Adsorption by Carbons: Novel Carbon Adsorbents
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Table of contents
- Table of Contentsvii
- Forewordxvii
- Prefacexxi
- List of Contributorsxxiii
- Part 1 Introduction1
- Chapter 1 Overview of Physical Adsorption by Carbons3
- 1.1 Introduction3
- 1.2 Physisorption on Nonporous Carbons5
- 1.3 Physisorption by Porous Carbons7
- 1.4 Concluding Remarks11
- References12
- Chapter 2 Overview of Carbon Materials in Relation to Adsorption15
- 2.1 Introduction15
- 2.2 Structures of Elemental Carbon: Carbon Allotropes and Polytypes17
- 2.3 The sp2 Carbon Forms: Graphitic, Graphitizable, and Nongraphitizable Carbons21
- 2.4 Structural Characterization of Carbon Materials: The Basic Structural Units and Their Stacking a24
- 2.4.1 Planar Orientation28
- 2.4.2 Axial Orientation30
- 2.4.3 Point Orientation34
- 2.4.4 Random Orientation36
- 2.5 Conclusions42
- Acknowledgments43
- References43
- Part 2 Fundamentals of Adsorption by Carbons51
- Chapter 3 Energetics of Gas Adsorption by Carbons: Thermodynamic Quantities53
- 3.1 Introduction53
- 3.2 Classical Thermodynamics54
- 3.3 Statistical Mechanics59
- 3.4 Thermodynamic Quantities and Experimental Results66
- 3.5 Conclusions71
- Acknowledgment71
- References72
- Chapter 4 Monte Carlo and Molecular Dynamics77
- 4.1 Introduction77
- 4.2 Overview of Computer Simulations78
- 4.2.1 Selecting the Model79
- 4.2.2 Initialization83
- 4.2.3 Generating Configurations83
- 4.2.4 Determining Properties from Configurations89
- 4.3 Conclusions97
- References98
- Chapter 5 Models of Porous Carbons103
- 5.1 Introduction103
- 5.2 Experimental Probes104
- 5.3 Molecular Models of Carbons106
- 5.3.1 Regular Porous Carbons106
- 5.3.2 Disordered Porous Carbons: Simple Geometric Models107
- 5.3.3 Disordered Carbons: More Realistic Models110
- 5.4 Adsorption, Diffusion, Reaction121
- 5.5 Conclusions127
- Acknowledgments128
- References128
- Chapter 6 The Reasons Behind Adsorption Hysteresis133
- 6.1 Introduction133
- 6.2 Capillary Condensation Hysteresis and the Kelvin Equation135
- 6.3 Hysteresis and Adsorption-Induced Strain of Adsorbents136
- 6.4 Low-Pressure Hysteresis137
- 6.5 Pore Network and Interconnectivity137
- 6.6 Some Peculiarities of the Adsorption Hysteresis for Carbonaceous Adsorbents138
- References140
- Chapter 7 The Surface Heterogeneity of Carbon and Its Assessment147
- 7.1 Introduction147
- 7.1.1 The Adsorptive Potential147
- 7.1.2 Thermodynamic Meaning of the Adsorption Potential149
- 7.2 Theoretical Background151
- 7.2.1 The Integral Equation of Adsorption151
- 7.2.2 Solving and Using the Integral Equation of Adsorption152
- 7.3 The Application of Density Functional Theory153
- 7.3.1 The Deconvolution Method154
- 7.4 Results for “Nonporous” Carbons156
- 7.4.1 Synthetic Graphitic Carbons157
- 7.4.2 Natural Graphites158
- 7.4.3 Carbon Blacks159
- 7.5 Activated Carbons160
- 7.5.1 Assumed Structure160
- 7.5.2 Example Applications of the Simple Model161
- 7.5.3 Advanced Activated Carbon Models163
- 7.6 Conclusions165
- References165
- Chapter 8 Wetting Phenomena167
- 8.1 Introduction167
- 8.2 Wetting on Carbon175
- 8.3 Conclusions180
- References181
