Thin layer electrochemical cell

An electrochemical vapor deposition (EVD) technique has been developed that produces thin layers of refractory oxides that are suitable for the electrolyte and cell interconnection in SOFCs (9). In this technique, the appropriate metal chloride (MeCl ) vapor is introduced on one side of a porous support tube, and H2/H2O gas is introduced on the other side. The gas environments on both sides of the support tube act to form two galvanic couples, ie. 

Method Abs, chemical reduction, monitored by absorption spectroscopy CD, chemical reduction, monitored by CD spectroscopy CD/OTTLE, electrochemical reduction using an optically transparent thin layer (OTTLE) cell, monitored by CD spectroscopy CV, cyclic voltammetry EPR, chemical reduction, monitored by EPR. 

Fig. 10. Flow-through electrochemical cell designs. I, Planar geometries, thin-layer (A) and wall-jet (B) flow cell designs. II, Cylindrical geometries, open tubular (A), wire in a capillary (B), and packed-bed (C) flow cell designs...

Figure 15.2 Schematic representation of different electrochemical cell types used in studies of electrocatalytic reactions (a) proton exchange membrane single cell, comprising a membrane electrode assembly (b) electrochemical cell with a gas diffusion electrode (c) electrochemical cell with a thin-layer working electrode (d) electrochemical cell with a model nonporous electrode. CE, counter-electrode RE, reference electrode WE, working electrode.

Investigation of intermediates of an electrode reaction and rapid determination of the electrochemical equivalents may be achieved by means of thin-layer electrolytic cell only about 10 im thick, consisting of two platinum electrodes which are the opposing spindle faces of an ordinary micrometer. 

Fig. 9. LEED Auger electrochemical UHV system with electrochemical thin layer cell. After [39].

The system developed by O Grady is reproduced in Fig. 9. A key element of this arrangement is the electrochemical thin layer cell, using a combined Pd-hydrogen reference and counter electrode, thus minimizing the amount of electrolyte necessary for the electrochemical treatment. This type of cell is particularly useful for double layer studies but cannot be used for gas evolution or corrosion experiments at higher current densities. For a collection and discussion of other transfer systems the reader is referred to the review article by Sherwood [43]. 

For the in situ studies, an electrochemical cell was designed to hold the nearly perfect copper crystal in contact with a thin layer (20 to 50 /Am) of electrolyte. Figures 34 and 35 show the cells employed in the ex situ and in situ experiments, respectively. In addition, Fig. 34 shows the voltammetric traces obtained for the deposition of T1 in the presence and absence of oxygen. In the... 

Bergstrom et al. [63] used HPLC for determination of penicillamine in body fluids. Proteins were precipitated from plasma and hemolyzed blood with trichloroacetic acid and metaphosphoric acid, respectively, and, after centrifugation, the supernatant solution was injected into the HPLC system via a 20-pL loop valve. Urine samples were directly injected after dilution with 0.4 M citric acid. Two columns (5 cm x 0.41 cm and 30 cm x 0.41 cm) packed with Zipax SCX (30 pm) were used as the guard and analytical columns, respectively. The mobile phase (2.5 mL/min) was deoxygenated 0.03 M citric acid-0.01 M Na2HP04 buffer, and use was made of an electrochemical detector equipped with a three-electrode thin-layer cell. The method was selective and sensitive for mercapto-compounds. Recoveries of penicillamine averaged 101% from plasma and 107% from urine, with coefficients of variation equal to 3.68 and 4.25%, respectively. The limits of detection for penicillamine were 0.5 pm and 3 pm in plasma and in urine, respectively. This method is selective and sensitive for sulfhydryl compounds. 

External reflectance. The most commonly applied in situ IR techniques involve the external reflectance approach. These methods seek to minimise the strong solvent absorption by simply pressing a reflective working electrode against the IR transparent window of the electrochemical cell. The result is a thin layer of electrolyte trapped between electrode and window usually 1 to 50 pm. A typical thin layer cell is shown in Figure 2.40. 

Spectroelectrochemical cells for use in the UV-visible region are not, of course, constrained by solvent absorption and can thus be of a reasonable size to give acceptable electrochemical behaviour. However, as with all the in situ techniques discussed in this book, a thin-layer approach is one of the methods employed. 

The major applications of the OTTLE cell are (i) to obtain spectra of electrogenerated species and thence to obtain the extinction coefficients of its major absorption bands, and (ii) to determine the standard redox potential of a reversible couple. The latter experiment relies on the thin-layer electrochemical characteristics of the cell. Thus, for the couple ... 

Figure 2.105 Optically transparent thin layer electrochemical (OTTLE) cell. A = PTFE cell body, B = 13 x 2 mm window, (C and E) = PTFE spacers, D = gold minigrid electrode, F = 25 mm window, G = pressure plate, H = gold working electrode contact, 1 = reference electrode compartment, J = silver wire, K = auxiliary electrode and L = solution presaturator. From Ranjith...

Figure 2.115 shows a schematic representation of the DEMS apparatus. In essence, the electrochemical cell is separated from a mass spectrometer by a porous, non-wetting PTFE membrane of very small pore size. The working electrode is then deposited as a porous metal layer on the thin... 

Fig. 3. Diagrams of electrochemical cells used in flow systems for thin film deposition by EC-ALE. A) First small thin layer flow cell (modeled after electrochemical liquid chromatography detectors). A gasket defined the area where the deposition was performed, and solutions were pumped in and out though the top plate. Reproduced by permission from ref. [ 110]. B) H-cell design where the samples were suspended in the solutions, and solutions were filled and drained from below. Reproduced by permission from ref. [111]. C) Larger thin layer flow cell. This is very similar to that shown in 3A, except that the deposition area is larger and laminar flow is easier to develop because of the solution inlet and outlet designs. In addition, the opposite wall of the cell is a piece of ITO, used as the auxiliary electrode. It is transparent so the deposit can be monitored visually, and it provides an excellent current distribution. The reference electrode is incorporated right in the cell, as well. Adapted from ref. [113],...

The starting potentials for most atomic layers, in this group, were obtained by studies of the voltammetry for an element on a Au electrode [130, 144-146], usually using a thin-layer electrochemical cell (TLEC) (Figure 13) [147, 148]. UPD potentials on Au are not expected to be optimal for growth of a compound however, they are generally a good start. 

Fig. 13. Schematic diagram of a thin layer electrochemical cell (TLEC).

Traditionally, the electrochemical analysis of thin layers of electrodeposited nonequilibrium alloys has simply involved either galvanostatic or potentiostatic dissolution of the electrodeposit under conditions where passivation and/or replacement reactions can be avoided [194, 195]. A technique based on ALSY at a RDE has also become popular [196], To apply this technique, a thin layer (a 10 pm) of the alloy of interest is deposited on a suitable electrode in a solution containing the reducible ions of the alloy components. The plated electrode is then removed to a cell containing an electrolyte solution that is devoid of ions that can be reduced at the initial potential of the experiment, and the complete electrodeposit is anodically dissolved from the electrode surface using slow scan ALSV while the electrode is rotated. 

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