Menu Expand
Bioelectrochemical Systems

Bioelectrochemical Systems

Korneel Rabaey | Lars Angenent | Uwe Schroder | Jurg Keller

(2009)

Additional Information

Book Details

Abstract

In the context of wastewater treatment, Bioelectrochemical Systems (BESs) have gained considerable interest in the past few years, and several BES processes are on the brink of application to this area. This book, written by a large number of world experts in the different sub-topics, describes the different aspects and processes relevant to their development. 
Bioelectrochemical Systems (BESs) use micro-organisms to catalyze an oxidation and/or reduction reaction at an anodic and cathodic electrode respectively. Briefly, at an anode oxidation of organic and inorganic electron donors can occur. Prime examples of such electron donors are waste organics and sulfides. At the cathode, an electron acceptor such as oxygen or nitrate can be reduced. The anode and the cathode are connected through an electrical circuit. If electrical power is harvested from this circuit, the system is called a Microbial Fuel Cell; if electrical power is invested, the system is called a Microbial Electrolysis Cell. 
The overall framework of bio-energy and bio-fuels is discussed. A number of chapters discuss the basics – microbiology, microbial ecology, electrochemistry, technology and materials development. The book continues by highlighting the plurality of processes based on BES technology already in existence, going from wastewater based reactors to sediment based bio-batteries. The integration of BESs into existing water or process lines is discussed. Finally, an outlook is provided of how BES will fit within the emerging biorefinery area. 


Table of Contents

Section Title Page Action Price
Half title 1
Series 2
Title 3
Copyright 4
Contents 5
Foreword 19
List of Contributors 21
Chapter 1: Bioelectrochemical Systems: a new approach towards environmental and industrial biotechnology 33
1.1 FUEL CELLS AND BIO-ELECTRICITY 33
1.2 UNDERLYING PRINCIPLES 37
1.2.1 Microorganisms and current 37
1.2.2 Microbial communities in BESs 38
1.2.3 From microbial metabolism to electrical current 39
1.3 MEASURING AND DEFINING PERFORMANCE 40
1.3.1 Measuring potentials 41
1.3.2 Rate based performance indicators 42
1.3.3 Efficiency based performance indicators 42
1.4 A PLETHORA OF APPLICATIONS 43
1.5 ACKNOWLEDGEMENTS 44
REFERENCES 45
Chapter 2: Microbial energy production from biomass 49
2.1 BIOMASS: SOLAR ENERGY STORED IN ORGANIC MATERIAL 49
2.2 THE ENERGY CONTENT OF BIOMASS 52
2.3 BIO-ALCOHOL PRODUCTION FROM BIOMASS 54
2.4 ANAEROBIC METHANOGENIC DIGESTION: WASTE STABILIZATION PLUS RENEWABLE ENERGY SOURCE 56
2.4.1 Process performance 56
2.4.2 The microbiology of methanogenesis 58
2.4.3 The importance of extracellular electron transfer in AD 59
2.4.4 Application of anaerobic digestion 61
2.4.4.1 Anaerobic Digestion (AD) for solid waste 61
