Solid State Ionics 120 (1999) 189–195

Polymerization of aniline in the galleries of layered HNbMoO 6

a a b b a,
Hyo-Jin Nam , Hongdoo Kim , Soon Ho Chang , Seong-Gu Kang , Song-Ho Byeon *
a
Department of Chemistry, College of Natural Sciences, Kyung Hee University, Kyung Ki 449 -701, Korea
b
Electronics and Telecommunications Research Institute, P.O. Box 106, Yusong, Taejon, 305 -600, Korea
Received 25 June 1998; accepted 21 October 1998

Abstract

Insertion of aniline molecules and subsequent polymerization using FeCl 3 as an oxidizing agent were examined in the
layers of rutile-type HNbMoO 6 . Although the polyaniline / host ratio was variable depending on the amount of intercalated
˚ regardless of the ratios. Comparison of FT-IR
aniline before polymerization, the interlayer spacing was constant as | 6.3 A
and FT-Raman spectra for (PANI) y NbMoO 6 (0.26 # y # 0.64) clearly showed that both quinoid and benzenoid forms exist
in the galleries of inorganic host. IR and Raman active modes of extracted PANI from the matrix were quite similar to those
of emeraldine salt.  1999 Elsevier Science B.V. All rights reserved.

Keywords: Polyaniline; Organic / inorganic hybrid; Rutile-type oxide; Polymerization

1. Introduction prepared in a channel of mesoporous host MCM-41

Chemical or electrochemical oxidative polymeri-
zation of aniline in aqueous acid solutions is of
practical importance for energy storage, electronic
and optical devices [1–4]. To develop a model for
the interpretation of physical properties of polymers,
the confined conducting polymers have been investi-
gated in suitable inorganic layered hosts such as
FeOCl, V2 O 5 xerogel, MoO 3 , Zr(HPO 4 ) 2 ? H 2 O,
HUO 2 PO 4 ? 4H 2 O, HCa 2 Nb 3 O 10 , and ZrO 2 [5–11].
Recently, conducting filament of polyaniline was
*Corresponding author. Tel.: 1 82-331-201-2457; fax: 1 82-
331-202-7337.
E-mail address: shbyun@nms.kyunghee.ac.kr (S.-H. Byeon)
[12]. In the course of searching for other host
materials with different structure, the polymerization
was explored in the gallery of a rutile-type oxide.
The layered host HMM9O 6 ? H 2 O, prepared by
proton exchange of trirutile-type LiMM9O 6 [13] in
dilute acidic solution, is one of the strong solid
Brønsted acids intercalating diverse organic bases
[14]. Host materials of this type and their amine
intercalates also show an interesting second har-
monic generation (SHG) response [15]. In this
report, we describe the intercalation behavior of
aniline in the layered HNbMoO 6 ? H 2 O and sub-
sequent polymerization yielding a new organic / inor-
ganic hybrid material. Since this host material does
not have a sufficient oxidizing power to initiate,

0167-2738 / 99 / $ – see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S0167-2738( 99 )00002-8
190 H. Nam et al. / Solid State Ionics 120 (1999) 189 – 195

FeCl 3 was used to polymerize the intercalated aniline to obtain FT-IR spectra. Only 5 mW power at 1064
monomer. nm as exciting laser source was used to minimize the
local heating during FT-Raman measurement.

