Chemistry of sustainable energy

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Chemistry of sustainable energy

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Chemistry of Sustainable Energy Chemistry of Sustainable Energy Nancy E Carpenter CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2014 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20131227 International Standard Book Number-13: 978-1-4665-7533-2 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com This book is dedicated to my mother, Olga Y Carpenter, who instilled in me love and respect for both the environment and for science, shaping my life’s direction and to Jim Togeas and the late Jim Gremmels—two wonderful colleagues, mentors, and friends whose wisdom and humor have guided my professional career as an educator and writer Contents Acknowledgments xv Author xvii Introduction xix Chapter Energy Basics 1.1 1.2 What Is Energy? Energy, Technology, and Sustainability 1.2.1 What Does Sustainability Mean? 1.2.2 Carbon Cycle .7 1.2.3 Resource Availability 1.3 Energy Units, Terms, and Abbreviations 11 1.4 Electricity Generation and Storage 14 Other Resources 16 References 17 Chapter Fossil Fuels 19 2.1 2.2 Formation of Oil and Gas 19 Extraction of Fossil Fuels 23 2.2.1 Conventional Petroleum 23 2.2.2 Nonconventional Sources 24 2.2.2.1 Shale Oil and Gas 24 2.2.2.2 Heavy Oil 26 2.2.2.3 Oil Sands 27 2.2.2.4 Coal Bed Methane and Methane Hydrates 29 2.3 Refining 30 2.3.1 Crude Petroleum 30 2.3.1.1 Distillation 31 2.3.1.2 Extraction 33 2.3.1.3 Cracking .34 2.3.1.4 Reforming 36 2.3.2 Natural Gas 36 2.4 Carbon Capture and Storage 37 2.4.1 Capture and Separation 38 2.4.1.1 Membrane Technology 40 2.4.1.2 Ionic Liquids 40 2.4.1.3 Solid Sorbents 42 2.4.2 Conversion and Utilization 43 2.4.2.1 Sequestration .44 2.4.2.2 Utilization 45 vii viii Contents 2.5 Summary 50 Other Resources 52 References 52 Chapter Thermodynamics 55 3.1 Introduction 55 3.2 First Law of Thermodynamics 56 3.3 Second Law and Thermodynamic Cycles: The Carnot Efficiency 57 3.4 Exergy and Life-Cycle Assessment 62 Other Resources 62 References 62 Chapter Polymers and Sustainable Energy 65 4.1 Polymer Basics 65 4.2 Synthesis 71 4.2.1 Step-Growth Polymerization 71 4.2.2 Chain-Growth Polymerization 73 4.2.3 Block Copolymers and CO2 Separation 73 4.2.4 Control in Polymer Synthesis 77 4.3 Characterization of Polymers 80 4.4 Polymer Properties 83 4.5 Polymer Chemistry and Wind Energy 86 4.5.1 Introduction 86 4.5.2 Resins 89 4.5.3 Reinforcing Fibers 91 4.5.4 Carbon Nanotubes and Polymer Matrix Composites 95 4.6 Green Chemistry 97 Other Resources 99 References 99 Chapter Catalysis and Hydrogen Production 103 5.1 Catalysis 103 5.2 Hydrogen Production 106 5.2.1 Steam Reforming 108 5.2.2 Aside: The Fischer–Tropsch Process 112 5.2.3 Gasification 112 5.2.4 Water and the Biological Production of Hydrogen 114 5.2.4.1 Microbial Electrolysis of Water 115 5.2.4.2 Hydrogenases 116 5.2.4.3 Photochemical Electrolysis of Water 119 5.3 Hydrogen Storage 122 5.3.1 Metal–Organic Frameworks 125 Contents ix 5.3.2 Metal Hydrides 128 5.3.3 Other CHS Materials 131 Other Resources 133 References 134 Chapter Fuel Cells 137 6.1 Introduction 137 6.1.1 Fuel Cell Basics 137 6.1.2 An Electrochemistry Review 140 6.2 Thermodynamics and Fuel Cells 142 6.2.1 Calculation of Cell Potential 142 6.2.2 Cell Potential and Gibbs Free Energy 143 6.2.2.1 State of Water 144 6.2.2.2 Effect of Temperature and Pressure 145 6.3 Efficiency and Fuel Cells 146 6.4 Cell Performance: Where Do Inefficiencies Come From? 147 6.4.1 Voltage, Current, and Power 147 6.4.2 Polarization 148 6.4.2.1 Loss Due to Activation 149 6.4.2.2 Ohmic Losses 149 6.4.2.3 Concentration Effects 149 6.4.3 Exchange Current 149 6.4.4 Cell Performance and Nernst Equation 150 6.5 Fuel Cell Electrocatalysts 150 6.5.1 Electrocatalysis 150 6.5.2 Oxygen Reduction Reaction 151 6.5.3 Characterization of Catalysts 154 6.6 Polymer Electrolyte Membrane Fuel Cell 154 6.6.1 Introduction 154 6.6.2 General Considerations 156 6.6.2.1 Membrane Electrode Assembly 156 6.6.2.2 Water Management 156 6.6.3 Polymer Development 157 6.6.3.1 Perfluorosulfonic Acid Membranes 157 6.6.3.2 Poly(Arylene Ether) Membranes 158 6.6.3.3 Polyimides and Imidazoles 162 6.6.3.4 Metal–Organic Frameworks 162 6.6.4 Direct Methanol Fuel Cells 167 6.6.4.1 Half-Cell Reactions 170 6.6.4.2 DMFC Electrocatalysts 172 6.7 Solid Oxide Fuel Cells 173 6.7.1 Introduction 173 6.7.2 Reactions 174 6.7.3 Electrode and Electrolyte Materials 175 Index Otto cycle, 61 reversible cycle, 59 Carrier multiplication (CM), 270 Catalysis, 98, 103, 318; see also Electrocatalysis bifunctional, 346 crown jewels of, 24 enzymatic, 346 FAME biodiesel production, 343 heterogeneous acidic, 345–346 heterogeneous basic, 344 lipases, 346 oxidative addition, 106 rate enhancement, 104 TOF, 103 transition metals, importance of, 104 Catalysts, 103 characterization, 154 for FCC, 34 FT, 112 lanthanum in, 9–10 in petroleum refining, 103 reforming, 36 for tar removal, 318 Wilkinson’s, 104, 105 Catalytic cracking, 34, 35 Catholyte, 194 Cationic fragmentation mechanisms, 35 CBD, see Chemical bath deposition (CBD) CdS, see Cadmium sulfide (CdS) CdTe, see Cadmium telluride (CdTe) Cellobiose, 292, 293 enzymatic cleavage, 328 Cell potential, 15, 141, 142 and Gibbs free energy, 143 state of water, 144–145 temperature and pressure effect, 145–146 thermodynamic data, 144 Cell threshold, 210 Cellular respiration, Cellulose, 93, 292 5-hydroxymethylfurfural formation, 306 properties, 292, 293 thermal decomposition, 300 Cell voltage, see Cell potential Centrifugation method, 369 CH3ONa, 343 Chain-growth polymerization, 73, 74, 75; see also Step-growth polymerization Chalcopyrite crystal, 223 Chemical bath deposition (CBD), 272 Chemical hydrogen storage (CHS), see Materials-based hydrogen storage Chemical looping combustion (CLC), 39 Chemical vapor deposition (CVD), 221 Chemisorption, 42 Chiral oxazolidinones, 49 403 CHP efficiency, see Combined heat and power efficiency (CHP efficiency) CIG, see Copper indium gallium (CIG) CIS, see Copper indium diselenide (CIS) CLC, see Chemical looping combustion (CLC) Closed fuel cycle, 369 CM, see Carrier multiplication (CM) CNT, see Carbon nanotubes (CNT) Coal-to-liquid process (CTL process), 112 Coal, 21 bed methane, 29 combustion, 15 gasification, 23, 113, 313 liquefaction, 112 types and properties, 22 Cobalt glyoximate compound dye, 123 Cobalt–porphyrin cofactor, 331 Cocurrent, see Downdraft Cogeneration power, see Combined heat and power efficiency (CHP efficiency) Combined heat and power efficiency (CHP efficiency), 146 Comminution, 301 Concentrating solar power (CSP), 207 Conductor, 208, 209 ion, 156, 174 Constants, 395 Controlled polymerization, 79 Controlled radical polymerization (CRP), 80 Conventional petroleum, 23, 24 Conversion option, 295–296 Copolymers, 65 Copper indium diselenide (CIS), 222 Copper indium gallium (CIG), 222, 223 Copper indium selenide, 222 chalcopyrite crystal structure, 223 CIGS/CIGSe cell configuration, 223, 224 CIGSSe cell, 224–225 CIGS solar cell architecture, 223 Copper thiocyanate (CuSCN), 268 Countercurrent, see Updraft Cracking catalytic, 34, 35 cationic fragmentation mechanisms, 35 