
Electrochemical Activation of Catalysis
Promotion, Electrochemical Promotion, and Metal-Support Interactions
By: Costas G. Vayenas, Symeon Bebelis, Costas Pliangos
Hardcover | 31 January 2002
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612 Pages
24.77 x 17.15 x 4.45
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Industry Reviews
"Electrochemical Activation of Catalysis contains a very full and detailed treatment of the mechanisms of electrochemical promotion. It is likely to remain the standard work on this remarkable new technology; for who other than the present authors will write a book with such a background of authority in the field? ...there is a great deal of substance to this book on the electrochemical promotion of catalysis. But the joy is that it has been set down in a very lucid way so that I seldom had to pause to scan a sentence a second time for meaning."
(John O'M. Bockris, Molecular Green Technology)
"From the reviews:
This book is well organized and well written. It integrates such diverse topics as catalytic promotion, spillover, metal-support interactions, solid-state physics, and transport modeling to show how these topics bear on electrochemical promotion of catalysis-and at the same time, illustrates how the study of electrochemical promotion can throw light on our understanding of these important topics of physical chemical research. Electrochemical Activation of Catalysis is recommended reading to anyone with some interest in chemical reactions on solid surfaces."
(Gary L. Haller, Yale University)
"Electrochemical Activation of Catalysis is a significant milestone in the literature of both electrochemistry and catalysis[...]The book's timing coincides with the present-day upsurge of interest in fuel cells of all sorts. For those new to its field, the book is an excellent learning opportunity. For the expert, it provides a rigorous quantitative framework and a thorough review of the literature. Therefore, the book will be a valuable tool for the student and practitioner alike."
(L. Louis Hegedus, Atofina Chemicals, Inc.)
"[...]The appendix of the book compiles most interesting questions, which will help the reader gain a better insight into the authors' views. The appendix also contains concrete advise on how to build a catalytic reactor and choose materials and equipment for experiments on the electrochemical promotion. All seventeen major research groups that work in this field are briefly characterized. The book contains an extensive bibliography, which includes a sufficient number of references to papers by Russian scientists. [...]The book is very interesting. It is prefaced by an intriguing and exciting article by J. O'M. Bockris, who greets the appearance in Greece of bright electrochemical talents and non-trivial electrochemical studies.'
(O.A. Petrii in Russian Journal of Electrochemistry, 38:9, 2002)
"This book provides a thorough understanding of a field that has tremendous growth potential, particularly in the area of electrochemical promotion of nonredox systems[...] I highly recommend it."
(Eugene S. Smotkin in JACS, 124, 2002)
"The electrochemical modification of catalytic activity is one of the most important developments in electrochemistry during the past 20 years. Today, more than 2000 papers have been published on this subject, many of them from the very active group of Costas G. Vayenas at the University of Patras in Greece and his coworkers[...] Owing to the work of Vayenas and his group there is growing interest in industry[...] The present book should be read by all scientists in the field of electrochemistry and heterogeneous catalysis, particularly if they are working in applied science[...] It took the main author 20 years to approach the current state of knowledge and to spread his ideas with enormous energy[...] The origin of electrochemical promotion is fundamental and the phenomenon itself leads to new concepts in solid state electrochemistry. The book is self-contained and its content can be understood without major difficulties by graduate students in chemistry[...]the book should be on the shelves of any laboratory that is working either in solid state electrochemistry or heterogeneous catalysis."
