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Strontium oxide quantum dot

decorated graphene composites for
liquid petroleum gas sensing
a a
Kailash R. Nemade & Sandeep A. Waghuley
a
Department of Physics , Sant Gadge Baba Amravati University ,
Amravati , India
Published online: 26 Sep 2013.

To cite this article: Kailash R. Nemade & Sandeep A. Waghuley (2013) Strontium oxide quantum dot
decorated graphene composites for liquid petroleum gas sensing, Journal of the Chinese Advanced
Materials Society, 1:3, 219-228, DOI: 10.1080/22243682.2013.838375

To link to this article: http://dx.doi.org/10.1080/22243682.2013.838375

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 Journal of the Chinese Advanced Materials Society, 2013
Vol. 1, No. 3, 219–228, http://dx.doi.org/10.1080/22243682.2013.838375

Strontium oxide quantum dot decorated graphene composites for

liquid petroleum gas sensing
Kailash R. Nemade and Sandeep A. Waghuley*
Downloaded by [Amravati University], [Sandeep Waghuley] at 02:42 27 September 2013

Department of Physics, Sant Gadge Baba Amravati University, Amravati, India

(Received 16 July 2013; revised 17 August 2013; accepted 23 August 2013)

Liquid petroleum gas-sensing behaviour of graphene/SrO quantum dots (QDs) compo-

sites was investigated. Structure and morphology of prepared materials were analysed
through X-ray diffraction (XRD) and transmission electron microscopy along with
selected-area diffraction pattern. The optical properties were analysed through
fluorescence spectroscopy. The thermal behaviour of optimized sensing material was
examined using thermogravimetric differential thermal analysis (TG-DTA). The
gas-sensing properties of composites were measured by resistance change as a
function of gas concentration. A notable better sensing performance was observed for
liquefied petroleum gas (LPG). The enhanced gas-sensing properties with increasing
amount of graphene are discussed by using defect chemistry. A good correlation is
observed between the fluorescence intensity ratio (IUV/IDL) and the sensing response
as a function of the amount of graphene.
Keywords: chemiresistor; graphene; SrO; quantum dots

1. Introduction
Liquefied petroleum gas (LPG) has only a very faint odour, and consequently, it is neces-
sary to add some odorant, which makes it detectable. When mixed with air at very high
concentrations, LPG vapour is an anaesthetic and subsequently asphyxiates by diluting
the available oxygen. The auto-ignition temperature of LPG is around 410–580
C and
hence it will not ignite at normal temperature. However, any electrical apparatus larger
than a digital wristwatch has the potential to generate sufficient energy to ignite LPG
vapour.[1] This is why it is necessary to find out efficient LPG-sensing material. There-
fore, objective of this research is to produce a highly selective and sensitive LPG-sensing
material. Hence, the present work comprises development of chemiresistors based upon
unattempted sensing material graphene/SrO quantum dots (QDs) composite.
Graphene-based composites have wide range of applications such as gas sensor,[2]
optics and energy-based applications.[3] The graphene-based, field-effect transistors have
reported the detection of absorption of a single gas molecule.[4] The gas-sensing mecha-
nism of graphene is based on the adsorption of gas molecules on the surface.[5] Jain et al.
reported the barium strontium titanate ceramic powder as a gas-sensing material for
detection of ammonia gas.[6] As the electronic property of material is mainly affected by
defects concentration, the gas response measured in terms of resistance is therefore
closely correlated to the intrinsic defects.[7,8] Kaur et al. [9] reported the sensing of H2S
gas at ppb level and demonstrated the sensing parameters strongly affected by defects

*Corresponding author. Email: sandeepwaghuley@sgbau.ac.in

Ó 2013 Chinese Advanced Materials Society

 220 K.R. Nemade and S.A. Waghuley

density. Lupan et al. [10] discussed the sensing mechanism for hydrogen gas and focused
on the role of defect chemistry.
In the present work, we are reporting the material graphene/SrO QDs composites for
LPG sensing, which is first time in the literature of material science. LPG sensing perfor-
mance of materials was studied at room temperature as well as at different temperatures.
The present work is devoted to the detection of LPG at low concentration and operating
temperature.