hydrocracking, 35, 36 thermal, 34 zeolites, 34 CRP, see Controlled radical polymerization (CRP) Crude petroleum, 30 cracking, 34–36 distillation, 31, 33 extraction, 33 petroleum refining process, 32 CSP, see Concentrating solar power (CSP) CTL process, see Coal-to-liquid process (CTL process) CuInSe2, see Copper indium diselenide (CIS) 404 Curing, 85 Current–voltage curve, 213 AM reference spectra, 217 current density, 214 dark current vs photocurrent, 215 IPCE, 218 QE, 217 relationship for PV device, 214 research cell efficiency timeline, 216 Shockley–Queisser limit, 215 CuSCN, see Copper thiocyanate (CuSCN) CVD, see Chemical vapor deposition (CVD) Cyclic voltammetry (CV), 231 Cycloalkanes, 31 CZTS cell, 277–279 D DADB, see Diammoniate of diborane (DADB) DAFC, see Direct alcohol fuel cell (DAFC) Dangling bonds, 220 Dark current, 215 DDG, see Dry distillers grains (DDG) Degree of polymerization (DP), 67 Dehydrohalogenative cross-coupling, see Direct arylation Densification, 301 Density functional theory, 154 Department of Energy (DOE), 127 Depleted uranium, 370–371 DHA, see Docosahexenoic acid (DHA) Diagenesis, 21 Diamide extraction (DIAMEX), 373 Diammoniate of diborane (DADB), 131 Differential scanning calorimetry (DSC), 83 Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), 80 Diffusion, see Effusion Dihydroxyacetone phosphate, 325 Dimethyl carbonate (DMC), 48 synthesis of, 50, 51 tin-catalyzed synthesis, 49 Dimethyl ether (DME), 47 Direct alcohol fuel cell (DAFC), 167 Direct arylation, 239 C–H bond in, 239 P3HT synthesis, 241 for terthiophene–thienopyrrolodione copolymer synthesis, 242 Direct methanol fuel cell (DMFC), 154, 167, 169, 170 alcohol oxidation reaction, 172 membrane electrode assembly for, 173 DMC, see Dimethyl carbonate (DMC) DMDOHEMA, see N, N′-dimethyl-N, N′-dioctyl-2, (2′-hexyloxyethyl) malonamide (DMDOHEMA) Index DME, see Dimethyl ether (DME) DMFC, see Direct methanol fuel cell (DMFC) Docosahexenoic acid (DHA), 340 DOE, see Department of Energy (DOE) Donor–acceptor copolymer, 238 Donor materials, 232, 233 aromatic and quinoid resonance contributors, 236 array of structural modification, 232 benzodithiophene copolymer synthesis, 238 direct arylation, 239, 242 electron-rich poly[3, 4-(ethylenedioxy) thiophene], 237 low bandgap polymer, 237 P3HT-grafted carbon nanotubes, 234 P3HT-grafted grapheme, 235 P3HT coupling pattern, 233 quinoid vs aromatic thiophene, 236 quinoxaline-carbazole donor–acceptor copolymer, 238 regioregular synthesis P3HT, 234 for two-layer OPV, 232 Doping, 210 of chromium(III) terephthalate MIL-101 MOF, 167 of electrolyte, 192 n-type and p-type, 211 of Nafion, 158 Double-walled carbon nanotubes (DWCNT), 95, 96 Downdraft, 316 DP, see Degree of polymerization (DP) DRIFTS, see Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) Dry distillers grains (DDG), 324 Drying, 300–301 DSC, see Differential scanning calorimetry (DSC) DSSC, see Dye-sensitized solar cell (DSSC) DWCNT, see Double-walled carbon nanotubes (DWCNT) Dye-sensitized solar cell (DSSC), 250, 252; see also Solar photovoltaic absorb light, 251 architecture, 251–252 conduction process, 253 dye sensitizer, 260–267 mechanism, 252–253 metal oxide, 254–259 redox mediator, 267–269 Dye sensitizer, 260 functional group classes using, 260 incident photon-to-current efficiency, 263 isothiocyanate ligands, 261 LUMO level, 260 natural dyes, 267 organic dye sensitizers, 264–266 405 Index ruthenium dyes for DSSCs, 260 zinc phthalocyanin DSSC dye, 263 E E-glass, 94 Earth’s energy budget, 206 EDS, see Energy-dispersive x-ray spectroscopy (EDS) EES, see Electrical energy storage (EES) Effusion, 369 EHP, see Electron–hole pair (EHP) EHPM, see Electron–hole pair multiplication (EHPM) Eicosapentenoic acid (EPA), 340 Electrical conduction in photovoltaic, 210 light harvesting, 213 photovoltaic effect, 210 p–n junction, 211, 212 Electrical energy storage (EES), 16, 183, 355; see also Fuel cells graphene, 197–199 lithium ion batteries, 184–191 redox flow batteries, 194–197 sodium-based batteries, 191–194 supercapacitors, 183 Electricity from nuclear energy, 360 production using hydrogen, 114 units and equations, 391 Electricity generation, 14 Coulomb’s law, 15 EES systems, 16 U S electrical generation, 15–16 Electric vehicles (EV), 183 Electrocatalysis, 150–151 Electrochemical cells, 137 Electrochemical energy storage, see Batteries Electrochemistry, 140 cathode, 196 cell potential, 141 fuel and oxidant, 140 Electrodes, 175, 176 anode materials, 179 cathode materials, 178–179 Electrohydrogenesis, 115 Electrolyte, see Redox couple Electrolytic reprocessing, 376 Electrolyzers, 115 Electromotive force (EMF), see Cell potential Electron-rich poly[3, 4-(ethylenedioxy) thiophene], 237 Electron–hole pair (EHP), 210 Electron–hole pair multiplication (EHPM), 270, 271 Endo-1, 4-β-d-glucanases, 328 Energy-dispersive x-ray spectroscopy (EDS), 154 Energy, 1, 56, 383 average rate of increase in, carbon cycle, 7–9 carrying capacity of earth, density, 13, 288 distribution of elements, EES systems, 16 electricity generation and storage, 14–16 energy value, 11, 12 using fossil fuels, geologic time scale, global carbon emissions, heat of combustion data, 12 HHV and LHV, 12 historical rate of growth, resource availability, 9–11 sustainability, 6, transformations, units and abbreviations, 13–14 U.S electrical generation, 15 value, 11, 12 World primary energy supply, Enhanced oil recovery method (EOR method), 27 Entropy, 57 Enzymatic catalysis, 346 EOR method, see Enhanced oil recovery method (EOR method) EPA, see Eicosapentenoic acid (EPA) EPR, see European Pressurized Reactor (EPR) Equation of state, 55 Ethylene oxide–propylene oxide block copolymer, 256 European Pressurized Reactor (EPR), 366 EV, see Electric vehicles (EV) Exchange current, 149–150 Exciton, see Electron–hole pair (EHP) Exergy, 62 Exo-1, 4-β-glucanases, 328 Extended x-ray absorption fine structure (XAFS), 154 External quantum efficiency, 279 F FAE biodiesel, 335, 336, 342, 344, 346 FAME biodiesel, 335, 343, 344 Fast-flux reactor, see Fast neutron reactor Fast breeder reactor (FBR), 365, 377 Fatty acid, 340 biochemistry of, 338 biosynthetic pathway, 339 melting points, 342 oils and fats component, 341 triacylglyceride, 338 FBR, see Fast breeder reactor (FBR) Feedstock, 314–315 406 Fermentation, 319, 321 acetalydehyde reduction, 328 aldolase-catalyzed formation, 325 α-Amylose, 321, 323 biomass sources, 320 fructose-6-bisphosphate, 324 fuel ethanol production and consumption, 320 of lignocellulosic biomass, 324–329 pyruvate conversion, 326 of starch, 321–324 sucrose, 322 TPP-catalyzed decarboxylation, 327 Fertile material, see Fissile material FF, see Fill factor (FF) FFA, see Free fatty acid (FFA) Field emission scanning electron microscopy images (FESEM images), 186 Fill factor (FF), 214, 279 Fischer–Tropsch process (FT process), 108, 112 Fissile material, 357 Fluidized catalytic cracking (FCC), see Catalytic cracking Fluorine-doped tin oxide (FTO), 251, 270 Fossil fuels, 19, 50 extraction, 23–30 oil and gas formation, 19–23 refining, 30–37 units, 393 Four-electron pathway, 151 Fracking, see Hydraulic fracturing Free fatty acid (FFA), 336 Fructose-6-bisphosphate, 324 FTO, see Fluorine-doped