Potential modulation

After this step, the understanding of microwave electrochemical mechanisms deepened rapidly. G. Schlichthorl went to the laboratory of L. Peter to combine potential-modulated microwave measurements with impedance measurements, while our efforts focused on laser pulse-induced microwave transients under electrochemical conditions. It is hoped that the still relatively modest knowledge provided will stimulate other groups to participate in the development of microwave photoelectrochemistry. 

Another technique consists of MC measurements during potential modulation. In this case the MC change is measured synchronously with the potential change at an electrode/electrolyte interface and recorded. To a first approximation this information is equivalent to a first derivative of the just-explained MC-potential curve. However, the signals obtained will depend on the frequency of modulation, since it will influence the charge carrier profiles in the space charge layer of the semiconductor. 

The combination of photocurrent measurements with photoinduced microwave conductivity measurements yields, as we have seen [Eqs. (11), (12), and (13)], the interfacial rate constants for minority carrier reactions (kn sr) as well as the surface concentration of photoinduced minority carriers (Aps) (and a series of solid-state parameters of the electrode material). Since light intensity modulation spectroscopy measurements give information on kinetic constants of electrode processes, a combination of this technique with light intensity-modulated microwave measurements should lead to information on kinetic mechanisms, especially very fast ones, which would not be accessible with conventional electrochemical techniques owing to RC restraints. Also, more specific kinetic information may become accessible for example, a distinction between different recombination processes. Potential-modulation MC techniques may, in parallel with potential-modulation electrochemical impedance measurements, provide more detailed information relevant for the interpretation and measurement of interfacial capacitance (see later discus-... 

Light intensity and potential-modulated microwave measurements <5//. SDU—t Microwave impedance spectroscopy ... 

Electrochemical impedance spectroscopy leads to information on surface states and representative circuits of electrode/electrolyte interfaces. Here, the measurement technique involves potential modulation and the detection of phase shifts with respect to the generated current. The driving force in a microwave measurement is the microwave power, which is proportional to E2 (E = electrical microwave field). Therefore, for a microwave impedance measurement, the microwave power P has to be modulated to observe a phase shift with respect to the flux, the transmitted or reflected microwave power APIP. Phase-sensitive microwave conductivity (impedance) measurements, again provided that a reliable theory is available for combining them with an electrochemical impedance measurement, should lead to information on the kinetics of surface states and defects and the polarizability of surface states, and may lead to more reliable information on real representative circuits of electrodes. We suspect that representative electrical circuits for electrode/electrolyte interfaces may become directly determinable by combining phase-sensitive electrical and microwave conductivity measurements. However, up to now, in this early stage of development of microwave electrochemistry, only comparatively simple measurements can be evaluated. 

Another technique for flatband determination is based on the measurement of potential-modulated microwave conductivity signals and is described further in the next section. 

An interesting special application has been proposed by Schlichthorl and Peter.31,41 It aims at deconvolution of electrochemical impedance data to separate space charge and surface capacitance contributions. The method relies on detection of the conductivity change in the semiconductor associated with the depletion of majority carriers in the space charge region via potential-modulated microwave reflectivity measurements. The electrode samples were n-Si(lll) in contact with fluoride solution. 

Figure 39. Potential-modulated (derived) microwave conductivity and potential-modulated current signals as a function of the electrode potential for a dark (a) and (b) illuminated n-WSej electrode in contact with a 50 mM [Fe(CN)fi]3-/4 electrolyte solution.

A linear expansion of this equation for a small-amplitude potential modulation, SU, leads to the microwave reflectivity change... 

Gutierrez, C. Potential-Modulated Reflectance Spectroscopy Studies of the Electronic Transitions of Chemisorbed Carbon Monoxide 28... 

The measurement of the electrode impedance has also been ealled Faradaie impedanee method. Since measurements are possible by applying either an electrode potential modulated by an AC voltage of discrete frequeney (which is varied subsequently) or by applying a mix of frequencies (pink noise, white noise) followed by Fourier transform analysis, the former method is sometimes called AC impedance method. The optimization of this method for the use with ultramicroelectrodes has been described [91Barl]. (Data obtained with these methods are labelled IP.)... 

