Double-layer emersion

The intimate relationship between double layer emersion and parameters fundamental to electrochemical interfaces is shown. The surface dipole layer (xs) of 80SS sat. KC1 electrolyte is measured as the difference in outer potentials of an emersed oxide-coated Au electrode and the electrolyte. The value of +0.050 V compares favorably with previous determinations of g. Emersion of Au is discussed in terms of UHV work function measurements and the relationship between emersed electrodes and absolute half-cell potentials. Results show that either the accepted work function value of Hg in N2 is off by 0.4 eV, or the dipole contribution to the double layer (perhaps the "jellium" surface dipole layer of noble metal electrodes) changes by 0.4 V between solution and UHV. 

HANSEN AND HANSEN Implications of Double-Layer Emersion... 

The results of Figure 2 (and other results (16,19,23) require rethinking as to the role of water in the double layer. It is still not known how much water is present in metal double layers emersed into gas ambient. But we have found in previous work that the amount of water in the emersed double layer on Au does not change with potential (23), and Koetz and Neff found that water was essentially absent in UHV (16) at all measured potentials. Results presented here do not decide the question of how much water is in the double layer in UHV, but they may severely restrict its role. Again, if water dipoles play an important role in double layer formation it is hard to see how their removal could cause a shift in work function which is constant with emersion potential. 

Double layer emersion continues to allow new ways of studying the electrochemical interphase. In some cases at least, the outer potential of the emersed electrode is nearly equal to the inner potential of the electrolyte. There is an intimate relation between the work function of emersed electrodes and absolute half-cell potentials. Emersion into UHV offers special insight into the emersion process and into double layer structure, partly because absolute work functions can be determined and are found to track the emersion potential with at most a constant shift. The data clearly call for answers to questions involving the most basic aspects of double layer theory, such as the role water plays in the structure and the change in of the electrode surface as the electrode goes frcm vacuum or air to solution. 

As a furtlier example for tire meaning of ex situ investigations of emersed electrodes witli surface analytical teclmiques, results obtained for tire double layer on poly crystalline silver in alkaline solutions are presented in figure C2.10.3. This system is of scientific interest, since tliin silver oxide overlayers (tliickness up to about 5 nm) are fonned for sufficiently anodic potentials, which implies tliat tire adsorjDtion of anions, cations and water can be studied on tire clean metal as well as on an oxide covered surface [55, 56]. For tire latter situation, a changed... 

Figure C2.10.3. Ex situ investigation of the electrochemical double layer on Ag after hydrophobic emersion from 1 M NaClO + 0.1 M NaOH. (a) Peak deconvolution of the XPS 01s signals after emersion at +0.2 V A surface...

Kolb D M, Rath D L, Wille R and Flansen W N 1983 An ESCA study on the electrochemical double layer of emersed electrodes Ber. Bunsenges. Phys. Chem. 87 1108-11 131... 

The presence of this backspillover formed effective double layer is important not only for interpreting the effect of electrochemical promotion, but also for understanding the similarity of solid state electrochemistry depicted in Fig. 7.3 with the case of emersed electrodes in aqueous electrochemistry (Fig. 7.2) and with the gedanken experiment of Trasatti (Fig. 7.1) where one may consider that H2O spillovers on the metal surface. This conceptual similarity also becomes apparent from the experimental results. 

In summary, the creation via ion spillover of an effective electrochemical double layer on the gas exposed electrode surfaces in solid electrolyte cells, which is similar to the double layer of emersed electrodes in aqueous electrochemistry, and the concomitant experimentally confirmed equation... 

Electrochemical reactions are driven by the potential difference at the solid liquid interface, which is established by the electrochemical double layer composed, in a simple case, of water and two types of counter ions. Thus, provided the electrochemical interface is preserved upon emersion and transfer, one always has to deal with a complex coadsorption experiment. In contrast to the solid/vacuum interface, where for instance metal adsorption can be studied by evaporating a metal onto the surface, electrochemical metal deposition is always a coadsorption of metal ions, counter ions, and probably water dipols, which together cause the potential difference at the surface. This complex situation has to be taken into account when interpreting XPS data of emersed electrode surfaces in terms of chemical shifts or binding energies. 