tin oxide (FTO) FT process, see Fischer–Tropsch process (FT process) Fuel cells, 137 cell potential calculation, 142, 143 conversions, 140 efficiency and, 146–147 electrocatalysts, 150–154 electrochemical cells, 137, 140 electrochemistry, 140–142 exchange current, 149–150 MFC, 180–183 Nernst equation, 150 polarization, 148–149 prototypical, 141 SOFC, 173–180 types, 138, 139 voltage, current, and power, 147, 148 Fuel reprocessing, 369, 371 Am(III) ion complex, 375 depleted uranium, 370–371 fuel composition, 370 nuclear waste, 372 ORTEP diagram, 376 Index P & T, 371 PUREX, 373 reprocessing technology, 371–376 SANEX process, 375, 376 TALSPEAK process, 374 Tri-n-butyl phosphate, 373 Fuels, 11, 360 Fullerenes, 239 BHJ and, 245 disadvantages in modification, 241 functionalization, 239, 241 insolubility, 241 PCMB preparation, 243 Fusion, 377 energy, 379 of hydrogen nuclei, 357 ITER project, 378 ITER tokomak fusion reactor, 378 nuclear, G Galvanic cells, see Electrochemical cells Gasification, 112, 313; see also Biomass agent, 315 of biomass, 301 catalysis, 318–319 catalysts, 113 contaminants, 318–319 feedstock, 314–315 for gaseous product, 313 pretreatment, 314–315 process parameters, 314 reaction, 317–318 reactor design, 316–317 steam reforming, 112 temperature, 315 Gel permeation chromatography (GPC), 69, 70 Generation IV reactor, 377 Geologic time scale, Global population growth, 384 Glucose-6-phosphate, 322 Glyceraldehyde-3-phosphate, 325 Glycoside, 291 GPC, see Gel permeation chromatography (GPC) Grain boundaries, 220 Graphene, 197 and graphene oxide, 197 Li–S battery, 199 plausible structure for N-doped, 198 Graphite, 360 Green chemistry, 97–98 Green polycarbonate synthesis, 72 Green polymer composite, 92 Gross calorific value, see Higher heating value (HHV) 407 Index H H-cluster, 117 H3N ⋅ BH3, see Ammonia–borane (AB) Haber–Bosch process, 107, 108 Half-cell reactions, 170 intermediates in ethanol oxidation, 171, 172 methanol and water values, 171 redox reactions of DMFC, 170 HAWT, see Horizontal axis wind turbine (HAWT) HDO, see Hydrodeoxygenation (HDO) HDPE, see High-density polyethylene (HDPE) Head-to-head (HH), 233 Head-to-tail (HT), 233 Heat, 56, 57 of combustion data for substances, 12 HHV, 12 waste, 57, 125 Heavy oil, 26, 27 Heavy water reactor, 363, 365 Hemiacetal, 296 Hemicellulose, 293 acetic acid formation, 326 sugar components in, 294 Hemiketal, see Hemiacetal HH, see Head-to-head (HH) HHV, see Higher heating value (HHV) High-density polyethylene (HDPE), 83 High-level nuclear waste (HLW), 370 Higher heating value (HHV), 12 Highest occupied molecular orbit (HOMO), 227 HIT cell, 221 HLW, see High-level nuclear waste (HLW) HOMO–LUMO gap, 227, 228 characterization of energy level, 230–231 ideal donor bandgap, 229 PBC-DFT study, 230 3T-TCBD-3T UV–visible spectrum, 231 Horizontal axis wind turbine (HAWT), 87 HT, see Head-to-tail (HT) Hydraulic fracturing in fossil fuels extraction, 25 in shale gas extraction, 26 Hydrocracking, 35, 36 Hydrodeoxygenation (HDO), 307 5-hydroxymethylfurfural, 306 BHJ formation, 243 butyric acid substituent alteration, 244 functionalization of fullerenes, 239–240 LUMO of, 229, 239 modification, 244 solubility, 241 UV–vis absorbance spectra, 245 Hydrogen, 40 bonding in benzoxazine dimmers, 82 economy, 106 nucleus, 364 thermodynamic data, 144 uptake performance of MOFs, 129 water and biological production, 114, 115 Hydrogenases formation of hydrogen, 118 H-cluster, 117 NiFe and FeFe, 117, 119 photosynthesis, 116 Hydrogenated amorphous silicon (a-Si:H), 220 Hydrogen bonding in benzoxazine dimers, 82 inter-and intramolecular, 81 Hydrogen production, 106 electrolyzers types, 115 feedstocks, 107 Fischer–Tropsch process, 112 gasification, 112–114 Haber–Bosch process, 107, 108 hydrogenases, 116–119 MEC, 115, 116 photochemical electrolysis, 119–122 SMR, 108–111 water and biological production, 114 Wilkinson’s catalyst, 106 Hydrogen storage, 122 chemical solutions, 124 CHS materials, 131–133 hydrogen fuel, 122 metal hydrides, 128–131 MOF, 125–128 Hydrolysis, 330 Hydroxyaldehyde, 296 Hydroxyketone, see Hydroxyaldehyde I IEA, see International Energy Agency (IEA) IGCC, see Integrated gasification combined cycle (IGCC) IGFC systems, see Integrated gasification fuel cell systems (IGFC systems) ILs, see Ionic liquids (ILs) ILW, see Intermediate-level waste (ILW) Imidazoles, 162 Imine, 322 Immobilization, 346–348 InAs, see Indium arsenide (InAs) Incident photon to current conversion efficiency (IPCE), 218 Indium arsenide (InAs), 272 Indium phosphide (InP), 272 Indium tin oxide (ITO), 251 Inelastic scattering, 357 Injection, 252 408 Inorganic solar cells, 218; see also Solar photovoltaic silicon, 218–220 thin-film, 221–226 InP, see Indium phosphide (InP) In situ leach mining (ISL), 368 In situ recovery mining (ISR), 368 Insulator, 208, 209 Integrated gasification combined cycle (IGCC), 23, 113 Integrated gasification fuel cell systems (IGFC systems), 174 Intermediate-level waste (ILW), 370 International Energy Agency (IEA), 356 International Thermonuclear Experimental Reactor (ITER), 378 International Union of Pure and Applied Chemistry (IUPAC), 79 Intrinsic semiconductor, 210 Inverse opal, 257, 259 Iodide/iodine system, 268–269 Ionic liquids (ILs), 40 cations for, 41 for CO2 capture, 42 organic salts, 40 postcombustion applications, 41 Ion impregnation method, 179–180 IPCE, see Incident photon to current conversion efficiency (IPCE) ISL, see In situ leach mining (ISL) ISR, see In situ recovery mining (ISR) ITER, see International Thermonuclear Experimental Reactor (ITER) ITO, see Indium tin oxide (ITO) IUPAC, see International Union of Pure and Applied Chemistry (IUPAC) J Joule, 56 K Kerogen, 21, 22 Kolbe–Schmitt synthesis, 46 L Landfill gas, 334–335 Landfill trash, see Municipal solid waste (MSW) Lanthanum, 9–10 LCA, see Life cycle assessment (LCA) LCB, see Lignocellulosic biomass (LCB) LDPE, see Low-density polyethylene (LDPE) LFTR, see Liquid fluoride thorium reactor (LFTR) Index LHV, see Lower heating value (LHV) Life cycle assessment (LCA), 62, 337 Light water reactor (LWR), 363 composition of spent fuel, 370 heavy water reactors and, 363, 365 Lignin cinnamyl alcohol units, 293 and constituents, 294 enzymatic decomposition of LCB, 328 hemicelluloses, 293, 294 lignin–carbohydrate complex, 295 phenolic, 305 plant biomass, 304 woody plant materials, 20 Lignite, 22, 23 Lignocellulosic biomass (LCB), 289 cellobiose enzymatic cleavage, 328 fermentation, 324, 328–329 pretreatment, 324–328 renewable fuel standards, 329 Lipases, 346, 347, 348 Lipids, 20, 21, 289 Liquid fluoride thorium reactor (LFTR), 367 Liquid organic hydrides, 131 Liquid organic hydrogen carriers, see Liquid organic hydrides Lithium–air batteries, 189 in discharge and charge modes, 191 discharge half-reactions, 189 energy storage densities comparison, 190 Lithium ion batteries, 184, 185; see also Sodium-based batteries anode materials, 184–185 carbon-free alloys, 186 cathode materials, 186, 187 dendrites formation, 185, 186 FESEM images, 188 Lithium–air batteries, 189–191 Lithium–Sulfur batteries, 187–189 materials in, 185 rocking horse redox chemistry, 184 Lithium polysulfidophosphates (LPSP), 187 Lithium–Sulfur batteries, 