Electrochemical catalysis

J. F. Rusling, Electrochemistry and Electrochemical Catalysis in Microemulsions, Plenum Press, 1994, Chapter 2. 

The Behavior of Intermediates in Electrochemical Catalysis Gileadi, E. Conway, B. E 3... 

Layered materials are of special interest for bio-immobilization due to the accessibility of large internal and external surface areas, potential to confine biomolecules within regularly organized interlayer spaces, and processing of colloidal dispersions for the fabrication of protein-clay films for electrochemical catalysis [83-90], These studies indicate that layered materials can serve as efficient support matrices to maintain the native structure and function of the immobilized biomolecules. Current trends in the synthesis of functional biopolymer nano composites based on layered materials (specifically layered double hydroxides) have been discussed in excellent reviews by Ruiz-Hitzky [5] and Duan [6] herein we focus specifically on the fabrication of bio-inorganic lamellar nanocomposites based on the exfoliation and ordered restacking of aminopropyl-functionalized magnesium phyllosilicate (AMP) in the presence of various biomolecules [91]. 

Zhou, Y., Hu, N., Zeng, Y. and Rusling, J.F. (2002) Heme protein-clay films Direct electrochemistry and electrochemical catalysis. Langmuir, 18, 211-219. 

L. Shen, R. Huang, and N.F. Hu, Myoglobin in polyacrylamide hydrogel films direct electrochemistry and electrochemical catalysis. Talanta 56, 1131-1139 (2002). 

R. Huang and N.F. Hu, Direct voltammetry and electrochemical catalysis with horseradish peroxidase in polyacrylamide hydrogel films. Biophys. Chem 104,199-208 (2003). 

Zhang, S. and Rusling, J.F. Dechlorination of polychlorinated biphenyls by electrochemical catalysis in a biocontinuous microemulsion. Environ. Sci. Technol, 27(7) 1375-1380, 1993. 

Intermolecular addition of radicals, generated by photo-electrochemical catalysis, to activated alkenes can also be brought about. The reaction of 66 is used as a key step in one synthesis of the insect pheromone, brevicomin [219]. The reaction of a secondary radical from 67 occurs at low cathode potentials and without photochemical assistance [219]. This illustrates the equiibrium between a secondary al-kylcobalt(m) species and the radical - cobalt(ii) pair. The carbon radical is eventually captured by reaction with the alkene. Further steps in the synthesis lead to four isomers of the pheromone, multistriatin, each of which is a pure enantiomer since... 

In the presence of PhBr and PhCH2Br, both Ni(BF4)2(bipy)3 and NiCl2(bipy) showed classical catalytic behavior. A peak for the product of the first oxidative addition of the reduced nickel complex appeared at p = —1.4 to —1.5V when the reactant was Ar(Ni)Br. In this case, the electrochemical catalysis was carried out by maintaining the potential of the working electrode at E" = —1.4 V vs. silver. 

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—... 

For many years the studies of surface modifications of synthetic diamond nanopowders have been conducted at the Institute for Superhard Materials. Our findings show that highly dispersed modified diamond powders hold a considerable promise in applications as adsorbents and catalysts of the oxidation and electrochemical catalysis [1-4], This promise is based on the following special features of the material ... 

The aim of the present work has been to study catalytic properties of detonation-synthesized diamond nanopowders and to extend their applications. The catalytic activity of diamond was studied in reactions electrochemical catalysis. 

The study of electrochemical catalysis implied the reaction of electrooxidation of hydrogen and electroreduction of oxygen into the diamond surface. 

Liu, H.-H., Wan, Y.-Q. and Zou, G.-L. (2006) Direct electrochemistry and electrochemical catalysis of immobilized haemoglobin in an ethanol-water mixture. Anal. Bioanal. Chem. 385, 1470-1476. 

Quan, X., S. Chen, J. Su, J.W. Chen and G.H. Chen (2004). Synergetic degradation of 2,4-D by integrated photo- and electrochemical catalysis on a Pt doped Ti02/Ti electrode. Separation and Purification Technology, 34(1-3), 73-79. 

The use of iV-aminophthalimide as a nitrogen source in aziridination reactions has been examined in some detail. One of the problems associated with A -aminophthalimide as a nitrogen source is the need for a strong oxidant. The use of electrochemical catalysis with A -aminophthalimide has proven to be an effective and mild route for aziridination (Scheme 139) <2005JOC932>. Both electron-rich and electron-poor substrates worked well in this reaction. 

Unactivated substrates also react with phenoxide ion with electrochemical catalysis in liquid NH3-Me2SO, to give diaryl ethers, presumably by the Sr I mechanism. Diaryl ethers can be prepared from activated aryl halides by treatment with a triaryl phosphate, (ArO)3PO. ... 

We have argued in this chapter that the iSf-LDOS (on which the nuclear spin-lattice relaxation rate of metals depends) is a useful concept to discuss variations in surface reactivity, bonding, and electrode potential effects among a series of related catalysts, in heterogeneous as well as in electrochemical catalysis. The f-LDOS is a... 

Liu Y, Huang LJ, Dong SJ et al (2007) Electrochemical catalysis and thermal stability characterization of laccase-carbon nanotubes-ionic liquid nanocomposite modified graphite electrode. Biosens Bioelectron 23 35-41... 

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