Methanol oxidation and direct methanol fuel cells: a selective review
TL;DR: A status report on development of the direct methanol fuel cell (DMFC) and relevant fundamental and applied electrochemistry is the objective of as discussed by the authors, where emphasis is put on strategies and approaches rather than on individual results.
About: This article is published in Journal of Electroanalytical Chemistry.The article was published on 1999-01-29. It has received 1217 citations till now. The article focuses on the topics: Direct methanol fuel cell & Methanol fuel.
Citations
More filters
04 Apr 2005
Abstract: Preface. Preface to the First Edition. Contributors. Contributors to the First Edition. Chapter 1. Fundamentals of Impedance Spectroscopy (J.Ross Macdonald and William B. Johnson). 1.1. Background, Basic Definitions, and History. 1.1.1 The Importance of Interfaces. 1.1.2 The Basic Impedance Spectroscopy Experiment. 1.1.3 Response to a Small-Signal Stimulus in the Frequency Domain. 1.1.4 Impedance-Related Functions. 1.1.5 Early History. 1.2. Advantages and Limitations. 1.2.1 Differences Between Solid State and Aqueous Electrochemistry. 1.3. Elementary Analysis of Impedance Spectra. 1.3.1 Physical Models for Equivalent Circuit Elements. 1.3.2 Simple RC Circuits. 1.3.3 Analysis of Single Impedance Arcs. 1.4. Selected Applications of IS. Chapter 2. Theory (Ian D. Raistrick, Donald R. Franceschetti, and J. Ross Macdonald). 2.1. The Electrical Analogs of Physical and Chemical Processes. 2.1.1 Introduction. 2.1.2 The Electrical Properties of Bulk Homogeneous Phases. 2.1.2.1 Introduction. 2.1.2.2 Dielectric Relaxation in Materials with a Single Time Constant. 2.1.2.3 Distributions of Relaxation Times. 2.1.2.4 Conductivity and Diffusion in Electrolytes. 2.1.2.5 Conductivity and Diffusion-a Statistical Description. 2.1.2.6 Migration in the Absence of Concentration Gradients. 2.1.2.7 Transport in Disordered Media. 2.1.3 Mass and Charge Transport in the Presence of Concentration Gradients. 2.1.3.1 Diffusion. 2.1.3.2 Mixed Electronic-Ionic Conductors. 2.1.3.3 Concentration Polarization. 2.1.4 Interfaces and Boundary Conditions. 2.1.4.1 Reversible and Irreversible Interfaces. 2.1.4.2 Polarizable Electrodes. 2.1.4.3 Adsorption at the Electrode-Electrolyte Interface. 2.1.4.4 Charge Transfer at the Electrode-Electrolyte Interface. 2.1.5 Grain Boundary Effects. 2.1.6 Current Distribution, Porous and Rough Electrodes- the Effect of Geometry. 2.1.6.1 Current Distribution Problems. 2.1.6.2 Rough and Porous Electrodes. 2.2. Physical and Electrochemical Models. 2.2.1 The Modeling of Electrochemical Systems. 2.2.2 Equivalent Circuits. 2.2.2.1 Unification of Immitance Responses. 2.2.2.2 Distributed Circuit Elements. 2.2.2.3 Ambiguous Circuits. 2.2.3 Modeling Results. 2.2.3.1 Introduction. 2.2.3.2 Supported Situations. 2.2.3.3 Unsupported Situations: Theoretical Models. 2.2.3.4 Unsupported Situations: Equivalent Network Models. 2.2.3.5 Unsupported Situations: Empirical and Semiempirical Models. Chapter 3. Measuring Techniques and Data Analysis. 3.1. Impedance Measurement Techniques (Michael C. H. McKubre and Digby D. Macdonald). 3.1.1 Introduction. 3.1.2 Frequency Domain Methods. 3.1.2.1 Audio Frequency Bridges. 3.1.2.2 Transformer Ratio Arm Bridges. 3.1.2.3 Berberian-Cole Bridge. 