ELSEVIER

Sensors

and Actuators

B 22 (1994) 97-100

An electroluminescence
optical sensor system based on Ti02 film
electrodes for continuous measurement of H202 concentration in
solution
SK. Poznyak, A-1. Kulak
Imtihdte of Physics-Chemical

Robbmzs,

Bekzrurian State CJniverdy, Minsk 220080, Beloncr

Received 19 May 1993; in revised form 17 May 1994; accepted 30 May 1994

Abstract
Electroluminescence
semiconductor
optrodes
(EJ_SOs), electrochemical
optical sensor systems based on recording the
electroluminescence
response from semiconductor electrodes, have been proposed for the detection and analysis of chemical
species in solution. The possibility of developing an ELSO sensitive to hydrogen peroxide in alkaline solutions has been
demonstrated
using TiOl film electrodes.
The electroluminescence
from this optrode arises under conditions of negative
polarization
as a result of hole injection in the TiOz from high-energy OIF radicals formed by the electroreduction
of H,O,
on the electrode surface. The integrated electmluminescence
response as well as a value of the electroluminescence
intensity
measured immediately after applying the pulsed polarization change linearly on a logarithmic scale when the HzOz concentration
changes in the range 1O-3-5X1O-
mol 1-l.
Keywo&: Electroluminescence optical sensor system: Electroluminescence

1. Introduction

Several types of sensors have been developed for

hydrogen peroxide determination in aqueous and organic solutions [l-9]. Chemical sensors with optical
transduction (so-called optrodes), having a number of
advantages (the use of fibre optics, the possibility of
using multiwavelength and temporal information, minimal influences of electrical interferences, etc.) relative
to other sensors, can be distinguished among them
[1,2]. For example, an optical sensor for the determination of hydrogen peroxide in solution has been
developed using peroxidase immobilized in polyacrylamide gel [l]. The chemiluminescence
response was
generated in the presence. of excess ltiol
as the
peroxide diffused into the peroxidase phase. Despite
attractive features, sensors of this type usually have
several limitations (long response times, short lifetime)
because of their use of complex organic molecules as
a reagent [lO-121.
In the present paper we propose electroluminescence
semiconductor optrodes (ELSOs) sensitive to hydrogen
peroxide which, in principle, do not have these limitations. The luminescence in an ELSO arises in the
bulk or/and on the surface of the semiconductor electrode under forward bias as a result of minority carrier

09754005/94/$07.00 Q 1994 Elsevier Science S.A. All rights reserved

SSDI 0925-4005(94)01245-D

semiconductor

optrodes; Hydrogen peroxide sensor; Titanium dioxide

injection into the semiconductor from the species in

solution. We describe the results of studying the electroluminescence processes at titanium dioxide film electrodes in contact with alkaline aqueous solutions containing hydrogen peroxide and demonstrate
the
possibility of making an electrochemical optical sensor
based on such an electrode system for continuous
measurement of H,O, concentration.

2. Experimental

To prepare the TiO, film electrodes, a definite amount

of 1% Ti(OC,I-L& solution in tert-butanol was deposited
on polished titanium plates. The plates were kept in
air for 30 min to evaporate the solvent and to hydrolyse
the Ti(OC4H& and then heated at 200 C. for 30 min
in a humid atmosphere to complete the hydrolysis. This
film-deposition procedure followed by heating was repeated three times. Finally the TiO, electrodes were
heated at 700 C for 1 h in a purified argon atmosphere.
The film thickness estimated by the interference method
was lOOf
nm. According to electron diffraction and
Raman spectroscopy data, the TiOz films obtained have
the crystal structure of rutile.

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S.K. Pomyak, A.I. Kulak I Semom and Actuators B 22 (1994) 97-100

Electroluminescence
(EL) measurements under negative polarization of the TiO, electrodes were taken
using a potent&tat with a programmer in a conventional
three-electrode cell with a platinum counter-electrode
and an Ag/AgC!l reference electrode (+ 0.201 V versus
NHE). All potentials are given with respect to this
reference electrode. The dependences of the EL intensity and cathodic current density on potential were
measured under a linear potential sweep at a rate of
4 mV s-l. Electroluminescence
spectra were obtained
using a Spex Fluorolog spectrofluorimeter
and were
corrected for the spectral sensitivity of the photomultiplier and for the transmission spectrum of the monochromator. We used pulsed polarization of the electrode
for obtaining the dependences of the EL response on
the analyte concentration:
the potential was pulsed
(pulse duration 12 ms) from 0 V to a more negative
potential with a frequency of 23 Hz. The pulsed polarization avoided some irreversible changes of the
electrode surface possible under negative polarization,
and, in addition, the lock-in technique used significantly
increased the sensitivity and the signal-to-noise ratio
of the detection system.
The solutions were prepared using doubly distilled
water and analytical-grade reagents. The electrolyte
was not stirred during the measurements.
The concentration unit, mol l-, is abbreviated to M in the
following.

