Mathias, D. Baker, J. Zhang, Y. Liu, and W. Meier and. Eigenberger , Transport parameters for the modelling of water transport in ionomer membranes for PEM-fuel cells , Electrochimica Acta , vol. Murphy, D. Hitchens, and. Manko , High power density proton-exchange membrane fuel cells , Journal of Power Sources , vol.
Meland and S. Kjelstrup , Three steps in the anode reaction of the polymer electrolyte membrane fuel cell. Meland, S. Kjelstrup, and D.
In other words, Pt-OH becomes available for reaction not only within its nominal reversible adsorption and desorption peak limits in regular mineral acid or base aqueous solutions, but depending on the reactant concentration, affinity, and its actual reaction rate, along a broad and extendable potential range. Roznyatovskii Aqueous electrochemistry of binuclear copper complex with Robson-type ligand: dissolved versus surface-immobilized reactant J. This is claimed to be the first and only volume to cover interfacial electrochemistry, as opposed to other facets of interfacial science. Antipov, M. Author s : Wolfgang E.
Bedeaux , Rate limiting proton hydration in the anode of the polymer electrolyte membrane fuel cell , Journal of Membrane Science , vol. Maranzana, T. Chupin et al. Mauritz and. Makharia, D. Mathias, and. Mainka, J. Maranzana, S. Dillet, O. Maranzana, J. Moyne, S. Power Sources , issue. Maillard, F. Martin, J. Gloaguen, and. Particle-size effect on the tolerance to methanol competition , Electrochimica Acta , vol. Nam and.
Nakamura, H. Nishikawa, T. Aoki, and Y. Ogami , The diffusion overpotential increase and appearance of overlapping arcs on the Nyquist plots in the low humidity temperature test conditions of polymer electrolyte fuel cell , Journal of Power Sources , vol. Nyikos and. Pajkossy , Fractal dimension and fractional power frequency-dependent impedance of blocking electrodes , Electrochimica Acta , vol. O-'hayre, S. Lee, F. Cha, and. Prinz , A sharp peak in the performance of sputtered platinum fuel cells at ultra-low platinum loading , J. Mark, B. Orazem, and. Tribollet , An integrated approach to electrochemical impedance spectroscopy , Electrochim.
Okada, Y. Xie, and. Tanabe , Theory of water management at the anode side of polymer electrolyte fuel cell membranes , Journal of Electroanalytical Chemistry , vol. Sousa, and. Mendes , Segmented polymer electrolyte membrane fuel cells??? A review , Renewable and Sustainable Energy Reviews , vol. Parthasarathy, C. Martin, S. Srinivasan, V. Paganin, C. Oliveira et al. Parthasarathy, S. Passalacqua, F. Squadrito, A. Lufrano, L. Pw04a, C. Pasaogullari, and. Wang , Two-phase transport and the role of microporous layer in polymer electrolyte fuel cells , Electrochim.
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Rai90 and. Raistrick , Impedance studies of porous electrodes , Electrochim. Randles , Kinetics of rapid electrode reactions. Discussion of the Faraday Society , Ramousse, O. Deseure, S. Lottin, D. Didierjean, and. Didierjean, D.
Lottin, and. Reu08 and. Rowe and. Li , Mathematical modeling of proton exchange membrane fuel cells , Journal of Power Sources , vol. Ramousse, S. Roy and. Roy, B. Tribollet, A. Rubatat, G. Rollet et al. Rodat, F. Sailler, P. Druart, Y. Thivel, P. Bultel et al. Rub03, M. Rubatat, A. Rubio, R. Urquia, S. Kuhn et al. John, R. Slattery, and. Bird , Calculation of the diffusion coefficient of dilute gases and of the self-diffusion coefficient of dense gases , AIChE J , vol. Schneider, A. Bayer, G. Wokaun, and. Sch03 and. Song, W. Lee , Optimal composition of polymer electrolyte fuel cell electrodes determined by the AC impedance method , Journal of Power Sources , vol.
Silva, A. Francesco, and. Pozio , Tangential and normal conductivities of Nafion?? Siegel, D. Ellis, M. Von, and. Sone, D.
