Counter and Reference Electrodes

As shown on Fig. 4.1, the counter and reference electrodes are deposited on the opposite side of the gas-impervious sohd electrolyte component, which is typically 500 pm to 2 mm thick. The electrolyte thickness is not crucial, but it is preferable to keep it low, so that the ohmic drop in it is small during operation, preferably below 100-600 mV. 

Both the counter and the reference electrodes are essential for fundamental NEMCA studies. They need not be of the same material with the catalyst. The counter electrode-solid electrolyte interface does not have to be polarizable. In fact, it is advantageous when it is not, because then most of the applied potential difference ends up as overpotential at the catalyst and not at the counter electrode. 

The reference electrode-solid electrolyte interface must also be non-polarizable, so that rapid equilibration is established for the electrocatalytic charge-transfer reaction. Thus it is generally advisable to sinter the counter and reference electrodes at a temperature which is lower than that used for the catalyst film. Porous Pt and Ag films exposed to ambient air have been employed in most previous NEMCA studies.1,19 

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The apparatus consists of a tip-position controller, an electrochemical cell with tip, substrate, counter and reference electrodes, a bipotentiostat and a data-acquisition system. The microelectrode tip is held on a piezoelectric pusher, which is mounted on an inchwomi-translator-driven x-y-z tliree-axis stage. This assembly enables the positioning of the tip electrode above the substrate by movement of the inchwomi translator or by application of a high voltage to the pusher via an amplifier. The substrate is attached to the bottom of the electrochemical cell, which is mounted on a vibration-free table [, and ]. A number... 

Figure Bl.28.8. Equivalent circuit for a tliree-electrode electrochemical cell. WE, CE and RE represent the working, counter and reference electrodes is the solution resistance, the uncompensated resistance, R the charge-transfer resistance, R the resistance of the reference electrode, the double-layer capacitance and the parasitic loss to tire ground.

The changes in the optical absorption spectra of conducting polymers can be monitored using optoelectrochemical techniques. The optical spectmm of a thin polymer film, mounted on a transparent electrode, such as indium tin oxide (ITO) coated glass, is recorded. The cell is fitted with a counter and reference electrode so that the potential at the polymer-coated electrode can be controlled electrochemically. The absorption spectmm is recorded as a function of electrode potential, and the evolution of the polymer s band stmcture can be observed as it changes from insulating to conducting (11). 

FIGURE 6-20 Configuration of a penicillin sensor based on an microarray electrode coated with a pH-responsive polypyrrole. Vq = gate voltage VD = drain voltage ID = drain current PS = potentiostat CE and RE = counter and reference electrodes, respectively. (Reproduced with permission from reference 76.)... 

In the single-chamber type reactor (Fig. 4.1b) all three electrodes (catalyst-working (W), counter (C) and reference (R)), electrode are all in the same chamber and are all exposed to the reactants and products.1 3 In this case the counter and reference electrodes must be made from a catalytically inert (e.g. Au) material for otherwise the catalytic rate on them will obscure the measured (via gas-chromatography or mass-spectrometry, Fig. 4.2) rate on the catalyst-working electrode. 

Figure 9.32. Experimental set-up (a) Machinable ceramic holders and two proton conducting pellets showing the location of catalyst, counter and reference electrodes, (b) Twenty four pellet unit, (c) High-pressure reactor, gas feed and analysis unit.43 Reprinted with permission from the American Chemical Society.

Figure 1. Schematic of the gas recycle electrocatalytic or catalytic reactor separator WE, CE and RE are the working, counter and reference electrodes respectively PCV product collection vessel.

Figure 2.25 Schematic representation of the STM head and electrochemical assembly. (I) Inchworm motor, (2) Inch worm, (3) Faraday cage around tube scanner, (4) Teflon electrochemical cell, (5) working electrode (i.e. sample), (6) stainless steel plates, (7) halved rubber O rings, (8) elasticated ropes attatched to baseplate. The counter and reference electrodes and the various electrical connections arc not shown for clarity. From Christensen (1992).

Figure 48. Anodic stability as measured on a spinel LL-Mn204 cathode surface for EMS-based electrolytes (a) Lilm (b) LiC104 (c) LiTf. In all cases, 1.0 m lithium salt solutions were used, and slow scan voltammetry was conducted at 0.1 mV s with lithium as counter and reference electrodes and spinel LiJV[n204 as working electrode. (Reproduced with permission from ref 75 (Figure 3). Copyright 1998 The Electrochemical Society.)...

The electrochemical properties of the microma-chined electrode arrays have been determined for several of the electrode materials. In these half-cell experiments, the electrode array served as the working electrode and lithium as the counter and reference electrodes. The first experiments were carried out on carbon arrays composed of powders of Ketjen Black. Reversible intercalation and deintercalation of lithium were obtained, and reversible capacities in the range of 0.4—0.5 mA h cm were reported. 

Fig. 3.5,19 Open-circuit voltage (K. ) for CdS formed in 9-layer CdAr films as a function of particle size (estimated from UV/visible absorption spectra). The electrolyte was 1.0 M Na2S03 at pH 7.25, and platinum and standard calomel electrodes were used as the counter and reference electrodes, respectively. (From Ref. 5.)...

Fig. 5.30 Cells for ITIES measurements (a) cell with a stationary interface for voltammetry and (b) cell with a dropping electrolyte electrode for polarography. 1 aqueous electrolyte phase 1 aqueous electrolyte drop 2 organic phase 3 Teflon capillary 4 reservoir of aqueous electrolyte. CE and RE denote the counter and reference electrodes.

There are several other methods of achieving stability in potentiostatic circuits. A capacitor may be added between the counter and reference electrodes to reduce phase shift in the critical frequency region. Some caution must be exercised since a low-resistance reference electrode then becomes the counterelectrode at high frequencies. A particularly interesting method is known as input lead-lag compensation a series RC is connected between the input terminals of the control amplifier, and a second resistor is connected between the noninverting input and common. This form of compensation has minimum effect on the slew rate of the control amplifier. Further details can be found in the book by Stout and Kaufman listed in the bibliography. 

A 663 VA Stand (Metrohm, Herisau, Switzerland) in connection with a PGSTAT 20 and a software version 4.4 were used for all potentiometric measurements. A glassy carbon electrode and a Ag/AgCl (0.1 mol/L KC1) served as the counter and reference electrodes in the cell. 

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