2.4.4.2 AD for wastewater treatment 62
2.4.4.3 Overall benefits and constraints of anaerobic digestion 64
2.5 BIO-HYDROGEN PRODUCTION FROM BIOMASS 66
2.6 FUTURE PERSPECTIVES 67
REFERENCES 68
Chapter 3: Enzymatic fuel cells and their complementarities relative to BES/MFC 71
3.1 INTRODUCTION 71
3.2 SIMILARITIES BETWEEN TYPES OF MICROBIAL AND ENZYMATIC BIOFUEL CELLS 75
3.2.1 Bioreactor design 76
3.2.2 In-situ bioreactor style 76
3.2.3 Catalyst in anolyte solution 77
3.2.4 Immobilized catalyst and/or mediator 78
3.2.5 Direct electron transfer catalysts 78
3.3 CATALYST SOURCES FOR MET AND DET SYSTEMS 79
3.4 COMPARISON OF PROPERTIES OF MICROBIAL AND ENZYMATIC FUEL CELLS 80
3.5 ENZYMES EMPLOYED IN ENZYMATIC BIOFUEL CELLS 81
3.6 DEEP AND/OR COMPLETE OXIDATION OF FUEL 84
3.7 CONCLUSIONS 84
3.8 ACKNOWLEDGEMENTS 85
REFERENCES 85
Chapter 4: Shuttling via soluble compounds 91
4.1 INTRODUCTION 91
4.2 REDOX SHUTTLES 93
4.3 EARLY EXPERIMENTS 94
4.4 EXOGENOUS REDOX MEDIATORS 95
4.4.1 Artificial mediators 95
4.4.2 Natural redox mediators in the subsurface environment 96
4.5 ENDOGENOUS REDOX MEDIATORS 97
4.5.1 Known microbially produced redox mediators 99
4.5.1.1 Phenazines 99
4.5.1.2 Flavins 99
4.5.1.3 Quinones 100
4.5.1.4 Cytochromes and soluble enzymes 101
4.5.1.5 Melanin 101
4.5.1.6 Other mediators 101
4.5.2 Unidentified endogenous mediators 102
4.6 METHODS FOR IDENTIFICATION OF SOLUBLE REDOX SHUTTLES 102
4.6.1 Potentiostat-controlled electrochemical cells 103
4.6.2 Environmental conditions 103
4.6.3 Batch experiments 103
4.6.4 Media formulation 103
4.6.5 Electrochemical methods 103
4.6.6 Medium change 104
4.6.7 Chemical structure of the mediator 104
4.7 RELEVANCE OF SOLUBLE REDOX MEDIATORS SHUTTLE TO MICROBIAL METABOLISM 104
4.8 SOLUBLE REDOX SHUTTLES IN BIOELECTROCHEMICAL DEVICES 106
4.8.1 Microbial fuel cells 106
4.8.1.1 Biosensors 106
4.8.1.2 Electrodes modified with redox mediators 107
REFERENCES 107
Chapter 5: A survey of direct electron transfer from microbes to electronically active surfaces 113
5.1 INTRODUCTION 113
5.2 EXTRACELLULAR ELECTRON TRANSFER – MICROBIAL CONNECTIONS 114
5.2.1 Localized sites for membrane associated EET 115
5.2.1.1 Shewanella cytochromes 115
5.2.1.2 Geobacter cytochromes 117
5.2.2 Bacterial nanowires 119
5.2.2.1 Geobacter nanowires 120
5.2.2.2 Shewanella nanowires 120
5.2.2.3 Nanowires produced by other microorganisms 122
5.2.3 Nanowire characterization 122
5.2.3.1 Composition 123
5.2.3.2 Regulation 123
5.2.3.3 Conductivity 124
5.2.3.4 Function 125
5.2.3.5 Prevalence 125
5.3 ECOLOGICAL SIGNIFICANCE OF EXTRACELLULAR ELECTRON TRANSFER 125
REFERENCES 127
Chapter 6: Genetically modified microorganisms for bioelectrochemical systems 133
6.1 INTRODUCTION 133
6.2 EXTRACELLULAR RESPIRATION IN SHEWANELLA ONEIDENSIS AND GEOBACTER SULFURREDUCENS 134
6.3 SCIENTIFIC MOTIVATION FOR HETEROLOGOUS GENE EXPRESSION 137
6.4 METHODS AND CHALLENGES FOR HETEROLOGOUS GENE EXPRESSION IN E. COLI 139