Potential/V
Fig. 1. Dependences of the overall EL intensity(a) and the cathodic
current density (b) on the potential for TiO? film electrodes in 0.1
M H202 + 0.1 M NaOH.

3. Results and discussion

The EL of TiO, electrodes under negative polarization arises as a result of the radiative recombination
of oxide electrons with holes injected into the valence
band of TiO, from OH radicals [13-161. These radicals,
in turn, were previously shown [17] to arise from the
reduction of H,O, by TiO, conduction-band electrons.
Fig. 1 shows the dependence of the overall EL intensity
(ZEL)on the electrode potential (E) (a) and the cathodic
current density (iJ versus potential curve (b). The EL
appears practically simultaneously with the appreciable
cathodic current related to the reduction of H202. At
potentials more negative than -1.3 to -1.4 V, the
cathodic current levels off owing to the diffusion limitation associated with the transport of species to the
electrode surface; at E < - 1.8 V, the current density
increases again due to the onset of the hydrogen
evolution reaction. The ZELversus E curve has a more
complex shape as compared with the i, versus E curve
(Fig. 1). There is a pronounced peak on the IX-E
curve in the potential region where the current density
does not change markedly with potential. The reasons
for this peak appearance associated with the change
of the EL mechanism were previously considered in
detail [15] and will not be discussed here. It is important

0
700

750

800

Wavelength/nm

850

900

Fig. 2. Spectral distributions of electroluminescence for TiOz film

electrodes measured at -1.0 V (1) and -1.4 V (2) in 0.1 M
HZO,+O.l M NaOH.

to note that at less negative potentials on the front

edge of the ZEL-E curve, the intensity of emitted light
is practically directly proportional to the rate of the
electrochemical reduction of H,O,, i.e., the current
efficiency of EL remains constant with changing potential. Thus, this potential region is the most suitable
for the purposes of H,O, concentration measurement.
The study of the spectral distribution of EL for TiOz
film electrodes revealed that in H,O, solutions the
spectrum of emitted light does not practically depend
on the potential and on the H,O, concentration. There
is only one band peaking at 850 nm in this spectrum
(Fig. 2).
Fig. 3 shows the EL response versus time curves
obtained after applying pulsed polarization in solutions

S.K

Pamy&

A.I. Kuiak I Sensors ad

Actuators

B 22 (1994)

99

97-100

log(C&mol

Time/min
Fig. 3. Time dependences of the EL response for Ti02 film electrodes
in solutions containing 0.01 M HZO,+O.l M NaOH (1) and 0.1 M
H,O,+O.l
M NaOH (2). The potential was pulsed from 0 to - 1.1
V (on, pulsed polarization switch on; off, pulsed polarization switch

I-)

Fig. 4. Dependences of the initial EL intensity measured immediately

after applying the pulsed polarization (1) and the integrated EL
intensity with an integration time of 10 s (2), 20 s (3) and 100 s
(4) on the concentration of H,02 on a logarithmic scale for TiOZ
film electrodes in solutions containing H20,+0.1
M NaOH. The
potential was pulsed from 0 to -1.1 V.

off).

containing H,O, against a background of 0.1 M NaOH.

As seen from Fig. 3, in dilute solutions, an initial sharp
drop in ZEL occurs. This drop is likely to be associated
with
depletion of the near-electrode
region by the
analyte and with the appearance of diffusion limitation
on the analyte transport to the electrode surface. This
assumption is supported by the fact that the Z=-T
curve is almost completely reproduced when applying
pulsed polarization repeatedly after keeping the electrode for some time (1-5 min) in solution under opencircuit conditions. Above 0.05-0.07 M HzOz, there is
no initial drop in the EL response, and even some
increase in I with time occurs (Fig. 3). The reasons
for such behaviour of the electrode system in more
concentrated solutions are not yet completely understood, and may be tentatively associated with the activation of the electrode surface due to the proceeding
electrochemical reaction. The absence of a rise in the
EL response when applying the pulsed polarization
repeatedly after reaching a steady-state value of ZEL
agrees with this assumption (Fig. 3).
Fig. 4 represents the dependence of the EL response
on the HzOz concentration. Curve 1 was plotted using
initial values of Z measured immediately after applying pulsed polarization, while curves 2-4 were plotted
using the data obtained as a result of integrating the
ZEL-T curves with different integration times. As seen
from Fig. 4, the initial values of ZEL and the integrated
EL responses are practically linear functions of the
H,O, concentration, on a logarithmic scale, from 10m3
to 5 X 10-l M. Above 5 X 10-l M, there is a change
in slope and the response levels off. The causes of this
levelling off are not yet clear, and additional investigation
is required.