Ekdunge, and. Schneider, D. Freunberger, A. Kramer, G. Wokaun et al.
Stamenkovic, B. Fowler, G. Mun, P. Wang et al. Saminathan, V. Kamavaram, A. Veedu, and. Kannan , Preparation and evaluation of electrodeposited platinum nanoparticles on in situ carbon nanotubes grown carbon paper for proton exchange membrane fuel cells , International Journal of Hydrogen Energy , vol. Stamenkovic and. Markovic , Oxygen reduction on platinum bimetallic alloy catalysts , Handbook of Fuel Cells -Fundamentals, Technology and Applications , p.
Saleh, M. Okajima, F. Hayase, T. Kitamura, and. Spk05a, B. Sun, K. Peppley, and. Karan , An improved two-dimensional agglomerate cathode model to study the influence of catalyst layer structural parameters , Electrochim. Spk05b, B. Springer and. Sauer, B. Sanders, T. Fricke, K. Saibuathong, K. Saejeng, M. Pruksathorn, N. Hunsom et al. Sepa, A. Vojnovic, and. Damjanovic , Reaction intermediates as a controlling factor in the kinetics and mechanism of oxygen reduction at platinum electrodes , Electrochimica Acta , vol.
Springer, S. Wilson, and. Seidenberger, T. Wilhelm, W. Schmitt, J. Lehnert et al. Zawodzinski, and. Springer, M. Zawodzinski, S. Tricoli, M. Carretta, and. Ticianelli, A. Derouin, S. Redondo, and. Thomas, S. Maranzana, O. Didierjean, J. This book presents a complete overview of the powerful but often misused technique of Electrochemical Impedance Spectroscopy EIS. The book presents a systematic and complete overview of EIS. The book carefully describes EIS and its application in studies of electrocatalytic reactions and other electrochemical processes of practical interest.
This book is directed towards graduate students and researchers in Electrochemistry. Concepts are illustrated through detailed graphics and numerous examples. The book also includes practice problems. Additional materials and solutions are available online. Electrochemistry is at the heart of this transverse approach through many scientific domains. Does not require a high level of mathematics: only prior knowledge of partial differentiation and integration With the help of this new tool, the modeling of physical phenomena becomes a fascinating cross-disciplinary exploration.
The graphs encourage a visual, unified comprehension of the relationships between physical concepts and variables, properties, and operators. Out-of-the-box and thought provoking, this book inspires lively discussions and fruitful thinking about the connections between mechanics, chemical reactivity, electrodynamics, thermodynamics, electrochemistry and more. More than 80 case studies are tackled through all domains. Editor: Minhua Shao Author s : R. Adzic, J. Chen, A. Wieckowski, C.
Rice, P. Pickup, E.
Antolini, K. Ozoemena, J. Zagal, P. Zelenay, J. Dodelet, Z. Chen, L. Dai, K. Ota, N. Alonso-Vante, J. Feliu, P. Strasser, S. Ball, J. Zhang, P. Balbuena, R. Atanasoski, W. Recent intensive research efforts have led to the development of less expensive and more abundant electrocatalysts for fuel cells. This book aims to summarize recent advances of electrocatalysis in oxygen reduction and alcohol oxidation, with a particular focus on low- and non-Pt electrocatalysts. The book is divided into two parts containing 24 chapters total.
All the chapters were written by leading experts in their fields. Part I contains 6 chapters and focuses on the electro-oxidation reactions of small organic fuels. The subsequent 18 chapters in Part II cover the oxygen reduction reactions on low- and non- Pt catalysts. The book is geared toward researchers in the field, postgraduate students and lecturers, and scientists and engineers at fuel cell and automotive companies.
It can even be a reference book for those who are interested in this area. This book titled "Recent Trend in Electrochemical Science and Technology" contains a selection of chapters focused on advanced methods used in the research area of electrochemical science and technologies; descriptions of electrochemical systems; processing of novel materials and mechanisms relevant for their operation. This book provides an overview on some of the recent development in electrochemical science and technology. Particular emphasis is given both to the theoretical and the experimental aspect of modern electrochemistry.
