Download or read book Molecular Control of Interfacial Inner sphere Electron written by Megan Nora Jackson and published by . This book was released on 2019 with total page 368 pages. Available in PDF, EPUB and Kindle. Book excerpt: The interconversion of electrical and chemical energy relies on the intimate coupling of protons and electrons to activate small molecules including 02, C0 2, and H20. The mechanistic pathways governing the proton- and electron-transfer steps are key to the efficiency of catalysis because they determine the rate and selectivity of the reaction. Energy conversion devices commonly use metallic heterogeneous electrocatalysts, so a deep understanding of the factors governing the rate and thermochemistry of interfacial proton transfer (PT) and electron transfer (ET) steps at electrode surfaces is critical for improving the efficiency and selectivity of energy conversion. This thesis focuses on developing a molecular-level understanding of interfacial inner-sphere PT and ET steps in two parts: (1) incorporation of molecular active sites into heterogeneous electrodes through graphite conjugation (Chapters 1-3), and (2) elucidation of the role of the proton donor in interfacial proton-coupled electron transfer steps through detailed kinetic studies (Chapters 4-6). Part 1 describes a class of catalysts that incorporate molecularly well-defined, highly-tunable active sites into heterogeneous graphite surfaces. These graphite-conjugated catalysts (GCCs) feature a unique conjugated linkage between a discrete molecular active site and the delocalized states of graphitic carbons. Electrochemical and spectroscopic investigations establish that GCCs exhibit strong electronic coupling to the electrode, leading to ET behavior that diverges fundamentally from that of solution phase or surface-tethered analogues. We find that: (1) ET is not observed between the electrode and a redoxactive GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET proceeds exclusively through inner-sphere mechanisms. We additionally demonstrate that the catalytic hydrogen evolution reaction (HER) at a Rh-based GCC proceeds via concerted electron transfer and substrate activation via elimination of the stepwise pathway. In these respects, GCC active sites behave like metallic solids, but with an unprecedented level of molecular control. Using the GCC platform, we demonstrate that pKa is a useful thermodynamic descriptor for proton-coupled electron transfer (PCET) reactions at surface sites, just as it is in molecular sites, providing a framework with which to understand the thermochemistry of inner-sphere ET processes at electrode surfaces. Part 2 investigates the role of the explicit proton donor in interfacial PCET steps that result in metal-H bond formation by using the rate of HER on Au as a proxy for the rate of PCET to the Au surface. Detailed mechanistic studies revealed that in nonaqueous electrolytes, a trialkylammonium proton donor with a less bulky steric profile not only has overall faster HER kinetics than its bulkier counterpart, but also displays a greater transfer coefficient and a greater H/D kinetic isotope effect, demonstrating that even small changes to the identity of the proton donor can drastically affect the intrinsic kinetics of PCET at an interface. In aqueous electrolytes, we also observed a strong dependence on the identity of the proton-donating species in solution and found that only proton donors that can pre-associate with acceptor sites on the electrode surface can accelerate the rate of interfacial CPET. Finally, we used an innocent mixed-buffer electrolyte to probe the pH-dependence of steady-state HER current on Au and found that, surprisingly, the loss in catalytic efficiency occurs between pH 1 and pH 4 rather than systematically decreasing across the entire pH range. These results highlight the crucial role of the proton donor in achieving selective and efficient electrochemical energy conversion across a range of solvent and pH conditions.
Download or read book Surface and Interface Science Volumes 7 and 8 written by Klaus Wandelt and published by John Wiley & Sons. This book was released on 2020-03-30 with total page 1002 pages. Available in PDF, EPUB and Kindle. Book excerpt: In ten volumes, this unique handbook covers all fundamental aspects of surface and interface science and offers a comprehensive overview of this research area for scientists working in the field, as well as an introduction for newcomers. Volume 1: Concepts and Methods Volume 2: Properties of Elemental Surfaces Volume 3: Properties of Composite Surfaces: Alloys, Compounds, Semiconductors Volume 4: Solid-Solid Interfaces and Thin Films Volume 5: Solid-Gas Interfaces I Volume 6: Solid-Gas Interfaces II Volume 7: Liquid and Biological Interfaces Volume 8: Interfacial Electrochemistry Volume 9: Applications of Surface Science I Volume 10: Applications of Surface Science II Content of Volumes 7 & 8: * Probing Liquid/Solid Interfaces at the Molecular Level * Structure and Dynamics of Liquid-Solid Interfaces * Adsorption of Biomolecules * Liquid Surfaces * Surfaces of Ionic Liquids * Superhydrophobicity * Cell Penetrating Peptides Targeting and Distorting Biological Membranes * Theory of Solid/Electrolyte Interfaces * Metal/Electrolyte Interfaces: An Atomic View * X-Ray Spectroscopy at Electro-Catalytic Interfaces * Fundamental Aspects of Electro-Catalysis * Non-Linear Processes at Solid/Liquid Interfaces
Download or read book Kinetics of Heterogeneous Catalytic Reactions written by Michel Boudart and published by Princeton University Press. This book was released on 2014-07-14 with total page 241 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These editions preserve the original texts of these important books while presenting them in durable paperback and hardcover editions. The goal of the Princeton Legacy Library is to vastly increase access to the rich scholarly heritage found in the thousands of books published by Princeton University Press since its founding in 1905.