6.5 BIOTECHNOLOGICAL APPLICATIONS – DESIGNING THE ‘SUPER BUG’ 142
6.5.1 The ‘super bug’ for BES applications 142
6.5.2 The ‘super bug’ for bioremediation applications 144
6.6 CLOSING REMARKS 145
6.7 ACKNOWLEDGEMENTS 145
REFERENCES 145
Chapter 7: Electrochemical losses 151
7.1 INTRODUCTION 151
7.2 INDIVIDUAL ELECTROCHEMICAL LOSSES 152
7.2.1 Activation polarization 153
7.2.1.1 Means to decrease the activation polarization 154
7.2.2 Ohmic polarization 154
7.2.2.1 Means to decrease the ohmic polarization 156
7.2.3 Concentration Polarization (Mass transfer and reaction polarization) 157
7.2.3.1 Means to decrease the concentration polarization 159
7.2.4 Reactant crossover – ‘internal currents’ 159
7.2.4.1 Means to decrease internal current losses 160
7.2.5 The pH splitting between anode and cathode 161
7.2.5.1 Means to prevent the pH splitting 161
7.3 METHODS 161
7.3.1 Experimental strategies for the recording of polarization plots 161
7.3.1.1 Current interrupt technique 162
7.4 CONCLUSIONS 163
REFERENCES 164
Chapter 8: Electrochemical techniques for the analysis of bioelectrochemical systems 167
Chapter 8.1: Cyclic voltammetry for the study of microbial electron transfer at electrodes 169
8.1.1 INTRODUCTION 169
8.1.2 TURNOVER VS. NON-TURNOVER VOLTAMMETRY EXPERIMENTS 172
8.1.2.1 General considerations 172
8.1.2.2 Voltammetry in the presence of substrates 173
8.1.2.3 Voltammetry in the absence of substrates 177
8.1.2.4 Concluding remarks 180
REFERENCES 180
Chapter 8.2: Importance of Tafel plots in the investigation of bioelectrochemical systems 185
8.2.1 INTRODUCTION 185
8.2.2 USE OF TAFEL PLOTS FOR PERFORMANCE EVALUATION OF MICROBIAL FUEL CELLS 188
8.2.2.1 Tafel plots for monitoring the electrocatalytic activity of anode materials toward microbial consortia 189
8.2.2.2 Tafel plots for examining charge transfer with microbial pure cultures 194
8.2.2.3 Estimating the maximum power production from Tafel plots 195
REFERENCES 197
Chapter 8.3: The use of electrochemical impedance spectroscopy (EIS) for the evaluation of the electrochemical properties of bioelectrochemical systems 201
8.3.1 INTRODUCTION 201
8.3.2 INSTRUMENTATION AND EXPERIMENTAL APPROACH 202
8.3.3 DISPLAY AND ANALYSIS OF EIS DATA 204
8.3.4 DETERMINATION OF KEY ELECTROCHEMICAL PARAMETERS FROM IMPEDANCE SPECTRA 207
8.3.5 APPLICATIONS OF ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY IN THE STUDY OF MFCS 208
8.3.5.1 Electrochemical characterization of anode and cathode properties 208
8.3.5.2 Determination and analysis of the internal resistance R⊂in 211
8.3.6 CONCLUSIONS 213
REFERENCES 213
Chapter 9: Materials for BES 217
9.1 INTRODUCTION 217
9.1.1 Electrode specific surface areas and material costs 219
9.2 ELECTRODE MATERIALS FOR MFCS 219
9.2.1 Anode 219
9.2.2 Cathode 221
9.2.3 Membranes 225
9.3 OTHER MATERIALS 229
9.3.1 Current collectors 229
9.3.2 Wires, resistors and loads 229
9.4 MATERIALS FOR MICROBIAL ELECTROLYSIS CELLS 230
9.5 CONCLUSIONS AND OUTLOOK 232