Since it was impossible to cover the rich diversity of electrochemical techniques and applications in a single issue, the focus is on the recent trends and achievements related to electrochemical science and technology. The book "Developments in Electrochemistry" contains five feature articles in recent advanced electrochemistry. These selected feature articles emphasize physical phenomena rather than mathematical formalisms of electrochemistry. The work represented in this book will be useful, effective, and beneficial to physicists, chemists, surface scientists, material scientists, engineers, and especially electrochemists.
Electrochemistry The Basics, with Examples. This book provides a balanced coverage of the thermodynamic and kinetic processes at the heart of electrochemical reactions and electrochemical systems. While the first half gives an overview of the fundamental concepts appropriate to undergraduate students, the second half gives an in depth account of electrochemical systems suitable to experienced scientists and course lecturers. The concepts are clearly explained and well illustrated.
Mathematical treatments are included but kept to a minimum. The book contains a number of problems with detailed worked out answers. The book ambitions to become a reference book in the fast-growing field of nanostructured materials for energy storage and conversion which is expected to shape the next-generation lithium-ion batteries driven by a highly demanding and fast-expanding market.
The book consists of 11 chapters covering the most critical aspects of the science and technology of nanomaterial electrodes for application in advanced lithium-ion batteries. The chapters include nanostructured anode materials based on Si, Ge, Sn, and other metals and metal oxides together with cathode materials of olivine, the hexagonal and spinel crystal structures. From the chemistry aspect, graphene is the extrapolated extreme of condensed polycyclic hydrocarbon molecules to infinite size.
Here, the concept of aromaticity, which organic chemists utilize, is applicable. Interesting issues appearing between physics and chemistry are pronounced in nano-sized graphene nanographene , as we recognize the importance of the shape of nanographene in understanding its electronic structure.
This book comprehensively discusses the fundamental issues related to the electronic, magnetic, and chemical properties of condensed polycyclic hyodrocarbon molecules, nanographene, and graphene. Many-electron Electrochemical Processes. Author s : Alexander A. The authors provide a unified concept for understanding multi-electron processes in electrochemical systems such as molten salts, ionic liquids, or ionic solutions. Therefore this monograph is a unique resource for basic electrochemical research but also for many important applications such as electrodeposition, electrorefining, or electrowinning of polyvalent metals from molten salts and other ionic media.
Electrochemical Dictionary, 2nd edition Editors: A. Bard, G. Inzelt, F. This second edition of the highly successful dictionary offers more than new or revised terms. A distinguished panel of electrochemists provides up-to-date, broad and authoritative coverage of terms most used in electrochemistry and energy research as well as related fields, including relevant areas of physics and engineering. Each entry supplies a clear and precise explanation of the term and provides references to the most useful reviews, books and original papers to enable readers to pursue a deeper understanding if so desired.
Almost figures and illustrations elaborate the textual definitions. Polymer electrolyte membrane and direct methanol fuel cell technology Volume 1: Fundamentals and performance of low temperature fuel cells Volume 2: In-situ characterisation techniques for low-temperature fuel cells. Author s : Christoph Hartnig, Christina Roth eds. PEMFCs and DMFCs represent promising low-temperature electrochemical power generation technologies that operate on hydrogen and methanol, respectively. Volume 1 covers the fundamental science and engineering of these types of fuel cell, while volume 2 is dedicated to sophisticated in-situ characterisation methods.
Author s : Keith B. Oldham, Jan C. Myland and Alan M. The book treats electrochemistry as a science in its own right, albeit firmly based on foundations provided by Chemistry, Physics and Mathematics. Early chapters discuss the electrical and chemical properties of materials from which electrochemical cells are constructed. The behavior of such cells is addressed in later chapters, with emphasis on the electrodes and the reactions that occur on their surfaces.
The role of transport to and from electrodes is a topic that commands attention , because it crucially determines cell efficiency. Final chapters deal with voltammetry, the methodology used to investigate electrode behavior. Self-Organization in Electrochemical Systems. I: General Principles of Self-Organization. Temporal Instabilities. The two-volume monograph which discusses both the theory and experimental manifestations of self-organization periodic and chaotic oscillations, multistability in electrochemical systems.
