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Design, simulation, fabrication and testing of


electrochemical NO2 gas sensor
CONFERENCE PAPER MARCH 2015
DOI: 10.1109/ISPTS.2015.7220127

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4 AUTHORS, INCLUDING:
Umesh Yadav

Ravindra Sarje

Savirtibai Phule Pune University

Savirtibai Phule Pune University

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Shashikala Gangal
Savirtibai Phule Pune University
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Available from: Ravindra Sarje


Retrieved on: 09 November 2015

Proceedings of the 2015 2nd International


Symposium on Physics and Technology of Sensors,
8-10th March, 2015, Pune, India

Design, simulation, fabrication and testing


of Electrochemical NO2 gas sensor
Umesh Yadav, Ravindra Sarje, A.D.Shaligram, S.A.Gangal
Dept. of Electronic Science, SP Pune University, Pune-411007
umeshy115@gmail.com,
Abstract - An electrochemical amperometric sensor measures the
electric current on the surface of the working electrodes and
estimates the concentration of chemical or biological species.
Electrochemical sensor is fast and selective but electrochemical
sensing is a complex phenomenon involving both physical and
chemical processes. With a view to understand the basic operation
of electrochemical sensor, present study demonstrates a steadystate analysis of the current drawn in a cell of electrolyte solution
with two and three electrode configuration. Simulations are
carried out for 2- dimensional geometry using COMSOL
Multiphysics suite. Effect of variation in cell dimensions,
electrolyte concentrations and electrode dimensions on the
performance of the sensor is studied. For validation of simulation
result, a two electrode electrochemical cell is fabricated and tested
for NO2 gas sensing
Fig.1. Electrochemical gas sensor schematic

KeywordsElectrochemical
Simulation.

I.

sensor,

Gas

sensor,

INTRODUCTION

Electrochemical gas sensors are gas detectors that measure the


concentration of a target gas by oxidizing or reducing the same
at an electrode and measuring the resulting current. The sensors
have two or three electrodes, occasionally four, in contact with
an electrolyte. The electrodes are typically made-up by fixing a
high surface area noble metal on to the porous hydrophobic
membrane. The working electrode is in contact with both the
electrolyte and the ambient air to be monitored usually via a
porous membrane. The electrolyte most commonly used is an
acid, but organic electrolytes are also used for some sensors.
The electrodes and electrolyte are usually placed in a plastic
housing which contains an exit hole for the gas and electrical
contacts.
The test gas diffuses into the sensor, through the back
of the porous membrane to the working electrode where it is
oxidized or reduced. (See Fig.1). This electrochemical reaction
results in an electric current that passes through the external
circuit. Voltage is applied across the sensor between the
working and counter electrodes for two electrode configuration
or between the working and reference electrodes for three
electrode configuration. At the counter electrode an equal and
opposite reaction occurs, such that if the working electrode is
performing an oxidation, then at the counter electrode it is
reduction.

978-1-4673-8018-8/15/$31.00 2015 IEEE

Present paper deals with the electrochemical gas


sensor for detection of the NO2 gas. The magnitude of the
current is controlled by how much of the NO2 gas is oxidized at
the working electrode. The oxidant, after its reaction with NO2,
can be re-oxidized directly at the electrode [1]. Many
researchers used H2SO4 as electrolyte for the sensing of NO2
gas [2, 3, 4]. Some of them used Ionic liquids and other
electrolytes like AgCl3, Ag/AgCl3 M NaCl and 10% PVC, 3%
tetrabutylammonium hexafluorophosphate [5, 6, 7].
P. Hrncirova et.al [5] reported solid electrolyte sensor.
Platinum is used as electrode material, with the cell dimensions
of 25x25x2 mm3 and obtained the output current of the order of
300nA for the NO2 gas sensing. Martina Nadherna et al [2] used
ionic liquid as electrolyte, glassy carbon and platinum as
electrode for sensing NO2 gas. Using these materials they
obtained the resultant current of the order of 200nA for the
constant potential 900mV. Pratic Jacquinot et al [8] got the
output current of the order of 1-5A for ppb levels of NO2 with
0.5 M H2SO4 acid as electrolyte. Jing-Shan Do et al [3] used
polyaniline/Nafion/Au electrode to get 30 - 240A current for
the 20 100ppm NO2.
In electrochemical sensor physical size, geometry,
selection of various components e.g. porosity of hydrophobic
membrane, electrolyte composition, sensing electrode materials
and the configuration such as two electrodes, three electrode
etc. usually depends on its intended use. Quite often the final
design results in a compromise between various performance
parameters of electrochemical sensors. They are sensitivity,
selectivity, response time, and operating life. A low
concentration gas sensor with very high sensitivity requires a
coarse-porosity hydrophobic membrane with less restricted
capillary. Larger pore size allows more gas molecules to pass