3.1.2.4 Considerations of Potentiostatic Control. 3.1.2.5 Oscilloscopic Methods for Direct Measurement. 3.1.2.6 Phase-Sensitive Detection for Direct Measurement. 3.1.2.7 Automated Frequency Response Analysis. 3.1.2.8 Automated Impedance Analyzers. 3.1.2.9 The Use of Kramers-Kronig Transforms. 3.1.2.10 Spectrum Analyzers. 3.1.3 Time Domain Methods. 3.1.3.1 Introduction. 3.1.3.2 Analog-to-Digital (A/D) Conversion. 3.1.3.3 Computer Interfacing. 3.1.3.4 Digital Signal Processing. 3.1.4 Conclusions. 3.2. Commercially Available Impedance Measurement Systems (Brian Sayers). 3.2.1 Electrochemical Impedance Measurement Systems. 3.2.1.1 System Configuration. 3.2.1.2 Why Use a Potentiostat? 3.2.1.3 Measurements Using 2, 3 or 4-Terminal Techniques. 3.2.1.4 Measurement Resolution and Accuracy. 3.2.1.5 Single Sine and FFT Measurement Techniques. 3.2.1.6 Multielectrode Techniques. 3.2.1.7 Effects of Connections and Input Impedance. 3.2.1.8 Verification of Measurement Performance. 3.2.1.9 Floating Measurement Techniques. 3.2.1.10 Multichannel Techniques. 3.2.2 Materials Impedance Measurement Systems. 3.2.2.1 System Configuration. 3.2.2.2 Measurement of Low Impedance Materials. 3.2.2.3 Measurement of High Impedance Materials. 3.2.2.4 Reference Techniques. 3.2.2.5 Normalization Techniques. 3.2.2.6 High Voltage Measurement Techniques. 3.2.2.7 Temperature Control. 3.2.2.8 Sample Holder Considerations. 3.3. Data Analysis (J. Ross Macdonald). 3.3.1 Data Presentation and Adjustment. 3.3.1.1 Previous Approaches. 3.3.1.2 Three-Dimensional Perspective Plotting. 3.3.1.3 Treatment of Anomalies. 3.3.2 Data Analysis Methods. 3.3.2.1 Simple Methods. 3.3.2.2 Complex Nonlinear Least Squares. 3.3.2.3 Weighting. 3.3.2.4 Which Impedance-Related Function to Fit? 3.3.2.5 The Question of "What to Fit" Revisited. 3.3.2.6 Deconvolution Approaches. 3.3.2.7 Examples of CNLS Fitting. 3.3.2.8 Summary and Simple Characterization Example. Chapter 4. Applications of Impedance Spectroscopy. 4.1. Characterization of Materials (N. Bonanos, B. C. H. Steele, and E. P. Butler). 4.1.1 Microstructural Models for Impedance Spectra of Materials. 4.1.1.1 Introduction. 4.1.1.2 Layer Models. 4.1.1.3 Effective Medium Models. 4.1.1.4 Modeling of Composite Electrodes. 4.1.2 Experimental Techniques. 4.1.2.1 Introduction. 4.1.2.2 Measurement Systems. 4.1.2.3 Sample Preparation-Electrodes. 4.1.2.4 Problems Associated With the Measurement of Electrode Properties. 4.1.3 Interpretation of the Impedance Spectra of Ionic Conductors and Interfaces. 4.1.3.1 Introduction. 4.1.3.2 Characterization of Grain Boundaries by IS. 4.1.3.3 Characterization of Two-Phase Dispersions by IS. 4.1.3.4 Impedance Spectra of Unusual Two-phase Systems. 4.1.3.5 Impedance Spectra of Composite Electrodes. 4.1.3.6 Closing Remarks. 4.2. Characterization of the Electrical Response of High Resistivity Ionic and Dielectric Solid Materials by Immittance Spectroscopy (J. Ross Macdonald). 4.2.1 Introduction. 4.2.2 Types of Dispersive Response Models: Strengths and Weaknesses. 4.2.2.1 Overview. 4.2.2.2 Variable-slope Models. 4.2.2.3 Composite Models. 4.2.3 Illustration of Typical Data Fitting Results for an Ionic Conductor. 4.3. Solid State Devices (William B. Johnson and Wayne L. Worrell). 4.3.1 Electrolyte-Insulator-Semiconductor (EIS) Sensors. 