2. Experimental
3. Results and discussion
LiNbMoO 6 were prepared by air-quenching at
6008C according to the literature [14]. The proton- LiMM9O 6 oxides, shown in Fig. 1a, crystallize in
exchange reaction of this parent oxide in 2 N HNO 3 trirutile-type structure in which there is a partial
solution at room temperature gave the host materials, disorder between M(V) and M9(VI) ions but Li(I)
HNbMoO 6 ? H 2 O, in 2 days. The water of hydration ions are ordered in every three layers perpendicular
was lost at around 2308C, giving anhydrous phase to the c axis [17]. The lithium ion in these layers is
HNbMoO 6 . The aniline molecules were inserted by topochemically exchanged with proton in acidic
stirring HNbMoO 6 ? H 2 O in neat aniline for 1 week. solutions to yield a layered HMM9O 6 ? nH 2 O. As
The intercalation products were filtered, washed with shown in Fig. 1b, the proton exchange induces a c
absolute ethanol, and dried in air or in vacuum. The axis doubling by 1 / 2 displacement of the adjacent
aniline / host ratio was in the range of 0.3–0.7 MM9O 6 slabs along [110] direction. In this work,
depending on the washing and drying condition. For MM9 5 NbMo pair was selected as a host material.
example, when the filtered aniline intercalate is
washed with ethanol 3–5 times and dried in air, the
aniline / host ratio is | 0.7. If it is dipped into ethanol
for more than 20 min or dried in vacuum, the
aniline / host ratio is | 0.3. Under intermediate con-
ditions, 0.3–0.7 of the ratio can be obtained. The
polymerization of intercalated aniline was explored
by a treatment of (ANI) x H 12x NbMoO 6 ? H 2 O
(ANI 5 aniline, 0.30 # x # 0.70) with several oxi-
dizing agents for 2 h. Due to the liberation of a large
amount of heat at the beginning of the oxidation
process [16], the initial addition of oxidizing agents
was carried out under ice-cooled condition. During
the reaction in an aqueous solution of FeCl 3 or
K 2 S 2 O 8 , the monomer intercalates turned from
yellowish-white to greenish-black. On the contrary,
they turned black upon treatment with (NH 4 ) 2 S 2 O 8
solution. Final greenish-black or black powder was
filtered, washed with water, and dried. To extract
polyaniline from the inorganic host, this powder was
dissolved in HF solution for more than 2 weeks. The
amounts of intercalated aniline and polyaniline in the
galleries of host were determined by thermogravi-
metric analysis (TGA). Scanning electron micro-
scopy (SEM) was used for the observation of surface
change before and after polymerization. The change
of basal spacing during intercalation and subsequent
polymerization was confirmed by powder X-ray Fig. 1. Idealized structure of (a) LiNbMoO 6 and (b)
diffraction (XRD). Samples were run as CsI pellets HNbMoO 6 ? H 2 O.
 H. Nam et al. / Solid State Ionics 120 (1999) 189 – 195 191

Table 1
Comparison of the aniline / host and polyaniline / host ratio, c-parameter, and interlayer distance for (ANI) x H 12x NbMoO 6 ? H 2 O and
(PANI) y NbMoO 6
Aniline / host ratio ˚
c (A) ˚
Dc (A)
a
Polyaniline / host ratio ˚
c (A) ˚
Dc (A)
a

0.30 17.10 6.40 0.26 16.93 6.23

0.47 18.40 7.70 0.41 16.99 6.29
0.70 22.89 12.19 0.64 16.98 6.28
a ˚ of anhydrous HNbMoO 6 due to a c axis doubling of the pristine host [14].
Dc was calculated by using the c / 2(10.70 A)