REFERENCES 233
Chapter 10: Technological factors affecting BES performance and bottlenecks towards scale up 237
10.1 INTRODUCTION 237
10.2 DESIGN CONSTRAINTS AS DETERMINED BY WASTEWATER APPLICATION 239
10.2.1 Footprint and energetic efficiency 239
10.2.2 Effect of conductivity 242
10.2.3 Effect of buffer capacity 244
10.2.4 Membrane separator or not 244
10.3 DESIGN CONSTRAINTS AS DETERMINED BY SCALE UP 245
10.3.1 Scale up and voltage losses 245
10.3.2 Hydrodynamics and mechanics 247
10.4 COSTS AND CHOICE OF MATERIALS 247
10.4.1 Material properties and costs 247
10.4.2 Anode 248
10.4.3 Cathode 249
10.4.4 Membranes 249
10.5 OVERCOMING DESIGN CONSTRAINTS 250
10.5.1 Constraints and solutions 250
REFERENCES 252
Chapter 11: Organics oxidation 257
11.1 INTRODUCTION 257
11.2 RESPIRATORY OXIDATION TO CARBON DIOXIDE 260
11.3 FERMENTATION AT MICROBIAL FUEL CELL ANODES 263
11.4 SYNTROPHY BETWEEN FERMENTERS AND ANODOPHILES 266
11.5 METHANOGENS COMPETE FOR FERMENTATION PRODUCTS 268
11.6 ELECTROCATALYTIC OXIDATION OF FERMENTATION PRODUCTS 269
11.7 SUMMARY 270
REFERENCES 271
Chapter 12: Conversion of sulfur species in bioelectrochemical systems 275
12.1 INTRODUCTION 275
12.2 PROPERTIES OF SULFUR SPECIES 276
12.2.1 Elemental sulfur 276
12.2.2 Sulfide and polysulfides 276
12.2.3 Sulfate and other oxyanions 277
12.2.4 Relationship of electrochemical potential and pH for sulfur species in aqueous systems 277
12.3 EXISTING SULFIDE AND SULFATE REMOVAL TECHNOLOGIES 279
12.3.1 Sulfide removal technologies 279
12.3.1.1 Physicochemical processes 280
12.3.1.2 Biological technologies 280
12.3.2 Sulfate removal technologies 281
12.3.3 Evaluation of existing technologies 281
12.4 ABIOTIC ELECTROCHEMICAL REMOVAL OF AQUEOUS SULFIDE 282
12.4.1 Introduction 282
12.4.2 Spontaneous sulfide oxidation and electricity generation 284
12.4.3 Final product of sulfide oxidation 284
12.4.4 Properties of electrodeposited sulfur 286
12.5 REMOVAL OF AQUEOUS SULFIDE IN BES 288
12.5.1 Introduction 288
12.5.2 Sulfide oxidation in a biotic cell 289
12.6 OUTLOOK 290
REFERENCES 291
Chapter 13: Chemically catalyzed cathodes in bioelectrochemical systems 295
13.1 INTRODUCTION 295
13.2 OXYGEN REDUCTION REACTION (ORR) 297
13.2.1 Introduction 297
13.2.2 Oxygen reduction catalysts 299
13.2.2.1 Platinum 299
13.2.2.2 Transition metal macrocycle based catalysts 300
13.2.2.3 Metal oxides 300
13.2.2.4 Enzymes 301
13.2.3 MFC cathode configurations 301
13.2.3.1 Aqueous cathodes 301
13.2.3.2 Air cathodes 301
13.3 HYDROGEN EVOLUTION REACTION (HER) 302
13.3.1 Introduction 302
13.3.2 Hydrogen evolution catalysts 306
13.3.2.1 Platinum 306
13.3.2.2 Nickel 308
13.3.2.3 Tungsten carbide 308
13.3.2.4 Enzymes 309
13.3.3 MEC cathode configurations 309
13.3.3.1 Aqueous cathodes 309
13.3.3.2 Gas diffusion cathodes 310
13.4 FUTURE POSSIBILITIES 311
REFERENCES 312
Chapter 14: Bioelectrochemical reductions in reactor systems 317
14.1 INTRODUCTION 317
14.2 AEROBIC BIOCATHODES 318
