ELECTROCHEMISTRY
Part I: Basic concepts 1 Basic concepts 3 11 Structure of interfaces 3 111 Electrical double layer at interfaces: metal/electrolyte 7 112 Electrochemical potential – potentials at interfaces: internal, surface, external potential 14 1121 Metal–solution interface at equilibrium: Nernst equilibrium potential 18 1122 Electron work function 20 113 Charge transfer processes across the metal/electrolyte interface 21 1131 Basic concepts of nonequilibrium thermodynamics 21 1132 “Reversible” electrode processes 27 1133 “Irreversible” electrode processes: basic concepts of electrochemical kinetics 32 1134 Briefly on Marcus, Hush, Levich, Dogonadze (MHLD) theory of electrode processes 37 Bibliography 39 12 Structure of the bulk of electrolytes: conductivity 40 121 Interactions in aqueous electrolytes 40 1211 Ion–solvent interaction; solvation 40 1212 Ion–ion interactions 41 122 Conductivity of electrolytes 44 13 Nonaqueous electrolytes 48 131 Ionic liquids 48 132 Molten salts 50 133 Solid electrolytes 51 Bibliography 53 14 Membranes and membrane potentials 53 141 Equilibrium potentials 53 142 Nonequilibrium potentials 56 Bibliography 63 2 Selected electrochemical methods applied in analytical chemistry and material science 64 21 Transient methods 64 211 Capacitive current 65 212 Faradaic current 67 22 Electrochemical impedance spectroscopy 70 221 Data presentation 74 23 Electrochemical quartz crystal microbalance method 82 Bibliography 87 Part II: Electrochemistry in material science – selected topics 3 Corrosion 91 31 General remarks 91 32 Corrosion – what does it mean? Mechanism of corrosion 91 33 Characterization of corrosion: corrosion potential, corrosion current 97 331 Stability of materials: potential/pH (Pourbaix) diagrams – the thermodynamic aspect 98 332 Stability of materials: current–potential (Evans) diagrams – the kinetic aspect 103 34 Evaluation of corrosion rate from electrochemical measurements 105 341 Linear scan voltammetry 106 342 Electrochemical impedance spectroscopy in corrosion 107 35 Localized corrosion: pits, crevices, intergranular corrosion – oxygen reduction as accompanying cathodic reaction 109 36 Hydrogen evolution as accompanying reaction – role in corrosion: embrittlement and cracking 111 37 Protection against corrosion 113 371 Electroplating 116 Bibliography 117 4 Electrocatalysis 118 41 General remarks 118 42 How to compare the activity of catalysts in electrochemical reactions? 120 43 Electrocatalysts 122 431 Metals, alloys, and oxides 122 432 Carbon catalysts and supports 124 44 Catalyst activity 125 441 Electron work function effect 126 442 Adsorption impact 126 443 Size effect 129 45 Electrocatalysts in hydrogen–oxygen fuel cells 131 451 Oxygen reduction reaction 132 452 Hydrogen evolution and oxidation reactions 135 Bibliography 136 5 Electrodeposition 138 51 General remarks 138 52 Electrocrystallization: nucleation and growth 139 521 Critical size of nuclei 141 522 Instantaneous and progressive nucleation 142 523 Analytical approach to experimental data 144 53 Deposit morphology 148 54 Practical aspects of electrodeposition 149 55 Electrodeposition of binary alloys and semiconductor compounds 152 Bibliography 156 6 Underpotential deposition (UPD) 157 61 General remarks 157 62 Experimental examples – UPD features 158 63 Underpotential deposits – catalytic properties 161 Bibliography 163 7 Electrochemical methods in the formation of nanostructures 164 71 General remarks 164 72 Template-assisted electrodeposition of nanostructures 165 721 Active template-assisted electrodeposition 165 722 Restrictive template-assisted deposition 166 7221 Porous anodic alumina (PAA) matrices 167 7222 Porous anodic titanium dioxide matrices 168 723 Concluding remarks 168 73 