268

through to produce enough signal (current or voltage) for better


sensitivity but at the same time it allows more of the
electrolytes water molecules to escape out to the environment
due to evaporation of moisture through the porous membrane.
This in turn reduces operating life of the sensor. Similarly, the
electrolyte composition and the sensing electrode material are
selected on the basis of chemical reactivity of the target gas.
The electrolyte and/or the sensing electrode can be selected to
achieve the selectivity towards the target gas, but at the same
time the sensitivity may reduce. Theoretical background on the
subject of electrochemistry may be referred from the reference
nos. [3] and [7].
Efforts done to understand the dependence of some of
these parameters on sensor performance parameters especially
sensitivity, are reported in the present paper.
II.

METHODOLOGY

1) Simulations of Electrochemical Cell:


In this work, simulations are carried out on the
electrochemical sensor model for detection of low
concentration of NO2 gas. As stated the variables of the
electrochemical sensor are physical size, geometry, porosity of
hydrophobic membrane, electrolyte composition, sensing
electrode material and configuration of electrochemical cell
such as two electrode or three electrode.
In this work we have used two as well as three electrode system.
2- Dimensional geometry is used to simulate the electrochemical
sensor. Fig.2 shows the geometry of the electrochemical cell.
Simulations are carried out for three physical sizes of the sensor
viz 4x4, 4x3 and 2x2 cm2. These are decided on the basis of
typical sizes of the commercial sensors. In this simulation the
target gas is inserted near the working electrode and thats why
the porosity of the hydrophobic membrane is not taken in to
consideration. Many researchers have reported H2SO4as the
electrolyte for NO2 gas sensing. The same is used here.
Concentration of the electrolyte is varied from 0.5M to
2.0M.The sensitivity of the sensor depends on surface area of the
working electrode. The electrode dimensions are varied from
0.4x 0.02cm2 to 0.4x 0.01cm2.Larger is the surface area higher
is the sensitivity .Output of the sensor is in terms of current
flowing through the external circuit. Simulations of the sensor
are carried out using the electrochemical module of COMSOL
Multiphysics suite. It uses basic electrochemical equations from
electrochemical theory [2].The current density for this reaction
is given by the electro analytical ButlerVolmer equation for an
oxidation.

(1)

Where, k0 is the conversion rate of the reaction, c is the
cathodic transfer coefficient, and is the supplied potential at
the working electrode. The diffusivity (conversion rate) of the
NO2 gas in the electrolyte is taken as 5 X 10-4 cm2 /s [11]. The
cathodic transfer coefficient is taken by the software itself which
is equal to 1X10-9.. The viscosity of the electrolyte is taken as
26.7 cP. [7].This is standard viscosity of the H2SO4 acid. The
simulation results are in the form of current density. From the

current density we can calculate the current by using the


following formula. Eqn. (2)

(2)

The ion mobility is not considered in the simulation. The rate of


this reaction (mol/m3) is given by a MichaelisMenten rate law
as

 




(3)

Where, Vmax is the maximum rate of the reaction, CNO2 is the gas
concentration and the parameter Km is a characteristic
Michaelis-Menten coefficient. The reaction rate is calculated
from the data obtained. Results on the simulations are reported
in this paper and discussed.

Fig.2.The geometry of the sensor cell.

III.

