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Electron Transfer Kinetics Of Redox Centers Anchored To Metal Surfaces Weak Versus Strong Overlap Reaction Pathways
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Book Synopsis Electron-Transfer Kinetics of Redox Centers Anchored to Metal Surfaces: Weak- Versus Strong-Overlap Reaction Pathways by : S. W. Barr
Download or read book Electron-Transfer Kinetics of Redox Centers Anchored to Metal Surfaces: Weak- Versus Strong-Overlap Reaction Pathways written by S. W. Barr and published by . This book was released on 1983 with total page 19 pages. Available in PDF, EPUB and Kindle. Book excerpt: Unimolecular rate constants k sub et are presented for the one-electron electroreduction of various CoIII(NH3)5X complexes bound to mercury, platinum, and gold surfaces via either small inorganic or extended organic ligands X. These 'surface intramolecular' rate parameters are compared with estimates of k sub et for outer-sphere pathways obtained from homogeneous rate data in order to ascertain the consequences of reactant-surface binding upon the electron-transfer energetics. Only small or moderate decreases in the elementary reorganization barrier Delta G* sub et occur upon surface attachment, suggesting the occurrence of weak-overlap pathways. Aside from the dependence of k sub et upon the bridging ligand X at a given electrode potential due to differences in thermodynamic driving force, the observed variations in k sub et appear to be due in part to variations in the electronic transmission coefficient k sub el. Measurements of electrochemical frequency factors for reactants containing a series of thiophenecarboxylate bridges indicate that the substantial decreases in k sub et observed upon interruption of ligand conjugation arise predominantly from decreases in k sub el. (Author).
Book Synopsis Scientific and Technical Aerospace Reports by :
Download or read book Scientific and Technical Aerospace Reports written by and published by . This book was released on 1984 with total page 558 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Proceedings of the Symposium on the Chemistry and Physics of Electrocatalysis by : J. D. E. McIntyre
Download or read book Proceedings of the Symposium on the Chemistry and Physics of Electrocatalysis written by J. D. E. McIntyre and published by . This book was released on 1984 with total page 700 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Author :United States. Air Force. Directorate of Chemical and Atmospheric Sciences Publisher : ISBN 13 : Total Pages :228 pages Book Rating :4.:/5 (31 download)
Book Synopsis AFOSR Chemical & Atmospheric Sciences Program Review by : United States. Air Force. Directorate of Chemical and Atmospheric Sciences
Download or read book AFOSR Chemical & Atmospheric Sciences Program Review written by United States. Air Force. Directorate of Chemical and Atmospheric Sciences and published by . This book was released on 1983 with total page 228 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Government Reports Annual Index by :
Download or read book Government Reports Annual Index written by and published by . This book was released on 1984 with total page 1296 pages. Available in PDF, EPUB and Kindle. Book excerpt: Sections 1-2. Keyword Index.--Section 3. Personal author index.--Section 4. Corporate author index.-- Section 5. Contract/grant number index, NTIS order/report number index 1-E.--Section 6. NTIS order/report number index F-Z.
Book Synopsis Applied Science & Technology Index by :
Download or read book Applied Science & Technology Index written by and published by . This book was released on 1985 with total page 2172 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Proton Coupled Electron Transfer Kinetics of Redox Centers Attached to Self-assembled Monolayers on Electrodes by : Nicholas Madhiri
Download or read book Proton Coupled Electron Transfer Kinetics of Redox Centers Attached to Self-assembled Monolayers on Electrodes written by Nicholas Madhiri and published by . This book was released on 2006 with total page 169 pages. Available in PDF, EPUB and Kindle. Book excerpt: Proton-coupled electron transfer (PCET) reactions play an important role in many biochemical systems and have been focus of great interest recently. These reactions can be represented by a general equation: Ox + ne - + hH+ ↔ Red
Book Synopsis Government Reports Announcements & Index by :
Download or read book Government Reports Announcements & Index written by and published by . This book was released on 1984-06 with total page 1056 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Intramolecular Electron Transfer at Metal Surfaces. V. Pendant Substituent Effects Upon Thiocarboxylate-Bridged Cobalt(III) Reduction Kinetics at Mercury and Gold Electrodes by : T. T. T. Li
Download or read book Intramolecular Electron Transfer at Metal Surfaces. V. Pendant Substituent Effects Upon Thiocarboxylate-Bridged Cobalt(III) Reduction Kinetics at Mercury and Gold Electrodes written by T. T. T. Li and published by . This book was released on 1985 with total page 17 pages. Available in PDF, EPUB and Kindle. Book excerpt: Unimolecular rate constants are reported for the reduction of pentaamminecobalt (III) anchored to mercury or gold electrodes via thiocarboxylate bridging ligands having the general form RSCH2COO ( - ). Since the carboxylate is bound to Co(III) and sulfur provides the surface binding group, the substituent R (where is various alkyl, carboxylate, ketone, or aromatic groups) will be pendant to the thiocarboxylate bridge linking the surface and cobalt reacting centers. Aleration of the pendant group R yields only small (ca. up to 4 fold) variations in unimolecular rate constants at a given electrode potential, although slightly larger variations occur in the stability of the precursor (absorbed reactant) state at mercury electrodes that are apparently due to specific interactions between R and the metal surface. The insensitivity of unimolecular rate constants to the pendant group is compared and contrasted with the effects of varying the substituent that bridges the redox center to the metal surface. Comparisons are also made with the pendent group effects for related redox processes in homogeneous solution. Originator furnished key words include: Bridging ligands, Pendent group effects, Surface excess, Percursor state.