The first volume describes self-organization as a function of time, without taking into account the spatial heterogeneity. The second volume is devoted to self-organization developing in space and time, leading to corresponding dissipative patterns, including a. Characteristics of experimental and model electrochemical systems is preceded by universal mathematical foundations of nonlinear dynamics.
Length of Book Pages : pages Vol. I ; pages Vol. I: ,85 Euro hardcover ; ,79 Euro eBook Vol. II: ,25 Euro hardcover ; ,64 Euro eBook. Author s : J. Bringing together the latest research this book applies new modelling techniques to corrosion issues in aircraft structures. It describes complex numerical models and simulations from the microscale to the macroscale for corrosion of the aluminium Al alloys that are typically used for aircraft construction, such as AA The approach is also applicable to a range of other types of structures, such as automobiles and other forms of ground vehicles.
The main motivation for developing the corrosion models and simulations was to make significant technical advancements in the fields of aircraft design using current and new materials , surface protection systems against corrosion and degradation and maintenance. The corrosion models address pitting and intergranular corrosion microscale of Al alloys, crevice corrosion in occluded areas, such as joints mesoscale , galvanic corrosion of aircraft structural elements macroscale , as well as, the effect of surface protection methods anodisation, corrosion inhibitor release, clad layer, etc.
The book describes the electrochemical basis for the models, their numerical implementation, and experimental validation and how the corrosion rate of the Al alloys at the various scales is influenced by its material properties and the surface protection methods. It will be of interest to scientists and engineers interested in corrosion modelling, aircraft corrosion, corrosion of other types of vehicle structures such as automobiles and ground vehicles, electrochemistry of corrosion, galvanic corrosion, crevice corrosion, and intergranular corrosion.
Topics examined in this volume include: single event electrochemistry, nanoparticle electrocatalysis, bipolar electrochemistry in the nanosciences, nanocarbon electrochemistry, electrochemistry within template nanosystems and electrochemistry within liquid nanosystems. The volume is a key reference in the field of electrochemistry, allowing the reader to become acquainted with the latest research and opinion. Purchasers of the print edition can register for free access to the electronic version. This book presents problems and worked examples for a wide range of theoretical and experimental subjects in the field of voltammetry.
The reader is assumed to have knowledge up to a Master's level of physical chemistry, but no exposure to electrochemistry in general, or voltammetry in particular. The problems range in difficulty from senior undergraduate to research level, and develop important practical approaches in voltammetry. The problems presented in the earlier chapters focus on the fundamental theories of thermodynamics, electron transfer and diffusion. Voltammetric experiments and their analysis are then considered, including extensive problems on both microelectrode and macroelectrode voltammetry.
Convection, hydrodynamic electrodes, homogenous kinetics, adsorption and electroanalytical applications are discussed in the later chapters, as well as problems on two rapidly developing fields of voltammetry: weakly supported media and nanoscale electrodes. This book provides an overview of biosensors based on amperometry, conductimetry, potentiometry, square-wave voltammetry, impedance, and electrochemiluminescence and describes the use of ultramicroelectrodes for the real-time monitoring and understanding of exocytosis.
Areas of particular interest are the use of silver and gold nanoparticles for signal amplification, photocurrent transduction, and aptamer design. Moreover, advanced insights in the innovative concept of self-powered biosensors derived from biofuel cells are also discussed. Author s : Alejandro A. This book focuses on the recent research progresses on the fundamental understanding of the materials degradation phenomena in PEFC, for automotive applications. On a multidisciplinary basis, this book provides a complete and comprehensive critical review on crucial scientific topics related to PEFC materials degradation, and ensures a strong complementarity between experimental and theoretical analysis experimental accelerated aging methods in ex-situ and in-situ conditions, stability properties of nanoparticles, structural and physicochemical characterization of methods of degradation, detailed theoretical modeling, elementary mechanisms, nano-electrocatalysts and carbon support behaviour under realistic operation conditions Laser-enabled measurements are valuable tools for the investigation of surfaces and interfaces or for the in situ investigation of interfacial processes including electrode processes.
In the first part of this book, the authors describe a range of techniques for investigating interfacial tension and surface stress, which is important for coatings, thin films, and fuel cells. The techniques covered comprise bending beam bending plate, bending cantilever, wafer curvature methods with different detection techniques.