EXPERIMENTAL

Two electrode, electrochemical cell was fabricated for


validation of simulation results. Dimensions were decided on
the basis of the simulation results. Experimental set up for
testing the performance of the electrochemical cell is shown in
Fig.3.Fig.3 (a) shows the block diagram of the set up and Fig.3
(b) shows the photograph of the set up. Experiments were
carried out for finding out the sensitivity of the cell. NO2 gas of
known concentration was introduced in the gas chamber in
which the electrochemical cell is kept (refer Fig.3 (b).The final
gas concentration was calculated from the known values of gas
chamber volume and the volume of the gas introduced. The cell
consists of electrolyte and electrodes. The results obtained are
reported and discussed in this paper.

269

Fig.3a.Block diagram of the experimental test set up

The largest current is found to be 18 A in 3 electrode system


and 15 A with two electrode system in case of cell dimension
of 4x4cm2, increase in current with increase in gas
concentration is attributed to the increased reactivity. It is also
clear from the figure that sensitivity (A/ppm slope of the
curve) of the sensor increases with increase in cell dimensions.
This increase is attributed to the increase in number of ions in
increased volume of electrolyte solution [9].
The output current in two electrode system is little
higher than that of the three electrode system. This happens
because, in two electrode system the current flowing in the
electrode randomly changes the potential applied between them
[10]. To avoid these fluctuations in the potential the third
electrode is (reference electrode) used in the three electrode
system. Reference electrode is given constant voltage equal to
redox reaction potential.
In order to see the effect of electrolyte concentration
on the performance of the cell, simulations are done at three
different electrolyte concentrations viz. 0.5, 1.0 and 2.0 M.
Fig.6 and Fig.7 show the output response of the sensor using
three electrode system and two electrode systems respectively
with varying electrolyte concentration. Here the cell dimension
is taken a 2 x2 cm2, electrode dimensions are taken as 0.4 x 0.02
cm2.

Fig. 4. Simulation result for varying cell dimensions (3Electrode system)


Fig.3b. Photograph of Experimental test setup

IV.

RESULTS AND DISCUSSION

Results on simulations carried out for 2-dimensional geometry


by varying the cell dimensions, electrolyte concentrations and
electrode dimensions and configuration (2 or 3 electrodes) are
discussed in this section. Fig.4 and fig.5 show the response of
the electrochemical cells of three different dimensions 2x2, 4x3
and 4x4 cm2 with 3- electrode system and 2 electrode system
respectively for sensing the NO2 gas in the gas concentration
range of 0 to 10 ppm. The electrolyte concentration is kept
constant at 0.5M and electrode dimensions are taken as 0.4 x
0.02 cm2. All the electrodes are taken of gold. The output
current is found to increase linearly with the gas concentration
and the slope is different for different dimensions of the cell.

Fig.5. Simulation result for varying cell dimensions


(2- Electrode system)

270

All the electrodes are of gold. It is found that the sensor


response is same for all the concentrations of the electrolyte.
The output current is not changing with the change in
electrolyte concentration because of constant redox potential
applied to the working electrode.
Fig.8 and Fig.9 show the sensor response using three electrode
system and two electrode system with at different electrode
dimensions 0.4 x 0.02 cm2 and 0.4 x 0.01 cm2. Here the cell
dimension is taken a 2x2 cm2 and electrolyte concentration is
kept constant at 0.5M. The output current of the sensor
increases with increase in electrode dimension. This is because
the higher surface area interacts with more number of NO2
atoms and the reaction rate is increases. Maximum current of 7
A in three electrode system and 6.2 A in two electrode
system with NO2 gas of 10 ppm is observed.

Fig.8. Simulation results for varying Electrode dimensions (3Electrode system)

Fig.6. Simulation results for varying Electrolyte concentration


(3- Electrode system)

Fig. 9. Simulation results for varying Electrode dimensions (2Electrode system)

Fig.7. Simulation results for varying Electrolyte concentration


(2- Electrode system)

The current in two electrode system is lower than the three


electrode system. This happens because of the change in
potential of working electrode.