14.3 ANOXIC AND ANAEROBIC BIOCATHODES 321
14.4 ELECTRON TRANSFER IN BIOCATHODES 326
14.5 LIMITING FACTORS 329
14.6 OUTLOOK 330
14.7 ACKNOWLEDGEMENTS 331
REFERENCES 331
Chapter 15: Bioelectrochemical systems (BES) for subsurface remediation 337
15.1 BIOREMEDIATION OF CONTAMINATED SOILS AND AQUIFERS 337
15.2 CHEMICAL VS. ELECTROCHEMICAL STRATEGIES OF ELECTRON DELIVERY 338
15.2.1 Chlorinated hydrocarbons 341
15.2.2 Inorganic pollutants 347
15.3 OUTLOOKS, PERSPECTIVES, AND CHALLENGES TOWARDS FIELD APPLICATIONS 351
REFERENCES 354
Chapter 16: Fundamentals of benthic microbial fuel cells: theory, development and application 359
16.1 INTRODUCTION 359
16.2 FUNDAMENTAL PRINCIPLES OF SEDIMENT REDUCTION-OXIDATION CHEMISTRY 360
16.3 PRINCIPLES OF DESIGN AND APPROACHES TO TESTING BENTHIC MICROBIAL FUEL CELLS (BMFCs) 361
16.4 ANODE MATERIAL AND DESIGN 362
16.5 CATHODE MATERIALS AND DESIGN 364
16.6 PERFORMANCE AND PRACTICAL CONSIDERATIONS OF BMFC DESIGNS 365
16.7 MICROBIAL ECOLOGY OF BMFCs 367
16.8 FACTORS GOVERNING POWER OUTPUT 370
16.9 SCALING AND ENVIRONMENTAL VARIABILITY IN BMFCs 372
16.10 COMMERCIAL VIABILITY OF BMFCs 373
REFERENCES 375
Chapter 17: Microbial fuel cells as biochemical oxygen demand (BOD) and toxicity sensors 379
17.1 INTRODUCTION 379
17.1.1 Dissolved oxygen probe-based BOD sensors 380
17.1.2 Photometric BOD sensors 380
17.1.3 Titration and respirometric sensors 381
17.1.4 Electrochemical BOD sensors with mediators 381
17.2 THE MEDIATOR-LESS MICROBIAL FUEL CELL 383
17.2.1 Electrochemically-active bacteria 383
17.2.2 Enrichment of an electrochemically-active bacterial community 384
17.2.3 Microbiology of a mediator-less MFC 385
17.2.4 Optimization of MFC performance 385
17.3 DESIGN AND PERFORMANCE OF AN MFC USED AS BOD SENSOR 387
17.3.1 MFC to measure BOD values higher than 10 mg/L 388
17.3.1.1 MFC design 388
17.3.1.2 Enrichment and operation 389
17.3.1.3 Performance 390
17.3.2 MFC to measure BOD values lower than 10 mg/l 391
17.3.2.1 Background 391
17.3.2.2 Oligotrophic sensor design and performance 391
17.3.3 BOD determination of samples containing oxygen and nitrate 392
17.3.3.1 Oxygen and nitrate reduce current and coulombic efficiency 392
17.3.3.2 Use of respiratory inhibitors 392
17.4 MFC AS A TOXICITY SENSOR 393
17.5 CONCLUSIONS 393
17.6 ACKNOWLEDGEMENTS 393
REFERENCES 394
Chapter 18: Feedstocks for BES conversions 401
18.1 INTRODUCTION 401
18.2 DEFINED SUBSTRATES UTILIZED BY BES 404
18.2.1 Volatile fatty acids and other fermentation end products 404
18.2.2 Soluble carbohydrates, amino acids and xenobiotics 408
18.3 COMPLEX SUBSTRATES AND WASTEWATERS UTILIZED BY BES 409
18.3.1 Cellulosic feedstocks 410
18.3.2 Chitin 411
18.3.3 Domestic wastewater 411
18.3.4 Simulated and actual industrial wastewaters 411
18.4 OTHER ASPECTS OF FEEDSTOCK COMPOSITION 413
18.5 FEEDSTOCKS AND BES INTEGRATION IN WASTEWATER TREATMENT PROCESSES 415
18.6 CONCLUSIONS 419
18.7 ACKNOWLEDGEMENTS 420