4.3.2 Solid Electrolyte Chemical Sensors. 4.3.3 Photoelectrochemical Solar Cells. 4.3.4 Impedance Response of Electrochromic Materials and Devices (Gunnar A. Niklasson, Anna Karin Johsson, and Maria Stromme). 4.3.4.1 Introduction. 4.3.4.2 Materials. 4.3.4.3 Experimental Techniques. 4.3.4.4 Experimental Results on Single Materials. 4.3.4.5 Experimental Results on Electrochromic Devices. 4.3.4.6 Conclusions and Outlook. 4.3.5 Time-Resolved Photocurrent Generation (Albert Goossens). 4.3.5.1 Introduction-Semiconductors. 4.3.5.2 Steady-State Photocurrents. 4.3.5.3 Time-of-Flight. 4.3.5.4 Intensity-Modulated Photocurrent Spectroscopy. 4.3.5.5 Final Remarks. 4.4. Corrosion of Materials (Digby D. Macdonald and Michael C. H. McKubre). 4.4.1 Introduction. 4.4.2 Fundamentals. 4.4.3 Measurement of Corrosion Rate. 4.4.4 Harmonic Analysis. 4.4.5 Kramer-Kronig Transforms. 4.4.6 Corrosion Mechanisms. 4.4.6.1 Active Dissolution. 4.4.6.2 Active-Passive Transition. 4.4.6.3 The Passive State. 4.4.7 Point Defect Model of the Passive State (Digby D. Macdonald). 4.4.7.1 Introduction. 4.4.7.2 Point Defect Model. 4.4.7.3 Electrochemical Impedance Spectroscopy. 4.4.7.4 Bilayer Passive Films. 4.4.8 Equivalent Circuit Analysis (Digby D. Macdonald and Michael C. H. McKubre). 4.4.8.1 Coatings. 4.4.9 Other Impedance Techniques. 4.4.9.1 Electrochemical Hydrodynamic Impedance (EHI). 4.4.9.2 Fracture Transfer Function (FTF). 4.4.9.3 Electrochemical Mechanical Impedance. 4.5. Electrochemical Power Sources. 4.5.1 Special Aspects of Impedance Modeling of Power Sources (Evgenij Barsoukov). 4.5.1.1 Intrinsic Relation Between Impedance Properties and Power Sources Performance. 4.5.1.2 Linear Time-Domain Modeling Based on Impedance Models, Laplace Transform. 4.5.1.3 Expressing Model Parameters in Electrical Terms, Limiting Resistances and Capacitances of Distributed Elements. 4.5.1.4 Discretization of Distributed Elements, Augmenting Equivalent Circuits. 4.5.1.5 Nonlinear Time-Domain Modeling of Power Sources Based on Impedance Models. 4.5.1.6 Special Kinds of Impedance Measurement Possible with Power Sources-Passive Load Excitation and Load Interrupt. 4.5.2 Batteries (Evgenij Barsoukov). 4.5.2.1 Generic Approach to Battery Impedance Modeling. 4.5.2.2 Lead Acid Batteries. 4.5.2.3 Nickel Cadmium Batteries. 4.5.2.4 Nickel Metal-hydride Batteries. 4.5.2.5 Li-ion Batteries. 4.5.3 Impedance Behavior of Electrochemical Supercapacitors and Porous Electrodes (Brian E. Conway). 4.5.3.1 Introduction. 4.5.3.2 The Time Factor in Capacitance Charge or Discharge. 4.5.3.3 Nyquist (or Argand) Complex-Plane Plots for Representation of Impedance Behavior. 4.5.3.4 Bode Plots of Impedance Parameters for Capacitors. 4.5.3.5 Hierarchy of Equivalent Circuits and Representation of Electrochemical Capacitor Behavior. 4.5.3.6 Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes. 4.5.3.7 Impedance Behavior of Supercapacitors Based on Pseudocapacitance. 4.5.3.8 Deviations of Double-layer Capacitance from Ideal Behavior: Representation by a Constant-phase Element (CPE). 4.5.4 Fuel Cells (Norbert Wagner). 4.5.4.1 Introduction. 4.5.4.2 Alkaline Fuel Cells (AFC). 4.5.4.3 Polymer Electrolyte Fuel Cells (PEFC). 4.5.4.4 Solid Oxide Fuel Cells (SOFC). Appendix. Abbreviations and Definitions of Models. References. Index.
