Bipotentiostat

Several designs for STM electrochemical cells have appeared in the literature [M]- hr addition to an airtight liquid cell and the tip insulation mentioned above, other desirable features include the incorporation of a reference electrode (e.g. Ag/AgCl in saturated KCl) and a bipotentiostat arrangement, which allows the independent control of the two working electrodes (i.e. tip and substrate) [ ] (figure BL19.11). 

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... 

Background current, 21, 65 Background subtraction, 40, 106 Bacteria electrode, 182 Band microelectrodes, 130, 135 Beryllium, 82 Bienzyme electrodes, 175 Biocatalytic devices, 172 Biological recognition, 171 Biosensors, 50, 171 Bipotentiostat, 106 Blood electrolyte, 165 Boltzmann equation, 19 Brain analysis, 40, 116 Butler-Volmer equation, 14... 

In the dual-electrode techniques, the potential of each electrode is controlled with a bipotentiostat so that a small constant potential difference is maintained across the polymer film as its potential is slowly scanned, relative to a reference electrode. Figure 10 shows the results of this type of experiment for poly(3-methylthiophene) in SO20).37... 

At the RRDE, however, so-called collection experiments, the actual purpose of its integrated construction, are often carried out, i.e., in a solution of, for instance, only ox of a reversible redox couple ox + ne red, a cathodic current at the disc iD produces red, which reaches the ring where it is completely reoxidized to ox, because the ring is maintained at a sufficiently positive potential ER an RE, generally an SCE, is used together with a bipotentiostat for precise adjustment of the potentials ED and ER required. 

For in situ investigations of electrode surfaces, that is, for the study of electrodes in an electrochemical environment and under potential control, the metal tip inevitably also becomes immersed into the electrolyte, commonly an aqueous solution. As a consequence, electrochemical processes will occur at the tip/solution interface as well, giving rise to an electric current at the tip that is superimposed on the tunnel current and hence will cause the feedback circuit and therefore the imaging process to malfunction. The STM tip nolens volens becomes a fourth electrode in our system that needs to be potential controlled like our sample by a bipotentiostat. A schematic diagram of such an electric circuit, employed to combine electrochemical studies with electron tunneling between tip and sample, is provided in Figure 5.4. To reduce the electrochemical current at the tip/solution... 

Marken F, Compton RG (1996) Electrochemistry in the presence of ultrasound the need for bipotentiostatic control in sonovoltammetric experiments. Ultrason Sonochem 3 S131 —S134... 

The first STM experiments were performed under UHV conditions, and so the bias potential was simply applied as a difference across the tip and sample. However, introducing an electrolyte above the sample brought with it some particular problems. It is no longer sufficient simply to apply a bias voltage equal to the potential difference between tip and sample as this means that the potentials of the tip and sample are undefined with respect to any fixed reference, a wholly undesirable situation. Consequently, modern electrochemical STM systems operate under bipotentiostatic control with the tip and sample controlled and monitored independently with respect to the reference electrode. The bias potential is then still given by (Fs — FT), but VT and Fs are now potentials with respect to the reference electrode. 

Electrochemical Equipment. Electrochemical experiments were performed using either a PAR Model 175 universal programmer and a PAR Model 363 potentiostat/galvanostat, or a Pine Instruments RDE-4 bipotentiostat, coupled with a Kipp and Zonen BD 91 X-y-y recorder. The current-time response for the chronoamperometry experiments was recorded with a Nicolet 4094 digital oscilloscope. All potentials were measured vs. a Ag/10"2 M Ag+ reference electrode. 

In addition, a bipotentiostat is used to control the tip potential with respect to the surface and independent of control of the surface potential with respect to the reference electrode. The tip potential E, is given by E, = Eg + E , where Eg is the bias potential that generates the tnnneling current between tip and surface, and E (a vital variable not typical of other applications of STM and AFM) is the potential of the surface relative to the reference electrode. 

Three-electrode control systems are widely available in the market and there are also four-electrode systems for double working electrodes. The construction is either integral or modular. It is perfectly possible to construct the necessary electronics in-house and, in this case, modular construction is suggested as being more flexible. Operational amplifiers and other components of high quality should be used, particularly for kinetic applications. The elements of a bipotentiostat (independent control of two working electrodes) and a galvanostat are described in ref. 139. 