Special attention is given to methods using optical detection by laser beam deflection or interferometry. The second part is devoted to the techniques based on the detection of refractive index gradients in the solution. The application of the techniques to surface-confined and solution electrochemical systems is described. Subsequently, a comparison with others techniques able to monitor ion fluxes is performed.
Compiling the cumulative research of the last two decades on theoretical considerations and practical applications of impedance spectroscopy, this book covers all of the topics that will help readers quickly determine whether this technique is an appropriate method of analysis for their own research problems, and how to apply it. Unique to this monograph is an emphasis on practical applications of impedance spectroscopy.
Impedance Spectroscopy is developed around a representative catalogue of the most commonly encountered impedance data examples for large variety of established, emerging, and non-conventional experimental and applied systems. The book also presents theoretical considerations for dealing with impedance data modeling, equivalent circuits, relevant complex domain mathematical equations, and physical and chemical interpretation of the experimental results for many problems encountered in research and industrial settings.
A review of impedance instrumentation, selection of best measurement methods for particular systems, and analysis of potential sources of error is further included. The book presents a comprehensive overview of the theory of the technological processes of lead-acid battery manufacture and their influence on battery performance parameters. It summarizes the current knowledge about the technology of lead-acid battery production and presents it in the form of an integral theory.
This theory is supported by ample illustrative material and experimental data, thus allowing technologists and engineers to control the technological processes in battery plants and providing university lecturers with a toll for clear and in-depth presentation of the technology of lead-acid battery production in their courses. The relationship between the technological processes and the performance characteristics of the batteries is disclosed too.
This volume introduces a variety of viable electrochemical methods to identify reaction mechanisms and evaluate relevant kinetic properties of insertion electrodes. Author s : Wolfgang E. Hansal and Sudipta Roy. This long awaited book appears after more than 25 years of the publication of the first pulse plating book in the mid-eighties. The book aims to cover pulse plating advancements over the quarter century following the first book - from mid-eighties to the first decade of the 21st century.
New understanding and developments on fundamental and applied aspects of pulse plating, which has been enabled by the rapid development of digital current rectifiers is a great differentiator against the first pulse plating book. Novel approaches to pulse plating, using knowledge based approaches such as modeling analysis, to solve particular problems have been elaborated. Nanotechnology has attracted billions of venture capital from research institutes, governments, and industries in recent years.
Traditional nanofabrication techniques, such as CVD, sol-gel, and self-assembly, have been intensively studied. However, the electrochemical nanofabrication technique, which offers huge benefits for manufacturing nanomaterials as well as broad applications in industry, has not been paid much attention compare with the traditional nanofabrication methods. This book fits the niche of such technology. This book summarizes different electrochemical nanofabrication methods and shows the various essential applications of them in areas such as batteries, sensors, and many future applications.
KEY FEATURES -Discusses the principles of electrochemical nanofabrications and their great potential in sensors, batteries, optoelectronics, and many future applications -Presents contributions by leading scientists and researchers in the field that review current state-of-the art and future prospects for electrochemical nanofabrications -A combination of truly worldwide contribution from leading scientists in the United Kingdom, China, Germany, Finland, and Spain-Includes an extensive bibliography for further reading.
Electrochemical Synthesis of Nanomaterials in Ionic Liquids. Nanomaterials in Electrochemical Devices. The modern demand of distributed diagnostics imposes new challenges to the world of electrochemistry. In particular, low cost, easy to use, light, miniaturized, point-of-care, implantable VLSI systems need to be designed and developed. The schematization of the spectral broadening as a function of the applied potential, when a PD is present in the electrolyte, for a gold electrode in a 0.
In this experimental system, water and pyrazine molecules experience different electric potentials as function of its z -position within the PD 45 distance normal to the electrode surface, see Fig. The intensity-normalized N 1 s and O 1 s core-level peaks are shown in Fig. The N 1 s raw spectra possess two different identifiable components: the low BE feature centred at From these data, we can observe that the Py ESF and the adsorbed hydroxyls do not shift in BE with the applied potential, meaning that the corresponding species are electrically connected to the grounded gold WE see the energy diagram reported in Supplementary Fig.
