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Electrocatalysis influence

Electrodes. At least three factors need to be considered ia electrode selection as the technical development of an electroorganic reaction moves from the laboratory cell to the commercial system. First is the selection of the lowest cost form of the conductive material that both produces the desired electrode reactions and possesses stmctural iategrity. Second is the preservation of the active life of the electrodes. The final factor is the conductivity of the electrode material within the context of cell design. An ia-depth discussion of electrode materials for electroorganic synthesis as well as a detailed discussion of the influence of electrode materials on reaction path (electrocatalysis) are available (25,26). A general account of electrodes for iadustrial processes is also available (27). [Pg.86]

In electrocatalysis, in contrast to electrochemical kinetics, the rate of an electrochemical reaction is examined at constant external control parameters so as to reveal the influence of the catalytic electrode (its nature, its surface state) on the rate constants in the kinetic equations. [Pg.523]

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. [Pg.551]

More than a decade ago, Hamond and Winograd used XPS for the study of UPD Ag and Cu on polycrystalline platinum electrodes [11,12]. This study revealed a clear correlation between the amount of UPD metal on the electrode surface after emersion and in the electrolyte under controlled potential before emersion. Thereby, it was demonstrated that ex situ measurements on electrode surfaces provide relevant information about the electrochemical interface, (see Section 2.7). In view of the importance of UPD for electrocatalysis and metal deposition [132,133], knowledge of the oxidation state of the adatom in terms of chemical shifts, of the influence of the adatom on local work functions and knowledge of the distribution of electronic states in the valence band is highly desirable. The results of XPS and UPS studies on UPD metal layers will be discussed in the following chapter. Finally the poisoning effect of UPD on the H2 evolution reaction will be briefly mentioned. [Pg.112]

The lure of new physical phenomena and new patterns of chemical reactivity has driven a tremendous surge in the study of nanoscale materials. This activity spans many areas of chemistry. In the specific field of electrochemistry, much of the activity has focused on several areas (a) electrocatalysis with nanoparticles (NPs) of metals supported on various substrates, for example, fuel-cell catalysts comprising Pt or Ag NPs supported on carbon [1,2], (b) the fundamental electrochemical behavior of NPs of noble metals, for example, quantized double-layer charging of thiol-capped Au NPs [3-5], (c) the electrochemical and photoelectrochemical behavior of semiconductor NPs [4, 6-8], and (d) biosensor applications of nanoparticles [9, 10]. These topics have received much attention, and relatively recent reviews of these areas are cited. Considerably less has been reported on the fundamental electrochemical behavior of electroactive NPs that do not fall within these categories. In particular, work is only beginning in the area of the electrochemistry of discrete, electroactive NPs. That is the topic of this review, which discusses the synthesis, interfacial immobilization and electrochemical behavior of electroactive NPs. The review is not intended to be an exhaustive treatment of the area, but rather to give a flavor of the types of systems that have been examined and the types of phenomena that can influence the electrochemical behavior of electroactive NPs. [Pg.169]

Two are the main factors governing the activity of materials (i) electronic factors, related to chemical composition and structure of materials influencing primarily the M-H bond strength and the reaction mechanism, and (ii) geometric factors, related to the extension of the real surface area influencing primarily the reaction rate at constant electronic factors. Only the former result in true electrocatalytic effects, whereas the latter give rise to apparent electrocatalysis. [Pg.252]

Moreover, the conductivity, and hence the catalytic decomposition of hydrogen peroxide, has been observed to influence the stability of the oxygen electrode. The stability of phthalocyanine catalysts is a decisive factor for the practical applicability of organic catalysts in fuel cells operating in an acid medium. This is therefore a very important observation. The observed disturbance of the delocalization of the n electrons (rubiconjugation) in Fe-polyphthalocyanines, in addition to the correlation between conductivity on the one hand, and electrocatalysis and catalytic decomposition of hydrogen peroxide on the other, leads to a special model of the electroreduction of oxygen on phthalocyanines. The model... [Pg.116]