Download or read book Molecular Control of Electron and Hole Transfer Processes written by and published by . This book was released on 1996 with total page 98 pages. Available in PDF, EPUB and Kindle. Book excerpt: Recent decades have seen remarkable advances in microscopic understanding of electron transfer (ET) processes in widely ranging contexts, including solid-state, liquid solution, and complex biological assemblies. The primary goal of this chapter is to report recent advances in the modeling, calculation, and analysis of electronic coupling in complex molecular aggregates, thereby allowing an assessment of current progress toward the goal of molecular-level control and design. The control of electron transfer kinetics (i.e., enhancing desired processes, while inhibiting others) involves, of course, system energetics (especially activation and reorganization energies) as well as electronic coupling, which is most directly relevant only after the system has reached the appropriate point (or region) along the reaction coordinate. Nevertheless, to focus the discussion in this chapter, the authors will consider such energetics, and the associated molecular and solvent coordinates which control then, only to the extent that they bear on the analysis of the electronic coupling. In the following sections they first discuss the formulation of basic ET models, including the definition of initial and final states, the role of orbitals and 1-particle models in a many-electron context, the utility of various effective Hamiltonians, and the role of vibronic as well as purely electronic effects. With these theoretical tools in hand, they then examine very recent applications to complex molecular systems using the techniques of computational quantum chemistry, followed by detailed analysis of the numerical results. They then conclude with some comments regarding the current ''state of the art'' and remaining challenges.
Download or read book Encyclopedia of Interfacial Chemistry written by and published by Elsevier. This book was released on 2018-03-29 with total page 5276 pages. Available in PDF, EPUB and Kindle. Book excerpt: Encyclopedia of Interfacial Chemistry: Surface Science and Electrochemistry, Seven Volume Set summarizes current, fundamental knowledge of interfacial chemistry, bringing readers the latest developments in the field. As the chemical and physical properties and processes at solid and liquid interfaces are the scientific basis of so many technologies which enhance our lives and create new opportunities, its important to highlight how these technologies enable the design and optimization of functional materials for heterogeneous and electro-catalysts in food production, pollution control, energy conversion and storage, medical applications requiring biocompatibility, drug delivery, and more. This book provides an interdisciplinary view that lies at the intersection of these fields. Presents fundamental knowledge of interfacial chemistry, surface science and electrochemistry and provides cutting-edge research from academics and practitioners across various fields and global regions
Download or read book Molecular Reaction Dynamics written by Raphael D. Levine and published by Cambridge University Press. This book was released on 2009-06-04 with total page 574 pages. Available in PDF, EPUB and Kindle. Book excerpt: Molecular reaction dynamics is the study of chemical and physical transformations of matter at the molecular level. The understanding of how chemical reactions occur and how to control them is fundamental to chemists and interdisciplinary areas such as materials and nanoscience, rational drug design, environmental and astrochemistry. This book provides a thorough foundation to this area. The first half is introductory, detailing experimental techniques for initiating and probing reaction dynamics and the essential insights that have been gained. The second part explores key areas including photoselective chemistry, stereochemistry, chemical reactions in real time and chemical reaction dynamics in solutions and interfaces. Typical of the new challenges are molecular machines, enzyme action and molecular control. With problem sets included, this book is suitable for advanced undergraduate and graduate students, as well as being supplementary to chemical kinetics, physical chemistry, biophysics and materials science courses, and as a primer for practising scientists.