2.7

-1.5

-1.0

-0.5

log(CnWa/mol

0.0

1-l)

Fig. 5. Dependences of the EL response on the concentration of

NaOH on a logarithmic scale for TiO, film electrodes in alkaline
solutions containing 0.1 M H202 (1) and 0.1 M H202+ 0.25 M Na,SO,
(2).

It should be noted that there is a definite effect of

pH on the EL response of TiO, electrodes in H,O,
solutions (Fig. 5). As seen from Fig. 5, in the region
of relatively low concentrations of alkali (CNaOH< 0.1
M), the shape of log(ZEL) versus log(CNaoH) curves
obtained in alkaline solutions containing 0.1 M H,O,
depends markedly on the presence of an indifferent
supporting electrolyte (for example, 0.25 M Na2S04).
This effect seems to be due to changing the conductivity
of the solutions. At CNaoH> 0.3 M NaOH, the EL
response decreases slightly with increasing alkali concentration. Therefore, for the purposes of H,O, analysis,
the optimal concentration of alkali may range from 0.2
to 0.6 M.
As to the selectivity of the proposed sensor system,
it should be noted that since the TiO, valence-band
edge is located deep in the energy scale, the injection
of minority carriers (holes) into the valence band directly
from most of the known redox species is not possible
[16,17]. Therefore the electrochemical
reduction of
various reducible species such as Fe3+, Fe(CN),3-, Iz,

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S.X Poznyak, A.I. Kulak I Sensors and Actuators B 22 (1994) 97-100

Br, and quinone does not result in the EL of TiO,

electrodes. The appearance of light emission in hydrogen
peroxide solutions occurs due to the specific two-step
mechanism of H,O, electroreduction producing active
intermediates (OH radicals) with a large positive redox
potential (+ 2.0 V versus NHE) during the first step
[ 171. It has previously been shown [ 13-181 that, according
to a similar mechanism (through SO, radicals), persulphate ions are also reduced, giving rise to EL of
the TiOz electrodes. The possibility of using the above
sensor system to measure the concentration of S,O,ions in aqueous solutions is currently under investigation
and results will be reported elsewhere. However, preliminary data suggest that the difference in the dependence of the EL spectrum on the potential for TiO,
electrodes in H202 solutions from that in persulphate
solutions can be used to detect S,O,- ions when they
coexist with H202 in solution.
4. Conclusions

PI
[71

[81

[91

I101

1111
iI.21

1131

In conclusion, we note that the TiOz film electrode

system studied is especially convenient for developing
an electrochemical optical sensor using fibre optics. A
thin film of TiO, may be deposited onto the end of
an optical fibre with an intermediate transparent layer
of conducting SnO, (ITO) providing uniform electric
contact to the TiO, film. The current supply to the
TiO, may be arranged directly along the fibre surface.
Along with photomultipliers, silicon diodes are suitable
for detecting the EL response, since the EL band
peaking at 850 nm falls well within the range of their
maximum spectral sensitivity. An advantage of such
optrodes is not only their high interference immunity
and suitability for on-line monitoring, but also the
possibility of their application for analysis in turbid
solutions.

[141

1151

1161

1171

1181

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Acknowledgement
This work was supported by the Fundamental
search Foundation of Belarus.

Re-

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Biographies
Sergey K. Pozryzk graduated from the Department
of Chemistry, Belorusian State University in 1980. He
received his Doctor (Candidate of Sci. (Chemistry))
degree from the Belorusian State University in 1986.
He is a senior researcher, working in the field of the
electrochemistry and photoelectrochemistry
of semiconductors.
Anafoly I. K&k graduated from the Department of
Chemistry, Belorusian State University in 1976. He is
a Doctor of chemistry and was appointed professor,
Belorusian State University, in 1990. He is a main
researcher, working in the field of the electrochemistry
and photoelectrochemistry
of semiconductors.