Electrochemical reactions electrocatalysts

Of practical importance is the contribution that is made by carbonaceous materials as an additive to enhance the electronic conductivity of the positive and negative electrodes. In other electrode applications, carbon serves as the electrocatalyst for electrochemical reactions and/or the substrate on which an electrocatalyst is located. In... 

In this section we treat some electrochemical reactions at interfaces with solid electrolytes that have been chosen for both their technological relevance and their scientific relevance. The understanding of the pecularities of these reactions is needed for the technological development of fuel cells and other devices. Investigation of hydrogen or oxygen evolution reactions in some systems is very important to understand deeply complex electrocatalytic reactions, on the one hand, and to develop promising electrocatalysts, on the other. 

Appreciable interest was stirred by the sucessful use of nonmetallic catalysts such as oxides and organic metal complexes in electrochemical reactions. From 1968 on, work on the development of electrocatalysts on the basis of the mixed oxides of titanium and ruthenium led to the fabrication of active, low-wear electrodes for anodic chlorine evolution which under the designation dimensionally stable anodes (DSA) became a workhorse of the chlorine industry. 

The experimental results are in complete agreement with the predictions of our computational screening approach the annealed BiPt sample shows enhanced HER activity compared with pure Pt. As mentioned above, this result is rather counterintuitive, given that Bi itself is a notoriously poor electrocatalyst for the HER [Trasatti, 1972]. Hence, it appears that our computational, combinatorial screening procedure is capable of identifying improved catalysts for electrochemical reactions that are not immediately apparent from simple intuitive arguments. 

Prussian blue-based nano-electrode arrays were formed by deposition of the electrocatalyst through lyotropic liquid crystalline [144] or sol templates onto inert electrode supports. Alternatively, nucleation and growth of Prussian blue at early stages results in nano-structured film [145], Whereas Prussian blue is known to be a superior electrocatalyst in hydrogen peroxide reduction, carbon materials used as an electrode support demonstrate only a minor activity. Since the electrochemical reaction on the blank electrode is negligible, the nano-structured electrocatalyst can be considered as a nano-electrode array. 

Synchotron based techniques, such as surface X-ray scattering (SXS) and X-ray absorption spectroscopy (XAS), have found increased use in characterization of electrocatalysts during electrochemical reactions.37 These techniques, which can be used for characterization of surface structures, require intricate cell designs that can provide realistic electrochemical conditions while acquiring spectra. Several examples of the use of XAS and EXAFS in non-precious metal cathode catalysts can be found in the literature.38 2... 

The ideal performance of a fuel cell depends on the electrochemical reactions that occur with different fuels and oxygen as summarized in Table 2-1. Low-temperature fuel cells (PEFC, AFC, and PAFC) require noble metal electrocatalysts to achieve practical reaction rates at the anode and cathode, and H2 is the only acceptable fuel. With high-temperature fuel cells (MCFC, ITSOFC, and SOFC), the requirements for catalysis are relaxed, and the number of potential fuels expands. Carbon monoxide "poisons" a noble metal anode catalyst such as platinum (Pt) in low-temperature... 

The electrochemical reactions occur on highly dispersed electrocatalyst particles supported on carbon black. Platinum (Pt) or Pt alloys are used as the catalyst at both electrodes. 

Electrochemical reactions take place at the catalyst layers of the fuel cell. At the anode and cathode, hydrogen is oxidized (eq 1) and oxygen is reduced (eq 2), respectively. These layers are often the thinnest in the fuel-cell sandwich but are perhaps the most complex because this is where electrochemical reactions take place and where all of the different types of phases exist. Thus, the membrane and diffusion media models must be used in the catalyst layer along with additional expressions related to the electrochemical kinetics on the supported electrocatalyst particles. 

A schematic of a typical fuel-cell catalyst layer is shown in Figure 9, where the electrochemical reactions occur at the two-phase interface between the electrocatalyst (in the electronically conducting phase) and the electrolyte (i.e., membrane). Although a three-phase interface between gas, electrolyte, and electrocatalyst has been proposed as the reaction site, it is now not believed to be as plausible as the two-phase interface, with the gas species dissolved in the electrolyte. This idea is backed up by various experimental evidence, such as microscopy, and a detailed description is beyond the scope of this review. Experimental evidence also supports the picture in Figure 9 of an agglomerate-type structure where the electrocatalyst is supported on a carbon clump and is covered by a thin layer of membrane. Sometimes a layer of liquid water is assumed to exist on top of the membrane layer, and this is discussed in section 4.4.6. Figure 9 is an idealized picture, and... 