187 charge and discharge reactions, 189 polysulfide S–S bonds, 188 S8 allotrope of sulfur, 189 LLW, see Low-level waste (LLW) Low-density polyethylene (LDPE), 83 in films and plastic bags, 83 high-density vs., 84 Low-energy metal-to-ligand charge transfer state, 261 Low-level waste (LLW), 370 Low bandgap donor–acceptor polymer, 237, 238 Lower heating value (LHV), 11, 61 409 Index Lowest unoccupied molecular orbital (LUMO), 227 donor molecule, 229 HOMO–LUMO energy levels, 228, 230, 236 of PCBM, 239 LPSP, see Lithium polysulfidophosphates (LPSP) LWR, see Light water reactor (LWR) M Magic-angle spinning (MAS), 81 Materials-based hydrogen storage, 124 Material’s energy value, 11 Maturation, 21 MEA, see Membrane electrode assembly (MEA) MEC, see Microbial electrolysis cell (MEC) Mechanical heat engine, 57–58, 61 MEG, see Multiple exciton generation (MEG) Membrane electrode assembly (MEA), 156 DMFC, 172, 173 PEMFC, 156 Mesoporous titanium oxide, 251–252 Metal hydrides, 128, 131 atomic hydrogen, 128 delivery of hydrogen gas, 129 magnesium borohydride, 130 Metal–organic frameworks (MOFs), 124 coordination network solids, 125 heterocycle-linked, 127 hydrogen uptake performance, 129 iron-aminoterephthalate, 165 ligands, 128 MOF-177 synthesis, 126 MOF-326 synthesis, 127 MOF-5, 126 Metal oxide, 254 alkali carbonates and, 113 anatase descriptor, 256 anatase nanocrystals, 256 bandgaps, 254 in CLC, 39 controlled anatase synthesis, 255 ethylene oxide–propylene oxide block copolymer, 256 inverse opal, 257 inverse opal TiO2 synthesis, 259 peroxide and two-electron pathway, 151 scanning electron micrograph, 258 surfactant and halide, 257 TiO2 morphologies controlling, 255 titanium and tin, 345 XRD results, 258 Methane clathrates, see Methane hydrates Methane hydrates, 29, 30 Methanogenesis, 331 Methanogens, 115, 334 Methanol, 302 di-n-butyldimethoxy tin, 48 diffusion of, 155 in direct methanol fuel cells, 47, 154, 170 for PEMFC, 167, 169 reduction of CO2, 46 thermodynamic values for, 171 transesterification with, 335 MFC, see Microbial fuel cells (MFC) Michael reaction, 299 Microbial electrolysis, see Electrohydrogenesis Microbial electrolysis cell (MEC), 115, 116 Microbial fuel cells (MFC), 153, 180, 181 anode fabrication, 182 biofuel cells, 180 cathode materials, 182–183 components, 181, 182 enzymatic electrocatalysts, 180 Minor actinides, 370, 371, 373 Mixture of uranium and plutonium oxides (MOX), 364, 372 MMD, see Molecular mass distribution (MMD) Moderator, 360, 364, 365 MOFs, see Metal–organic frameworks (MOFs) Molar mass distribution, 67, 70 Molecular mass distribution (MMD), 69, 70 Monomer, 65 aromatic, 71 donor and acceptor, 237 olefin, 73 polyfunctional, 77 styrene, 89 MOX, see Mixture of uranium and plutonium oxides (MOX) MSW, see Municipal solid waste (MSW) Multiplate, 31 Multiple exciton generation (MEG), 270 Municipal solid waste (MSW), 180, 289 N n-type doping, 211 Nafion® membranes, 157 conductivity and durability, 162 copolymer structure, 157 doping of, 158 fuel cell membrane, 345 hydrated, 165 Nanostructured thin-film (NSTF), 153 Naphthalenic polyimides, 162, 166 Napthenes, see Cycloalkanes National Renewable Energy Laboratory (NREL), 215, 307 410 Natural gas, 36, 37 amine capture technology, 41 Carnot efficiency for, 61 and coal-fired power plants, 16 conventional source, 36 for electrical generation, 15 extraction, 11 firedamp, 29 shale gas, 25 steam reforming, 108 Natural gas combined cycle (NGCC), 36, 37 Nernst equation, 150 Net calorific value, see Lower heating value (LHV) Neutron, 356; see also Proton breeder reactor, 365 in elastic collisions, 357 energies of, 363 U-238, 364 NGCC, see Natural gas combined cycle (NGCC) Nickel cermet, 179 N, N′-dimethyl-N, N′-dioctyl-2, (2′-hexyloxyethyl) malonamide (DMDOHEMA), 375, 376 Nonconventional sources, 24 coal bed methane, 29 fracking fluid composition, 27 heavy oil, 26, 27 horizontal drilling, 25 hydraulic fracturing, 25, 26 methane hydrates, 29, 30 oil sands, 27–29 shale oil and gas, 24 NREL, see National Renewable Energy Laboratory (NREL) NSTF, see Nanostructured thin-film (NSTF) Nuclear chain reaction, 358, 359 Nuclear chemistry binding energy vs mass number, 358 general chemistry, 356–357 lanthanides and actinides, 359 Nuclear energy, 355, 357, 358, 360 fusion, 377–379 generation IV reactor, 377 lanthanides and actinides, 359 nuclear chain reaction, 359 nuclear reactor, 360–367 Nuclear fission, 357 Nuclear fuel cycle, 367, 370 Nuclear fusion, 357 Nuclear power, conventional, 360 Cadmium-113, 364 control rods in reactor vessel, 364 hydrogen nucleus, 364 neutron energy, 363 PWR power plant, 363 Index reactor core, 363 Nuclear reactors, 360 advanced PWR, 366 breeder reactors, 365–366 conventional nuclear power, 360, 363–365 heavy water reactors, 365 thorium reactors, 366–367 types, 361–362, 365–367 Nucleon, 356, 378 Nylon 6,6 synthesis, 65, 66 O OEC, see Oxygen-evolving complex (OEC) Oil sands, 27 bitumen or asphalt, 27 in northern Alberta, 29 polycyclic aromatic hydrocarbons, 28 Oil shale, 21, 27 Oligomers, 65, 162 Once-through cycle, 367 OPV, see Organic photovoltaics (OPV) Organic dye sensitizers, 264–266 Organic photovoltaics (OPV), 226, 243, 245, 247; see also Solar photovoltaics acceptor, 239–241 acetone addition, 248 architecture, 241–243 BHJ approach, 244, 245, 246 bird’s eye view of P3HT nanopillars, 250 cartoon, 246 cell performance, 249 donors, 232–239 HOMO–LUMO gap, 227, 228–231 improvements and innovation in, 249 morphology, 243–250 ordered bulk heterojunction, 248 P3HT:PCBM, 247 PEDOT:PSS preparation, 246 photoelectric conduction process, 227 TEM result, 246 ORR, see Oxygen reduction reaction (ORR) Otto cycle, 61 Overpotential, see Polarization Overvoltage, see Polarization Oxidative addition, 105, 106 Oxycombustion, 39 Oxygen levels of Earth’s atmosphere, thermodynamic data, 144 Oxygen-evolving complex (OEC), 121 Oxygen reduction reaction (ORR), 151 crystallographic plane, 152 inroads via nanotechnology, 153 intermediates in, 152 non-PGM electrocatalysts, 153 pathways, 151 Index P p-type doping, 211 Cadmium telluride, 225 CZTS and Se materials, 278 DSSC, 251 P & T, see Partitioning and transmutation (P & T) P3HT, see Poly-3-hexylthiophenes (P3HT) PAN, see Polyacrylonitrile fibers (PAN) Paraffins, see Saturated hydrocarbons Partitioning and transmutation (P & T), 371 PAT, see Polyalkylthiophenes (PAT) PBC-DFT, see Periodic boundary conditionDensity functional theory (PBC-DFT) PBI, see Polybenzimidazoles (PBI) PC71BM, see [6, 6]-phenyl-C71-butyric acid methyl ester (PC71BM) PCBM, see [6, 6]-phenyl C61 butyric acid methyl ester (PCBM) PCE, see Power conversion efficiency (PCE) PDI, see Perylene-3,4:9,10-bis[dicarboximide] (PDI); Polydispersity index (PDI) PEBAX® membranes, 75, 76 hypothetical representation, 77 permeability, 75 PEDOT, see Polymerized 3,4-ethylenedioxythiophene (PEDOT) PEMFC, see Polymer electrolyte membrane fuel cell (PEMFC) Perfluorosulfonic Acid membranes (PFSA membranes), 157, 158 Periodic boundary condition-Density functional theory (PBC-DFT), 230 Perovskite unit cell, 177 Perylene-3, 10-bis(dicarboximide) (PDI), 4:9, 121 Perylene–iridium complex, 124 PES, see Polyethersulfone (PES) PET, see Polyethylene terephthalate (PET) PFSA