses were
carried out on a Philips wide-angle PW 1050/25 vertical goni-
ometer equipped with a graphite-diffracted beam monochro-
mator. The radiation applied was CoKa (1.7902 Å) from a long
fine focus Co tube operating at 35 kV and 40 mA. The samples
were measured at 50% relative humidity in stepscan mode with
steps of 0.02∞ 2q and a counting time of 2s.
The finely powdered samples were combined with oven
dried spectroscopic-grade KBr (containing approximately 1
wt% sample) and pressed into a disc under vacuum. The spec-
tra of the samples were recorded in triplicate by accumulating
512 scans at 4 cm–1 resolution in the spectral range 400–4000
cm–1 using a Perkin-Elmer 1600 series Fourier-transform in-
frared spectrometer equipped with a LITA detector or a Nicolet
Magna 750 Fourier transform infrared spectrometer equipped
with a DTGS detector. For each sample, 512 scans were re-
corded in the spectral range between 400 and 4000 cm–1 in the
absorbance mode with a resolution of 4 cm–1.
The Fourier-transform Raman spectroscopic (FT-Raman)
analyses were performed on a Perkin Elmer System 2000 Fou-
rier-transform spectrometer equipped with a Raman accessory
comprising a Spectron Laser Systems SL301 Nd:YAG laser
operating at a wavelength of 1064 nm. For the hydrotalcites
containing various anions 1000 scans were obtained by back-
scattering from pressed pellets at a spectral resolution of 4
cm –1 in order to obtain an acceptable signal/noise ratio.
Spectral processing such as baseline adjustment, smooth-
ing, and normalization were performed using the Spectracalc
software package GRAMS (Galactic Industries Corporation,
N.H., U.S.A.). Band component analysis was carried out using
the Peakfit software package by Jandel Scientific. Lorentz-
Gauss cross product functions were used throughout and
peakfitting was carried out until squared correlation coefficients
with r2 greater than 0.995 were obtained.
RESULTS AND DISCUSSION
Crystal chemistry
All the samples synthesized for this study were identified
as Mg/Al-hydrotalcites. Figure 1 shows the XRD patterns of
the synthesized hydrotalcites. The hydrotalcites synthesized
with carbonate, nitrate and sulfate as the interlayer anion clearly
show one crystalline phase. The value of 7.8 Å is characteristic
for the 003 reflection of carbonate-bearing hydrotalcite
(Kloprogge and Frost 1999a; Kloprogge and Frost 1999b;
Kloprogge et al. 1999). Replacement of carbonate by nitrate as
Counts
the interlayer anion results in a slight expansion from 7.8 Å to
around 8.1 Å, which is slightly smaller than the value of 8.36
Å reported by Marino and Masculo (1982). Incorporation of
the sulfate ion gives a 003 reflection at 8.9 Å which agrees
well with data reported by, e.g., Miyata and Okada (1977), Bish
(1980), and Sato et al. (1986). The sample with perchlorate as
the interlayer anion, however, clearly shows a second phase
with a 003 reflection similar to that of carbonate-bearing
hydrotalcite in addition to a stronger reflection at 9.3 Å, which
agrees with data reported by Miyata and Kumura (1973) and
625
Brindley and Kikkawa (1980). A similar observation of two
separate phases containing perchlorate and carbonate was made
by Brindley and Kikkawa (1979). Infrared spectroscopy was
used at this stage as a quick reference tool to identify the
interlayer anions in the synthetic hydrotalcites. This confirmed
the presence of the carbonate ion in the perchlorate system. A
similar observation was made in the infrared spectra of the ni-
trate-bearing hydrotalcite, which probably also explains the
slightly smaller 003 value and the broadening of the reflection
compared to that of the carbonate-containing hydrotalcite.