Download or read book Progress in Inorganic Chemistry Volume 41 written by Kenneth D. Karlin and published by John Wiley & Sons. This book was released on 2009-09-17 with total page 860 pages. Available in PDF, EPUB and Kindle. Book excerpt: This comprehensive series of volumes on inorganic chemistry provides inorganic chemists with a forum for critical, authoritative evaluations of advances in every area of the discipline. Every volume reports recent progress with a significant, up-to-date selection of papers by internationally recognized researchers, complemented by detailed discussions and complete documentation. Each volume features a complete subject index and the series includes a cumulative index as well.
Download or read book Encyclopedia of Surface and Colloid Science written by P. Somasundaran and published by CRC Press. This book was released on 2006 with total page 962 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Scientific and Technical Aerospace Reports written by and published by . This book was released on 1991 with total page 1102 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book STAR written by and published by . This book was released on 1965 with total page 2216 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Interfacial Electrochemistry written by Wolfgang Schmickler and published by Springer Science & Business Media. This book was released on 2010-08-26 with total page 273 pages. Available in PDF, EPUB and Kindle. Book excerpt: Electrochemistry is an old branch of physical chemistry. Due to the development of surface sensitive techniques, and a technological interest in fuel cells and batteries, it has recently undergone a rapid development. This textbook treats the field from a modern, atomistic point of view while integrating the older, macroscopic concepts. The increasing role of theory is reflected in the presentation of the basic ideas in a way that should appeal to experimentalists and theorists alike. Special care is taken to make the subject comprehensible to scientists from neighboring disciplines, especially from surface science. The book is suitable for an advanced course at the master or Ph.D. level, but should also be useful for practicing electrochemists, as well as to any scientist who wants to understand modern electrochemistry.
Download or read book Electron Transfer Reactions in Organic Chemistry written by Lennart Eberson and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 245 pages. Available in PDF, EPUB and Kindle. Book excerpt: The subject of the book is electron transfer reactions in organic chemistry, with the emphasis on mechanistic aspects. The theoretical framework is that of the Marcus theory, well-known from its extensive use in inorganic chemistry. The book deals with definitions of electron transfer, theory of electron transfer reactions (Marcus' and Pross-Shaik's approach) experimental diagnosis of electron transfer reactions, examples from inorganic/organic reactants and purely organic reactants, electro- and photochemical electron transfer, electron transfer catalyzed reactions, connections between electron transfer and polar mechanisms, and applications of electron transfer, such as electrosynthesis of organic chemicals, photochemical energy storage, conducting organic materials and chemiluminescence. The approach is new in so far as no comparable book has been published. The book will be of value to anyone interested in keeping track of developments in physical organic chemistry.
Download or read book Interfacial Electrochemistry written by Andrzej Wieckowski and published by Routledge. This book was released on 2017-11-22 with total page 1008 pages. Available in PDF, EPUB and Kindle. Book excerpt: This text probes topics and reviews progress in interfacial electrochemistry. It supplies chapter abstracts to give readers a concise overview of individual subjects and there are more than 1500 drawings, photographs, micrographs, tables and equations. The 118 contributors are international scholars who present theory, experimentation and applications.
Download or read book Atomic Scale Modelling of Electrochemical Systems written by Marko M. Melander and published by John Wiley & Sons. This book was released on 2021-09-09 with total page 372 pages. Available in PDF, EPUB and Kindle. Book excerpt: Atomic-Scale Modelling of Electrochemical Systems A comprehensive overview of atomistic computational electrochemistry, discussing methods, implementation, and state-of-the-art applications in the field The first book to review state-of-the-art computational and theoretical methods for modelling, understanding, and predicting the properties of electrochemical interfaces. This book presents a detailed description of the current methods, their background, limitations, and use for addressing the electrochemical interface and reactions. It also highlights several applications in electrocatalysis and electrochemistry. Atomic-Scale Modelling of Electrochemical Systems discusses different ways of including the electrode potential in the computational setup and fixed potential calculations within the framework of grand canonical density functional theory. It examines classical and quantum mechanical models for the solid-liquid interface and formation of an electrochemical double-layer using molecular dynamics and/or continuum descriptions. A thermodynamic description of the interface and reactions taking place at the interface as a function of the electrode potential is provided, as are novel ways to describe rates of heterogeneous electron transfer, proton-coupled electron transfer, and other electrocatalytic reactions. The book also covers multiscale modelling, where atomic level information is used for predicting experimental observables to enable direct comparison with experiments, to rationalize experimental results, and to predict the following electrochemical performance. Uniquely explains how to understand, predict, and optimize the properties and reactivity of electrochemical interfaces starting from the atomic scale Uses an engaging “tutorial style” presentation, highlighting a solid physicochemical background, computational implementation, and applications for different methods, including merits and limitations Bridges the gap between experimental electrochemistry and computational atomistic modelling Written by a team of experts within the field of computational electrochemistry and the wider computational condensed matter community, this book serves as an introduction to the subject for readers entering the field of atom-level electrochemical modeling, while also serving as an invaluable reference for advanced practitioners already working in the field.
