MODULATED INFRARED-SPECTROSCOPY AT THE ELECTROCHEMICAL INTERFACE

被引:12
作者
CHAZALVIEL, JN
DUBIN, VM
MANDAL, KC
OZANAM, F
机构
[1] Laboratoire de Physique de la Matirère Condensdèe, CNRS, Ecole Polytechnique
[2] Minsk Radioengineering Institute, Minsk
关键词
INFRARED; MODULATION; ELECTROCHEMISTRY; INTERFACE;
D O I
10.1366/0003702934067658
中图分类号
TH7 [仪器、仪表];
学科分类号
0804 ; 080401 ; 081102 ;
摘要
Performing infrared spectroscopy of chemical species at the electrochemical interface represents a difficult challenge in terms of sensitivity (1 monolayer approximately 10(15) species/cm2) and selectivity (presence of the electrolyte). These problems are efficiently addressed by using modulation coupled with lock-in detection of the optical signal. The electrode potential, which governs the interface behavior, is the most straightforward physical quantity that can be modulated. Such a modulation technique may be combined with Fourier transform spectroscopy by using an interferometer with a very slow scanning speed of the movable mirror (approximately 1-10 mum/s). This approach allows one to reach high sensitivity (typical minimum detectable signal DELTAI/I approximately 10(-6) in a single-reflection arrangement). In some special cases, other modulations may be of interest, for example, modulation of the light at a semiconducting photoelectrode. A common benefit of these modulation techniques is that the resulting response can be analyzed as a function of the modulation frequency or by consideration of the phase of the signal at a given frequency. As can be shown for several examples, this analysis allows one to distinguish between the various physical and electrochemical processes taking place at the interface: change of free-carrier concentration beneath the electrode surface or of ion populations in the ionic double layer, adsorption-desorption effects, and Faradaic processes, for which useful information on the reaction mechanisms may be obtained.
引用
收藏
页码:1411 / 1416
页数:6
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