Although not the subject of this article, double layer studies are briefly discussed in this paragraph in order to demonstrate that ex situ XPS studies indeed provide information about the state of the electrode exposed to an electrochemical environment at a defined potential. A crucial step in any ex situ experiment is the emersion of the electrode. Here the question arises whether the electrochemical double layer or part of it is preserved at the interface after emersion and transfer. Winograd et al. [10,11] first demonstrated that the electrode under UHV conditions still remembers the electrode potential applied at the time of emersion. These authors investigated oxide formation on Pt and the underpotential deposition of Cu and Ag on Pt by means of XPS and proved that the electrochemically formed oxide layer and... 

The XPS results obtained by Kolb and Hansen are reproduced in Fig. 6 and they clearly demonstrate not only that cations as well as anions stay on the surface but also that the amount of ions exhibits the expected potential dependence even in the case of specific adsorption. The preservation of the double layer charge after emersion was also shown by other techniques like charge monitoring [28] and electroreflectance measurements [29],... 

These measurements have verified that the work function of an electrode, emersed with the double layer intact, depends only on the electrode potential and not on the electrode material or the state of the electrode (oxidized or covered with submonolayer amounts of a metal) [20]. Work function measurements on emersed electrodes do not serve the same purpose as in surface science investigations of the solid vacuum interface. At the electrochemical interface, any change of the work function by adsorption is compensated by a rearrangement of the electrochemical double layer in order to keep the applied potential i.e. overall work function, constant. Work function measurements, however, could well be used as a probe for the quality of the emersion process. Provided the accuracy of the measurement is good enough, a combination of electrochemical and UPS measurements may lead to a determination of the components of equation (4). 

Emersion has been shown to result in the retention of the double layer structure i.e, the structure including the outer Helmholtz layer. Thus, the electric double layer is characterised by the electrode potential, the surface charge on the metal and the chemical composition of the double layer itself. Surface resistivity measurements have shown that the surface charge is retained on emersion. In addition, the potential of the emersed electrode, , can be determined in the form of its work function, , since and represent the same quantity the electrochemical potential of the electrons in the metal. Figure 2.116 is from the work of Kotz et al. (1986) and shows the work function of a gold electrode emersed at various potentials from a perchloric acid solution the work function was determined from UVPES measurements. The linear plot, and the unit slope, are clear evidence that the potential drop across the double layer is retained before and after emersion. The chemical composition of the double layer can also be determined, using AES, and is consistent with the expected solvent and electrolyte. In practice, the double layer collapses unless (i) potentiostatic control is maintained up to the instant of emersion and (ii) no faradaic processes, such as 02 reduction, are allowed to occur after emersion. 

Thus, emersion results in the retention of the double layer of some 10A. However, the substrates commonly employed fall into two categories, depending on whether any additional electrolyte is left behind on the surface or not. 

As was discussed above, it is essential to determine the effect, if any, that the emersion process has on the double layer. To do this, Wilhelm and colleagues have performed the definitive type of blank experiment. CO was adsorbed onto the Pt working electrode from sulphuric acid electrolyte. After adsorption, the CO-saturated solution was replaced with pure electrolyte. The potential of the electrode was then ramped in order to oxidise off the adsorbate, as C02, and the voltammogram so obtained is shown in Figure 2.118(a). The experiment was then repeated CO was adsorbed as before, but the electrode was emersed and transferred into the UHV chamber, before being re-immersed and the potential ramp applied. The voltammogram so... 

Such a comparison has formed the basis, for example, for the assertion that the double layer can be emersed essentially intact from solution /8/. A common ambiguity, although for different reasons, in both emersion and UHV model experiments is the difference in the amount of solvent present either at the emersed or synthesized interface, compared to the in-situ situation. In the UHV the total amount of solvent adsorbed, and its distribution into the first and subsequent layers, can in many instances directly be determined, but this information is difficult to obtain and not yet available for the emersed and the real interface. To gather such missing pieces in the interfacial puzzle is the motivation for the work described in this paper. One important prerequisite for any model of the double layer is, for example, the density of solvent molecules in the inner layer as a function of the charge on the interfacial capacitor. 

Emersion of an electrode from electrolyte with its double layer intact is now a widely accepted phenomenon and technique. Not only is it a phenomenon which deserves careful consideration and study, but also a process which opens up a new set of experimental methods to the study of the electrochemical double layer. Electrode emersion involves the careful removal of an electrode from electrolyte under potentiostatic control, usually hydrophobically 11-5). When fairly concentrated electrolyte parts ("unzips") from the electrode surface during hydrophobic emersion, the double layer remains essentially intact on the electrode surface and no electrolyte outside the double layer remains. This phenctnenon is not due to the presence of organics or other impurities as seme have suggested. The emersion process works well with rigorously clean electrode surfaces (5). 

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