Ceramics International xxx (xxxx) xxx–xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

One-pot synthesis of zinc oxide - polyaniline nanocomposite for fabrication

of efficient room temperature ammonia gas sensor
⁎
Mausumi Das, D. Sarkar
Department of Physics, Gauhati University, Guwahati 781014, Assam

A R T I C L E I N F O A BS T RAC T

Keywords: Development of efficient room temperature ammonia (NH3) gas sensor from one pot synthesized zinc oxide
Zinc oxide (ZnO) – polyaniline (PANI) nanocomposite is reported in the present article. Prior to gas sensing study, the
Polyaniline material is characterized to understand the structural, morphological, compositional, optical and thermal
Nanocomposite properties. Structural and morphological studies indicate good incorporation of ZnO particles in PANI matrix.
Ammonia sensor
The gas sensing efficiency of ZnO-PANI nanocomposite is examined at room temperature for ethanol
(C2H5OH), methanol (CH3OH) and NH3 gas. The results confirm that ZnO-PANI nanocomposite to be highly
selective for NH3 with fast response time and better stability. The response and recovery times are observed to
be significantly dependent on NH3 concentration and the lowest detectivity limit of the sensor for NH3 is found
10 ppm. ZnO-PANI nanocomposite shows better gas sensing efficiency as compared to the sensors developed
from single phase PANI film.

1. Introduction
Ammonia (NH3) is one of the major toxic pollutants which are
widely used in chemicals, fertilizers, material processing, refrigeration
etc [1–4]. The presence of NH3 in the environment might affect
respiratory and cardiac systems of human body. So its detection in
presence of other gases in environment and industry is of utmost
requirement. This can be fulfilled by a highly selective and sensitive
NH3 gas sensor. To develop a sensitive gas sensor, one requires the
materials with high surface area (to provide larger surface for gas
exposure), high flexibility and tuneable properties. Conducting poly-
mers (CP) like polyaniline (PANI), polypyrrole (PPy) etc. meet these
requirements to a large extent. For this reason, these types of materials
get utmost attention in terms of development of gas sensors. Properties
which are particularly to be looked into are: tuneable electrical
conductivity, redox property and fair stability at the ambient [5].
Generally CP molecules have planar structure, i.e., have much larger
surface area compared to thickness. This is very essential for a highly
sensitive gas sensor to lower the response time and detection limit. The
surface area and morphology of CPs can be easily tuned by changing
the dopant species [6]. Polyaniline (PANI) is one of the most important
conducting polymers which show excellent environment stability, ease
of polymerization [7] and tuneable electrical and optical properties
[8,9]. However, poor mechanical strength [10] is always an issue with
PANI which in turn results in comparatively low response and lack of
specificity. Doping with various organic and inorganic material have
shown to reduce these problems by increasing its mechanical strength
and creating more active sites by changing its structure [11]. In the
present work, we have chosen an inorganic material, ZnO to incorpo-
rate in PANI matrix to fabricate the sensor.
The choice of ZnO arises from the fact that the material has received
much attention in recent years due to its direct wide band gap (Eg =
3.4 eV), large exciton binding energy (~60 meV), biocompatibility,
nontoxicity, high chemical stability, high electron transfer capability
and good mechanical strength [12–15]. However, there are some
disadvantages with this material too when used as gas sensors. ZnO
sensor is efficient at moderately high temperature (350–450 °C), not
that effective at room temperature. High temperature reduces the
sensor life and involves larger power consumption [16]. So, it is very
much desirable to develop a gas sensor that operates at room
temperature. Apart from this, the material should have good mechan-
ical strength to ease operational requirement and to increase the sensor
life. Hybrid materials like organic (CP) and inorganic (metal oxide)
composites are currently of great interest for exploring enhanced
sensor characteristics. On combining these, one achieves not only the
advantageous properties of individual materials, but also many other
unique characteristics specific to the composite. Ample works in this
direction are already in progress, to cite a few, Tai et al. developed
PANI-TiO2 composite film for gas sensing [17], Sadek et al. developed
an acoustic wave gas sensor based on PANI/In2O3 composites [18] and

⁎
Corresponding author.
E-mail address: sarkardeepali@gmail.com (D. Sarkar).

