Hydrogen electrochemical techniques

A wide variety of enzymes have been used in conjunction with electrochemical techniques. The only requirement is that an electroactive product is formed during the reaction, either from the substrate or as a cofactor (i.e. NADH). In most cases, the electroactive products detected have been oxygen, hydrogen peroxide, NADH, or ferri/ferrocyanide. Some workers have used the dye intermediates used in classical colorimetric methods because these dyes are typically also electroactive. Although an electroactive product must be formed, it does not necessarily have to arise directly from the enzyme reaction of interest. Several cases of coupling enzyme reactions to produce an electroactive product have been described. The ability to use several coupled enzyme reactions extends the possible use of electrochemical techniques to essentially any enzyme system. 

As the reader might have noticed, many conclusions in electrocatalysis are based on results obtained with electrochemical techniques. In situ characterization of nanoparticles with imaging and spectroscopic methods, which is performed in a number of laboratories, is invaluable for the understanding of PSEs. Identification of the types of adsorption sites on supported metal nanoparticles, as well as determination of the influence of particle size on the adsorption isotherms for oxygen, hydrogen, and anions, are required for further understanding of the fundamentals of electrocatalysis. 

Figure 25. Schematic illustration of the principle of the electrochemical hydrogen permeation technique.

The electrochemical hydrogen permeation technique has proved to be a valuable tool in the study of these reaction mechanisms. This is mainly due to the ability to estimate the amount of an intermediate (Hads) in the reaction scheme. Such studies have been presented, for example, by Devanathan and Stachurski, by Bockris et and by Iyer et The applicability of the Volmer-Tafel reaction scheme can be evaluated by considering the kinetic expressions for reactions (22) and (23), together with equilibrium in the absorption process (25)... 

The electrochemical hydrogen permeation technique has been used in efforts to establish threshold hydrogen concentrations in steel below which no cracking occurs. The threshold concentration depends largely on the type of failure under investigation, the chemical and physical properties of the steel, and the magnitude of applied and residual stress. 

The electrochemical hydrogen permeation technique can be useful in a variety of investigations. Mechanistic information on the hydrogen evolution reaction can be obtained owing to the ability of the technique to quantify the amount of adsorbed atomic hydrogen intermediary formed in the process. 

Rate constants for the protonation of radical-anions in dimethylformamide by added phenol can be determined by electrochemical techniques [8], Pulse radiolysis methods have been used to measure the rate constants in an alcohol solvent. This technique generates the radical-anion on a very short time scale and uv-spectroscopy is then be used to follow the protonation of this species to give the neutral radical with different uv-absorption characteristics [9]. In the case of anthracene, the protonation rate is 5 x 10 M" s with phenol in dimethylformamide and 5 x 10 s in neat isopropanol. Protonation by hydrogen ions approaches the diflusion-controlled limit with a rate constant of 10 M s in ethanol [9]. 

At temperatures below 100°C, Eh values are usually measured directly using electrochemical techniques. At elevated temperatures, however, it is usually more convenient to measure hydrogen pressures in equilibrium with the system being investigated. The Teflon hydrogen diffusion membrane is a device which directly measures H2 pressures in equilibrium with the... 

Cyclic voltammetry is a well-adapted electrochemical technique to elucidate the mechanism and kinetics of reversible hydrogen storage. An example of voltammetry characteristics, using a microporous activated carbon cloth (ACC) from viscose (ACC . S BEX = 1390 m2 g-1) in 3 mol L 1 KOH, is shown in Figure 8.17. The minimum potential is shifted of -100 mV for each cycle, i.e., toward hydrogen evolution. 

Platinized platinum catalysts were modified by submonolayers of lead, deposited and characterized by electrochemical techniques. Their activity was tested in liquid phase hydrogenation of C C bonds. 

However, in heterogeneous catalysis, metals are usually deposited on nonconducting supports such as alumina or silica. For such conditions electrochemical techniques cannot be used and the potential of the metallic particles is controlled by means of a supplementary redox system [8, 33]. Each particle behaves like a microelectrode and assumes the reversible equilibrium potential of the supplementary redox system in use. For example, with a platinum catalyst deposited on silica in an aqueous solution and in the presence of hydrogen, each particle of platinum takes the reversible potential of the equilibrium 2H+ + 2e H2, given by Nemst s law as... 

Since these hydrides are thermodynamically stable in the metal, the passive oxide can only be considered as a transport barrier, not as an absolute barrier. Various electrochemical techniques including EIS and photoelectrochemical measurements have been used to identify the mechanism by which the Ti02 may be rendered permeable to hydrogen, and to identify the conditions under which absorption is observable (31). These determinations show that H absorption into the Ti02 (and hence potentially into the metal) occurs under reducing conditions when redox transformations (Ti1 —> Tim) in the oxide commence. However, the key measurement, if H absorption is to be coupled to passive corrosion, is that of the absorption efficiency. 

Cathodic protection is an electrochemical technique of providing protection from corrosion [38]. The object to be protected is made the cathode of an electrochemical cell and its potential driven negatively to a point where the metal is immune to corrosion. The metal is then completely protected. The reaction at the surface of the object will be oxygen reduction and/or hydrogen evolution. Cathodic protection may be divided into two types, that produced using sacrificial anodes and the second by impressed current from a d.c. generator [39]. 

The region of the cyclic voltammogram, corresponding to anodic removal of Hathermal desorption spectra of platinum catalysts. However, unlikely the thermal desorption spectra, the cyclic-voltammetric profiles for H chemisorbed on Pt are usually free of kinetic effects. In addition, the electrochemical techniques offer the possibility of cleaning eventual impurities from the platinum surface through a combined anodic oxidation-cathodic reduction pretreatment. Comparative gas-phase and electrochemical measurements, performed for dispersed platinum catalysts, have previously demonstrated similar hydrogen and carbon monoxide chemisorption stoichiometries at both the liquid and gas-phase interfaces (14). 

Transport-Controlled Deposition and Dissolution of Metals Electrochemical Techniques to Study Hydrogen Ingress in Metals Metal Displacement Reactions... 

United Technologies Corporation Fuel Cells (UTCFC) has developed and applied a new and novel in-situ electrochemical technique to quantify hydrogen crossover in membranes. 

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