Opposite to these observations, the use of nitrate salts in the
case of the carbonate-containing hydrotalcite resulted in the
incorporation of a minor amount of nitrate as well, as was ear-
lier observed by Kloprogge and coworkers, (Hickey et al. 2000;
Kloprogge et al. 2000). Since this study is focused on the
interlayer region of the hydrotalcite, the variations in the chemi-
cal compositions of the hydroxide layers compared to their theo-
retical starting composition are small and insignificant and
therefore not reported here in detail. For example, the carbon-
ate containing hydrotalcite with a theoretical composition of
Mg6Al2(OH)16CO3◊nH2O) was determined to have a composi-
tion of Mg5.8Al2.2(OH)16(CO3)0.92(NO3)0.26◊nH2O.
Vibrational spectroscopy
Interlayer carbonate CO32–. The most commonly observed
interlayer anionic group in hydrotalcites, due to its strong af-
finity to the hydroxide layers, is CO32–. Compared to the free
anion in solution changes can be expected when the carbonate
ion is intercalated in the hydrotalcite structure as it will be ef-
fected by interactions with interlayer water molecules and/or
OH groups from the LDH layers. In comparison with free CO32–
a shift toward lower wavenumbers, a splitting of bands, and
the appearance of new bands should be observed (Nakamoto
1997). Interaction between interlayer water molecules and the
carbonate ion is reflected by the presence in the OH-stretching
region of the infrared spectrum around 3000–3100 cm–1 (see,
e.g., Kloprogge and Frost 1999a). This band has been attrib-
uted to the bridging mode H2O-CO32–. The shift toward lower
wavenumbers of the carbonate bands is an indication of a low-
∞2q
FIGURE 1. XRD patterns of hydrotalcite with (a) CO32–, (b) NO3–,
(c) ClO4– and (d) SO42–.
626 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS

ering of the symmetry from D3h to possibly C2v or Cs. The in-
frared spectrum of the carbonate-containing hydrotalcite clearly
shows an asymmetric broadening caused by the splitting of the
n3 mode around 1365 and 1400 cm–1 as shown by band compo-
nent analysis together with weak n2 and n4 modes around 870
and 667 cm–1 (Fig. 2). The n2 and n4 modes are often not ob-
servable due to strong overlap with vibrational modes of the
hydroxide sheets of the hydrotalcite. In addition to these three
IR active modes, the n1 mode is also activated and is observed
as a very weak band around 1012 cm–1. Table 3 gives an over-
view of all bands observed. Some papers have only reported
the activated n1 mode in combination with a single n3 band
(Labajos and Rives 1996; Labajos et al. 1996; Rousselot et al.
1999). In these cases the n3 vibrational mode seems to be broad-
ened due to an overlap of the two split modes n3 and n3a.
Rey et al. (1992) showed that upon heating Mg/Al-LDH to
100 ∞C the water-carbonate bridging mode around 3165 cm–1
disappeared together with the water-bending mode around 1616
Rel. Intensity
cm–1 as expected with dehydration. At the same time the rela-
tively broad carbonate n3 mode at 1363 cm–1 splits into two
bands around 1357 and 1391 cm–1 together with a strong sharp
band around 1538 cm–1 indicating a change in the carbonate
symmetry upon dehydration of the hydrotalcite. The authors
interpreted the split of the initial n3 as being the 1391 and 1538
band with a Dn3 of 147 cm–1. This might be due to the forma-
tion of a monodentate carbonate-metal complex with dehydra-
tion (Wijnja and Schulthess 2000).
Only a very limited number of Raman studies have been
reported so far on the interlayer carbonate anion in LDHs. The
Raman spectrum shows a very strong n1 mode at 1061 cm–1
plus weak n3 and n4 bands around 1403 and 695 cm–1 (Fig. 2).
These values agree well with those reported by Moroz and
Arkhipenko (1991). The n2 mode is not observed. The band at
1061 cm–1 shows an overlap with a strong band at 1053 cm–1.