For validation of simulation results an electrochemical cell is


fabricated with dimensions of 2 X 4 X 2 cm3 (length x height x
width). Electrode dimensions are taken to be 4 X 0.002cm2=
0.0008 cm2. The area of electrodes is same as that taken for
simulation (0.4 X 0.02 cm2). Electrolyte concentration was kept
at 0.5M. In the validation experiment gas concentration was
varied from 2 ppm to 10 ppm. Fig.10 show response (output
current versus gas concentration) of the fabricated sensor. The
current varies from 7.5 to 8.5 A when the concentration of NO2
gas is varied between 2 ppm to 10ppm. The simulated and
practical results are compared. Since simulations are done in two
dimensions the simulated curve for 2 x4 (width x height) with
the symbol ( ) in Fig.4 is compared with the practical results.
Simulated sensitivity (0.8 A / ppm) of the sensor is found to be
much larger than the one practically obtained (o.12 A/ppm).
The difference seen may be attributed to the fact that simulation
current is zero for zero ppm whereas practically the current is
around 7.5 A. The difference may also be due to the third
dimension in practical electrochemical cell. As can be seen from
the fig. 10 slope of the current versus concentration curve is
different above gas concentration of 10 ppm. This may be
attributed to the change in reactivity of the sensor. The order of

271

currents obtained in the present experiments are similar to the


ones reported in the literature [2, 8]

[8]. Yoshitaka Mizutania, Hiroyuki Matsuda, Improvement of electrochemical


NO2 sensor by use of carbonfluorocarbon gas permeable
electrodeSensors and Actuators B 108 (2005) 815819
[9]. Electrochemical Systems 5, 305-313 (2002) Modelling of an
electrochemical cell, Jin Hyung Chang, P.hD thesis.
[10]. Stephen Lower, Professor Emeritus (Simon Frasier U.)Chem1 Virtual
Textbook
[11]. Jing-Shan Doa, Kanq-Jiuan Wu Ming-Liao Tsai, Amperometric NO gas
sensor in the presence of diffusion barrier: selectivity, mass transfer of
NO and effect of temperature, Sensors and Actuators B 86 (2002) 98
105.

Fig.10. Result of fabricated sensor

V.

CONCLUSION

The electrochemical NO2 gas sensor was designed, simulated,


fabricated and tested successfully. The simulation of the sensor
was done by the electrochemical module from the COMSOL
Multiphysics suite. The sensor shows the good sensitivity for
gold electrode with 0.5 molar concentration H2SO4 as
electrolyte.
VI.

ACKNOWLEDGEMENT

Authors acknowledge with thanks the financial support


provided by ISRO-UoP STC for this work.
VII.

REFERENCES

[1]. Deganit Barak-Shinar, Moshe Rosenfel and Shimon Abboud, Numerical


Simulations of Mass-Transfer Processes in 3D Model of Electrochemical
SensorJournal of The Electrochemical Society, 151 ~12! H261-H266
~2004!
[2]. Nadherna, Frantisek Opekar and Jakub Reiter, Ionic liquidpolymer
electrolyte for amperometric solid-state NO2 sensorSensors and Actuators
B 161 (2012) 811 817.
[3]. Jing-Shan Do, Wen-Biing Chang, Amperometric nitrogen dioxide gas
sensor: preparation of PAn/Au/SPE and sensing behaviourSensors and
Actuators B 72 (2001)
[4]. Wen-Tung Hung and Kuo-Chuan Ho, An Electrochemical Gas Sensor for
Nitrogen Dioxide based on Pt/Nafion Electrode, , Journal of New Materials
for Electrochemical Systems 5, 305-313 (2002).
[5]. P. Hrncirova,F. Opekar and K. Stulk, An amperometric solid-state
NO2sensor with a solid polymer electrolyte and a reticulated vitreous
carbon indicator electrodeSensors and Actuators B 69 _2000. 199
204.Martina
[6]. Patrick Jacquinot,Alexia W.E. Hodgson, Peter C. Hauser, Amperometric
detection of NO and NO2 in the ppb range with solid-polymer electrolyte
membrane supported noble metal electrodesAnalytica Chimica Acta 443
(2001) 5361
[7]. P. Atkins, J. de Paula, Physical Chemistry, 9th Edition.

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