Electrochemistry perspectives

K. R. BuUock, "The Development and AppHcations of Storage Batteries—Historical Perspectives and Future Prospects," in Proceedings, 7th Australian Electrochemistry Conference, 1988. 

The recognition of the lack of molecular-level information on electrocatalytic phenomena and the resolve to have this weakness rectified is now firmly established within the electrochemical and surface science communities. This is evidenced by recent international conferences and workshops devoted solely to electrochemical problems (11-4). It is also well-realized that electrochemistry cannot advance further unless the practitioners in this field begin to view electrodesolution processes from a molecular-level perspective. 

Without doubt, the advent of carbon nanotubes has opened up iimovative perspectives for research and development of carbon electrodes. In this chapter, we have attempted to highlight the electrochemical properties of carbon nanotubes by rooting them mainly on their structural, electronic and chemical properties. If chirality of SWNTs could be controlled, it would be possible to probe electrochemically the unique electronic properties of the tubes with their corresponding unique DOS distribution and establish direct correlations between electronic structure and electrochemistry. However, so far, most of their electrochemical applications are based on ensembles of CNTs (MWNTs or SWNTs) in thin films supported on conductive surfaces or composites. Such ensembles, not so well defined from the structural point of view, contain a mixture of tubes with different diameters and DOS... 

Such achievements have been made possible because of the substantial progresses obtained in other areas of chemistry and physics—particularly concerning the synthesis and characterization of complex chemical systems, and the study of surfaces and interfaces. In this perspective, electrochemistry is a very powerful tool not only for characterizing a supramolecular system, but also for operating the device. Indeed, molecular devices, as their macroscopic counterparts, need energy to operate and signals to communicate with the operator. Electrochemistry can be an interesting... 

The SH analysis of the copper system is a bit more complicated from several perspectives. The electrochemistry is not as well known for copper and trace amounts of oxygen can disrupt the deposition process [151]. The integrated deposi-... 

From a practical perspective the chlorozincate liquids are easier to make and handle than the corresponding chloroaluminates as they are less susceptible to hydrolysis. As with the aluminum-based liquids the electrochemistry is dominated by the complex anions present in the liquid, which depend upon the composition and the relative Lewis acidity. There is some evidence, however, that hydrolysis of zinc Lewis basic melts does occur as Hsiu et al. used fast atom bombardment mass spectroscopy (FAB MS) to show that some zinc species do contain oxygen [105]. 

Protein function at solid-liquid interfaces holds a structural and a dynamic perspective [31]. The structural perspective addresses macroscopic adsorption, molecular interactions between the protein and the surface, collective interactions between the individual adsorbed protein molecules, and changes in the conformational and hydration states of the protein molecules induced by these physical interactions. Interactions caused by protein adsorption are mostly non-covalent but strong enough to cause drastic functional transformations. All these features are, moreover, affected by the double layer and the electrode potential at electrochemical interfaces. Factors that determine protein adsorption patterns have been discussed in detail recently, both in the broad context of solute proteins at solid surfaces [31], and in specific contexts of interfacial metalloprotein electrochemistry [34]. Some important elements that can also be modelled in suitable detail would be ... 

In all of these systems, certain aspects of the reactions can be uniquely related to the properties of a surface. Surface properties may include those representative of the bulk material, ones unique to the interface because of the abrupt change in density of the material, or properties arising from the two-dimensional nature of the surface. In this article, the structural, thermodynamic, electrical, optical, and dynamic properties of solid surfaces are discussed in instances where properties are different from those of the bulk material. Predominantly, this discussion focuses on metal surfaces and their interaction with gas-phase atoms and molecules. The majority of fundamental knowledge of molecular-level surface properties has been derived from such low surface area systems. The solid-gas interface of high surface area materials has received much attention in the context of separation science, however, will not be discussed in detail here. The solid-liquid interface has primarily been treated from an electrochemical perspective and is discussed elsewhere see Electrochemistry Applications in Inorganic Chemistry). The surface properties of liquids (liquid-gas interface) are largely unexplored on the molecular level experimental techniques for their study have begun only recently to be developed. The information presented here is a summary of concepts a more complete description can be found in one of several texts which discuss surface properties in more detail. ... 

From a materials perspective, the field of semiconductor electrochemistry and photoelectroehemistry has evolved from the use of semiconduetor single crystals to polycrystalline thin films and, more recently, to nanocrystalline films. The latter have been variously termed membranes, nanoporous or nanophase films, meso-porous films, nanostructured films, etc. they are all distinguished from their poly-... 

The complexity of the system implies that many phenomena are not directly explainable by the basic theories of semiconductor electrochemistry. The basic theories are developed for idealized situations, but the electrode behavior of a specific system is almost always deviated from the idealized situations in many different ways. Also, the complex details of each phenomenon are associated with all the processes at the silicon/electrolyte interface from a macro scale to the atomic scale such that the rich details are lost when simplifications are made in developing theories. Additionally, most theories are developed based on the data that are from a limited domain in the multidimensional space of numerous variables. As a result, in general such theories are valid only within this domain of the variable space but are inconsistent with the data outside this domain. In fact, the specific theories developed by different research groups on the various phenomena of silicon electrodes are often inconsistent with each other. In this respect, this book had the opportunity to have the space and scope to assemble the data and to review the discrete theories in a global perspective. In a number of cases, this exercise resulted in more complete physical schemes for the mechanisms of the electrode phenomena, such as current oscillation, growth of anodic oxide, anisotropic etching, and formation of porous silicon. 

This chapter is organized into sections corresponding to various electrochemical characteristics of nanometallic particles. The introduction gives a brief idea of the basics of colloids together vith related literature. Subsequently, the electrochemistry with nanoparticles and ensembles of nanoelectrodes is explained followed by the electrochemical coulomb staircase behaviour of monolayer-protected nanometallic clusters. The investigation of nanoparticles using techniques based on combinations of different spectroscopic and electrochemical techniques is then reviewed. Sensors and electrocatalysis form the next sections and finally a summary and perspectives are given. 

Fundamentals, Applications, and Perspectives of Solid-State Electrochemistry A Synopsis... 

Wei, R. P., Corrosion and Corrosion Fatigue in Perspective, Proceedings from Chemistry and Electrochemistry of Stress Corrosion Cracking A Symposium Fionoring the Contributions of R. W. Staehle, R. H. Jones, ed.. The Minerals, Metals and Materials Society, Warrendale, PA (2001). 

D.M. Kolb, Report on Symposium "Atomic and Molecular Perspectives in Interfacial Electrochemistry", 46ISE Meeting, Xiamen, China, 1995. 

To be able to provide simple explanations for complex biological phenomena is most gratifying and reinforces our resolve to pursue the mechanistic understanding of life processes. However, we refrain from a proclamation of the victory of the mechanistic approach because we believe the debate between the mechanistic approach and the neovitalistic approach is endless and futile. Whereas it is impossible to prove the validity of the mechanistic approach by a finite number of successful attempts, it is equally impossible to prove the validity of the neovitalistic approach by the sheer absence of available mechanistic explanations to a specific problem. An abundance of historic lessons show that when the capability of existing sciences is about to be exhausted, lingering puzzles actually usher in new sciences. In our present case, the solutions to our puzzles do not even require a new science, but rather a new perspective and a new point of view that use the existing knowledge of electrochemistry. 

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