This band is due to the incorporation of minor amounts of ni-
trate as a second interlayer anion due to the synthesis from
metal nitrates, which might explain not only the strong and
sharp 1053 cm–1 band, but also the sharp peak at 1385 cm–1 on
top of the 1403 cm–1 band. Similar to the infrared spectra, both
n3 and n4 bands show a minor shift of 10 to 15 cm–1 to lower
wavenumbers (Table 3). However, for the n4 mode in accor-
dance with the results of this study Kloprogge and Frost (1999a)
reported a minor sharp band at 694 cm–1, which indicates a

similar sized shift but in opposite direction. A reasonable ex-

planation for this band was given by Kagunya et al. (1998),
who showed the presence of a band at 698 and 695 cm–1 in the
Raman spectra of Mg/Al-LDHs associated with M-OH of the
hydroxide layer and CO32– as interlayer anion, respectively. They
assigned this vibration to the Eg(T) mode. This band will then
fully overlap the much weaker carbonate n4 mode. Detailed
examination of the 694 cm–1 band indicates a broadness sup-
porting an overlap between these two bands. Similarly, Kagunya
Wavenumber/cm–1
et al. (1998) gave an alternative assignment for the 1061 cm–1
FIGURE 2. Spectra of hydrotalcite containing CO32– (a) Raman, (b) band as the Eg(R) (OH) mode, which they observed in both the
IR. carbonate and the hydroxyl interlayered LDHs. A similar ob-
servation was made recently by Kloprogge et al. (2001) in par-
TABLE 3. Vibrational modes of free and interlayer CO32–, NO3–, tially deuterated hydrotalcites for the n2 mode which overlaps
SO42–, and ClO42– with both the n2 mode of the nitrate and a mode from the hy-
Free CO32– (Ross 1972) Observed in hydrotalcite droxide layer. Deuteration resulted in a clear separation of these
IR/cm–1 Raman/cm–1 IR/cm–1 Raman/cm–1 three bands. In addition partial deuteration seems to increase
n1 – 1063 1012 1053
n2 880 – 870 –
the symmetry again as the degeneracy of the n3 mode disap-
n3 1415 1415 1365/1400 1403 pears while the n4 mode disappears. Kloprogge et al. (2001)
n4 680 680 667 694 indicated a band at 1048 cm–1 that is more likely to be due to
Free NO3– the n1 mode of nitrate than to that of carbonate.
n1 – 1049 ? 1044 Based on X-ray diffraction, ionic size, and charge density,
n2 830 – 827 – it has been widely accepted that the orientation of the carbon-
n3 1350 1355 1360 1355
n4 680 690 667 712 ate anion within the interlayer space is such that its C3 axis is
perpendicular to the hydroxide sheets of the LDH (Alzamora
Free SO42–
n1 – 981 982 982
et al. 1981). Based on the observed shift and the facts that in
n2 – 451 ? 453 the infrared spectrum the n1 mode has become active and the
n3 1104 1104 1092/1144 1134? n3 mode is degenerate, while in the Raman spectrum nothing
n4 613 613 614 611
changed and the n2 mode remained inactive, it has to be con-
Free ClO4– cluded that the site symmetry of the carbonate anion bridged
n1 – 928 935 936 to interlayer water molecules and hydrogen bonded to the hy-
n2 – 460 – 461
n3 1128 1128 1096/1145 1110 droxyl groups of the hydrotalcite layers is lowered from D3h to C2v.
n4 645 645 626/635 626 Interlayer nitrate NO3–. After carbonate, nitrate is the sec-
 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS
ond mostly observed interlayer anion in hydrotalcites. Although
its symmetry in the free state is identical, the behavior of the
nitrate ion as an interlayer anion in hydrotalcite is different.
Firstly, the interaction with interlayer water is not directly ob-
served, as no nitrate-water bridging mode is present in the in-
frared spectrum. This is not unexpected as the nitrate ion is not
only larger than the carbonate ion, but it also has a lesser charge.