http://dx.doi.org/10.1016/j.ceramint.2017.05.159
Received 14 December 2016; Received in revised form 19 May 2017; Accepted 22 May 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Das, M., Ceramics International (2017), http://dx.doi.org/10.1016/j.ceramint.2017.05.159
M. Das, D. Sarkar
Gong et al. prepared PANI-TiO2 fibres to study NH3 gas sensing [19].
Still, lot remain to be explored. Keeping these in mind, an effort has
been made to develop a room temperature ammonia sensor based on
ZnO-PANI composite film by preparing ZnO in PANI matrix in-situ.
Composite films of PANI are prepared for four different Zn source
concentrations viz., 0.001 M, 0.01 M, 0.05 M and 0.1 M. We are
encouraged by our earlier study on ZnS-PANI composites which shows
tailoring properties by incorporation of different Zn concentrations
[20]. Apart from the gas sensing study, the structural, morphological,
optical and thermal properties of the synthesized composites are also
carried out using XRD, TEM, EDAX, UV–Vis absorption spectroscopy
and TGA techniques respectively.
2. Experimental details
2.1. Materials used
Materials used for the synthesis of the composite are: aniline,
Dodecyl benzene sulphonic acid (DBSA) as dopant as well as surfac-
tant, ammonium per sulphate (APS) as oxidant, zinc acetate [Zn
(O₂CCH₃)₂] as Zn source and sodium hydroxide (NaOH) as oxygen
source. Aniline is obtained from SD Fine Chemicals limited, DBSA
from Sigma-Aldrich (India), APS from Fisher Scientific (India), zinc
acetate and sodium hydroxide are from Merck (India). Aniline is
vacuum distilled repeatedly prior to use. All the other reagents are of
high purity (99.9%) and are used without further purification.
Deionised water is used as solvent throughout the reaction process.
2.2. Synthesis procedure
ZnO doped PANI composite is prepared by synthesizing ZnO from
co-dispersion of Zn and O sources in the same pot which has been used
for polymerization of aniline. To be specific about the reaction process,
to10 ml of aqueous HCl (1 M) solution of 0.1 M of DBSA is added and
stirred for 2 h. To this 0.2 M of aniline and HCl aqueous solution are
added and the resultant mixture is stirred for another 2 h. 0.25 M APS
solution is then added to the DBSA/aniline solution. The colour of the
solution changes from white to green indicating PANI formation. In the
same solution, Zn Acetate (0.1 M) and NaOH (0.1 M) are added and
stirred for 2 more hours to get the precipitate of ZnO-PANI composite.
The precipitate is washed with deionised water, methanol and finally
with acetone for several times to remove any impurities and residual
unreacted monomers present. The synthesis process is repeated for
three other concentrations of Zn-acetate (0.05 M, 0.01 M and 0.001 M)
keeping the concentration of NaOH constant. Films are spin cast from
the solution of the composite, dried and set for various studies.
2.3. Characterization techniques
The composite films are characterized by XRD, UV–Visible spectro-
scopy, TEM and EDAX respectively for structural, optical, morpholo-
gical and chemical species identification. The gas sensing behaviour is
studied through measurement of change in resistance of the film on gas
intake. X-ray diffraction (XRD) studies are carried out using a Philips
powder X-ray diffractometer (Model: Xpert PRO phillips). The XRD
patterns are recorded in the range of 2ϴ value of 10–80° with step