Applications of nanostructured materials 170 731 Catalysis 170 732 Batteries: supercapacitors 171 733 Photoelectrochemical devices: solar cells 171 734 Biological applications: nanozymes 171 Bibliogaphy 172 8 Electrochemistry in energy conversion and storage 175 81 Batteries 175 811 Electrochemical cell – fundamentals 175 812 Characteristics of batteries 179 813 Classification of batteries and examples 183 8131 Primary batteries 183 8132 Secondary batteries 184 8133 Lithium batteries 186 8134 Fuel cells 188 82 Supercapacitors 192 821 General remarks 192 822 Capacitor versus electrochemical cell/battery 193 823 Working characteristics of supercapacitors 198 Bibliography 200 9 Interfacing applied electrochemistry and biology 202 91 General remarks 202 92 Bioelectrocatalysis 203 93 Biosensors 208 94 Biofuel cells 212 941 Design and enzymes used in biofuel cells 214 9411 Biocatalysts and design of biocathodes 214 9412 Biocatalysts and design of bioanodes 216 942 Energy and power of the biofuel cells 217 Bibliography 221 Part III: Photoelectrochemistry in materials science – selected topics 10 Semiconductors electrochemistry and photoelectrochemistry: fundamentals 229 101 Basic characteristics of semiconductors 229 1011 Semiconductor under illumination 232 1012 Recombination 235 1013 Carriers and electric field 236 102 Semiconductor–electrolyte interface 237 1021 Model of semiconductor–electrolyte interface 237 1022 Space charge layer 239 1023 Polarization of semiconductor–electrolyte interface 242 103 Fundamentals of electrochemical reactions on the SC electrode 243 104 Photoeffects at/in semiconductor electrode in electrolyte 250 105 Influence of surface states 254 106 Corrosion, photocorrosion, and stability 258 Bibliography 262 11 Solar energy conversion in photoelectrochemical cells 264 111 General remarks 264 112 Efficiency and key parameters 265 113 Photoelectrochemical cells: classification – principle of operation 267 1131 Liquid photovoltaic cells 267 1132 Dye-sensitized solar cells 269 1133 Quantum dot-sensitized solar cells 271 1134 Photoelectrosynthetic cells 272 Bibliography 278 12 Semiconductor particles in photocatalysis 280 121 General remarks 280 122 Size effect and dimensionality 281 123 Photocatalytic degradation of organic/inorganic pollutants 284 Bibliography 288 Part IV: Electrochemistry in environmental science – selected topics 13 Sensing the environment 291 131 General remarks 291 132 Electrochemical sensors 292 1321 Amperometric sensors 293 1322 Potentiometric sensors 302 1323 Conductometric sensors 307 133 Future perspectives and challenges 310 Bibliography 312 14 Green fuel: hydrogen production 313 141 General remarks 313 142 Water electrolysis 314 1421 Thermodynamics, energy losses, and efficiency 314 1422 Methods and technologies 321 14221 Alkaline water electrolysis (AWE) 322 14222 Polymer electrolyte membrane electrolysis (PEM) 323 14223 Solid oxide electrolysis (SOE) 325 14224 Seawater electrolysis 326 14225 Microbial electrolysis (MEC) 329 143 Solar energy in photo water splitting 331 1431 Thermodynamics, energy losses, and efficiency 333 1432 Photoelectrolysis of water: trends 340 1433 Photocatalysis of water: trends 345 References 350 15 Electrochemical and photocatalytic methods in pollutant removal 352 151 General remarks 352 152 Removal and recovery of heavy metals: electrochemical treatment 353 1521 Electrodeposition and electrodialysis 354 1522 Electrocoagulation and electroflotation 357 153 Degradation and removal of organic pollutants: electrochemical treatment 361 1531 Fenton and electro-Fenton oxidation 361 1532 Anodic oxidation 363 154 Solar energy: pollutant degradation and removal 367 1541 Inorganic pollutants 368 1542 Organic pollutants 370 References 372