Ex situ low-energy electron diffraction

Ex Situ Low-Energy Electron Diffraction and Auger Electron Spectroscopy and Electrochemical Studies of the Underpotential Deposition of Lead on Cu(lOO) and Cu(lll)... 

As mentioned previously, this can be attributed in part to the lack of structure-sensitive techniques that can operate in the presence of a condensed phase. Ultrahigh-vacuum (UHV) surface spectroscopic techniques such as low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), and others have been applied to the study of electrochemical interfaces, and a wealth of information has emerged from these ex situ studies on well-defined electrode surfaces.15"17 However, the fact that these techniques require the use of UHV precludes their use for in situ studies of the electrode/solution interface. In addition, transfer of the electrode from the electrolytic medium into UHV introduces the very serious question of whether the nature of the surface examined ex situ has the same structure as the surface in contact with the electrolyte and under potential control. Furthermore, any information on the solution side of the interface is, of necessity, lost. 

Surface analytical methods — Important ex situ methods for surface analysis are X-Ray Photoelectron Spectroscopy (XPS) UV-Photoelectron Spectroscopy (UPS), Auger Electron Spectroscopy (AES), Ion Scattering Spectroscopy (ISS), Rutherford Backscattering (RBS), Secondary Ion Mass Spectroscopy (SIMS), Scanning Electron Microscopy (SEM), Electron Microprobe Analysis (EMA), Low Energy Electron Diffraction (LEED), and High Energy Electron Diffraction (RHEED). 

In the case of alloy electrocatalysts, the identification of the alloy constituent (at the topmost layers) during the electrocatalytic reaction is rather difficult. Therefore, the assumption of stability after the reaction makes the study rather simpler. In this case, the UHV conditions can be applied only in the ex situ variation, and then an idea of the process mechanism is also required. Not many techniques can be used for the identification of the alloy constituents. However, techniques under a high vacuum condition are applied x-ray photoelectron spectroscopy (XPS), Auger spectroscopy, low-energy ion scattering, and low-energy electron diffraction. 

Among the ex situ methods that can be employed in surface analysis, low-energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) can give the crystal structure and the nature of the surface ad-layers after the electrochemical and adsorption experiments as explained in this chapter [31,32]. Among the in situ non-electrochemical techniques, the radiotracer method [33] gives information about the adsorbed quantities however, infrared spectroscopy in FTIR mode [34] allows the identity of the bonding of the adsorbed molecules, and finally ellipsometry [35] makes possible the study of extremely thin films. Recently, some optical methods such as reflectance, x-ray diffraction, and second harmonic generation (SHG) [36] have been added to this list. 

Ex situ macroscopic properties of adsorbates and interphases not sensitive towards a transfer of the sample from the electrochemical cell into an analysis system (in most cases a UHV chamber) can be studied with additional techniques. The crystallographic data can be derived from low energy electron diffraction (LEED) [72] this is possible only if the sample has a minimum degree of ordering. 

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