The observed spectral broadening and BE shifts for the components within the liquid phase that is, within the EDL constitute the essential results of this work. The error bars were determined via repeated measurements of the FWHM of a given core level, propagated with the experimental spectral resolution see Methods section. Although the linear trend of the BEs as a function of the applied potential inherently carries information about the PD within the EDL, the peak FWHM trend allows an easier and direct comparison with the double-layer capacitance trend derived from electrochemical investigations , as shown in Fig.
In this manner, the core-level peak FWHM represents the direct link between spectroscopy and electrochemistry. The PZC, defined as the observed potential at which no net charge is present on the electrode surface and no PD is present in the EDL can be determined both electrochemically Fig. The trend of the double-layer capacitance reported in Fig. This agreement reflects the linkage between the double-layer capacitance and the trend of the peak FWHM values, thus establishing a clear correlation between an electrochemical property of the EDL and a pure spectroscopic feature.
It is noteworthy to report that the findings discussed above are valid also in case of a pyrazine free electrolyte, since the direct probing of EDL can be performed, as reported in Fig. More details are provided in Supplementary Fig. Additionally, we observed that the FWHM trends as a function of the applied potential implicitly carries the functional dependency fingerprint of the PD Fig.
The step and linear PD models were selected to test the fit to our data as well as our ability to distinguish the shape of the EDL structure, and thus do not represent a modern theory for the EDL structure. This approach provides the ability to objectively evaluate the agreement between the data and models for all applied potentials and electrolyte concentrations that is, EDL thicknesses, d EDL. As well documented by Fig. Due to the exponential decay of the photoelectron intensity, the spectral components localized at the IHP do not significantly contribute to the summation over all the initial states.
Future experimental and instrumental modifications are being planned to help improve this limitation. Moreover, the utilization of the SW-APXPS approach to provide a higher degree of spatial resolution near the electrode surface will be explored 42 , 47 , in particular towards the study of surface adsorbates, ion-specific adsorptions and charge transfers at the IHP, and their interplay in the faradaic processes occurring at the electrified interface. To get more insights into the EDL structure as a function of the electrolyte concentration, we have modulated the EDL thickness d EDL by gradually increasing the electrolyte concentration, passing from 0.
The N 1 s , O 1 s and Au 4 f data for each investigated electrolyte concentration are reported in Supplementary Fig. Further details are also reported in Supplementary Note 3. By using the aforementioned linear fitting procedure applied to the experimental FWHM trends as a function of the applied potential, we have determined the PZC values and described the evolution of the exponential potential profile directly from the spectroscopy data shown in Fig.
However, with the current signal-to-noise ratio, the definitive discrimination between an exponential and a linear shape for the PD is challenging to achieve. Potential of zero charge PZC determination and comparison between the experimental and simulated spectral full-width at half-maximum FWHM trends, as function of the applied potentials E and for an aqueous electrolyte containing 1. Future improvements of the experimental set-up will enhance spectral resolution and signal-to-noise ratio, which will improve our ability to discern the fine features of the PD functional dependency carried by the core-level spectral broadening.
The simulations of the PD profiles, similarly to what has been experimentally performed, have been generated as a function of the applied potential for different electrolyte concentrations that is, for different EDL thicknesses. The comparison between the experimental and simulated FWHM provides the ability to directly access and visualize the PD within the EDL that leads to the observed spectral broadening.
The resulting simulated exponential potential profiles are reported in Fig. This possibility paves the way toward a new type of EDL and its inherent properties such as the PD investigations under real electrochemical and photoelectrochemical reactions. Finally, for KOH concentrations higher than those shown in Fig. This result is consistent with a thinner EDL that can be expected from an increased ionic strength of the supporting electrolyte.
There is not enough signal from the molecules in the EDL to be resolved from the total O 1 s and N 1 s photoelectron intensity. Therefore, there is a concentration limit for this technique to discern the electrical potential profile within the EDL. The schematization reported in Supplementary Fig.