membranes, see Perfluorosulfonic Acid membranes (PFSA membranes) PGM, see Platinum group metals (PGM) [6, 6]-phenyl-C71-butyric acid methyl ester (PC71BM), 239, 243 [6, 6]-phenyl C61 butyric acid methyl ester (PCBM), 229, 243; see also Poly-3hexylthiophene (P3HT) Phosphoric acid-doped polybenzimidazole, 167 Photochemical electrolysis chlorophyll and carotenoid compounds, 120 cobalt glyoximate compound dye, 123 electron transport chalcogel, 123 iron–rhenium triad, 122 OEC, 121 perylene–iridium complex, 124 411 photosynthetic Z-scheme, 120 solar fuel, 119 of water, 119 Photoelectric effect, 208, 209, 210 Photosystem I (PSI), 119 Photovoltaics (PV), 205; see also Solar photovoltaics bandgaps for, 209 band theory, 208–210 current–voltage curve, 213–218 electrical conduction in, 210–213 metal chalcongenides in, 222 photoelectric effect, 208–210 Physisorption, 42, 43, 125 p–i–n architecture, 222 Plant biomass, 292 chemical composition of, 292 components, 304 feedstock of animal waste with, 301 inorganic elements in, 295 Platinum alloys, 152, 153, 172 Platinum group metals (PGM), 10, 151 Plutonium uranium refining by extraction (PUREX), 373 SANEX process, 375 tri-n-butyl phosphate, 373 p–n junction, 211 conduction process, 212 and depletion zone evolution, 211 electron–hole pairs, 225 Polarization cell potentials, 148 concentration effects, 149 curve, 149 loss of potential, 149 Ohmic losses, 149 Poly-3-hexylthiophenes (P3HT), 80, 232 bird’s eye view of nanopillars, 250 coupling patterns, 233 direct arylation method, 241 nanopillars vs standard bilayer cell performance, 250 P3HT-grafted carbon nanotubes, 234 P3HT-grafted graphene, 235 regioregular synthesis, 234 TEM results, 246 Poly-4-stryenesulfonic acid (PSS), 241, 245, 246 Poly(arylene ether) membranes, 158 cross-linking of SPEEK membrane, 159, 160 hydrolysis, 162 poly(ether)sulfone coupling, 161 sulfonated poly(ether)ether ketone, 158 Poly(p-phenylenevinylene) (PPV), 73 Poly(vinyl alcohol) (PVA), 182, 183 Poly[2-(methylacryloyloxy)ethyl] trimethylammonium ionic liquid, 42 Polyacrylonitrile fibers (PAN), 94, 95 412 Polyalkylthiophenes (PAT), 232 donor materials, 232 regioselectivity of coupling for, 81 synthesis, 233 Polybenzimidazoles (PBI), 157, 162 polytriazole blend, 169 SPI–PBI blend, 168 Polycarbonates aliphatic, 72 with aromatic monomers, 71 green polycarbonate synthesis, 72 regiochemistry of, 79 use of CO2, 47 Polydispersity index (PDI), 77 Polyethersulfone (PES), 159, 161 Polyethylene terephthalate (PET), 71 Polyimides, 75, 162 Polymer electrolyte membrane fuel cell (PEMFC), 150, 155; see also Fuel cells direct methanol fuel cells, 167, 169, 170 Fe-MIL-101-NH2 and polymer conglomerate, 169 half-cell reactions, 170–172 hydrogen, 154 hydrolysis-resistant PEM, 163 imidazoles, 162 MEA, 156 metal–organic framework, 162, 165 methanol crossover problem, 155, 156 oxazole-containing copolymer, 164 PBI and polytriazole blend, 169 PEM membranes, 158 PES, 161 PFSA membranes, 157, 158 phosphoric acid-doped polybenzimidazole, 167 polyimides, 162 polymer development, 157 proton conduction performance, 170 SPEEK membrane, 158, 159 SPI–PBI blend, 168 1H-1,2,4-triazole, 169 triazole-containing copolymer, 164 water management, 156 Polymerized 3,4-ethylenedioxythiophene (PEDOT), 241, 243 porous matrix of, 275 structures and preparation, 246 Polymer matrix composites, 86, 89 applications of CNT-reinforced, 95 glass types in, 94 reinforcing fibers in, 92 Polymers, 65 1H NMR spectra for P3HT isomers, 82 behavior, 66 carbon nanotubes, 95–97 chemistry and wind energy, 86 Index curing, 85 DP, 67 evolution of wind power, 88 glass transition temperature, 83, 84 GPC, 69 green chemistry, 97–98 growth in wind electricity generation, 87 HDPE and LDPE, 84 hydrogen bonding, 82 infrared spectrum of polyvinyl alcohol, 81 Kevlar®, 67 molecular weight distribution, 69 physical and mechanical properties, 83 polymer matrix composites, 95–97 regioselectivity of coupling, 81 reinforcing fibers, 91–95 resins, 89–91 SEC, 68 stereoregularity, 84 styrene–butadiene rubber, 67 synthesis, 71–80 tensile stress–strain curves, 86 thermoplastic or thermoset, 65 vertical axis wind turbine, 97 vibrational spectroscopic techniques, 80 wind turbines, 88, 89 yield point, 86 Polyose, see Hemicellulose Polypropylene isomers, stereoregularity of, 84 Polytetrafluoroethylene (PTFE), 156, 157 Polyvinyl alcohol, 81 Polyvinyl chloride (PVC), 65, 66 Postcombustion capture, 39, 40 Potential voltage, see Thermoneutral cell potential Power conversion efficiency (PCE), 218, 228 PPV, see Poly(p-phenylenevinylene) (PPV) Pressurized water reactor (PWR), 363 advanced, 366 and BWR, 363 Proton, 356 conduction of, 156, 165, 170 hydrogenases, 116 hydrogen storage and, 125 SOFC, 174 in uranium, 368 PSI, see Photosystem I (PSI) PSS, see Poly-4-stryenesulfonic acid (PSS) PTFE, see Polytetrafluoroethylene (PTFE) PUREX, see Plutonium uranium refining by extraction (PUREX) PV, see Photovoltaics (PV) PVA, see Poly(vinyl alcohol) (PVA) PVC, see Polyvinyl chloride (PVC) PWR, see Pressurized water reactor (PWR) 413 Index Pyrolysis, 302; see also Thermochemical process 5-hydroxymethylfurfural formation, 306 bio-oil cleanup, 308 bio-oil deoxygenation, 310 fragmentation mechanism in, 307 phenolic lignin breakdown products, 305 process, 302–303 product, 303–304 reactions, 304 reactions in catalytic upgrading, 309 time and temperature changes, 303 upgrading bio-oil, 304–313 ZSM-5 zeolite framework, 311 Pyrolysis oil, see Bio-oil Pyroprocessing, see Electrolytic reprocessing Pyruvate conversion, 326 carbonyl, 322 to ethanol, 326 TPP-catalyzed decarboxylation, 327 Q Quantum-dot sensitized solar cells (QDSSC), 269 Quantum dot solar cells (QD solar cells), 208, 269; see also Solar photovoltaics decay process, 277 EHPM, 270, 271 electrode materials, 274–275 mechanism for QDSSC, 275–277 photoconduction process, 276 in QDSSC, 272 redox mediator, 274–275 semiconductor, 271–272 SILAR method, 273 size and bandgap relationship, 270 TEM images for TiO2/CdSe, 274 X-ray diffraction pattern, 273 Quantum efficiency (QE), 217, 243 Quantum yield (QY), 270 R Radioactive decay, 356 Reactivity pattern, 296 aldol condensation, 298 α, β-unsaturated carbonyl compound, 299 biomass energy conversion, 296 cellulose thermal decomposition, 300 equilibrium of glucose, 297 hydrolysis of amides, 300 structural differences, 298 Reactor-grade uranium, 368 Reactor core, 363, 364, 377 Reactor design, 316 fluidized bed reactor, 317 gasifier designs, 316 heat transfer, 303 nuclear, 361–362 process parameters and, 314 steam reforming, 108 Rectisol® method, 40 Redox couple, 251, 253 Redox flow batteries, 194 anolyte and catholyte, 194 performance, 197 steps in charging mechanism, 196 vanadium redox flow battery, 195 Redox mediator, 267 and electrode materials, 274–275 iodide/iodine system, 268–269 quasi solid-state, 268 requirements for, 267 Reforming process, 36, 110 Regiochemistry, 79 Regiocontrol, 77, 239 Reinforcing fibers, 91 carbon fibers, 94 cellulose, 93 glass and carbon, 91, 94 in polymer matrix composites, 92 Relative humidity (RH), 156 Resins acidic ion-exchange, 345 epichlorohydrin and bisphenol A, 91 phthalic polyester resin structure, 90 polyester, 89 styrene and unsaturated