Sensors and Actuators B 76 (2001) 605609

New approaches for developing transient electrochemical

multi-component gas sensors
Zhong-Bai Zhou*, Liang-Dong Feng, Wen-Jun Liu, Zhi-Gang Wu
Department of Chemistry, Wuhan University, Wuhan 430072, PR China

Abstract
According to the thin-layer electrochemistry and transient electrochemistry principles, both all-new approaches for developing transient
electrochemical multi-component gas sensors ``porous thin-layer electrode coulometry (PTLEC)'' and ``modulated pulse potential
amperometry (MPPA)'' were proposed in this paper. As compared with steady electrochemical methods for conventional electrochemical
gas sensors, they have made a new breakthrough in optimizing the gas sensing performance characteristics and developing the sensor
functions, as illustrated by the case of detection of O2 N2 O (gas anaesthetic) and O2 CO2 (biorespiratory gases) gas mixtures.
# 2001 Elsevier Science B.V. All rights reserved.
Keywords: Porous thin-layer electrode coulometry (PTLEC); Modulated pulse potential amperometry (MPPA); Transient electrochemistry; Thin-layer cell;
Multi-component gases

1. Introduction

2. Experimental

The currently successful electrochemical gas sensors are

mostly steady-type, or rather, the response of these sensors is
measured with steady electrochemical methods under steady
operating state, such as Clark electrode-type amperometric
gas sensors and Nernst's potentiometric gas sensors. As a
result, the further improvement of sensor characteristics is
restricted by such a ``steady-state''. And usually, this kind of
steady electrochemical gas sensors is only able to detect
single gas component.
In order to optimize the electrochemical sensor performance characteristics and to develop the sensor functions,
we report here both all-new approaches for developing
transient electrochemical multi-component gas sensors
``porous thin-layer electrode coulometry (PTLEC)'' and
``modulated pulse potential amperometry (MPPA)'' that
work on the thin-layer electrochemistry and transient electrochemistry principles, respectively. The multi-component
gas-sensing characteristics as well as the transient electrochemical sensing mechanisms of both the new approaches
are discussed.

The working electrode used in the PTLEC was constructed by using a hydrophobic porous thin-layer
(<0.5 mm) gas electrode. It consists of a hydrophobic porous
layer made from a mixture of teon and acetylene black, a
thin hydrophilic layer of catalyst, and a current collector
between both layers. The actual experimental apparatus is
shown schematically in Fig. 1. The principle of operation of
such a porous thin-layer electrode (PTLE) is also illustrated
in the same gure. The PTLE is rst exposed to the gas
samples (12 s) so that the composition of the gas within the
pores of the electrode becomes in equilibrium with the
environment. Then the electrolyte level is raised with the
help of a leveling bulb until the PTLE is fully immersed, and
the electrochemical measurement is carried out at ambient
temperature. Voltammograms of the PTLE were recorded
with the common LPSV (linear potential scan voltammetry)
technique. The amount

of charge consumed in exhaustive
R
electrolysis Q I dt was obtained by integration of the
peak area in the Current (I)time (t) curves.
The MPPA were established by combining computercontrolled fast modulated potential technique with microelectrode method. A block diagram of the measuring unit
used in this study is outlined in Fig. 2. The works were
performed with the experimental set-up controlled by a
computer via a AD/DA converter. The controlling and
measuring software programs for the approach were written

Corresponding author. Tel.: 86-27-87882661;

fax: 86-27-87882661.
E-mail address: zbzhou@whu.edu.cn (Z.-B. Zhou).

0925-4005/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 5 - 4 0 0 5 ( 0 1 ) 0 0 6 5 4 - 2

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Z.-B. Zhou et al. / Sensors and Actuators B 76 (2001) 605609

Fig. 1. Apparatus and operation of the PTLEC: (a) (1) working electrode (PTLE); (2) counter electrode; (3) reference electrode; (4) electrolyte; (5)
leveling bulb; (6) gas inlet; (7) gas outlet, (b) (1) hydrophobic layer; (2) catalyst layer, (c) (1) position of PTLE for sampling; (2) position of PTLE for
measurement.

Fig. 2. Block diagram of the MPPA.

by oneself. Fig. 3 illustrates the electrochemical gas detector

embodiment. The working electrode (WE) was a Pt microdisc electrode (diameter 60 mm) sealed in a glass rod. A ringshaped Pt wire served as the counter/reference electrode
(CE/RE). The electrolyte layer thickness on electrode surface, i.e. the distance between the working electrode and
gas-permeable membrane (porous polytetrauoroethylene),
could be adjusted by rotating the electrode holder so as to
observe a reasonably fast response signal.
The multi-component gas samples were prepared using
O2 N2 O and N2 or O2 CO2 and N2 of high purity which
were accurate to 1% (volume percentage under the normal
atmosphere pressure, v/v), relative to the selected ratio.
3. Results and discussion
3.1. Porous thin-layer electrode coulometry (PTLEC)
In principle, the thin-layer cell concept [1,2] should be
applicable to the construction of gas sensors by combining a
gas electrode with a porous thin gap as gas reservoir. This
approach is dened as the PTLEC. Since the basic prerequisite of a thin-layer device may be expressed as
l ! 2Dt1=2 , where l is the width of thin layer, D the

