EC-Lab – Application Note #12
2005
UV-Visible spectroscopy and electrochemistry coupling:
Spectroelectrochemical experiment feasibility on a polypyrrol film
I – INTRODUCTION instrument such as a rotating disk electrode or
Electrochemistry alone is no longer deemed a temperature control unit.
sufficient for discrimination and the
advantages of coupling techniques are In our experiment, the potentiostat was
becoming increasingly attractive to synchronized with a UV-visible spectrometer
researchers. for a spectroelectrochemical study of a
polypyrrol film. During a potential sweep, the
Instruments for electrochemical studies must spectroscopic measurements are performed
be able to connect to other external in the visible wavelength range. The diode
instruments. Coupling techniques can make array allows for absorbance measurements at
electrochemistry a powerful means of the same time for all the visible wavelengths.
characterisation. For example, polypyrrol
films have been widely studied in The aim of this paper is to show the feasibility
electrochemistry especially the of spectroelectrochemical measurements
electropolymerisation process [1-3]. Only using the Bio-Logic potentiostat product
using electrochemistry is not now sufficient to range. A polypyrrol film is electrochemically
fully describe the whole electropoly- coated on an ITO glass. The absorbance
merisation process. measurement is synchronized with the
One can easily understand the interest of potential sweep of a cyclic voltammetry using
coupled methods in studying species with a trigger signal.
spectroscopic properties. Electrochemistry
coupled with spectroscopic methods is now a II – EXPERIMENTAL PART
common discriminating technique for
II - 1 ELECTROPOLYMERIZATION
polypyrrol studies [4-7]. Coupling methods
The polypyrrol film was coated on an ITO glass
often results in technical set-up problems
using cyclic voltammetry (20 cycles). The ITO
when synchronizing electrochemical
glass was bulked in an acetonitril solution
experiments and recording external
measurements and variables. (Bu4NPF6 0.2 M) containing 1-methylpyrrol
monomer with a concentration of 10-2 M. The
Our instruments are equipped with auxiliary potential sweep was used instead of a
inputs/outputs. They have been designed to polymerization in potentiostatic mode in
interface external instruments with the order to obtain a smoothed film. The potential
potentiostat with the possibility to sweep was performed from -0.2 V to
synchronize both experiments. Auxiliary 1.015 V/AgCl with a 100 mV/s scan rate. We
inputs/outputs contain a trigger input and a used a three electrode cell with an ITO glass
trigger output either to synchronize an as a working electrode, a platinum wire as a
external instrument with the beginning of the counter electrode, and a saturated calomel
potential sweep on the potentiostat or to electrode as a reference electrode.
synchronize the potentiostat with an external
instrument. All depends on the instrument II - 2 SPECTRO-ELECTROCHEMISTRY
that is sending the trigger. Two auxiliary The spectro-electrochemical measurements
analog inputs are also available and can be were performed in the visible wavelength
used to record auxiliary variables in the range (300 to 750 nm) with a homemade
electrochemistry data file. An analog output spectro-electrochemical cell. The spectro-
can be used to control the external meter used was a diode array with 256 diodes
Bio-Logic Science Instruments, 4 Rue de Vaucanson, 38170 Seyssinet-Pariset, FRANCE
Tel: +33 476 98 68 31 – Fax: +33 476 98 69 09 www.bio-logic.net
1
EC-Lab – Application Note #12
2005
(MOS-DA) allowing 256 simultaneous species are overlaid, showing the stability of
absorbance measurements. The quartz cell the film.
including three electrodes (working, counter,
and reference) and the electrolytic solution The reversibility of the charge transfer in such
(Bu4NPF6 0.1 M) was illuminated with a a polymer film is often deposition mode-
tungsten white light source (acquisition rate: dependent (quasi-reversible in this example).
1 spectra/2 ms). Before the spectroscopic
measurement on the polymer, a spe- Figure 3 shows the 3D spectral plot of the film
ctroscopic blank was made on an ITO glass absorbance vs. time. The time variation is
equivalent to a potential linear variation from
without a polymer in the same conditions. The
-0.2 V vs. AgCl (t = 1 s) to 1 V vs. AgCl (t = 14 s).