REFERENCES 420
Chapter 19: Integrating BES in the wastewater and sludge treatment line 425
19.1 INTRODUCTION 425
19.2 BES AS THE SINGLE BIOLOGICAL TREATMENT UNIT (A) OR FOLLOWED BY AN ACTIVATED SLUDGE SYTEM AS A POLISHING STEP (B) 428
19.3 PREACIDIFICATION OF ORGANIC WASTEWATER BEFORE BES (C) 430
19.4 ANAEROBIC DIGESTERS FOR SLUDGE STABILIZATION FOLLOWED BY BES (D) 431
19.5 GENERATING CAUSTIC IN THE CATHODE OF BES TO CONTROL ANAEROBIC DIGESTER pH (E) 433
19.6 DENITRIFICATON IN THE CATHODE OF BES TO REMOVE NUTRIENTS FROM WATER (F) 434
19.7 GENERATING CHEMICAL REAGENTS AT CATHODES FOR TREATMENT PURPOSES (G) 435
19.8 OUTLOOK 436
19.9 ACKNOWLEDGEMENTS 437
REFERENCES 437
Chapter 20: Peripherals of BES – small scale yet feasible (demonstrated) applications 441
20.1 INTRODUCTION 441
20.2 ARTIFICIAL SYMBIOSIS 442
20.3 MICROBIAL FUEL CELLS AND THEIR CONFIGURATIONS 443
20.3.1 Definition of peripherals 443
20.3.2 Bridging the power divide 444
20.3.3 Minimal peripheral requirements for continuous and autonomous operation 447
20.3.4 Complexity in stacks 448
20.3.5 Microbial Electrolysis Cells (MECs) that transform organic feedstocks into other types of energy (hydrogen or methane) but require input of electrical power in the process 451
20.3.6 Microbial Electrolysis Cells (MECs) that consume electrical power to drive useful reactions (e.g. denitrification) 452
REFERENCES 452
Chapter 21: Towards a mathematical description of bioelectrochemical systems 455
21.1 INTRODUCTION 455
21.2 MATHEMATICAL MODELLING 456
21.2.1 Model characteristics 457
21.2.1.1 Mechanistics vs. empirism 457
21.2.1.2 Dynamic vs. stationary models 458
21.2.1.3 Level of segregation/aggregation 458
21.2.2 How do model characteristics affect the model user? 459
21.3 BESs MODELLING OBJECTIVES 459
21.4 KEY ELEMENTS FOR BESs MODELLING 461
21.5 EXISTING BESs MODELS 461
21.6 CURRENT CHALLENGES IN BESs MODELLING 468
21.6.1 Bioelectrode kinetics 469
21.6.2 Electron transfer mechanisms 471
21.6.3 Microbial activity: bioenergetics and kinetics 472
21.6.4 Mass transport – convection, diffusion and migration 475
21.6.5 Biofilm and spatial modelling 476
21.7 BESs MODELLING PERSPECTIVES 477
21.8 ACKNOWLEDGEMENTS 478
REFERENCES 478
Outlook: Research directions and new applications for BES 481
22.1 BES RESEARCH – FOCUS ON THE APPLICATION 481
22.2 FUNDAMENTAL RESEARCH DIRECTIONS 482
22.2.1 Understanding bioelectrochemical process fundamentals 482
22.2.2 Practically inspired fundamental research areas 484
22.3 APPLIED RESEARCH OPPORTUNITIES 485
22.3.1 Contributions and limitations of current research activities 485
22.3.2 BESs for wastewater treatment? 487
22.3.3 Is power the best product from BESs? 488
22.4 POTENTIAL NEW BES APPLICATIONS 489
22.4.1 Novel options for cathodic reductions 489
22.4.2 Novel options for anodic oxidations 491
22.5 BES INTEGRATION INTO PRACTICAL APPLICATIONS 491
22.6 CONCLUDING THOUGHTS ON THE FUTURE OF BES 493
REFERENCES 494
Index 499