diffusion coefcient of reactive species and t the duration

of the measurement, and D values are usually several order
of magnitude higher in the gas phase than in the liquid phase,
it should be easier to construct thin-layer gas electrodes.
The response signal measured by the PTLEC is a transient
peak-current (I), and the total amount of charge (Q) consumed in exhaustive electrolysis of the gas samples within
the pores of the PTLE should be proportional to the concentration of the monitored species. The typical measured
results of the detection of anaesthetic O2 N2 O gas mixtures are shown in Fig. 4 (corresponding operating condition
are given in the gure caption). The linearity of the
responses (Q) of both component gases was found to be
quite satisfactory (Fig. 5). This clearly indicates that current
peaks with a difference of their peak-potentials 0.3 V can
be well-separated even if the electrode processes are totally
irreversible, as in the reduction of O2 and N2O. Thus, it is
possible to achieve well-separated consecutive electrochemical reaction of three to four gas components within a
potential range 1.01.5 V in favorable cases. That is to say,
this PTLEC approach offers a great potential for developing
transient electrochemical multi-component gas sensors.
Furthermore, the method is fast and simple, and, since
the gas concentration is determined coulometrically, it eliminates the need for a reference gas standard.

Z.-B. Zhou et al. / Sensors and Actuators B 76 (2001) 605609

Fig. 3. Gas detector embodiment for the MPPA. (1) Counter/reference

electrode; (2) microdisc working electrode; (3) electrolyte; (4) gaspermeable membrane; (5) electrode holder; (6) cell body; (7) `O'-ring.

In addition, the sampling duration of such PTLE devices

was so short (<2 s) that their operational stability was not
nearly inuenced by the changes from environment. The
temperature coefcient of calibration curves lies in the range
of 0.1 to 0.3%/8C, which is much lower than that of gas
sensors based on the steady-state limiting current concept.
The magnitude of the temperature coefcient can be
explained by the ideal-gas-law [3].
Nevertheless, there is a factor that must be considered. In
the case of detection of O2 N2 O gas mixtures, a decrease
of the Q values at a rate of ca. 0.3% per day was observed in
5 mol/l KOH medium. This experimental phenomenon,
apparently, is due to gradual wetting of the hydrophobic
matrix in strong alkali. The volume of gas pores in the PTLE,
i.e. Q can remain constant over a long period, if the PTLE is
washed after use and stored dry.

607

Fig. 4. Voltammograms of the PTLE in O2 N2 O gas mixtures (counter

electrode: Pt; reference electrode: Hg/HgO; electrolyte: 5 mol/l KOH;
electrocatalyst: Pd; scan rate: 12 mV/s). (a) Pure O2; (b) 50% O2
50% N2 O; (c) pure N2O.

totally reduced to superoxide ion (O2 ) in dimethylsulfoxide (DMSO) solution containing 0.1 mol/l tetraethylammonium perchlorate (TEAP). The portion of the O2
reacted immediately with the CO2 present in the aprotic
solvent according to the reaction: 2CO2 2O2  !
C2 O6 2 O2 . Soon afterwards, when the anodic pulse
potential Ea 0:40 V) was applied, the unreacted
O2 was oxidized to O2. At the same time, the dynamic

3.2. Modulated pulse potential amperometry (MPPA)

For example of rapid simultaneous detection of respiratory gases O2 and CO2, the principle of operation of such a
MPPA is schematically represented in Fig. 6. Based on the
chemical/electrochemical behavior of coexisting system of
both O2 and CO2 [4,5], we designed a special modulated
pulse potentialtime waveforms as the dynamic excitation
signal upon the working electrode. In the starting period of
the cathodic pulse potential Ec 1:60 V), all the O2 was

Fig. 5. Relationship between the Q and composition for O2 and N2O.

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Z.-B. Zhou et al. / Sensors and Actuators B 76 (2001) 605609

Fig. 7. (a) Calibration curve for O2 concentration; (b) relationship between

the Ia and CO2 concentration when O2 concentration is kept constant at
20% per v/v.