Although the hydrotalcite has incorporated some CO32– the in-
frared spectrum shows a very strong n3 mode at 1360 cm–1 with
a very weak n2 mode at 827 cm–1 (Fig. 3). The n4 mode is ob-
served at 667 cm–1, although it is largely obscured by the
hydrotalcite lattice modes. In contrast to the interlayer carbon-
ate the n1 mode is not activated, while the n3 mode shows no
degeneracy (Table 3).
In contrast to these observations Miyata (1975) reported a
complex spectrum with a weak n1 vibration around 1050 cm–1
together with split n2 and n3 modes. The n2 mode was observed
as two bands around 820 and 840 cm–1 while for n3 four bands
were observed around 1230, 1380, 1490, and 1690 cm–1. The
degenerate n3 mode was interpreted as belonging to two pairs
around 1390 and 1490 cm–1 and around 1230 and 1690 cm–1.
The splitting of approximately 100 and 460 cm–1 plus the much
lower intensity of the second pair was explained by attributing
the first pair to a majority of monodentate nitrate anions in the
interlayer together with a small amount of bidentate nitrate
anions. This however seems highly unlikely in the constrained
hydrotalcite interlayer space. Hernandez-Moreno et al. (1985)
also reported a split n2 mode around 840 and 825 cm–1 and n3
around 1425 and 1385 cm–1 for a Li/Al-layered double hydrox-
ide. The split of the n2 mode supports the vision of Miyata
(1975), but the presence of only two bands for n3 contradicts
this interpretation. An alternative explanation may be that the
840 cm–1 band, as argued above in the case of interlayer car-
bonate, is actually associated with the Eu(R) (OH) mode nor-
mally observed around 857 cm–1, thus leaving a single n2 mode
around 825 cm–1 plus a split n3 mode around 1425 and 1385
cm–1. This type of splitting of the n2 and n3 modes was not
observed in other studies. For example, Kagunya et al. (1998)
reported only two bands around 1000 and 1385 cm–1 as the
symmetric and antisymmetric anion modes, while López et al.
Rel. Intensity
Wavenumber/cm–1
FIGURE 3. Spectra of hydrotalcite containing NO3– (a) Raman, (b)
IR.
627
(1997) reported bands around 1382, 830, and 668 cm–1. The
Raman spectrum shows a strong band at 1044 cm–1 with a
weaker band at 712 cm–1 (Fig. 3). The n3 mode at 1355 cm–1 is
obscured by a broad band due to the presence of CO32–.
Based on the observations in this study, where no activa-
tion of the n1 or degeneracy of any other mode in the infrared
spectrum is observed, it has to be concluded that the nitrate
anion present in the interlayer of hydrotalcite does not seem to
change its symmetry. The shift of all the nitrate modes to slightly
lower wavenumbers might be explained by small interactions
with interlayer water molecules or the hydroxide layers of the
hydrotalcite which do not result in reduced symmetry. The split
of the n2 mode as observed in some studies (Hernandez-Moreno
et al. 1985; Miyata 1975) can clearly be explained by the over-
lap of this mode with a mode of the hydroxide layer of the
hydrotalcite. The presence of both bidentate and monodentate
nitrate in the interlayer of hydrotalcite seems very unlikely. An
alternative explanation not considered by Miyata (1975) might
be the presence of absorbed nitrate on the outer surface of the
crystals.
Interlayer sulfate SO42–. In naturally occurring hydrotalcite-
type minerals, in addition to the normally present carbonate
anion, sulfate forms an important second interlayer anion. Good
examples are honessite, hydrohonessite, and carrboydite (Bish
and Livingstone 1981; Nickel and Clarke 1976; Nickel and
Wildman 1981). Bish and Livingstone (1981) observed for
honessite the sulfate n1, n2, n3, and n4 modes at 980, 500, 1140,
and 650 cm–1, respectively. The n3 mode was clearly split but
no separate band positions were reported. The infrared spec-
trum of synthetic hydrohonessite was very similar to that of
naturally occurring honessite (Nickel and Wildman 1981). The
fact that all four modes are infrared active indicates that the
symmetry of the sulfate anion has been lowered from Td for the
free anion to C3 or C3v, which would result in activation of the
two infrared inactive modes plus splitting of the n3 mode (Ross
1972).