The first chelate found to be electrocatalytic was cobalt phthalocyanine x>, which functions as an oxygen catalyst in alkaline electrolytes. Soon afterwards we were able to show 3,4,10,11) -that several phthalocyanines are also active in commercially important, sulfuric acid containing media. A comparison of various central atoms showed that activity increased in the order Cu Ni iron phthalocyanine, the nature of the carbon substrate plays a very important part FePc is more active on a carbon substrate with basic surface groups than on one with acid surface groups3). This property is however specific to phthalocyanines (Pc). [Pg.138]

Further steps to finally get 02 will be beyond the rds and hence not of primary influence on the electrocatalysis process. They could be... [Pg.564]

Work on the modification of electrode surfaces is of more recent origin, but the research has already gathered considerable momentum. Coordination compounds have not played a unique role in this development, but they have on occasion made important advances possible. Some authors believe that this work will influence the direction of electrochemistry for many years to come. It certainly has implications for electrocatalysis, electronic devices, visual display units and photoelectricity to mention but a few topical objectives which currently drive the research. [Pg.1]

If correlations do exist for simple metals, predictions are much more difficult for composite materials. On the other hand, cathode activation has two aims (i) to replace active but expensive materials with cheaper ones, and (ii) to enhance the activity of cheaper materials so as to approach or even surpass that of the more expensive catalysts. In the case of pure metals there is little hope to find a new material satisfying the above requirements since in the volcano curve each metal has a fixed position which cannot be changed. Therefore, activation of pure metals can only be achieved by modifying its structure so as to enhance the surface area (which has nothing to do with electrocatalysis in a strict sense), and possibly to influence the mechanism and the energetic state of the intermediate in the wanted direction. This includes the preparation of rough surfaces but also of dispersed catalysts. Examples will be discussed later. [Pg.7]

As the particle size decreases, the ratio between the number of atoms at the surface to those in the bulk increases with a parallel decrease in the average coordination number for the metal atom, which is also expected to be a factor of electrocatalysis. It has been calculated for Pt that the minimum size of a crystallite (cluster) for all atoms to be on the surface is 4 nm, corresponding to a specific surface area of 280 m2g-1 [322] (note that this is larger than the critical particle size where absorption of H atoms disappears on Pd) [333]. It is also interesting that dispersed catalysts can in turn influence the electronic properties of the support so that an interesting combination of sites with varied properties can result [330]. At low catalyst loadings, spillover of intermediates is also possible. [Pg.34]

The changes in the potential profile of the interfacial region because specific adsorption do indeed affect the electrode kinetics of charge transfer processes, particularly when these have an inner sphere character [13, 26] (see Fig. 1.12). When this influence leads to an improvement of the current response of these processes, the global effect is called electrocatalysis. ... [Pg.26]

Effect of HS on the electrochemical reduction of p-nitrophenol (PNP) was studied by Simoes et al. (2006). PNP is the main hydrolysis product of methylpara-thion (MP), one of the most commonly used organophosphate insecticides in the world. The study was conducted using electroanalytical and UV-vis techniques, to understand how the HS can influence PNP degradation in the environment. Electroanalytical results showed that the HS experience the reduction of the nitro group of PNP by electrocatalysis (Figure 16.27a). [Pg.692]

Szpyrkowicz, L., M. Radaelli, and S. Daniele (2005). Electrocatalysis of chlorine evolution on different materials and its influence on the performance of an electrochemical reactor for indirect oxidation of poUutants. Catal. Today 100,425 429. [Pg.244]

Potential-assisted photocatalysis combines the advantages of photocatalysis with those of electrocatalysis. It is a combined technology that improves the efficiency of photocatalysis by the applicahon of an external potential. This potential difference can either be simply a result of the resting potentials of the differing electrodes, or the apphcation of an external electrically applied bias. This concept was first introduced by Honda and Fujishima, as they demonstrated the photoelectrocatalysis of water under the influence of an anodic bias [1]. [Pg.766]


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Electrocatalysis

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