polymer, 90 urea–formaldehyde, 46 vinyl ester polymer, 91 Resource availability, global geopolitics, hydrogen gas, 11 Lanthanum, 9–10 materials in photovoltaics, 10 PV technology, 277 Retorting process, 27 Retro-aldol reaction, 304, 307, 322 RH, see Relative humidity (RH) Ruthenium, 261 dye sensitizers, 262, 269 dyes for DSSCs, 260 octahedral ruthenium pyridyl systems, 260, 261 Rutile, 254 S S-glass, 94, 95 Saccharides, see Carbohydrates Saccharification, 321 SANEX, see Selective actinide extraction (SANEX) Saturated hydrocarbons, 31 414 Scanning electron microscopy (SEM), 154 inverse opal TiO2 scaffold, 259 tin and nickel anodes, 194 Scanning transmission electron microscopy (STEM), 154 SEC, see Size-exclusion chromatography (SEC) Sedimentation process, 19 Selective actinide extraction (SANEX), 373, 375, 376 Selexol® process, 40 SEM, see Scanning electron microscopy (SEM) Semiconductor anode–semiconductor–QD layers, 271, 272 electrical circuit creation, 218 extrinsic, 210, 211 intrinsic, 210, 211 metal-oxide, 251, 252, 254 n-type material, 251, 254 p-type material, 251 PV device, 208, 210 Sequestration, 44 carbon, 287 CO2 storage, 44 mineralization problem, 45 Shale gas, 24 hydraulic fracturing, 25, 26 Shockley–Queisser limit, 215, 278 SILAR, see Successive ionic layer adsorption and reaction (SILAR) Silicon, 218 architecture, 218–219 materials, 219–220 thin “fingers” of solar, 219 Siloxanes, 331 Single-walled carbon nanotubes (SWCNT), 76, 95 Sintering aids, 180 SI units, 387 Size-exclusion chromatography (SEC), 68 Slick water, 25 SMR, see Steam reforming (SMR) Sodium-based batteries, 191, 192 cathode, 193, 194 electrolyte, 192–193 operation, 191 tin and nickel anodes SEM image, 194 SOFC systems, see Solid oxide fuel cell systems (SOFC systems) Soil, 288 Solar constant, 205 Solar fuel, 119 Solar photovoltaics, 205 band theory, 208–210 current–voltage curve, 213–218 CZTS cell, 277–279 Index Earth’s energy budget, 206 molecular orbital bands, 209 photoelectric effect, 208–210 photovoltaic, 277–279 solar panel array, 207 solar radiation spectrum, 206 solar thermal concentrator tower, 207 sustainability, 277–279 Solar radiation spectrum, 205, 206 Solid oxide fuel cell systems (SOFC systems), 142, 173, 176 Arrhenius plots, 178 electrodes, 175, 176 electrolytes, 176 fabrication and characterization, 179–180 fluorite crystal structure, 177 IGFC systems, 174 oxidation of CO, 175 perovskite unit cell, 177 reactions, 174, 175 stationary power sources, 173 Solid sorbents, 42, 43 Soybean oil transesterification, 343 SPEEK membrane, 158, 159 silated and cross-linked, 160 SPI, see Sufonated polyimides (SPI) SRE, see Steam reforming of ethanol (SRE) Steam reforming (SMR), 108 bioethanol, 110 ethanol steam reforming, 111 synthesis gas production and use, 108 WGS reaction, 109 Steam reforming of ethanol (SRE), 110, 111 STEM, see Scanning transmission electron microscopy (STEM) Step-growth polymerization, 71 green polycarbonate synthesis, 72 outcomes in, 78 PET synthesis, 71 styrene polymerization, 73 Straight-run fractions, 34 Strontium titanate(SrTiO3), 179 Structural oil trap, 23, 24 Styrene–butadiene rubber, 67 Styrene polymerization, 73 Subbituminous coal, 22 Successive ionic layer adsorption and reaction (SILAR), 272 Sucrose-laden biomass, 321 Sucrose, 291, 296, 322 Sufonated polyimides (SPI), 162, 165 Sulfonated poly(ether)ether ketone, 158 SWCNT, see Single-walled carbon nanotubes (SWCNT) Sweetening process, 36 Syngas, see Synthesis gas Synthesis gas, 47 415 Index T Tacticity, 83 TAG, see Triacylglyceride (TAG) Tail-to-tail (TT), 233 Tailing, 370 TALSPEAK, see Trivalent actinide–lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) Tar sands, 27 TCO, see Transparent conducting oxide (TCO) TEM, see Transmission electron microscopy (TEM) Tensile strength, 85, 95 TETA, see Triethylenetetramine (TETA) Tetrahydroazaborine, 132, 133 Thermal cracking, 34 Thermalization, 363 Thermochemical process, 301; see also Biomass gasification, 313–319 using plant biomass, 301 Thermodynamic(s), 55 Carnot efficiency, 57–61 cycles, 57 equation of state, 55 exergy, 62 first law of, 56–57 LCA, 62 state function, 56 state of system, 55 Thermoneutral cell potential, 143 THGE-PE, see 1,1,1-tris(p-hydroxyphenyl) ethane triglycidyl ether (THGE-PE) Thin-film silicon, 221 alloys, 222–225 CdS/CdTe solar cell, 225 CdTe, 225–226 chalcopyrite crystal structure, 223 CIGSe cells, 224 CIGS solar cell, 223, 224 copper indium selenide, 222–225 HIT cell, 221 p–i–n architecture, 222 Thorium reactor, 366–367 Titania (TiO2), 254 electron micrograph scanning, 258 inverse opal TiO2 scaffold, 259 surfactant and halide impact, 257 templated inverse opal TiO2 synthesis, 259 XRD results, 258 TOF, see Turnover frequency (TOF) Toluene 2, 4-diisocyanate, 77 Transition metal-catalyzed carbonate formation, 49 Transmission electron microscopy (TEM), 154 Transmutation, 356 Transparent conducting oxide (TCO), 218, 241, 251 Transuranic extraction (TRUEX), 373 Triacylglyceride (TAG), 335, 338 1H-1,2,4-triazole, 169 Triethylenetetramine (TETA), 91 1,1,1-tris(p-hydroxyphenyl) ethane triglycidyl ether (THGE-PE), 91 Trivalent actinide–lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK), 373 TRUEX, see Transuranic extraction (TRUEX) TT, see Tail-to-tail (TT) Turnover frequency (TOF), 103 Two-electron peroxide pathway, 151 Type I kerogen, 21, 22 U Unit conversions, 389–390 Updraft, 316 Uranium, 358, 366 depleted, 370–371 proton in, 368 reactor-grade, 368 Uranium oxide (UOX), 364, 367 Uranium production, 367; see also Nuclear energy enrichment, 368–369 fuel reprocessing and waste handling, 369–376 mining, 367–368 V Valence band (VB), 208 Vanadium redox flow battery, 195 Vertical axis wind turbine, 97 Vibrational spectroscopic techniques, 80 Vinyl ester polymer, 91 Vitrification, 371 Voltaic cells, see Electrochemical cells W “Waste” gas, 383 Waste handling, 369–370 depleted uranium, 370–371 fuel composition, 370 reprocessing technology, 371–376 Water, 11, 288 hydrogen production, 114–115 management, 156 microbial electrolysis, 115–116 photochemical electrolysis, 119–122 state of, 144–145 thermodynamic data, 144, 171 use and quality issues, 25 416 Water gas shift reaction (WGS reaction), 109 Wilkinson’s catalyst, 104, 105 Wind turbines, 88, 89 Wood alcohol, see Methanol Work, 1, 56 World primary energy supply, X X-ray diffraction (XRD), 154 X-ray photoelectron spectroscopy (XPS), 154 XAFS, see Extended x-ray absorption fine structure (XAFS) Index Y Yellowcake, 367 Young’s modulus, 86 Yttrium-stabilized zirconia (YSZ), 176 Z Z-scheme, 120 Zeolites, 34, 35 Zinc phthalocyanin DSSC dye, 263 Zircaloy, 364 Zirconia (ZrO2), 176 ZSM-5 zeolite framework, 311 ... of power (equivalent to 1 J/s), but a watt-hour (more familiarly, kilowatt hour, kWh) is the unit that reflects a quantity of energy The types of energy, the amount Chemistry of Sustainable Energy. .. individual survival energy to plow, energy to irrigate, energy to transport crops, energy to build for crop storage energy to support a new way of life The use of wind as a source of energy blew onto.. .Chemistry of Sustainable Energy Chemistry of Sustainable Energy Nancy E Carpenter CRC Press Taylor & Francis Group 6000 Broken