Book Synopsis Government Reports Annual Index: Keyword A-L by :
Download or read book Government Reports Annual Index: Keyword A-L written by and published by . This book was released on 1984 with total page 1000 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Intramolecular Electron Transfer at Metal Surfaces. III. Influence of Bond Conjugation on Reduction Kinetics of Cobalt(III) Anchored to Metal Surfaces Via Thiophenecarboxylate Ligands by : T. T. T. Li
Download or read book Intramolecular Electron Transfer at Metal Surfaces. III. Influence of Bond Conjugation on Reduction Kinetics of Cobalt(III) Anchored to Metal Surfaces Via Thiophenecarboxylate Ligands written by T. T. T. Li and published by . This book was released on 1983 with total page 32 pages. Available in PDF, EPUB and Kindle. Book excerpt: Unimolecular rate constants, K sub et, are reported for the one-electron electroreduction of pentaamminecobalt (III) anchored to mercury, gold, or copper electrodes via various thiophenecarboxylate ligands where the thiophene sulfur acts as the surface binding group and the carboxylate is coordinated to the cobalt reactants. At mercury, the rate parameters were found to be sensitive to the bridging ligand structure, substantially (ca. 10-20 fold) smaller values of K sub et being found for ligands containing one or more methylene groups between the thiophene sulfur and carboxylate oxygen than those featuring uninterrupted bond conjugation between the metal surface donor and Co(III) acceptor sites. Various contributions to these reactivity differences are asse-sed on the basis of the measured variations in the stability constants of the adsorbed precursor state, the rate constants for the homogeneous reduction of these complexes by hexammineruthenium (II), the unimolecular frequency factors obtained from the electrochemical activation parameters, and by comparison with ele-trochemical outer-sphere rate data. Taken together, these results provide strong evidence that the smaller values of K sub et values of the electronic transmission coefficient than are achieved with the conjugated ligands. Comparison is made with analogous results for intramolecular electron transfer via extended organic ligands in homogeneous solution. (Author).
Book Synopsis Structural Effects in Electron Transfer Reactions: Comparative Interfacial Electrochemical Kinetics for Cis- Versus Trans-Dioxorhenium(V)(bi)pyridine Oxidation by :
Download or read book Structural Effects in Electron Transfer Reactions: Comparative Interfacial Electrochemical Kinetics for Cis- Versus Trans-Dioxorhenium(V)(bi)pyridine Oxidation written by and published by . This book was released on 1993 with total page 26 pages. Available in PDF, EPUB and Kindle. Book excerpt: We have been exploring the proton-coupled reductions of various dioxorhenium(V) species because of the more general insights they provide into the kinetics and thermodynamics of multielectron transfer processes. The rhenium (V) complexes are also amenable, however, to proton-decoupled one-electron oxidation-both optically (via metal-to-ligand charge-transfer excitation; Our prior studies of electron transfer (ET) thermodynamics revealed a strong dependence of the Re (VI/V) formal potential on ligand substituent characteristics (most notably, substituent electron donating or withdrawing characteristics). The studies also showed-independent of ligand substituent identify-a strong dependence of E (sub f) on isomeric form cis versus trans coordination geometry. In all cases the cis form was more easily oxidize than the corresponding trans, generally by about 600mV.