However, future experimental and instrumental modifications previously mentioned that is, SW-APXPS will allow us to overcome these current limitations 42 , The method has general applicability and is not restricted to one specific class of solids or liquids. We have shown that the FWHM trend of the core-level peaks of electrolyte as a function of the applied potential is strongly correlated to the double-layer capacitance trend. We have also demonstrated that the PZC obtained from spectroscopy is in line with the electrochemically-derived values, providing a synergistic correlation between electrochemistry and photoelectron spectroscopy.
Exploiting the element-specificity and potential-sensitivity of photoelectron spectroscopy, we have directly probed the PD within the EDL by studying the broadening of the core-level photoelectron spectra of the elements belonging to the liquid phase, as a function of the applied potential. Furthermore, by using numerical simulations, we have shown that our method provides the ability to identify the functional dependency that describes the PD within the double layer, providing a spectroscopic support for the current electrified interface theories.
A schematic representation of our combined experimental and simulation-based approach is reported in Supplementary Fig. The coupling between our APXPS performed under polarization conditions with the use of a solvent- or an independent probe-related core level, sets a paradigm for probing the properties of the EDL under realistic conditions.
The current results may open the door for studying the EDL dynamics in more complicated systems, such as redox reactions at photoactive semiconductor interfaces and in non-aqueous electrolytes, to name a few see Supplementary Note 1. The knowledge gained from this method may thus impact a wide range of scientific fields, including electrochemical conversion and storage of energy, environmental sciences and biology 14 , 15 , Beamline 9. The measurements were taken using a photon energy of 4.
During the fitting procedure, the Shirley background was optimized as well, together with the spectral components, increasing in this manner the precision and reliability of the fitting procedure 49 , 50 , In this work, we have used the FWHM for the quantification of the spectral broadening. The chemicals here employed were high purity reagents and they were used as received without further operations.
The working and counter electrodes Au and Pt polycrystalline foils respectively, Aldrich were polished to a mirror finish with silicon carbide papers of decreasing grain size Struers, grit: 2, and 4, Once the three electrodes were mounted on the manipulator 39 Supplementary Fig. The cleaning procedure was stopped after reaching the OCP of the cell from the cathodic side that is, after HER, to start the EDL probing on a cleaned metal surface Before its introduction into the experimental chamber, the electrolyte KOH 0.
The first two models were considered to test the ability of distinguishing between different PD functional dependencies. The core algorithm was developed in Igor C-oriented language. An example of the performed simulations is reported in Supplementary Fig. Simulated N 1 s or O 1 s photoelectron peaks have been generated by using the envelope function-derived method 52 , by summing the different spectral contributions within the diffuse layer each one shifted according to the potential profile and in the bulk electrolyte rigidly shifted because of the shift of the liquid phase with the applied potential, see energy diagram reported in Supplementary Fig.
Then, by performing the summation over all the shifted N 1 s or O 1 s spectral components with a coefficient determined by the exponential dumping of the photoelectron intensity Beer—Lambert law , it is possible to finally obtain a simulated spectrum that can be compared with the experimental data.
The envelope function S BE at the base of the calculation, describing the final convolution of the simulated photoelectron peak as reported in equation The measurement was performed studying a thick drop of solution hanging from the WE, to rule out interfacial contribution and obtain the O 1 s and N 1 s photoelectron peaks exclusively from water and solvated pyrazine molecules in the bulk electrolyte, respectively.
The spectral components within the bulk electrolyte are instead fully shifted by the applied potential E. The two integers i and j vary over the PD within the EDL and the bulk region of the electrolyte layer B , respectively. The simulations were conducted probing both the EDL and the bulk electrolyte every 0.
The algorithm developed for the calculation of the simulated spectra as described by equation 1 is characterized by a good stability also for a significant number n of total elements in the summation; the complexity class of the algorithm belongs to O n. The D i,j coefficients that damps the intensity of the single summation elements are calculated according to the Beer—Lambert law equation 2. The data that support the findings of this study are available from the corresponding author upon request.
How to cite this article: Favaro, M. Zaera, F. Devanathan, M. The structure of the electrical double layer at the metal—solution interface. Delahay, P. Double layer studies. Grahame, D. The electrical double layer and the theory of electrocapillarity. Parsons, R. Electrical double layer: recent experimental and theoretical developments. Bard, A.