5,212 citations
TL;DR: Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.5.2.
Abstract: 5.1. Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.1. Cu−Ag 866 5.1.2. Cu−Au 867 5.1.3. Ag−Au 870 5.1.4. Cu−Ag−Au 872 5.2. Nanoalloys of Group 10 (Ni, Pd, Pt) 872 5.2.1. Ni−Pd 872 * To whom correspondence should be addressed. Phone: +39010 3536214. Fax:+39010 311066. E-mail: ferrando@fisica.unige.it. † Universita di Genova. ‡ Argonne National Laboratory. § University of Birmingham. | As of October 1, 2007, Chemical Sciences and Engineering Division. Volume 108, Number 3
3,114 citations
TL;DR: A general strategy for the synthesis of highly ordered, rigid arrays of nanoporous carbon having uniform but tunable diameters is described, which gives rise to promising electrocatalytic activity for oxygen reduction and could prove to be practically relevant for fuel-cell technologies.
Abstract: Nanostructured carbon materials are potentially of great technological interest for the development of electronic1,2, catalytic3,4 and hydrogen-storage systems5,6. Here we describe a general strategy for the synthesis of highly ordered, rigid arrays of nanoporous carbon having uniform but tunable diameters (typically 6 nanometres inside and 9 nanometres outside). These structures are formed by using ordered mesoporous silicas as templates, the removal of which leaves a partially ordered graphitic framework. The resulting material supports a high dispersion of platinum nanoparticles, exceeding that of other common microporous carbon materials (such as carbon black, charcoal and activated carbon fibres). The platinum cluster diameter can be controlled to below 3 nanometres, and the high dispersion of these metal clusters gives rise to promising electrocatalytic activity for oxygen reduction, which could prove to be practically relevant for fuel-cell technologies. These nanomaterials can also be prepared in the form of free-standing films by using ordered silica films as the templates.
2,352 citations
TL;DR: In this article, three major ways to utilize nanostructures for the design of solar energy conversion devices are discussed: (i) mimicking photosynthesis with donor−acceptor molecular assemblies or clusters, (ii) semiconductor assisted photocatalysis to produce fuels such as hydrogen, and (iii) nanostructure semiconductor based solar cells.
Abstract: The increasing energy demand in the near future will force us to seek environmentally clean alternative energy resources. The emergence of nanomaterials as the new building blocks to construct light energy harvesting assemblies has opened up new ways to utilize renewable energy sources. This article discusses three major ways to utilize nanostructures for the design of solar energy conversion devices: (i) Mimicking photosynthesis with donor−acceptor molecular assemblies or clusters, (ii) semiconductor assisted photocatalysis to produce fuels such as hydrogen, and (iii) nanostructure semiconductor based solar cells. This account further highlights some of the recent developments in these areas and points out the factors that limit the efficiency optimization. Strategies to employ ordered assemblies of semiconductor and metal nanoparticles, inorganic-organic hybrid assemblies, and carbon nanostructures in the energy conversion schemes are also discussed. Directing the future research efforts toward utiliza...