ITO glass absorbance will be automatically
subtracted from the other spectroscopic data
This 3D graph shows the polymer film
points by the MOS-DA.
spectroscopic response during its oxidation (p
doping). Some characteristic peaks of
During the spectroelectrochemical mea-
polypyrrol can be seen for λ = 350 nm.
surement, the working electrode potential
(ITO) is controlled by the potentiostat and py _ _ pp
<I> vs. f( Ew e ), cycle 16
swept from -0.2 to 1 V/AgCl (and back to -
0.2 V) with a 100 mV/s scan rate. 0.6
The description of the spectroelectrochemical
assembly can be seen on figure 1. The 0.4
computer is used to manage the diode array
<I>/mA
0.2
with BioKine software and store and plot data
0
points. It is also used to manage the
potentiostat with EC-Lab® software and store -0.2
electrochemical data points. Both instru-
-0.4
ments are triggered together with EC-Lab in 0 0.5 1
order to start the potential sweep and spe- Ewe/V vs. AgCl/Ag
ctroscopic measurement at the same time. Figure 2: Voltammetric response of the polypyrrole
film coated on ITO in a Bu4NPF6 0.1 M solution
(v = 100 mV/s).
Figure 1: Scheme of the spectro-electrochemical
assembly.
III – RESULTS AND DISCUSSION
Figure 2 shows the voltammetric response of
the polymer film in an acetonitril solution
(Bu4NPF6 0.1 M). The voltammogram of Figure
2 shows the stability of the polymer film
coated on the ITO working electrode. Several
cycles made in a solution without monomer
Bio-Logic Science Instruments, 4 Rue de Vaucanson, 38170 Seyssinet-Pariset, FRANCE
Tel: +33 476 98 68 31 – Fax: +33 476 98 69 09 www.bio-logic.net
2
EC-Lab – Application Note #12
2005
Figure 3: 3D spectroscopic response of the polypyrrol 7) E. Krivan, G. Peintler, C. Visy, Electrochim.
film coated on ITO to a potential sweep from -0.2 V vs. Acta, 50 (2005) 1529.
AgCl to 1 V vs. AgCl in a Bu4NPF6 0.1 M solution.
Revised in 08/2019
IV – CONCLUSION
The results presented above show the
feasibility of spectroelectrochemical mea-
surements using our potentiostat product
range. Triggered with the diode array, the
potential sweep, made by the potentiostat,
and the spectroscopic measurement, made by
the diode array, start at the same time. With
BioKine software, the 3D curve can easily be
turned and switched to a 2D curve (either
versus time or versus wavelength).
The spectro-electrochemical cell used in this
experiment has not been specifically designed
for this experiment. It is often difficult to have
a standard cell for this kind of experiment that
can be used by every customer. Fortunately,
we can develop and design particular cells
upon customers' requests.
Using Analog inputs of the potentiostat, the
user can store, plot, and analyze data
generated by an external instrument.
Data files can be found in : C:\Users\xxx-
\Documents\EC-Lab\Data\Samples\-
Fundamental Electrochemistry\CV_QCA
REFERENCES
1) M. Zhou, J. Heinze, Electrochim. Acta, 44
(1999) 1733.
2) M. Zhou, J. Heinze, J. Phys. Chem B, 103
(1999) 8443.
3) M. Zhou, J. Heinze, J. Phys. Chem B, 103
(1999) 8451.
4) W. Plieth, G.S. Wilson and C. Gutierrez De
La Fe, Pure and Appl. Chem., 70 (7) (1998)
1395.
5) C. Visy, E. Krivan, G. Peintler, J. Of
Electroanal. Chem., 462 (1999) 1.
6) K. Crowley, J. Cassidy, J. Of Electroanal.
Chem., 547 (2003) 75.
Bio-Logic Science Instruments, 4 Rue de Vaucanson, 38170 Seyssinet-Pariset, FRANCE
Tel: +33 476 98 68 31 – Fax: +33 476 98 69 09 www.bio-logic.net
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