(Juergen Janek in Journal of Solid State Electrochemistry, 7, 2002)
| Introduction, Brief History and Basic Concepts | |
| The Phenomenon of Electrochemical Promotion | p. 1 |
| Basic Concepts and Terminology | p. 8 |
| Structure of This Book | p. 10 |
| Promotion in Heterogeneous Catalysis | |
| Introduction | p. 15 |
| Catalysis, Chemical and Electrochemical Promotion: An Example | p. 17 |
| Chemisorption and Catalytic Kinetics | p. 20 |
| Catalytic Kinetics and Promoters | p. 22 |
| Interactions of Adsorbates Acting as Promoters or Poisons with Catalyst Surfaces | p. 23 |
| Definitions | p. 23 |
| Electropositive (Electron Donor) and Electronegative (Electron Acceptor) Promoters | p. 24 |
| Electropositive Promoters: Alkali Metals | p. 24 |
| Electronegative Promoters | p. 30 |
| Adsorption on Surfaces Modified by Electropositive or Electronegative Promoters | p. 35 |
| Adsorption of Gases on Surfaces Modified by Alkali Promoters | p. 35 |
| Adsorption of Gases on Surfaces Modified by Electronegative Adatoms | p. 56 |
| Catalytic Activity on Surfaces Modified by Promoters or Poisons | p. 72 |
| CO Oxidation on Li-doped Pt(111) Surfaces | p. 73 |
| Ethylene Epoxidation | p. 74 |
| Synthesis Gas Conversion Reactions | p. 77 |
| Summarizing Comments and Rules | p. 82 |
| Solid Electrolytes, Catalysis and Spillover | |
| Solid Electrolytes | p. 91 |
| Solid Electrolyte Potentiometry (SEP) | p. 94 |
| Electrocatalytic Operation of Solid Electrolyte Cells | p. 96 |
| Spillover-backspillover Phenomena | p. 101 |
| Phenomenology | p. 101 |
| Mechanisms: Donor and Acceptor Phases | p. 101 |
| Thermodynamics and Kinetics of Spillover-Backspillover Between a Solid Electrolyte and a Metal Catalyst-Electrode | p. 104 |
| Electrochemical Promotion of Catalytic Reactions | |
| Experimental Setup | p. 111 |
| The Reactor and the Gas Analysis System | p. 111 |
| The Catalyst Film | p. 113 |
| Counter and Reference Electrodes | p. 117 |
| Quasireference Electrodes | p. 118 |
| Catalyst-Electrode Film Characterization | p. 118 |
| Catalytic Characterization: Measurement of the Metal/Gas Interface Area A[subscript G] | p. 119 |
| Electrochemical Characterization: Measurement of the Catalyst-Solid Electrolyte Exchange Current I[subscript 0] | p. 121 |
| A NEMCA Experiment: Galvanostatic and Potentiostatic Transients | p. 128 |
| Electrochemical Promotion Using O[superscript 2-] Conductors | p. 128 |
| Electrochemical Promotion Using Na[superscript +] Conductors | p. 131 |
| General Features and Comparisons | p. 137 |
| Catalyst Work Function Variation with Potential in Solid Electrolyte Cells | p. 138 |
| Definitions, Phenomenology and Key Aspects of Electrochemical Promotion | p. 140 |
| NEMCA Time Constant [tau] | p. 140 |
| Enhancement Factor or Faradaic Efficiency | p. 141 |
| Rate Enhancement Ratio [rho] | p. 146 |
| Promotion Index PI[subscript i] | p. 148 |
| Electrophobic and Electrophilic Reactions | p. 151 |
| Dependence of Catalytic Rates and Activation Energies on Catalyst Potential U[subscript WR] and Work Function [Phi] | p. 152 |
| Activation Energy and Preexponential Factor Dependence on Work Function | p. 164 |
| Selectivity Modification | p. 168 |
| Promotional Effects on Chemisorption | p. 170 |
| "Permanent NEMCA" | p. 176 |
| Prediction of the Magnitude of the Faradaic Efficiency | p. 179 |
| Synopsis of the Phenomenology: Reactions Studied so Far | p. 181 |
| Origin of NEMCA | |
| Problems and Methods | p. 189 |
| A Galvanostatic NEMCA Transient Revisited | p. 191 |
| Analysis of Rate Time Constants During Galvanostatic Transients | p. 198 |
| Introduction | p. 198 |
| Time constants During Galvanostatic Transients and Faradaic Efficiency | p. 200 |
| Transient Analysis and Promotion Index | p. 200 |
| Work Function and Electrochemical Promotion | p. 203 |
| Work Function, Fermi Level, Vacuum Level, Galvani and Volta Potentials, Dipole Moments | p. 203 |