2,119 citations
TL;DR: In this article, the hydrogen (H2) and oxygen (O2) fuel cell is the one with zero carbon emission and water as the only byproduct, which is essential to ensure higher life cycle and less decay in cell efficiency.
Abstract: Increasing demand for finding eco-friendly and everlasting energy sources is now totally depending on fuel cell technology. Though it is an eco-friendly way of producing energy for the urgent requirements, it needs to be improved to make it cheaper and more eco-friendly. Although there are several types of fuel cells, the hydrogen (H2) and oxygen (O2) fuel cell is the one with zero carbon emission and water as the only byproduct. However, supplying fuels in the purest form (at least the H2) is essential to ensure higher life cycles and less decay in cell efficiency. The current large-scale H2 production is largely dependent on steam reforming of fossil fuels, which generates CO2 along with H2 and the source of which is going to be depleted. As an alternate, electrolysis of water has been given greater attention than the steam reforming. The reasons are as follows: the very high purity of the H2 produced, the abundant source, no need for high-temperature, high-pressure reactors, and so on. In earlier days,...
1,757 citations
References
More filters
TL;DR: In this paper, the proton conductivity, water content, and methanol vapor permeability of polybenzimidazole films doped with phosphoric acid are investigated as potential polymer electrolytes for use in hydrogen/air and direct methanoline fuel cells.
Abstract: Polybenzimidazole films doped with phosphoric acid are being investigated as potential polymer electrolytes for use in hydrogen/air and direct methanol fuel cells. In this paper, we present experimental findings on the proton conductivity, water content, and methanol vapor permeability of this material, as well as preliminary fuel cell results. The low methanol vapor permeability of these electrolytes significantly reduces the adverse effects of methanol crossover typically observed in direct methanol polymer electrolyte membrane fuel cells.
1,161 citations
TL;DR: In this paper, a review of recent electrochemical literature concerning the oxidation of small organic molecules as potential fuels for fuel cells is presented, and the nature of poisoning species and reaction intermediates are discussed.
1,125 citations
12 Apr 1990
TL;DR: In this paper, Fleig et al. discuss nonlinear dynamics in electrochemical systems, Katharina Krischer the electrochemistry of diamond, Yuri V. Pleskov passivity of metals, Hans-Henning Strehblow.
Abstract: Microelectrodes in solid-state ionics, Jurgen Fleig nonlinear dynamics in electrochemical systems, Katharina Krischer the electrochemistry of diamond, Yuri V. Pleskov passivity of metals, Hans-Henning Strehblow.
1,108 citations
TL;DR: In this paper, the catalytic activity of single-phase polycrystalline Pt-Ru bulk alloys toward the electrooxidation of methanol in sulfuric acid electrolyte at room temperature was measured for the first time on well-characterized alloy surfaces, in terms of surface composition and true surface area.
Abstract: The catalytic activity of single-phase polycrystalline Pt-Ru bulk alloys toward the electrooxidation of methanol in sulfuric acid electrolyte at room temperature was measured for the first time on well-characterized alloy surfaces, in terms of surface composition and true surface area. Sputter-cleaned and annealed alloys were prepared in ultrahigh vacuum (UHV) and the surface composition of oxygen-free surfaces was assessed via low-energy ion scattering (LEIS). Pt-Ru alloy surfaces annealed in UHV were strongly enriched in Pt, whereas the surface composition of sputter-cleaned alloys was essentially identical to their bulk composition. It was shown that the sputter-cleaned alloy with a Ru surface of [approx equal] 10 atomic % gave the highest catalytic enhancement (over pure Pt) for the steady-state electrooxidation of methanol at 25[degree]C and 0.5 V, viz., by a factor of 12 in 5.0 mM CH[sub 3]OH solution and by a factor of 30 in 0.5 M CH[sub 3]OH. It was found that the balance between the rate of methanol adsorption and the rate of the oxidative removal of dehydrogenated fragments determines the activities of Pt-Ru alloys with different Ru surface compositions. 51 refs., 9 figs., 2 tabs.
875 citations