For these low-temperature fuel cells, the development of catalytic materials is essential to activate the electrochemical reactions involved. This concerns the electro-oxidation of the fuel (reformate hydrogen containing some traces of CO, which acts as a poisoning species for the anode catalyst methanol and ethanol, which have a relatively low reactivity at low temperatures) and the electroreduction of the oxidant (oxygen), which is still a source of high energy losses (up to 30-40%) due to the low reactivity of oxygen at the best platinum-based electrocatalysts. 

The Institute of Chemical Engineering and High Temperature Chemical Processes (ICE/HT) works on design, construction and testing of PEM components, electrochemical reactions/reactors, electrocatalysts for PEMs, hydrogen production by catalytic processes and water splitting. 

The chemistry of electrochemical reaction mechanisms is the most hampered and therefore most in need of catalytic acceleration. Therefore, we understand that electrochemical catalysis does not, in principle, differ much fundamentally and mechanistically from chemical catalysis. In addition, apart from the fact that charge-transfer rates and electrosorption equilibria do depend exponentially on electrode potential—a fact that has no comparable counterpart in chemical heterogeneous catalysis—in many cases electrocatalysis and catalysis of electrochemical and chemical oxidation or reduction processes follow very similar if not the same pathways. For instance as electrochemical hydrogen oxidation and generation is coupled to the chemical splitting of the H2 molecule or its formation from adsorbed hydrogen atoms, respectively, electrocatalysts for cathodic hydrogen evolution—... 

The enzyme can be incorporated into an amperometric sensor in a thick gel layer, in which case the depletion region due to the electrochemical reaction is usually confined within this layer. Alternatively, enzyme can be immobilized at the surface of the electrode or even within the electrode material itself, in which case the depletion region extends into the solution in the same way as it would for an unmodified electrode. In the latter case, the enzyme can then be seen as a true electrocatalyst that facilitates the interfacial electron transfer, which would otherwise be too slow. The general principles of the design and operation of these biosensors is illustrated on the example of the most studied enzymatic sensor, the glucose electrode (Fig. 2.14, Section 2.3.1). 

The final two chapters discuss modeling of PEFCs. Mukherjee and Wang provide an in-depth review of meso-scale modeling of two-phase transport, while Zhou et al. summarize both the simulation of electrochemical reactions on electrocatalysts and the transport of protons through the polymer electrolyte using atomistic simulation tools such as molecular dynamics and Monte Carlo techniques. 

For electrocatalysts we generally define the reaction rate in terms of an electrode polarization equation. The polarization equation describes the transfer of charge from the matrix to the solution. For an electrochemical reaction O + ne R, this can be written in the Butler-Volmcr form1,7... 

It is a point peculiar to electrochemical reaction kinetics (77), however, that the rates of charge-transfer processes at electrodes measured, as they have to be, at some well-defined potential relative to that of a reference electrode, are independent of the work function of the electrocatalyst metal surface. This is due to cancellation of electron-transfer energies, O, at interfaces around the measuring circuit. In electrochemistry, this is a well-understood matter, and its detailed origin and a description of the effect may be found, among other places, in the monograph by Conway (77). 

Pericyclic electrochemical reactions are increasingly developed. They involve chain reactions with a radical cation as chain transferring step or the generation of reactive dienophiles (see Chapter 22, Sec. V). Transition metal complexes are increasingly applied in electrochemistry as electrocatalysts for reductive carboxylation [47], acylation or alkylation [41], or activation [51]. 

Different electron-conducting polymers (polyaniline, polypyrrole, polythiophene) are considered as convenient substrates for the electrodeposition of highly dispersed metal electrocatalysts. The preparation and the characterization of electronconducting polymers modified by noble metal nanoparticles are first discussed. Then, their catalytic activities are presented for many important electrochemical reactions related to fuel cells oxygen reduction, hydrogen oxidation, oxidation of Cl molecules (formic acid, formaldehyde, methanol, carbon monoxide), and electrooxidation of alcohols and polyols. 

The kinetics of electrochemical reactions are often modified by the nature of the electrode material, and by the presence of atomic and molecular species either adsorbed on the surface or in the bulk solution [14]. Electrocatalysis is primarily concerned with the study of this phenomenon and, particularly, with the factors that govern enhancements in the rates of redox processes. Implicit in this general statement is the ability of the species responsible for these effects, or electrocatalyst, or the electrode itself, to carry out the reaction numerous times before undergoing possible deactivation. Electrocatalytic processes in which the electrode simply serves as a source or sink of electrons to generate solution phase species that... 

The noble metals or their oxides are the most convenient substrates for most electrochemical reactions taking place in fuel cells or in industrial electrolysis, for example. Because of this, the activated electrodes are introduced, consisting of a conducting, inert support coated with a thin layer of electrocatalyst. In this way, not only the chemical nature of the electrode can be modified but also its morphology and structure in dependence on the procedure of preparation.1... 

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