Fig. 6. Schematic representation of principle of the MPPA. (a) Modulated

pulse potentialtime waveforms; (b) transient current responses.

response signals on the working microdisc electrode, i.e. the

reaction current varying with time shown in Fig. 6b, could be
acquired in real-time. Thus, it can be seen that the simultaneous detection and measurement of gas concentration of
both O2 and CO2 should be achievable by the transient
current responses (O2 reduction current Ic and
O2 oxidation current Ia). However, it should be noted that
the following two potential problems related to the MPPA as
they affect accuracy and long-term stability of this approach.
Firstly, the measuring process involves such a nonfaradaic
charging process arising from the double-layer capacitor at
the electrode/solution interface. The inuence of the doublelayer charging current (I DL C d dE/dt, where Cd is the
double-layer capacity and dE/dt the changing rate of the
electrode potential) on the true transient current responses,
which is associated with faradaic processes, is inevitable,
especially in the initial stage after applying pulse potential.
For solving this problem, in the MPPA we chose to use a
microelectrode of small `time constant' (t Ru C d , where
Ru is the uncompensated resistance) as working electrode. It
is demonstrated by experiment that the IDL on the Pt
microdisc electrode decreased to nearly zero at the potential
pulse duration of 1 ms due to the shortened charging time for
the double-layer capacitor. Thus, the instantaneous response
signal (Ic or Ia) acquired at or after 1 ms of a potential pulse
applied could achieve sufciently high signal-to-noise ratio.
Furthermore, when the O2 reduction duration (1 ms) was
relatively short, the O2 reduction current (Ic) would not vary

with the CO2 concentration in a CO2O2/N2 gas mixtures.

This indicates that the Ic measured at 1 ms after the application of the reduction potential pulse was not affected by the
double-layer charging current nor the coexistent CO2. As
shown in Fig. 7, the calibration curve for O2 concentration
exhibited a straight line through origin, and the relationship
between the O2 oxidation current (Ia) and the CO2 concentration was also highly reproducible under a xed O2
concentration.
Secondly, the use of a periodic cathodic/anodic pulse
potential for the dynamic excitation signal on the working
electrode is conducive to keeping the nature of the electrode
surface stable. Nevertheless, in the case of detection of both
gases O2 and CO2, we still found that the O2 reduction
current decreased gradually after the measurement lasted a
few minutes. At the moment, if the electrode potential was
swept (scan rate: 0.5 V/s) from Ea to a sufciently positive
value of 0.70 V, where C2O62 oxidation could occur, then
the O2 reduction current would recover right away. Apparently, the accumulation of the reaction product C2O62 in
thin-layer electrolyte on electrode surface could lead to the
decay of the electrode activity, whereas C2O62 could be
removed by oxidation in a sufciently positive potential
region, which would maintain the long-term stability of this
approach. Therefore, special attention must be paid to the
design of a modulated potentialtime waveforms for the
MPPA approach based on the chemical/electrochemical
behavior of coexisting multi-component gases monitored.
In practice, the data measured in preliminary calibration
were inputted into computer to simulate the corresponding
empirical formulas. The response signals acquired in situ
were then used, and the concentration of each component in
the multi-component gas mixtures could be calculated from
their empirical formulas. Thus, such a PPMA approach

Z.-B. Zhou et al. / Sensors and Actuators B 76 (2001) 605609

provided a real-time and dynamic transduction technique

integrated with acquisition, treatment and display of signals
for rapid simultaneous detection of multi-component gases,
such as biorespiratory gases CO2 and O2. For additional
details of detecting both gases O2 and CO2, see [5].

[2]
[3]
[4]

4. Conclusion
The results reported above demonstrate that such new
approaches for developing transient electrochemical multicomponent gas sensors ``PTLEC'' and ``MPPA'' possess
their own unique and advantageous properties compared
with conventional steady electrochemical gas sensors. In
particular, such a search for new combinations of transient
electrochemistry principles and computer techniques will be
captivating for optimizing the sensor performance, developing the sensor functions and exploiting all-new transient
electrochemical multi-component gas sensors.
Acknowledgements
Support of this work by the National Natural Science
Foundation of China (Grant No. 39970211) is gratefully
appreciated.
References
[1] F.E. Woodard, C.N. Reilley, Thin layer cell techniques, in: E. Yeager,
J.O'M. Bockris, B.E. Conway, S. Sarangapani (Eds.), Comprehensive

[5]

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oxygenation of carbon dioxide by superoxide ion in aprotic media
to form the C2O62 species, J. Am. Chem. Soc. 106 (1984) 4667
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Biographies
Zhong-Bai Zhou is a professor in the Department of Chemistry, Wuhan
University, China. He was a visiting scholar at the Electronics Design
Center, Case Western Reserve University, USA, working with professor
C.C. Liu in 19911993 and is now a member of the Gas and HumiditySensing Committee of the China Electronics Society. His research interests
are in the areas of electrode process kinetics, electrochemical sensors and
its application, and the fabrication of miniature electrochemical sensors
using micromachining techniques.
Liang-Dong Feng is a graduate student working on electrochemistry for a
Masters degree in Wuhan University.
Wen-Jun Liu received his PhD degree in chemistry from Wuhan University
in 1996, and is now an assistant professor of chemistry at Shenzhen
University, China.
Zhi-Gang Wu received his MS degree in chemistry from Wuhan University
in 1987, and is now an associate professor at Tongji Medical University,
China.