The powder X-ray diffraction patterns of aniline
intercalates are compared with that of the host
HNbMoO 6 ? H 2 O in Fig. 2. While the (110) reflec-
tion determining the a-parameter of tetragonal unit
cell is constant for all aniline intercalates (a | 4.70
Fig. 2. Powder X-ray diffraction pattern of (a) pristine host
HNbMoO 6 ? H 2 O, (b) (ANI) 0.30 H 0.70 NbMoO 6 ? H 2 O, (c)
(ANI) 0.47 H 0.53 NbMoO 6 ? H 2 O, (d) (ANI) 0.70 H 0.30 NbMoO 6 ? H 2 O,
and (e) (PANI) y NbMoO 6 . Although y values depend on the
amount of intercalated aniline before polymerization, no differ-
ence was observed in XRD patterns of (PANI) y NbMoO 6 with
different y values.
˚ a systematic shift of (00l) reflection is observed
A),
as a function of the aniline / host ratio. Estimated
c-parameters and interlayer distances of intercalates
with different guest / host ratios are listed in Table 1.
As the aniline / host ratio of hybrid increases, the
c-directional axis gradually expands up to 22.89 A. ˚
Compared with that of the anhydrous HNbMoO 6
[14], the additional expansion of the c axis is 12.19
Å when the aniline / host ratio is about 0.70. This
expansion is similar to those found in aniline interca-
lates of TaS 2 [18], Zr(HPO 4 ) 2 ? 2H 2 O [8], and
HCa 2 Nb 3 O 10 [10], suggesting a bilayer arrangement
of aromatic rings with perpendicular orientation to
the host slabs. With the aniline / host ratio 0.30, the
interlayer spacing increment is only 6.40 A, ˚ which is
consistent with a monolayer arrangement of interca-
lated aniline perpendicular to the host slabs. With
different class of host materials such as V2 O 5 xerogel
[6] and MoO 3 [9], the expansion of 6–7 A ˚ is
observed upon intercalation of aniline. Intermediate
expansions observed in those of 0.30 , aniline / host
ratio , 0.70 reveal the change of molecular arrange-
ment from monolayer to bilayer arrangement with
increasing the amount of intercalated aniline. A
similar change in arrangement of guest molecules
was observed when the intercalated molecules are
partially removed from the host [19].
For the polymerization of intercalated aniline
monomers, an aqueous solution of (NH 4 ) 2 S 2 O 8 is
generally used as an oxidizing agent. When this
solution was used in our work, the XRD pattern of
black product gave a new c parameter of | 14 A. ˚
Such a lattice parameter is contributed by an expan-
˚ for one interlayer spacing with
sion of | 3.3 A
respect to the anhydrous HNbMoO 6 . This amount of
expansion would be insufficient even for a coplanar
arrangement of polyaniline because of non-zero
192 H. Nam et al. / Solid State Ionics 120 (1999) 189 – 195
dihedral angle between aromatic rings 1 . As shown in
Fig. 3b–d, furthermore, a strong band was observed
at 1401 cm 21 in FT-IR spectra of the products after
polymerization of (ANI) x H 12x NbMoO 6 ? H 2 O using
(NH 4 ) 2 S 2 O 8 solution. Such a band is absent in the
IR spectrum of bulk polyaniline (Fig. 3f) but ob-
served in NH 4 NbMoO 6 ? H 2 O (Fig. 3e) which is
obtained by a treatment of HNbMoO 6 ? H 2 O host
with NH 4 Cl solution. This band is accordingly
assigned to a bending mode of NH 1 4 . Such a
comparison suggests that an addition of (NH 4 ) 2 S 2 O 8
Fig. 3. FT-IR spectra of (a) pristine host HNbMoO 6 ? H 2 O, the
product after polymerization of (b) (ANI) 0.30 H 0.70 NbMoO 6 ? H 2 O,
(c) (ANI) 0.47 H 0.53 NbMoO 6 ? H 2 O, and (d)
(ANI) 0.70 H 0.30 NbMoO 6 ? H 2 O when (NH 4 ) 2 S 2 O 8 solution was
used as an oxidizing agent, (e) NH 4 NbMoO 6 ? H 2 O, and (f) bulk
PANI (emeraldine salt).
1
Considering van der Waals radius of carbon atom (1.65–1.70 A), ˚
an expected minimum expansion is close to 3.35 A ˚ even for a
parallel orientation of aromatic rings in an ideally flat layer.
solution induced an ion-exchange reaction between
ammonium and anilinium ions before polymeriza-
tion. It is thus evident that actual polymerization
occurred in the surface rather than in the layer of
host.
In order to avoid such an exchange reaction, the
polymerization in this work was therefore carried out
with an aqueous solution of FeCl 3 . In contrast to
black bulk polyaniline, the aniline intercalates turned
from yellowish-white to greenish-black in color
during polymerization. The different electronic ab-
sorptions are related to polyaniline form of different
chain lengths and levels of protonation [20]. There-
fore, it is inferred that the degree of protonation in
the proton rich layer is different from that in the
bulk. Compared with those of aniline monomer
intercalates, much smaller weight loss below
| 2008C for polyaniline intercalates indicated that
almost all water molecules in the host were expelled
from the interlayer spaces upon polymerization.
Total weight loss in TG analysis gave the PANI / host
ratio (PANI 5 polyaniline) in the range of 0.26–0.64
(Table 1). These values are determined as a function
of the amount of intercalated aniline monomers. It is
interesting, however, that the X-ray diffraction pat-
terns of polyaniline intercalates are independent of
the PANI / host ratio as shown in Fig. 2e. A derived c
parameter ( | 17 A)˚ was common for all y values of
(PANI) y NbMoO 6 . Such a value results from an