The reflectance, R, is defined as the ratio of the reflected light intensity to the intensity of the incident beam. Usually, one determines the change in reflectance, A/ , induced by some parameter, such as the electrode potential. Experimentally, one measures only the intensity of the reflected beam, 4. So if the incident intensity remains constant, the reflected beam gives hJl/R = A4/4. Experimental results are presented as plots of A/J/R vs. the parameter of interest, such as the frequency of the incident light or electrode potential. Modulation schemes, wherein the beam is chopped or the potential is modulated, are used to enhance the signal-to-noise ratio. 

Analysis of Zje and Z- as a function of the frequency of potential modulation (Randles plots) provides the phenomenological ET rate constant [63,74]. It should be noted that the extrapolation of Z at high frequency gives effectively the sum 7 ct + where 7 ct is the charge transfer resistance. 

FIG. 9 Real component of the AC current (a) and imaginary part of the normalized potential-modulated reflectance (b) for the TCNQ reduction by ferrocyanide at the water-DCE interface. Experimental conditions as in Fig. 5. The potential modulation was 30 mV rms at 3.2 EIz. (c) Optical Randles plot obtained from the frequency-dependent analysis of the PMR responses. (Reprinted from Ref 43 with permission from Elsevier Science.)... 

Electrochemically Modulated Infra-Red Spectroscopy (EMIRS) [23] consists of applying a square-wave potential modulation to the working electrode and analyzing the modulated part of the IR detector response using a dispersive instrument. 

Other than an effect on backbone solvation, side chains could potentially modulate PPII helix-forming propensities in a number of ways. These include contributions due to side chain conformational entropy and, as discussed previously, side chain-to-backbone hydrogen bonds. Given the extended nature of the PPII conformation, one might expect the side chains to possess significant conformational entropy compared to more compact conformations. The side chain conformational entropy, Y.S ppn (T = 298°K), available to each of the residues simulated in the Ac-Ala-Xaa-Ala-NMe peptides above was estimated using methods outlined in Creamer (2000). In essence, conformational entropy Scan be derived from the distribution of side chain conformations using Boltzmann s equation... 

In general, biomolecules such as proteins and enzymes display sophisticated recognition abilities but their commercial viability is often hampered by their fragile structure and lack of long term stability under processing conditions [69]. These problems can be partially overcome by immobilization of the biomolecules on various supports, which provide enhanced stability, repetitive and continuous use, potential modulation of catalytic properties, and prevention of microbial contaminations. Sol-gel and synthetic polymer-based routes for biomolecule encapsulation have been studied extensively and are now well established [70-72]. Current research is also concerned with improving the stability of the immobilized biomolecules, notably enzymes, to increase the scope for exploitation in various... 

If the crystal is a semiconductor such as Si, it can be used as the working electrode itself and this was the means employed in the early experiments. However, the limited number of suitable electrode materials available was a severe restriction and attempts to use metal-coated crystals suffered severely from the low sensitivity caused by the attenuation of the IR beam by the coating. In addition, lock-in detection is mainly limited to those electrochemical systems capable of responding sufficiently rapidly to the imposed potential modulation. 

The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

The intensity difference, A R/R, observed in a potential-modulation IR experiment may result from several sources ... 

The spectra in Figure 2.44(b) show the dependence of the EMIRS response on the amplitude of the potential modulation. These were reported to indicate a decrease in coverage by adsorbed species on entering the region of sustained methanol oxidation, as would be expected. 

Polarisation modulation infrared rejiection-absorption spectroscopy (PM-IRRAS or JRRAS). Potential modulation IR studies rely on switching the potential at a reflective electrode between rest and active states, generating difference spectra. However, the EMIRS technique has several drawbacks the relatively fast potential modulation requires that only fast and reversible electrochemical process are investigated the absorption due to irreversibly chemisorbed species would be gradually eliminated by the rapid perturbation. Secondly, there is some concern that rapid modulation between two potentials may, to some extent, in itself induce reactions to occur. 

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