| The Work Function of Catalyst Films Deposited on Solid Electrolytes | p. 205 |
| The Work Function of Catalyst Films Deposited on Solid Electrolytes: Rationalization of the Potential-Work Function Equivalence | p. 218 |
| Spatial Variations | p. 222 |
| Transients and Measurement of Dipole Moments | p. 223 |
| Deviations from the Equality in the Changes of Extraction Potential and Electrode Potential | p. 224 |
| Temperature Programmed Desorption (TPD) | p. 228 |
| Solid Electrolyte Cyclic Voltammetry | p. 233 |
| Detection of Adsorbed Species | p. 233 |
| Potential Programmed Reduction | p. 237 |
| AC Impedance Spectroscopy | p. 237 |
| General Features | p. 237 |
| Measurement of the tpb Length | p. 243 |
| XPS Investigations | p. 244 |
| XPS in Catalysis and Solid State Electrochemistry | p. 244 |
| XPS Studies of Metals Supported on Na[superscript +] Conductors | p. 254 |
| UPS Investigations | p. 255 |
| SERS Investigations | p. 256 |
| PEEM Investigations | p. 257 |
| Scanning Tunelling Microscopy | p. 259 |
| Direct Atomic Scale Observation of Electrochemically Controlled Spillover/Backspillover | p. 259 |
| Ordered Promoter Adlattices and Electrochemical Promotion | p. 264 |
| Quantum Mechanical Calculations | p. 267 |
| The Effective Double Layer | p. 271 |
| Rules and Modeling of Promotion | |
| Electron Acceptor and Electron Donor Adsorbates | p. 279 |
| Electrophobic, Electrophilic, Volcano and Inverted Volcano Reactions: Rationalization, Rules, and Predictions | p. 281 |
| Similarities and Differences Between Electrochemical and Classical Promotion | p. 283 |
| Promotional Rules | p. 285 |
| Connection Between [Phi]and Adsorbate Coverage | p. 295 |
| Local Promotional Rules | p. 296 |
| Practical Considerations | p. 298 |
| Rationalization of the Promotional Rules | p. 299 |
| Derivation of the Experimental Local Rules L1 and L2 from the Fundamental Rules F1 and F2 | p. 299 |
| Experimental Confirmation and First Principle Rationalization of Rules F1 and F2 | p. 300 |
| Summary of Promotion Rules | p. 302 |
| Mathematical Modelling of Electrochemical Promotion and Classical Promotion | p. 305 |
| Introduction | p. 305 |
| Adsorption in Presence of a Double Layer | p. 306 |
| Adsorption in Absence of Coadsorbing Species | p. 312 |
| Adsorption Isotherms, Nernst Equation and Potential-Work Function Equivalence | p. 313 |
| Catalytic Kinetics in Presence of a Double Layer | p. 315 |
| The Absolute Potential | |
| Introduction | p. 333 |
| Absolute Potential Scales in Aqueous Electrochemistry | p. 334 |
| Absolute Potential Scale and Zero Energy Level of Electrons in Solid State Electrochemistry | p. 336 |
| The Nature of the Effective Double Layer | p. 338 |
| Experimental Establishment of the Absolute Potential Scale | p. 340 |
| The Work Function of Catalyst Films Deposited on Solid Electrolytes: Rationalization of the Potential-Work Function Equivalence | p. 345 |
| Definition and Properties of the Absolute Potential Scale in Solid Electrochemistry | p. 351 |
| Potential Distribution in a Solid Electrolyte Cell | p. 356 |
| Absolute Potential of Supported Catalysts | p. 358 |
| Electrochemical Promotion with O[superscript 2-] Conductors | |
| The Use of O[superscript 2-] Conductors | p. 363 |
| Complete Oxidation Reactions | p. 363 |
| Partial Oxidation Reactions | p. 393 |
| Dehydrogenation and Hydrogenation Reactions | p. 403 |
| NO Reduction Reactions | p. 411 |
| The Use of F[superscript -] Conductors | p. 420 |
| CO Oxidation on Pt/CaF[subscript 2] | p. 420 |
| The Use of Mixed Conductors | p. 420 |
| C[subscript 2]H[subscript 4] Oxidation on Pt/TiO[subscript 2] | p. 420 |
| C[subscript 2]H[subscript 4] Oxidation on Pt/CeO[subscript 2] | p. 428 |
| Electrochemical Promotion with Cationic Conductors | |
| The Use of Alkali Ion Conductors | p. 435 |
| Ethylene Oxidation on Pt/[beta]"-Al[subscript 2]O[subscript 3] | p. 435 |
| Ethylene Oxidation on Pt/NASICON | p. 440 |