width of 0.02 using CuKα radiation (λ = 1.5406 A°). The UV–Visible
absorption spectroscopic studies are done by CARY (model 300)
spectrophotometer in the wavelength range of 400–900 nm.
Morphological study is carried out using transmission electron micro-
scopy (TEM Model: JEOL JEM 2100) with electron accelerating
voltage of 200 kV. Elemental compositional analysis is assigned by
energy dispersive analysis of X-ray (EDAX Model: Oxford INCA 350).
Thermogravimetric analyses are done by STA 6000. Gas sensing
studies are done by measuring change in resistance using Keithley
Source meter (Model: 2400).
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Fig. 1. XRD patterns of (a) ZnO, (b) PANI and (c) ZnO-PANI composite.
3. Results and discussions
3.1. Structural properties (XRD)
Fig. 1 shows XRD patterns of PANI, ZnO and PANI-ZnO nano
composites. For PANI, characteristic diffraction peak is observed at 2ϴ
value of 25° corresponding to the diffraction from (110) planes
resulting due to periodicity of the PANI chain [21–25]. On ZnO
incorporation, XRD spectra show peaks for both PANI and ZnO.
Further, the peaks are shifted a little towards higher 2ϴ value and
the intensity is enhanced on ZnO incorporation. Shift in peaks and
change in intensity of the peaks may be a consequence of the change in
bond length and bond stretching in the composite. This indicates that
the in-situ formed ZnO are well incorporated into the polymer matrix
[26]. The d-spacing (d) corresponding to the most intense peak (first
order diffraction) is calculated by using Bragg's equation [27] for n=1
d = λ /(2 Sin θ ) (1)
The calculated value of d-spacing is found to decrease with increase
of concentration of Zn in PANI matrix. During dispersion polymeriza-
tion, the polymer chains are expected to be in closer proximity resulting
to a lower value of lattice spacing. The degree of crystallinity (Cr %) of
the samples is calculated from the ratio of crystalline peak area to the
total peak area. Degree of crystallinity is found to increase from 25% to
69% with increase of Zn source concentration from 0.001 to 0.1. The
higher the degree of regularity in the arrangement and ordering of the
polymer chains, the higher is the degree of crystallinity. The inter-chain
separation length (R) corresponding to the most intense peak of the
prepared sample is calculated from the relation given by Klug and
Alexander [28].
R = 5λ /(8 Sin θ ) (2)
Inter-chain separation length is observed to decrease with increas-
ing Zn concentration. This fact ascertains that the polymer chains are
more compact and close for the highest Zn concentration in PANI, the
compactness decreases with decrease of Zn concentration and ulti-
mately attains the minimum value for PANI without ZnO incorpora-
tion. With the decrease in d-spacing and interchain separation, the
probability of interchain hopping in the composite is increased [29].
Calculated d spacing (d), inter-chain separation length (R) and degree
of crystallinty (Cr %) are listed in Table 1.
3.2. Optical properties
Optical properties of the materials are studied through UV–Visible
absorption spectra for the wavelength range of 300–900 nm. Fig. 2
shows the absorption spectra of PANI doped with ZnO for (a) 0.001 M,
(b) 0.01 M, (c) 0.05 M and (d) 0.1 M of Zn source concentrations. The
M. Das, D. Sarkar Ceramics International xxx (xxxx) xxx–xxx