2. Experimental
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Graphene and SrO QDs were synthesized as reported previously.[11,12] The graphene/
SrO QDs composites were prepared by mixing graphene in constant 1 g SrO QDs in
20 ml acetone as organic media. The solution was mixed using magnetic stirrer for
30 min at room temperature. The obtained solution was kept overnight for evaporation of
acetone. In this manner, the prepared composite was sintered at 373 K for 1 h for com-
plete evaporation of acetone. The graphene was varied from 20 to 80 wt.%.
The X-ray diffraction (XRD)
patterns of samples were recorded on a Rigaku Miniflex
using CuKa radiation (λ ¼ 1.54 A) in the range 20
70
. The morphology of the samples
was studied using electron-imaging techniques, transmission electron microscopy
selected-area diffraction pattern (TEM-SADP) (JEOL-1200ex) and high-resolution trans-
mission electron microscopy (HR-TEM) (Philips Tecnai F-30107). The fluorescence
analysis was done on FL Spectrophotometer (Model: HITACHI, F-7000). The thermogra-
vimetric differential thermal analysis (TG-DTA) was carried out on Shimadzu DTG-60H
thermal analyser under nitrogen atmosphere. The temperature of the sample was varied
from room temperature to 775 K.
The chemiresistors were prepared by screen-printing technique on glass substrate of
size 25 mm  25 mm. The prepared chemiresistors were dried at room temperature for
24 h. Heating treatment was given to the film at 373 K for 3 h. For surface resistance
measurement, electrodes of silver were deposited on adjacent sides of the film and then
kept for heating at 353 K for 15 min in an argon atmosphere to make an Ohmic contact.
The sensing response was measured from resistance change of the chemiresistor with dif-
ferent concentrations (ppm) and at different temperatures. The electrical resistance was
measured by using a voltage drop method used by Waghuley et al.[13] The gas-sensing
response of the chemiresistor is defined as follows:

DR jRg  Ra j
S¼ ¼ ð1Þ
Ra Ra

where Ra is the resistance of chemiresistor in air and Rg is the resistance chemiresistor in

gas. The response time was determined by injecting the required amount of gas in the
chamber keeping the chemiresistor at room temperature. The required gas concentration
inside the system was achieved by injecting a known volume of test gas using a gas-
injecting syringe of volume 50 ml. The time taken by the chemiresistor to achieve 90%
of its highest value was considered as response time. Similarly, the recovery time of the
chemiresistor was defined as the time taken for its resistance to be reduced by 90% from
its highest value. The heater was fixed on the base plate to heat the sample under test up
to required operating temperatures. A Cr–Al thermocouple was used to determine the
operating temperature.
 Journal of the Chinese Advanced Materials Society 221

3. Results and discussion

3.1. Materials characterization
Figure 1(a)–(f) shows the XRD patterns of (20–80 wt.%) graphene/SrO QDs composites
along with graphene and SrO QDs. XRD pattern shown in Figure 1(a) indicates the for-
mation of graphene. There are two peaks, (002) and (100), which are main peaks of gra-
phene. The sharp peak at 2u ¼ 26.3
indicates a highly organized structure.[14] The
broad peak at 2u ¼ 44.2
may be assigned for lower degree of crystallization. Figure 1(b)
indicating the structural purity of SrO QDs. There are five peaks observed in the XRD
pattern, (111), (200), (220), (311) and (222), which are characteristic peaks of SrO QDs.
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All the peaks are exactly

indexed to cubic structure of SrO, and the cell parameters are
a ¼ b ¼ c ¼ 5.16 A (PDF 01-075-6979). The average crystallite size was determined
using the Debye–Scherrer equation, and was found to be 5.5 nm. The XRD patterns of
20–80 wt.% composites are shown in Figure 1(c)–(f). It is observed that average crystal-
lite size for composites ranges between 4.7 and 6.2 nm.
Figure 2(a) and 2(b) depicts the TEM, SADP and HR-TEM image of the optimized
sample discussed later, 80 wt.% graphene/SrO QDs composite. Figure 2(a) shows the dis-
tinct grain boundaries and less spherical shape of the 80 wt.% composite. The inset shows

Figure 1. XRD patterns of (a) graphene, (b) SrO QDs, (c) 20 wt.% graphene/SrO QDs,
(d) 40 wt.% graphene/SrO QDs, (e) 60 wt.% graphene/SrO QDs and (f) 80 wt.%. graphene/SrO
QDs.
 222 K.R. Nemade and S.A. Waghuley
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Figure 2. (a) TEM image of 80 wt.% graphene/SrO QDs composites and the inset shows the
SADP image; (b) HR-TEM image of SrO QDs.