| CO Oxidation on Pt/[beta]"-Al[subscript 2]O[subscript 3] | p. 442 |
| Ethylene Epoxidation on Ag/[beta]"-Al[subscript 2]O[subscript 3] | p. 445 |
| NO Reduction Studies on Pt/[beta]"-Al[subscript 2]O[subscript 3] | p. 446 |
| Benzene Hydrogenation on Pt/[beta]"-Al[subscript 2]O[subscript 3] | p. 452 |
| CO[subscript 2] Hydrogenation on Pd | p. 453 |
| Selective C[subscript 2]H[subscript 2] Hydrogenation on Pt/[beta]"-Al[subscript 2]O[subscript 3] and Pd/[beta]"-Al[subscript 2]O[subscript 3] | p. 453 |
| NH[subscript 3] Decomposition on Fe/K[subscript 2]YZr(PO[subscript 4])[subscript 3] and on CaZr[subscript 0.9]In[subscript 0.1]O[subscript 3-[alpha] | p. 456 |
| Hydrogen Oxidation on Pt/glass | p. 456 |
| The Use of H[superscript +] Conductors | p. 456 |
| Hydrogen Oxidation on Pt/Nafion | p. 456 |
| Isomerization of 1-Butene on Pd-Black Cathodes/Nafion 117 | p. 466 |
| Ethylene Cathodes Hydrogenation on Ni/CsHSO[subscript 4] | p. 467 |
| Ammonia Synthesis on Fe Supported on a Proton (CaZr[subscript 0.9]In[subscript 0.1]O[subscript 3-[alpha]) Conductor | p. 468 |
| Methane Dimerization Using Proton Conductors | p. 470 |
| C[subscript 2]H[subscript 4] Oxidation on Pt/CaZr[subscript 0.9]In[subscript 0.1]O[subscript 3-[alpha] | p. 470 |
| NEMCA with Aqueous Electrolytes and Inorganic Melts | |
| H[subscript 2] Evolution and Aldehyde Oxidation at Ib Metals in Alkaline Solutions | p. 475 |
| Hydrogen Oxidation on Pt in Aqeous Alkaline Solutions | p. 476 |
| Maleic Acid Hydrogenation on Pt in Aqueous Acidic Solutions | p. 481 |
| Production of Ammonium Polysulfide | p. 482 |
| SO[subscript 2] Oxidation in V[subscript 2]O[subscript 5]-K[subscript 2]S[subscript 2]O[subscript 7] Melts | p. 482 |
| Electrochemical Promotion and Metal-Support Interactions | |
| Metal-Support Interactions | p. 487 |
| Experimental Confirmation of the Mechanistic Equivalence of NEMCA and Metal-Support Interactions | p. 490 |
| Mathematical Modeling: Dimensionless Numbers Governing Electrochemical Promotion and Metal-Support Interactions | p. 500 |
| Modeling | p. 501 |
| Numerical Examples | p. 507 |
| Summary of Modelling Results | p. 509 |
| Interrelation of Promotion, Electrochemical Promotion and Metal-Support Interactions: The Double-Layer Model of Catalysis | p. 509 |
| Practical Applications, Summary and Perspectives | |
| Classical Promoter Selection | p. 516 |
| Material Cost Minimization: Dispersed and Commercial Catalysts | p. 516 |
| Electrochemical Promotion with Highly Dispersed Catalysts | p. 518 |
| Electrochemical Promotion of Commercial Catalysts | p. 520 |
| Bipolar Electrochemical Promotion | p. 521 |
| Electrochemical Promotion of C[subscript 2]H[subscript 4] Oxidation on Pt Using a Bipolar Design | p. 521 |
| Electrochemical Promotion of C[subscript 2]H[subscript 4] Oxidation on Pt Using Multi-Stripe and Multi-Dot Bipolar Catalysts | p. 523 |
| Electrochemical Promotion Using a Bipolar Monolithic Reactor | p. 524 |
| Electrochemical Promotion of Particulate Matter (Soot) Combustion Using a Ceria-Gadolinia Solid Electrolyte and a Dispersed Perovskite Catalyst | p. 525 |
| Summary and Perspectives | p. 528 |
| Common Questions about Electrochemical Promotion | |
| Questions | p. 533 |
| Answers | p. 536 |
| Materials and Instrumentation for Starting Electrochemical Promotion Experiments | |
| Catalyst-Electrodes, Solid Electrolytes | p. 543 |
| Instrumentation | p. 547 |
| Apparatus | p. 550 |
| Procedures | p. 553 |
| Main Research Groups | p. 559 |
| Index | p. 567 |
| Table of Contents provided by Syndetics. All Rights Reserved. |
ISBN: 9780306467196
ISBN-10: 0306467194
Published: 31st January 2002
Format: Hardcover
Language: English
Number of Pages: 612
Audience: Professional and Scholarly
Publisher: Springer Nature B.V.
Country of Publication: US
Dimensions (cm): 24.77 x 17.15 x 4.45
Weight (kg): 1.33
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