Table 1
d-spacing (d), inter-chain separation length (R), degree of crystallinty (Cr%), band gap and elemental composition for PANI and ZnO-PANI nanocomposites.

Sample Name Position of most d-spacing (in Inter-chain separation Degree of crystallinity Band gap Elemental composition (%)
intense peak (2ϴ) Ǻ) length (R) (in Ǻ) (Cr%) (in eV) from EDX analysis

C- 76.35

PANI 25.09 3.54 4.43 – 2.51 O- 10.56

N- 5.06
S- 8.03
ZnO-PANI (Zn 34.54 2.59 3.24 45 2.92 –
0.001 M)
ZnO –PANI (Zn 34.68 2.58 3.22 58 3.01 –
0.010 M)
ZnO –PANI (Zn 34.72 2.57 3.20 62 3.09 –
0.050 M)

ZnO –PANI (Zn C- 68.26

0.100 M) 34.80 2.56 3.19 69 3.11 O- 13.56

N- 8.06
Zn- 10.12

absorption spectrum for PANI shows peaks at 363, 451, and 810 nm
attributed to π-π* transition within benzenoid segments [30], polaron-
π* transition and π-polaron transition respectively [11,31]. In ZnO-
PANI (0.1 M) the peaks occur at 343, 430 and 800 nm. Such shift could
be attributed to energy confinement produced from surface plasmon-
excitation in ZnO-PANI composite [32]. The enhancement in intensity
of the polaron peak says about the enhancement of doping of PANI on
ZnO incorporation as polaron peak in PANI type of CP comes due to
moderate doping. The optical band gaps Eg of PANI and the composite
films are estimated from the plots of (αhν)2 vs hν using Tauc's relation
[33].
(αhν ) = k(hν − Eg)1/2
where hν is the energy of the incident light and k is a constant.
Intercept of the linear part of the αhν vs hν curve on the x-axis gives the
value of Eg. The Tauc plots for PANI and ZnO-PANI nanocomposites
are shown in Fig. 3. The calculated band gaps are also shown in
Table 1. Fig. 4 shows the variation of band gap of the composites with
Zn concentration. Band gap increases nearly exponentially with
increase of Zn concentration to saturate beyond 0.05 M concentration.
So, we can claim that ZnO incorporation leads to tune the band gap of
PANI. This in turn has correlation with particle size obtained from the
TEM micrographs detailed in the subsection to follow.
3.3. Morphology and elemental study
Fig. 5(a–e) shows the TEM micrographs of PANI and ZnO-PANI
composites. The effect of Zn incorporation in PANI matrix is very clear
from these TEM images. The nanoparticles appear to be of spherical
shape with average particle size in the range of 25–7 nm for undoped
to the highest ZnO doped PANI. That is, the particle size decreases with
increase in Zn concentration. One of the reasons for such behaviour in
the composites lies in the fact that the in-situ formed ZnO which is
known to have negatively charged surface has more affinity towards
PANI which is known to possess positively charged surface. For that
reason there is decrease in overlap of p-orbitals present in carbon
(3) atoms of the PANI molecules on ZnO incorporation. These results are
well corroborated with the results of UV–Visible absorption spectra
which show increase in band gaps with increase in Zn concentrations.
This correlates with conventional phenomena of quantum confinement
in nanomaterials which says that smaller crystallites have larger band
gap. As the particle size of a material decreases, the availability of active
sites on the surface increases, another well known phenomena in
nanomaterials to have larger surface/volume ratio in lowering the
dimension. This in turn facilitates larger area in the film available for
exposure of the analyte (gas/vapour) [27,34]. The sensitivity of a
sensor can be measured from the change in resistance of the sensor on
gas intake. The more the number of surface active sites more would be
the change in resistance of the sensor. Hence particle size or band gap
tuning is essential in efficient sensor making.

Fig. 2. UV–Visible absorption spectra of PANI and PANI-ZnO composites.