expansion of | 6.3 A ˚ for one interlayer spacing with
respect to the anhydrous HNbMoO 6 . This interlayer
spacing is close to those reported for PANI-V2 O 5
(5.19 A)˚ [6], PANI-MoO 3 (6.7 A) ˚ [9], and PANI-
˚
HCa 2 Nb 3 O 10 (5.3 A) [10]. The interlayer distance of
|6 A ˚ in these hybrids was explained by a model that
polyanilines are intercalated with their aromatic rings
roughly perpendicular to the inorganic slabs. A
similar model could be suggested for the polyaniline
intercalates in this work. Such a behavior was
generally observed for the same family of host
materials such as HNbWO 6 ? nH 2 O, HTaMoO 6 ?
nH 2 O, and HTaWO 6 ? nH 2 O.
Fig. 4 shows FT-IR spectra of
(ANI) x H 12x NbMoO 6 ? H 2 O, (PANI) y NbMoO 6 , ex-
tracted PANI from (PANI) y NbMoO 6 , and chemically
synthesized PANI in the bulk. The spectra of aniline
 H. Nam et al. / Solid State Ionics 120 (1999) 189 – 195
Fig. 4. FT-IR spectra of (a) pristine host HNbMoO 6 ? H 2 O, (b)
(ANI) 0.30 H 0.70 NbMoO 6 ? H 2 O, (c) (ANI) 0.70 H 0.30 NbMoO 6 ? H 2 O,
(d) (PANI) 0.26 NbMoO 6 , (e) (PANI) 0.64 NbMoO 6 , (f) extracted
PANI from (PANI) 0.26 NbMoO 6 , (g) extracted PANI from
(PANI) 0.64 NbMoO 6 , and (h) bulk PANI (emeraldine salt).
intercalates show a characteristic sharp absorption
band at 1495 cm 21 of anilinium ions [20] whose
relative intensity with respect to those of host is
dependent on the degree of intercalation. The spectra
of (PANI) y NbMoO 6 show the vibrations at around
1559, 1473, 1305, 1138 cm 21 indicating an existence
of emeraldine salt [21]. The relative band intensities
are also dependent on the amount of polyaniline in
the layer. However, their shapes and frequencies are
not identical to those of bulk PANI. This is likely
due to a difference in orientation and protonation of
polymer chain between in confined proton rich space
and in open space. FT-IR spectra of extracted
products are virtually identical to that of bulk
emeraldine salt.
Additional evidence of the emeraldine unit in
193
Fig. 5. FT-Raman spectra of (a) (ANI) 0.70 H 0.30 NbMoO 6 ? H 2 O, (b)
(PANI) 0.26 NbMoO 6 , (c) (PANI) 0.64 NbMoO 6 , (d) extracted PANI
from (PANI) 0.26 NbMoO 6 , (e) extracted PANI from
(PANI) 0.64 NbMoO 6 , and (f) bulk PANI (emeraldine salt).
inorganic host derives from FT-Raman spectra (Fig.
5). Five Raman bands at 1300–1400 and about 1506
cm 21 are characteristic of the protonated conductive
form of polyaniline and the band at about 1171 cm 21
corresponds to C–H in-plane bending [22,23]. The
spectral positions are shifted depending on the
excitation wavelength because of different resonance
conditions [24]. The spectra of (PANI)y NbMoO 6
show strong bands at around 1619, 1585, 1498,
1375, 1344, 1167 cm 21 , which are indicative of the
emeraldine salt. Similar to IR spectra, however, their
shapes and frequencies are different from those of
bulk PANI.
According to Quillard et al. [25], C–H bending
mode at 1188 cm 21 and C–C stretching vibration
mode at 1621 cm 21 were attributed to the benzenoid
194 H. Nam et al. / Solid State Ionics 120 (1999) 189 – 195
Fig. 6. Schematic presentation of the arrangement of intercalated
(a) anilines and (b) polyanilines in the galleries of host.
form of PANI whereas the quinoid form gave 1166
cm 21 of C–H bending and 1581 cm 21 of C=C
stretching mode. Fortunately, our FT-Raman spectra
of PANI in layered host are well resolved as shown
in Fig. 5b and c and clearly indicate that both
quinoid and benzenoid forms exist inside the host.
This observation may be mainly due to two dimen-
sional confinement of polyaniline as well as the
higher degree of protonation inside of the host rather
than in bulk. After PANI is extracted from the
matrix, the observed spectra would be the same as
that of the bulk. The active modes of extracted PANI
from the matrix (Fig. 5d and e) are indeed quite
similar to those of emeraldine salt (Fig. 5f).
The four-probe conductivity of pressed
(PANI) y NbMoO 6 was around 10 25 S / cm which is
about five orders of magnitude lower than that for
bulk PANI. In contrast, the extracted PANI had a
room-temperature conductivity of 10 22 S / cm. This
result is consistent with the intercalated model of
PANI in an insulating two-dimensional host. Similar
behavior is observed in most of the PANI / inorganic
hybrids [6,9,10,12]. Scanning electron microscope
(SEM) images of polyaniline intercalates also
showed a clean plate-like crystal morphology with
no amorphous impurities that could be attributed to
the polyaniline in the surface of crystal.
4. Conclusion
We have shown that HNbMoO 6 ? H 2 O of rutile-
derivative structure is one of the host materials to
intercalate polyaniline within its galleries. A plaus-
ible arrangement of aniline molecules, which de-
pends on the guest / host ratio, is proposed in Fig. 6a.
Based on the XRD, FT-IR, and FT-Raman data, the
emeraldine salt form of PANI in the interlayer spaces
of the host is rearranged as shown in Fig. 6b
regardless of the guest / host ratios. Such an orienta-
tion is general in most PANI / layered inorganic
hybrids.
Acknowledgements
This work was supported by Kyung Hee Universi-
ty and Ministry of Education (BSRI-97-3421).
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