Download or read book Handbook of Electrochemistry written by Cynthia G. Zoski and published by Elsevier. This book was released on 2007-02-07 with total page 935 pages. Available in PDF, EPUB and Kindle. Book excerpt: Electrochemistry plays a key role in a broad range of research and applied areas including the exploration of new inorganic and organic compounds, biochemical and biological systems, corrosion, energy applications involving fuel cells and solar cells, and nanoscale investigations. The Handbook of Electrochemistry serves as a source of electrochemical information, providing details of experimental considerations, representative calculations, and illustrations of the possibilities available in electrochemical experimentation. The book is divided into five parts: Fundamentals, Laboratory Practical, Techniques, Applications, and Data. The first section covers the fundamentals of electrochemistry which are essential for everyone working in the field, presenting an overview of electrochemical conventions, terminology, fundamental equations, and electrochemical cells, experiments, literature, textbooks, and specialized books. Part 2 focuses on the different laboratory aspects of electrochemistry which is followed by a review of the various electrochemical techniques ranging from classical experiments to scanning electrochemical microscopy, electrogenerated chemiluminesence and spectroelectrochemistry. Applications of electrochemistry include electrode kinetic determinations, unique aspects of metal deposition, and electrochemistry in small places and at novel interfaces and these are detailed in Part 4. The remaining three chapters provide useful electrochemical data and information involving electrode potentials, diffusion coefficients, and methods used in measuring liquid junction potentials. * serves as a source of electrochemical information * includes useful electrochemical data and information involving electrode potentials, diffusion coefficients, and methods used in measuring liquid junction potentials * reviews electrochemical techniques (incl. scanning electrochemical microscopy, electrogenerated chemiluminesence and spectroelectrochemistry)
Download or read book Effective Control Strategies for Highway Nonpoint Pollution written by John Joseph Sansalone and published by . This book was released on 1997 with total page 188 pages. Available in PDF, EPUB and Kindle. Book excerpt: Storm water drainage from urban highways often transports elevated levels of metal elements, solids and dissolved constituents. The goals of this research were the characterization of lateral pavement sheet flow and based on characterization results, development of passive in-situ treatment for metal elements and solids transported in storm water drainage.
Download or read book Handbook of Materials Modeling written by Sidney Yip and published by Springer Science & Business Media. This book was released on 2007-11-17 with total page 2903 pages. Available in PDF, EPUB and Kindle. Book excerpt: The first reference of its kind in the rapidly emerging field of computational approachs to materials research, this is a compendium of perspective-providing and topical articles written to inform students and non-specialists of the current status and capabilities of modelling and simulation. From the standpoint of methodology, the development follows a multiscale approach with emphasis on electronic-structure, atomistic, and mesoscale methods, as well as mathematical analysis and rate processes. Basic models are treated across traditional disciplines, not only in the discussion of methods but also in chapters on crystal defects, microstructure, fluids, polymers and soft matter. Written by authors who are actively participating in the current development, this collection of 150 articles has the breadth and depth to be a major contributor toward defining the field of computational materials. In addition, there are 40 commentaries by highly respected researchers, presenting various views that should interest the future generations of the community. Subject Editors: Martin Bazant, MIT; Bruce Boghosian, Tufts University; Richard Catlow, Royal Institution; Long-Qing Chen, Pennsylvania State University; William Curtin, Brown University; Tomas Diaz de la Rubia, Lawrence Livermore National Laboratory; Nicolas Hadjiconstantinou, MIT; Mark F. Horstemeyer, Mississippi State University; Efthimios Kaxiras, Harvard University; L. Mahadevan, Harvard University; Dimitrios Maroudas, University of Massachusetts; Nicola Marzari, MIT; Horia Metiu, University of California Santa Barbara; Gregory C. Rutledge, MIT; David J. Srolovitz, Princeton University; Bernhardt L. Trout, MIT; Dieter Wolf, Argonne National Laboratory.