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M. Das, D. Sarkar
Fig. 3. Tauc's plots for PANI and ZnO doped PANI composites.
Fig. 4. Band gap vs Zn concentration plot.
Elemental and chemical composition of PANI and one of the
representative ZnO-PANI composites are investigated through EDAX
analysis. These results are incorporated in the inset of respective TEM
images (Fig. 5a and e). Characteristic peaks of C, S, N, Zn and O
ascertain the presence of constituents of ZnO and PANI in the films.
The extracted element content and weight percent of the elements are
also displayed in Table 1 along with other parameters.
3.4. Thermogravimetric analysis (TGA)
Present work is targeted to develop a material which would be
suitable to detect gases or vapours at room temperature. ZnO based
sensors are known to have fair sensitivity at much elevated tempera-
ture but do not suit room temperature application on the other hand
PANI suits room temperature application but its thermal stability is
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poor. TGA analysis is carried out to inspect whether ZnO incorporation
in PANI is increasing its thermal stability or not and also to test higher
temperature applicability of the composite. Fig. 6(a and b) shows the
TGA and DTG (differential thermogravimetry) profile for pure PANI
and ZnO-PANI nanocomposite respectively. It is evident from the plots
that for pure PANI there are two stages of weight loss, the first weight
loss up to 90 °C is due to the loss of absorbed water vapour which is
also confirmed by an endothermic peak in the DTG curve at 100 °C
[35–37]. The second weight loss is observed from 240 °C onwards due
to the thermo-oxidative decomposition of PANI [38]. On the other
hand ZnO-PANI nanocomposite shows only one stage of weight loss.
Almost no mass loss up to 100 °C suggests that moisture content in the
composite is very low. The DTG curve shows complex decomposition
steps. One small peak observed at 313 °C is related to the decomposi-
tion of dopant and the major endothermic peak observed at 330 °C is
due to the complete thermo-oxidative decomposition of the composite.
Important thing to notice is that thermal decomposition of the PANI
composite starts at higher temperature than pure PANI. One can say
that PANI sensor would be suitable up to temperature of room
temperature to 90 °C and the composite upto 100 °C without any
difficulty. Thus ZnO incorporation leads to increased thermal stability
and widen temperature range of sensing.
The activation energies for the thermo-oxidative degradation of
pure and composite PANI are evaluated using Broido equation [39,40].
ln(ln (1/Y)) = − Ea /RT + C
and Y = (wt − w∞)/(w0 − w∞) (4)
where wt is the weight at particular temperature, w∞ and w0 are the
final and initial weight respectively. Plot of ln (ln1/Y) versus 1000/T is
shown in Fig. 7(a and b) whose slopes give the activation energies (Ea).
The activation energies of PANI and the ZnO doped PANI are obtained
as 17.96 kJ and 28.64 kJ respectively. That is, the activation energy of
the doped PANI is higher than that of the pure PANI. This may be due
M. Das, D. Sarkar
Fig. 5. TEM images of (a) PANI, (b) ZnO-PANI (0.001 M), (c) ZnO-PANI (0.01 M), (d) ZnO-PANI (0.05 M) and (d) ZnO-PANI (0.1 M) composites.
Fig. 6. TGA and DTG profile for (a) pure PANI and (b) ZnO-PANI nanocomposite.
to the strong interaction between PANI and in situ formed ZnO
nanoparticles, which in turn results in increase of thermal stability.
3.5. Gas sensing studies
The gas sensing properties of ZnO doped PANI film is studied for
different NH3 gas concentrations by measuring the change in resistance
on gas intake. The sensitivity of the sensor is defined as
S = (Rg − R a)/R a*100%
where Rg and Ra are the resistances of the sensor film in presence of air
and target gas. Fig. 8(a and b) shows the change in sensitivity as a
function of time with exposure and removal of NH3 for pure PANI and
ZnO-PANI film for 20, 50, 70 and 100 ppm NH3 concentrations.
Ceramics International xxx (xxxx) xxx–xxx
Initially the sensitivity (which is related to change in resistance) is
seen to increase rapidly and then saturates. The increase in resistance
is due to the removal of free electrons from the conduction band of the
composite by the adsorbed oxygen species which act as trapped states.
The limit of detection (LOD) is a vital parameter to characterize a
sensor which defines about the minimum amount that a sensor can
sense. The limit of detection (LOD) is calculated by using the formula
LOD = (3.0*σ )/S (6)
(5)
where σ is the relative standard deviation and S is the slope of the
calibration curve. We have included these plots in Fig. 8(c and d) for
different NH3 concentrations for sensors made of PANI and its ZnO
composite respectively. The curves show a good linear fit for both the
samples. The calculated LOD for PANI and the composite are found to
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Fig. 7. Broido's plot for (a) pure PANI and (b) ZnO-PANInanocomposites.

be 18.89 and 10.04 ppm respectively. So one can state that ZnO-PANI
sensor has minimum detectivity limit of ~10 ppm of NH3.
3.5.1. Selectivity, response and recovery time and ageing effect of
ZnO doped PANI sensor
In order to check the selectivity of the sensor to NH3, we have tested
it for two other vapours, namely methanol (CH3OH) and ethanol
(C2H5OH). Fig. 9 shows the response graph of ZnO-PANI film towards
CH3OH, C2H5OH and NH3 for 100 ppm concentration. ZnO-PANI film
shows negligible response to the other two gases compared to NH3 at
room temperature (300 K). This indicates that the composite film is
very selective towards NH3 gas and is thus reliable for practical use to
detect NH3 in presence of other gases. Next important parameters to
measure in a sensor are its response and recovery times, physically

Fig. 8. Sensitivity curve for (a) pure PANI and (b) ZnO-PANI nanocomposite for different concentrations of ammonia (c) and (d) for respective Calibration curves for calculating limit of
detection.