The infrared spectrum of synthetic Mg/Al-hydrotalcite con-
taining sulfate as the interlayer anion shows the presence of a
strong but broad n3 mode at 1126 cm–1, a n4 mode at 614 cm–1,
and a very weak n1 mode at 981 cm–1 (Fig. 4). The n2 mode in
contrast to honessite and hydrohonnesite, is not observed as a
separate band due to overlap with the O-M-O bending mode of
the hydroxide sheet at 450 cm–1 (Kloprogge et al. 2001). The
Raman spectrum is characterized by a very strong n1 mode at
982 cm–1 plus medium n2 and n4 modes at 453 and 611 cm–1,
respectively. The n3 mode cannot be identified as a separate
band, although a broad band can be seen around 1134 cm–1
(Fig. 4). This means that when sulfate is incorporated in the
interlayer space of hydrotalcite the infrared n2 mode might be-
come inactive, while the n1 mode is activated. In contrast to
the other modes n3 is much broader suggesting the presence of
two overlapping bands due to splitting. Band component analy-
sis indicates the presence of two bands at 1092 and 1144 cm–1
(Table 3).
Hernandez-Moreno et al. (1985) reported that for Li/Al-lay-
ered double hydroxides the n1 mode is observed around 985
cm–1 together with a split n3 mode around 1110 and 1160 cm–1,
and a n4 mode around 620 cm–1. The n2 mode was not reported
628 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS
Rel. Intensity
Wavenumber/cm–1
FIGURE 4. Spectra of hydrotalcite containing SO42– (a) Raman, (b)
IR.
as a separate band due to strong overlap with other lattice vi-
brations, although a minor band is shown in the spectrum near
465 cm–1. Several other studies of layered double hydroxides
show only a broad band around 1100-1150 cm–1 without vis-
ible splitting for the n3 mode, but still with all other three vi-
brational modes infrared active (Bish 1980; Kooli et al. 1993;
Lopez et al. 1997). This broadening was explained by López et
al. (1997) to be due to the presence of an overlap with the band
around 1059 cm–1 assigned to M-O vibrations. But after heat-
ing to 150 ∞C, where a differentiation is observed between the
lattice mode at 1023 cm–1 and the sulfate mode n3 around 1148
cm–1, no splitting of the n3 mode was observed. After heating
to 600 ∞C a shoulder was observed around 1162 cm–1 in addi-
tion to the strong major band around 1102 cm–1, proving the
presence of two initially similar strong overlapping bands.
Dutta and Puri (1989) observed three weak Raman bands
around 457, 467, and 620 cm–1 plus two bands at 986 and 1116
cm–1 (broad) for the sulfate anion in a Li/Al-layered double
hydroxide compound. The splitting of n2 and the broadening
of the antisymmetric stretching mode n3 indicate a significant
symmetry lowering. Dutta and Puri (1989) suggested D2 which
is however not compatible with the infrared data where all four
bands have been observed. For similar reasons the C3 site sym-
metry as suggested by Bish (1980) is not compatible with the
Raman data. Therefore, based on combined observations in both
the infrared and Raman spectra the conclusion has to be that
the site symmetry is most probably C2v with n1 infrared and
Raman active, n2 infrared and Raman active, and n3 and n4 in-
frared and Raman active.