SADP image indicating the presence of finely dispersed nanocrystals. Figure 2(b) shows
that SrO QDs strongly anchored on the surface of graphene.
As discussed in Section 1, defects concentration strongly influences the sensing
properties. Fluorescence spectroscopy is a straight approach of measurement of defects
density in the material. The defect concentration can be estimated by using the intensities
ratio between the ultraviolet (IUV) and visible deep levels (IDL).[10] As the QDs are fluo-
rescent nanocrystals due to quantum confinement, their fluorescence analysis becomes
important. The emission spectrum of graphene, SrO QDs along with 20–80 wt.%
graphene/SrO QDs composites recorded under irradiation by 254 nm in the range
300–700 nm is shown in Figure 3. The IUV, IDL and (IUV/IDL) ratio values for graphene,
SrO QDs and 20–80 wt.% graphene/SrO QDs composites are listed in Table 1.
Figure 4 shows the TG-DTA of 80 wt.% graphene/SrO QDs composites, in order to
study the thermal stability during the heat treatment to the material. The TG-DTA analy-
sis was carried out from room temperature to 775 K in nitrogen atmosphere.
According to the % TGA curve, the sample shows a sharp weight loss upto 345 K and
the DTA curve shows an endothermic pick at 344 K corresponding to the evaporation of

Figure 3. Emission spectra of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites.
 Journal of the Chinese Advanced Materials Society 223

Table 1. IUV/IDL ratio for graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites.

Sample IUV IDL IUV/IDL ratio

Graphene 26.51 1.51 17.55

SrO QDs 25.99 4.52 5.75
20 wt.% 26.85 1.37 19.59
40 wt.% 31.07 1.34 23.18
60 wt.% 38.84 1.37 28.35
80 wt.% 46.66 1.27 36.47
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absorbed water. The total mass loss from room temperature to 425 K was about 14.41%.
This mass loss is continued up to 625 K.

3.2. LPG sensing characterization

To know about the selective behaviour of the chemiresistors towards the oxidizing and
reducing species, its response to CO2 (30 ppm) and LPG (30 ppm) at 398 K was studied,
respectively. As LPG is composed of CH4, C3H8, C4H10, etc., these gases were chosen
for studying selective behaviour as a representative species. The results are presented in
Figure 5. It is notable that selective behaviour of composites towards the LPG enhanced
with wt.% of graphene. The highest value of sensing response was obtained for the
80 wt.% chemiresistor.
The gas-sensing properties of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs
composites chemiresistors for LPG were examined at room temperature as a function of
concentration of LPG is as shown in Figure 6. We have reported that the 80 wt.% gra-
phene/SrO QDs composites chemiresistor possesses good sensing response for LPG at
room temperature. Moreover, the responses of 20–80 wt.% graphene/SrO composites

Figure 4. TG-DTA curve of 80 wt.% graphene/SrO QDs composites.

 224 K.R. Nemade and S.A. Waghuley
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Figure 5. Response of chemiresistors towards CO2 (30 ppm) and LPG (30 ppm) at 398 K.

chemiresistors have almost linear behaviour. From the plot, it is analysed that sensing
response increases with an increase in the amount of graphene. This may be due the
smaller crystallite size which provides a larger surface-to-volume ratio for gas–solid
interaction.[15]
The response of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites
chemiresistor towards LPG as a function of temperatures was illustrated for 50 ppm dis-
played in Figure 7.
It can be seen that graphene/SrO QDs composites chemiresistors exhibited the maxi-
mum response at 423 K for LPG. This may be due to an oxygen adsorption rate is maxi-
mum around 423 K.[16] The maximum response value was found to be for 80 wt.%
graphene/SrO QDs composites chemiresistor. The 80 wt.% chemiresistor possesses maxi-
mum sensing response value at room temperature as well as a function of temperature.
This may be due to small particle size, which is related with the surface-to-volume ratio.

Figure 6. Sensing responses of graphene, SrO QDs and 20–80 wt.% graphene/SrO QDs composites
chemiresistors as a function of LPG concentration.
 Journal of the Chinese Advanced Materials Society 225
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Figure 7. Sensing responses of graphene, SrO QDs and 20–80 wt.% towards LPG as function of
temperatures at 50 ppm.