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  • Chemistry of Sustainable Energy

  • Contents

  • Acknowledgments

  • Author

  • Introduction

    • Suggested texts for additional general reading

  • 1 Energy Basics

    • 1.1 What Is Energy?

    • 1.2 Energy, Technology, and Sustainability

      • 1.2.1 What Does Sustainability Mean?

      • 1.2.2 Carbon Cycle

      • 1.2.3 Resource Availability

    • 1.3 Energy Units, Terms, and Abbreviations

    • 1.4 Electricity Generation and Storage

    • Other Resources

      • Books

      • Online Resources

    • References

  • 2 Fossil Fuels

    • 2.1 Formation of Oil and Gas

    • 2.2 Extraction of Fossil Fuels

      • 2.2.1 Conventional Petroleum

      • 2.2.2 Nonconventional Sources

        • 2.2.2.1 Shale Oil and Gas

        • 2.2.2.2 Heavy Oil

        • 2.2.2.3 Oil Sands

        • 2.2.2.4 Coal Bed Methane and Methane Hydrates

          • 2.2.2.4.1 Coal Bed Methane

          • 2.2.2.4.2 Methane Hydrates

    • 2.3 Refining

      • 2.3.1 Crude Petroleum

        • 2.3.1.1 Distillation

        • 2.3.1.2 Extraction

        • 2.3.1.3 Cracking

          • 2.3.1.3.1 Thermal Cracking

          • 2.3.1.3.2 Catalytic Cracking

          • 2.3.1.3.3 Hydrocracking

        • 2.3.1.4 Reforming

      • 2.3.2 Natural Gas

    • 2.4 Carbon Capture and Storage

      • 2.4.1 Capture and Separation

        • 2.4.1.1 Membrane Technology

        • 2.4.1.2 Ionic Liquids

        • 2.4.1.3 Solid Sorbents

      • 2.4.2 Conversion and Utilization

        • 2.4.2.1 Sequestration

        • 2.4.2.2 Utilization

    • 2.5 Summary

    • Other Resources

      • Books

      • Online Resources

      • Online Resources Related to Carbon Capture and Sequestration

    • References

  • 3 Thermodynamics

    • 3.1 Introduction

    • 3.2 First Law of Thermodynamics

    • 3.3 Second Law and Thermodynamic Cycles: the Carnot Efficiency

    • 3.4 Exergy and Life-Cycle Assessment

    • Other Resources

      • Books

    • References

  • 4 Polymers and Sustainable Energy

    • 4.1 Polymer Basics

    • 4.2 Synthesis

      • 4.2.1 Step-Growth Polymerization

      • 4.2.2 Chain-Growth Polymerization

      • 4.2.3 Block Copolymers and CO2 Separation

      • 4.2.4 Control in Polymer Synthesis

    • 4.3 Characterization of Polymers

    • 4.4 Polymer Properties

    • 4.5 Polymer Chemistry and Wind Energy

      • 4.5.1 Introduction

      • 4.5.2 Resins

      • 4.5.3 Reinforcing Fibers

      • 4.5.4 Carbon Nanotubes and Polymer Matrix Composites

    • 4.6 Green Chemistry

    • Other Resources

      • Books

      • Online Resources

    • References

  • 5 Catalysis and Hydrogen Production

    • 5.1 Catalysis

    • 5.2 Hydrogen Production

      • 5.2.1 Steam Reforming

      • 5.2.2 Aside: The Fischer–Tropsch Process

      • 5.2.3 Gasification

      • 5.2.4 Water and the Biological Production of Hydrogen

        • 5.2.4.1 Microbial Electrolysis of Water

        • 5.2.4.2 Hydrogenases

        • 5.2.4.3 Photochemical Electrolysis of Water

    • 5.3 Hydrogen Storage

      • 5.3.1 Metal–Organic Frameworks

      • 5.3.2 Metal Hydrides

      • 5.3.3 Other CHS Materials

    • Other Resources

      • Books

      • Online Resources

    • References

  • 6 Fuel Cells

    • 6.1 Introduction

      • 6.1.1 Fuel Cell Basics

      • 6.1.2 An Electrochemistry Review

    • 6.2 Thermodynamics and Fuel Cells

      • 6.2.1 Calculation of Cell Potential

      • 6.2.2 Cell Potential and Gibbs Free Energy

        • 6.2.2.1 State of Water

        • 6.2.2.2 Effect of Temperature and Pressure

    • 6.3 Efficiency and Fuel Cells

    • 6.4 Cell Performance: Where Do Inefficiencies Come From?