The specific electrochemical behaviour of IDAs is result of its design [97], i.e. two arrays intercalated and individually addressed in a bipotentiostatic system where reversible redox species can be cycled between one array (generator) and the other array (collector) (Fig. 32.3). The feedback obtained, greatly enhances the current and high sensitive detection can be achieved. An important application of IDAs is the electrochemical detection of p-aminophenol when it is generated from p-aminophenyl phosphate, by enzymatic reaction with alkaline phosphatase (like enzymatic label), in geno- [98-100] and immunoassays [101-103]. Another interesting feature of IDAs is the possibility of... 

Fig. 37.1. Schematic setup of the SECM. Depending on the experiment, the sample may or may not be connected to the second channel of a bipotentiostat.

Biotin 629, 808 Biphasic system el45 Bipotentiostat 909 Bis(l-butylpentyl)adipate 60 Bis-pyrene 821 Bismuth electrodes 144 based metal sensor 136 Blood 6 electrolytes 5 gases 5 plasma 6... 

The scanning electrochemical microscope (SECM) consisted of a positioning system from Marzhauser (Wetzlar, Germany), a bipotentiostat CH701 (CH Instruments, Austin, TX, USA) and a homemade control software. 

Instrumentation. All electrochemical experiments were carried out in a conventional one-compartment cell. Potentials were applied to the cell with a bipotentiostat (Pine Instruments Inc., USA) model RDE4. Current-time responses were recorded on a XYY recorder model BD 91 (Kipp Zonen, USA) equiped with a time base module. All potentials were measured and quoted against a saturated calomel electrode (SCE). 

Apparatus Cyclic voltammetry and amperometric current-time curves were obtained with a Pine Instrument Inc., Model RDE4 bipotentiostat and Kipp Zonen BD 91 XYY recorder equipped with a time base module. All measurements were performed in a conventional single-compartment cell with a saturated calomel electrode as the reference electrode and a Pt mesh as the auxiliary electrode at room temperature. Chronoamperometry was made with EG G Princeton Applied Research potentiostat/galvanostat Model 273 equipped with Model 270 Electrochemical Analysis Software. 

Figure 1 shows a schematic diagram of the basic SECM instrument employing an amperometric microprobe. An UME tip is attached to a three-dimensional (3D) piezo positioner controlled by a computer, which is also used for data acquisition. A bipotentiostat (i.e., a four-electrode potentiostat) controls the potentials of the tip and/or the substrate versus the reference electrode and... 

Many SECM experiments require biasing the substrate. A bipotentiostat in Fig. 1 is used to control both the tip and substrate potentials. Unless transient measurements are made, the response of the bipotentiostat does not have to be fast. More importantly, it should be capable of measuring a broad range of current responses a picoamp scale (or even sub-pA) tip current and a much higher current at a macroscopic substrate. For this reason, it is convenient to have several choices of preamplifiers/current-to-voltage transducers. 

Fig. 7.8. Bipotentiostat circuit for control of the potential of two working electrodes. All resistances are equal, except RD and RK which are variable.

A bipotentiostat controls the potential of two working electrodes independently, and measures the current that they pass. A typical circuit is shown in Fig. 7.8. Bipotentiostats are necessary in performing studies with double hydrodynamic electrodes (Sections 8.5-8.7). 

Bipotentiostat — An instrument that can control the potential of two independent -> working electrodes. A - reference electrode and an -> auxiliary electrode are also needed therefore the cell is of the four-electrode type. Bipotentiostats are most often employed in electrochemical work with rotating ring-disk electrodes and scanning electrochemical microscopes. They are also needed for monitoring the electrode-reaction products with probe electrodes that are independently polarized. All major producers of electrochemical equipment offer this type of potentiostat. The instruments that can control the potential of more than two working electrodes are called multipotentiostats. 

An often-adopted sonovoltammetric design is that shown in Fig. 35 built around a conventional three-electrode cell and which allows the ultrasound intensity and the distance between the horn and electrode to be continuously varied at a fixed ultrasound frequency of typically 20 kHz. This arrangement is much less sensitive to the shape and dimensions of the electrochemical cell than when a sonic bath is utilized. A further and important point of contrast is that the direct contact of the (metallic) horn with the electrochemical system may dictate the use of a bipotentiostat to control its electrical potential relative to that of the reference electrode (Marken and Compton, 1996). Alternatively, the horn may be electrically isolated (Huck, 1987 Klima et al., 1994). A significant merit of the design shown in Fig. 35 is that the mass transport characteristics may be empirically but reliably established. It is to this essential topic we next turn. 

Horn must be electrically insulated, requiring a bipotentiostat... 

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