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M. Das, D. Sarkar
Fig. 9. Gas response of PANI-ZnO nanocomposite towards different gases.
interpreted as the time it requires to change its parameter appreciably
on gas intake and the time it is near its basic state on gas removal
respectively. These can be quantified respectively as the time required
by the sensor to reach 90% of its saturation value of Rg from Ra on gas
intake and the time taken by the sensor to reach 10% value of Ra on gas
withdrawal. Fig. 10 shows the response and recovery time of pure PANI
and ZnO-PANI nanocomposite for different concentrations of NH3 gas.
For pure PANI the response time is found to decrease from 61 to 48 s
and recovery time to increase from 62 to 120 s, whereas in ZnO doped
PANI the response time is found to decrease from 35 to 21 s and
recovery time from 35 to 61 s with increase in NH3 concentration from
20 to 100 ppm. A decrease in response times can be attributed to the
favourable dedoping due to the formation of localized polaron band in
the presence of metal oxides and higher surface roughness [41]. The
relatively fast recovery time of ZnO-PANI composite film is due to the
presence of ZnO and sulphate ions present in the PANI chain. The
minimum value of the response time of ZnO-PANI composite film is
about 21 s, which is much smaller than some of the earlier reported
works [41–45]. The recovery coefficient, n given as (Rm-R)/(Rm- R0)
[46], where Rm is maximum resistance, R0 the initial resistance and R
the recovery resistance. For NH3 concentration of 20, 50, 70 and
100 ppm, the values of recovery constant are found as 98.0%, 96.5%,
94.2% and 93.0% respectively. That is the value decreases with increase
of NH3 concentration.
In order to check the ageing effect of the sensor, the change in
resistance is studied at an interval of 5 days up to a total span of 90
days for 100 ppm of NH3 concentration. Fig. 11 shows these curves for
Fig. 10. Response and recovery time plot for (a) pure PANI and (b) ZnO-PANI nanocomposites.
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Fig. 11. Plots showing ageing effect of (a) pure PANI and (b) ZnO-PANI nanocomposite.
PANI and one composite film. It can be seen that the composite film
show better stability (90%) in terms of ageing, as for pure PANI film the
value is found to be 70% only. The response of the film drops initially
and stabilise after 10 days. This may be due to the interface modifica-
tion of the hybrid sensor during the sensing operation [41,47]. The
decrease in sensitivity is due to the ageing effect of the polymer part
[26].
3.6. NH3 sensing mechanism
PANI is known to be a p-type material or an acceptor, on the other
hand NH3 is a donor so these interact to form donor-acceptor complex
and the resistance of the film increases on NH3 intake due to decrease
in free charge carriers (as some of these are used up in complex
formation). According to Le Chatelier's principle equilibrium of the
system to move in the forward direction to compensate the increased
concentration of NH3 gas [42]. On the contrary when ammonia is
removed the system equilibrium shifts toward backward direction. In
NH3 gas, nitrogen is more electronegative than hydrogen. So there will
be formation of partial polar bond between N and H on NH3
incorporation on PANI based compounds. That will increase the
interchain separation in PANI. This in turn reduces the probability of
electron hopping (essentially the conduction mechanism in PANI
systems) between adjacent chains to result in the increase of the
resistance of the film. For highest concentration of NH3 vapour PANI
emeraldine salt is converted to PANI emeraldine base form [44]. On
removal of NH3 vapour emeraldine base again converts to emeraldine
M. Das, D. Sarkar
Fig. 12. Schematic of ammonia sensing mechanism of ZnO-PANI nanocomposite.
salt form which ascertains the recovery of the sensor. Fig. 12 schema-
tically illustrates the sensing mechanism of PANI film towards NH3.
4. Conclusion
Zinc oxide (ZnO) - polyaniline (PANI) nanocomposite is synthe-
sized by in-situ dispersion of ZnO in the same pot which has been used
for the fabrication of PANI. The morphological studies of the composite
from TEM show near spherical particles with average diameter in the
range of 7–25 nm. TGA and DTG curves show higher stability of the
composite compared to the bare PANI film. The sensor fabricated from
the composite film shows fair selectivity towards ammonia with low
detection limit, rapid response and fast recovery along with high
stability at room temperature. In brief we would claim that a much
improved ammonia sensor has been developed by the incorporation of
ZnO in PANI.
Acknowledgment
The authors thank University Grant Commission (UGC) for its
financial support through the project grant no. 40-458/2011 (SR) for
infrastructure and financial support to one of the authors (M D)
through UGC-BSR grant. Thanks are also to NEHU Shillong and
USIC department of Gauhati University, Guwahati for TEM and XRD
measurements respectively.
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