Another reason may be defects density. The decrease in particle size is recognized from
XRD analysis, as the peaks are broadened with the increase in the amount of graphene.
The smaller particle size affords a larger surface area for gas–solid interface that
improved sensing response. Similarly, the increase in defects density was confirmed from
fluorescence measurements. As the temperature increases, defect density on graphene
surface also increases, resulting in enhancement of sensing response at high temperature .
The sensing response decreases beyond particular temperature. This may be due to
removal of adsorbed oxygen by thermal excitation.[17]
The increase in defects concentration on the graphene surface confirmed through
(IUV/IDL) ratio using fluorescence measurement. Figure 8 shows the variation of IUV/IDL
ratio (obtained from fluorescence measurements) and sensing response (estimated from
sensing response measurements) with the wt.% of graphene.
It is noticeable that excellent correlation exists between the IUV/IDL ratio (defects den-
sity) and gas-sensing response. It is also observed that the defects density linearly

Figure 8. The variation of IUV/IDL ratio and LPG sensing response with the wt.% of graphene.
 226 K.R. Nemade and S.A. Waghuley

increased with wt.% of graphene. The density of defects may increase due to damage to
the graphene surface during addition into SrO QDs, or by the interaction between SrO
QDs and graphene. This may produce vacancies or dangling bonds.[18] This is one of the
possible reasons for enhancement in sensing response with the amount of graphene.
Another possible reason for the increase in sensing response is that at low graphene level,
electron transfer is mainly due to SrO QDs and electrons flow by hopping between QDs.
On the other hand, at high grapheme level, it overlaps on to the SrO QDs and the
resistance of graphene is lower than that of SrO QDs. Thus, the adsorption of LPG on
sensing surface increases with an increase in defect density. Therefore, the synergistic
effect between these two materials would effectively increase gas-sensing properties.
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Gas-sensing action is related to defects through the oxygen vacancies, which can act as
adsorption sites for gas molecules. The reaction for adsorbed oxygen ions are as
follows [17]:

O2 ðgasÞ ! O2 ðadsÞ ð2Þ

O2 ðadsÞ þ e ! O
2 ðadsÞ ð3Þ
O
2 ðadsÞ
 
þ e ! 2O ðadsÞ ð4Þ

When the chemiresistor is exposed to LPG that is composed of CH4, C3H8, C4H10,
etc., it interacts with the adsorbed oxygen ions and forms H2O and CO2. The reaction
between LPG and adsorbed oxygen ions are as follows [15]:

Cn H2nþ2 þ 2O ðadsÞ ! H2 O þ Cn H2n : O þ e ð5Þ

 
Cn H2n : O þ O ðadsÞ ! CO2 þ H2 O þ e ð6Þ

For stability measurements of chemiresistors, its sensing responses towards 100 ppm
of LPG at room temperature were measured for 30 days. This result is depicted in
Figure 9. The chemiresistors possess nearly constant response to LPG, indicating good
stability. The transient response characteristics for 80 wt.% chemiresistor towards LPG is
shown in the inset of Figure 9. In this measurement, gas is inserted in the chamber and

Figure 9. (a) Transient and (b) stability response of 80 wt.% graphene/SrO QDs composite to LPG
at room temperature.
 Journal of the Chinese Advanced Materials Society 227

chemiresistor is set to achieve its highest stable sensing response value. The fast response
of around 16 s for LPG is shown by 80 wt.% chemiresistor. While the chemiresistor is
exposed to air, the time taken by it to reduce by 90% of its highest value is known as
recovery time. The 80 wt.% chemiresistors achieved recovery in 22 s for both gases.

4. Conclusions
We have demonstrated the chemiresistive gas-sensing application of graphene/SrO QDs
composites towards LPG. The structural purity of samples were analysed by XRD. The
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TG-DTA study suggested that the material is stable thermally. The 80 wt.% chemiresistor
is a good candidate for practical use in detection of LPG as it shows good sensing
response, stability, fast response and recovery. The gas-sensing mechanism is discussed
effectively using defect chemistry.

Acknowledgements
The authors wish to thank the Head, Department of Physics, Sant Gadge Baba Amravati University,
Amravati, and the Head, Department of Chemical Science, North Maharashtra University, Jalgaon,
for providing necessary facilities. One of the authors, K.R. Nemade, also extends thanks to Sant
Gadge Baba Amravati University, Amravati, for awarding the late M.N. Kale scholarship for the
PhD work.

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