      • 6.4.1 Voltage, Current, and Power

      • 6.4.2 Polarization

      • 6.4.3 Exchange Current

      • 6.4.4 Cell Performance and Nernst Equation

    • 6.5 Fuel Cell Electrocatalysts

      • 6.5.1 Electrocatalysis

      • 6.5.2 Oxygen Reduction Reaction

      • 6.5.3 Characterization of Catalysts

    • 6.6 Polymer Electrolyte Membrane Fuel Cell

      • 6.6.1 Introduction

      • 6.6.2 General Considerations

        • 6.6.2.1 Membrane Electrode Assembly

        • 6.6.2.2 Water Management

      • 6.6.3 Polymer Development

        • 6.6.3.1 Perfluorosulfonic Acid Membranes

        • 6.6.3.2 Poly(Arylene Ether) Membranes

        • 6.6.3.3 Polyimides and Imidazoles

        • 6.6.3.4 Metal–Organic Frameworks

      • 6.6.4 Direct Methanol Fuel Cells

        • 6.6.4.1 Half-Cell Reactions

        • 6.6.4.2 DMFC Electrocatalysts

    • 6.7 Solid Oxide Fuel Cells

      • 6.7.1 Introduction

      • 6.7.2 Reactions

      • 6.7.3 Electrode and Electrolyte Materials

        • 6.7.3.1 Electrolytes

        • 6.7.3.2 Electrodes

      • 6.7.4 Fabrication and Characterization

    • 6.8 Microbial Fuel Cells

      • 6.8.1 Introduction

      • 6.8.2 Components

        • 6.8.2.1 Anode Fabrication

        • 6.8.2.2 Cathode Materials

    • 6.9 Fuel Cell Summary

    • 6.10 Electrochemical Energy Storage

      • 6.10.1 Lithium Ion Batteries

        • 6.10.1.1 Lithium–Sulfur Batteries

        • 6.10.1.2 Lithium–Air Batteries

      • 6.10.2 Sodium-Based Batteries

        • 6.10.2.1 Electrolyte

        • 6.10.2.2 Cathode

      • 6.10.3 Redox Flow Batteries

      • 6.10.4 Graphene

    • 6.11 Summary

    • Other Resources

      • Books

      • Online Resources

    • References

  • 7 Solar Photovoltaics

    • 7.1 Introduction

    • 7.2 Solar PV Basics

      • 7.2.1 Band Theory and the Photoelectric Effect

      • 7.2.2 Electrical Conduction in a PV Device

      • 7.2.3 Current–Voltage Curve and Efficiency

    • 7.3 Inorganic Solar Cells

      • 7.3.1 Silicon

        • 7.3.1.1 Architecture

        • 7.3.1.2 Materials

      • 7.3.2 Thin-Film Inorganic Solar Cells

        • 7.3.2.1 Thin-Film Silicon

        • 7.3.2.2 Copper Indium Selenide and Alloys

        • 7.3.2.3 Cadmium Telluride

    • 7.4 Organic Photovoltaics

      • 7.4.1 Introduction

      • 7.4.2 Mechanism

        • 7.4.2.1 HOMO–LUMO Gap

        • 7.4.2.2 Characterization of HOMO–LUMO Energy Levels

      • 7.4.3 Materials

        • 7.4.3.1 Donors

        • 7.4.3.2 Acceptors

      • 7.4.4 Architecture and Morphology

        • 7.4.4.1 Architecture

        • 7.4.4.2 Morphology

    • 7.5  Dye-Sensitized Solar Cells

      • 7.5.1 Introduction

      • 7.5.2 Architecture

      • 7.5.3 Mechanism

      • 7.5.4 Materials

        • 7.5.4.1 Metal Oxide

        • 7.5.4.2 Dye Sensitizer

        • 7.5.4.3 Redox Mediator

    • 7.6  Quantum Dot Solar Cells

      • 7.6.1 Introduction

      • 7.6.2 Architecture and Materials

        • 7.6.2.1 Semiconductor

        • 7.6.2.2 Quantum Dots

        • 7.6.2.3 Redox Mediator and Electrode Materials

      • 7.6.3 Mechanism

    • 7.7 Sustainability, Photovoltaics, and the CZTS Cell

    • 7.8 Conclusions

    • Other Resources

      • Books

      • Online Resources

    • References

  • 8 Biomass

    • 8.1 Introduction

      • 8.1.1 Carbon Neutrality

      • 8.1.2 Biomass Considerations

        • 8.1.2.1 Energy Density and Land Use

        • 8.1.2.2 Soil and Water

      • 8.1.3 What Is Biomass?

      • 8.1.4 What Are Biofuels?

      • 8.1.5 Some Basic Biochemistry

    • 8.2 Chemical Composition of Biomass

    • 8.3 Reactivity and Conversion Options

      • 8.3.1 Conversion Options

      • 8.3.2 General Reactivity Patterns

    • 8.4 Biomass Beginnings: Harvesting and Processing

      • 8.4.1 Drying

      • 8.4.2 Comminution

      • 8.4.3 Densification

    • 8.5 Thermochemical Processes

      • 8.5.1 Introduction

      • 8.5.2 Pyrolysis

        • 8.5.2.1 Introduction

        • 8.5.2.2 Process

        • 8.5.2.3 Product

        • 8.5.2.4 Pyrolysis Reactions

        • 8.5.2.5 Upgrading Bio-Oil

      • 8.5.3 Gasification

        • 8.5.3.1 Introduction

        • 8.5.3.2 Process Parameters and Reactor Design

          • 8.5.3.2.1 Feedstock and Pretreatment

          • 8.5.3.2.2 Temperature

          • 8.5.3.2.3 Gasification Agent

          • 8.5.3.2.4 Reactor Design

        • 8.5.3.3 Gasification Reactions

        • 8.5.3.4 Contaminants and Catalysis

      • 8.5.4 Conclusions

    • 8.6 Biochemical Processes

      • 8.6.1 Fermentation

        • 8.6.1.1 Fermentation of Starch

        • 8.6.1.2 Fermentation of Lignocellulosic Biomass

          • 8.6.1.2.1 Pretreatment

          • 8.6.1.2.2 Fermentation

      • 8.6.2 Anaerobic Digestion

        • 8.6.2.1 Biochemistry of Digestion

        • 8.6.2.2 Process and Parameters

        • 8.6.2.3 Landfill Gas

      • 8.6.3 Biodiesel

        • 8.6.3.1 Introduction

        • 8.6.3.2 Feedstocks

        • 8.6.3.3 Biochemistry of Fatty Acids

        • 8.6.3.4 Production and Catalysis

          • 8.6.3.4.1 Introduction

          • 8.6.3.4.2 Heterogeneous Basic Catalysis

          • 8.6.3.4.3 Heterogeneous Acidic Catalysis

          • 8.6.3.4.4 Bifunctional Catalysis

          • 8.6.3.4.5 Enzymatic Catalysis

          • 8.6.3.4.6 Lipases

          • 8.6.3.4.7 Immobilization

          • 8.6.3.4.8 Process Conditions

        • 8.6.3.5 Conclusions

    • 8.7 Summary

    • Other Resources

      • Books

      • Online Resources

    • References

  • 9 Nuclear Energy

    • 9.1 Introduction

    • 9.2 Nuclear Chemistry Basics

      • 9.2.1 General Chemistry Review

      • 9.2.2 Birth of Nuclear Energy

      • 9.2.3 Nuclear Reactors

        • 9.2.3.1 Conventional Nuclear Power

        • 9.2.3.2 Other Types of Nuclear Reactors

          • 9.2.3.2.1 Heavy Water Reactors

          • 9.2.3.2.2 Breeder Reactors

          • 9.2.3.2.3 Advanced Pressurized Water Reactors

          • 9.2.3.2.4 Thorium Reactors

    • 9.3 Uranium Production

      • 9.3.1 Uranium Mining

      • 9.3.2 Uranium Enrichment

      • 9.3.3 Fuel Reprocessing and Waste Handling

        • 9.3.3.1 Depleted Uranium

        • 9.3.3.2 Reprocessing Technologies

    • 9.4 Future of Nuclear Energy

      • 9.4.1 Generation IV Reactors

      • 9.4.2 Fusion

    • 9.5 Summary

    • Other Resources

      • Books

      • Online Resources

    • References

  • 10 Closing Remarks

    • References

  • Appendix I: SI Units and Prefixes

  • Appendix II: Unit Conversions

  • Appendix III: Electricity: Units and Equations

  • Appendix IV: Fossil Fuel Units and Abbreviations

  • Appendix V: Important Constants

  • Appendix VI: Acronyms

  • Index

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