Book Synopsis Electron Transfer Reactions by : Roderick David Cannon
Download or read book Electron Transfer Reactions written by Roderick David Cannon and published by Butterworth-Heinemann. This book was released on 1980 with total page 376 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Electron Transfer Kinetics at the Polycrystalline Silver-aqueous Interface by : Kendall Louis Guyer
Download or read book Electron Transfer Kinetics at the Polycrystalline Silver-aqueous Interface written by Kendall Louis Guyer and published by . This book was released on 1981 with total page 588 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Electron Transfer Reactions by : Stephan S. Isied
Download or read book Electron Transfer Reactions written by Stephan S. Isied and published by . This book was released on 1997 with total page 472 pages. Available in PDF, EPUB and Kindle. Book excerpt: Begins with a historical overview by Henry Taube. Overviews the advances pioneered by Taube, including mechanisms of electron transfer reactions, charge transfer complexes, and *p back bonding effects in metal-ligand interactions. Discusses applications of principles of electron transfer to diverse areas of chemistry and biology such as the selective and controlled oxidation of organic functional groups, polymerization catalysis, metal biological interactions with DNA, biological electron transfer reactions, and new imaging agents in diagnostic medicine.
Book Synopsis Towards Next Generation Energy Storage Technologies by : Minghua Chen
Download or read book Towards Next Generation Energy Storage Technologies written by Minghua Chen and published by John Wiley & Sons. This book was released on 2024-12-23 with total page 482 pages. Available in PDF, EPUB and Kindle. Book excerpt: summarizes the fundamental energy storage mechanisms, critical achievements, and critical challenges from the view of practical application.
Book Synopsis Cation-coupled Electron Transfer to Polyoxovanadate-alkoxide Clusters by : Eric Schreiber
Download or read book Cation-coupled Electron Transfer to Polyoxovanadate-alkoxide Clusters written by Eric Schreiber and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: "The cation-coupled electron transfer properties of metal oxides have made them widely applicable materials in a variety of energy-related technologies such as Li-ion batteries and electrochemical catalysts. These valuable properties have garnered interest from researchers in understanding the fundamental steps involved in these processes as well as optimizing material performance to improve current technologies. However, the scale of these materials makes development of an atomic-level understanding of the precise structures and mechanisms involved in redox reactions highly challenging. To study metal oxides with atomic precision, researchers have turned to polyoxometalates, a class of compounds which feature analogous compositions, surface structures, and multimetallic cooperativity to their nano and bulk-scale congeners. A significant advantage to these complexes is that, by their solubility, in situ measurements can be made over the course of a reaction to observe a reaction in real-time and identify mechanistic details. In this work, we employ a class of organofunctionalized polyoxovanadate-alkoxide complexes which, on top of the ability to track speciation in situ, allow us to interrogate the relationship between the inorganic core and ligand spheres in nanomaterials. In Chapter 2, we present the electrochemical implications of electrolyte species on POV-alkoxide clusters, revealing the uptake of alkali cations to the surface of the cluster upon reduction. The different binding modes of Li versus the other alkali ions enables for cation selectivity in mixed-salt conditions, with cluster surface modifications further enhancing this activity. The uptake of protons to reduced clusters is investigated in Chapter 3, wherein it is observed that organosaturated POV-alkoxides are protonated at the terminal V=O, which subsequently forms an O-atom defect. Interested in controlling this reactivity, we probe the charge-state dependence of cluster protonation, determining how the oxidation states of distal metal centers affect the reactivity of a particular site. This reactivity is built upon in Chapter 4, wherein the generation of defects with H-atom donors provides a new pathway to access activated clusters surfaces. The overall concerted proton-electron transfer reaction is similarly found to have a thermochemical dependence on charge state in analogy to results found on metal oxide particles. This dissertation is concluded with Chapter 5, in which we study the PCET reactivity of a POV-alkoxide with a bridging oxygen defect. It is found that the core electronic structure of the molecule shifts the regioselectivity for H-atom installation from the terminal oxo to the bridging oxide upon cluster reduction, with the enhanced basicity of the bridging moiety resulting in accelerated rates of PCET. In sum, our molecular approach to studying charge transfer reactions provides thermochemical and kinetic insights into processes at metal oxide surfaces. By probing reactions with atomic precision, we determine physicochemical factors which influence material activity, providing synthetic cues for tuning material properties."--Pages xii-xiii.