Interlayer perchlorate ClO4–. The free ClO4– anion is, in
terms of structure and symmetry, quite similar to the SO42– an-
ion. However, the ClO4 tetrahedron is very easily distorted re-
sulting in activation of the n1 mode in the IR spectrum, while
n3 and n4 are often split (Ross 1972). This distortion is clearly
reflected in the IR spectrum of the perchlorate-bearing
hydrotalcite with both the n3 and n4 modes showing degen-
eracy with maxima around 1096 and 1145 cm–1 and around
626 and 635 cm–1 (Fig. 5). A very small n1 mode is observed
around 935 cm–1. The corresponding Raman spectrum (Fig. 5)
shows a very strong and shifted n1 mode at 936 cm–1, com-
pared to 928 cm–1 for the free anion, plus n2 and n4 modes at
Rel. Intensity
Wavenumber/cm–1
FIGURE 5. Spectra of hydrotalcite containing ClO4– (a) Raman, (b)
IR.
461 and 626 cm–1, respectively. The n3 mode cannot be clearly
recognized, but a broad and complex band is visible around
1110 cm–1 (Table 3).
Miyata reported for perchlorate-bearing hydrotalcite n1 and
n2 modes around 943 and 476 cm–1, while n3 was split into four
bands at 1150, 1126, 1112, and 1095 cm–1. He was not as sure
about n4 splitting into two or three bands around 640 and 629–
633 cm–1. Based on the observed band positions and splitting
in comparison to those of [Cu(biph)SO4] he concluded that the
perchlorate ion has to be present as a bridging-type bidentate.
It has been shown for several of these types of compounds that
the strength of the n1 mode, the band positions, and the size of
the splitting are not necessarily proof for the presence of mono-
or bidentate ligands as chelate or bridging types (Ross 1972).
Based on the quality of the spectrum presented the splitting,
especially of the n4 mode, is questionable, but one can con-
clude that the site symmetry of the perchlorate has been low-
ered upon intercalation in the interlayer of hydrotalcites due to
distortion of the free perchlorate tetrahedron. This will then
lead to activation of the n1 and n2 modes and splitting of the
other two modes.
Brindley and Kikkawa (1980) have reported the exchange
of carbonate by perchlorate in hydrotalcite by treatment with
perchloric acid. At high crystallinity they observed a larger basal
spacing indicating the presence of water molecules associated
with the perchlorate ions in the interlayer. Drying resulted in a
decrease in basal spacing. Although they did not give a de-
tailed description of the corresponding infrared spectra, some
general observation can be made. In the most crystalline mate-
rial a band observed around 1100 cm–1 was ascribed to the per-
chlorate n3 mode. This band is accompanied by a shoulder
around 1150 cm–1 indicating that the mode is split. The n1 mode
is very weak and hardly visible while the n4 mode gives a clear
peak around 630 cm–1 together with a very strong peak at 450
cm–1, which can be ascribed to the n2 mode overlapping with a
hydroxide lattice bending mode (O-M-O) of the hydrotalcite.
Symmetry lowering is due not only to the distortion of the
perchlorate itself but also because of the loss of freedom in the
confined interlayer space of the hydrotalcite structure that re-
sults in activation of the n1 mode. In addition, the n2 mode is
probably also activated based on limited literature observations
 KLOPROGGE ET AL.: INFRARED AND RAMAN STUDY OF INTERLAYER ANIONS
and a degeneracy of the n3 mode in the infrared spectrum while
a clear shift of the n1 is observed in the Raman spectrum. This
is indicative of a site symmetry and point group lowering from
Td for the non-distorted free anion to Cs with a perchlorate struc-
ture in which two oxygen atoms are symmetrical toward each
other with respect to the chloride cation while the other two
oxygen atoms are considered to be non-symmetrical.
ACKNOWLEDGMENTS
The financial and infra-structural support of the Queensland University of
Technology Centre for Instrumental and Developmental Chemistry is gratefully
acknowledged.
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MANUSCRIPT RECEIVED DECEMBER 15, 2000
MANUSCRIPT ACCEPTED DECEMBER 18, 2001
MANUSCRIPT HANDLED BY JAMES KUBICKI