- Chapter 9 Adsorbed Gases in Bundles of Carbon Nanotubes: Theory and Simulation187
- 9.1 Introduction187
- 9.2 Endohedral Adsorption190
- 9.2.1 General Remarks190
- 9.2.2 Axial-Phase Transition194
- 9.2.3 Other Endohedral Transitions196
- 9.3 Adsorption in Interstitial Channels198
- 9.4 External Surface202
- Acknowledgments206
- References206
- Chapter 10 Energetic Topography Effects211
- 10.1 Introduction211
- 10.2 The Adsorptive Energy Surface214
- 10.3 Generalized Gaussian Model216
- 10.4 Simulations on Ideal Heterogeneous Systems221
- 10.5 Comparison Test for the GGM223
- 10.6 Bivariate Model and Simulation Method225
- 10.7 Adsorption Results227
- 10.7.1 Repulsive Interactions227
- 10.7.2 Attractive Interactions228
- 10.8 Scaling Behavior and Temperature Dependence230
- 10.9 Conclusions233
- Acknowledgments234
- References234
- Part 3 Adsorption for Characterization of Carbon Materials237
- Chapter 11 Porous Texture Characterization from Gas–Solid Adsorption239
- 11.1 Introduction239
- 11.1.1 Carbon Structure240
- 11.2 Potential Models240
- 11.2.1 Fluid–Fluid Potential Models241
- 11.2.2 Solid–Fluid Potential Energy244
- 11.3 Classical Methods for Pore Characterization246
- 11.3.1 Barrett, Joyner, and Halenda Method246
- 11.3.2 Broekhoff–de Boer Method246
- 11.3.3 Dubinin Methods247
- 11.3.4 Horvath–Kawazoe Method and its Modifications248
- 11.3.5 Enhanced Potential Method of Do and Coworkers250
- 11.4 Density Functional Theory253
- 11.4.1 Introduction of DFT253
- 11.4.2 DFT Applications to Pores (Slit and Cylinder)255
- 11.5 Monte Carlo Simulations257
- 11.5.1 Ensembles Used in Simulations of Adsorption257
- 11.5.2 Monte Carlo Simulation for Slit Pores260
- 11.5.3 Monte Carlo Simulation for Cylindrical Pores261
- 11.6 Additional Features262
- 11.6.1 Energetic Heterogeneity262
- 11.6.2 Pore Shape, Length, and Connectivity262
- 11.6.3 Numerical Inversion for Determining PSD262
- 11.7 Conclusions263
- Acknowledgment264
- References264
- Chapter 12 Porous Texture and Surface Characterization from Liquid–Solid Interactions: Immersion C273
- 12.1 Introduction273
- 12.2 Immersion Calorimetry of Carbons into Pure Liquids274
- 12.2.1 Experimental274
- 12.2.2 Thermodynamics of Immersion280
- 12.2.3 Applications282
- 12.3 Characterization of Carbons by Adsorption from Solution289
- 12.3.1 Thermodynamics290
- 12.3.2 Applications295
- References297
- Chapter 13 Surface Chemical Characterization of Carbons from Adsorption Studies301
- 13.1 Introduction301
- 13.2 Hydrophilic Carbon Surfaces302
- 13.3 Surface Oxides of Carbon304
- 13.3.1 Generation of Surface Oxides304
- 13.3.2 Functional Carbon Groups306
- 13.4 Amphoteric Character of Carbons308
- 13.4.1 Adsorption of Bases308
- 13.4.2 Adsorption of Acids312
- 13.5 Electrokinetic Phenomena318
- 13.6 Effects on the Adsorption of Inorganic ions321
- References323
- Chapter 14 Adsorption on Fullerenes329
- 14.1 Introduction329
- 14.2 Adsorption for Porosity Characterization330
- 14.3 Adsorption in the Study of Surface Energetics: Nonreactive Permanent Gases332
- 14.4 Adsorption of Organic Gases and Vapors338
- 14.5 Oxygen Adsorption341
- 14.6 Adsorption Studies using IR Spectroscopy343
- 14.7 Hydrogen Adsorption: Gas Storage346
- 14.8 Adsorption from Solution: Environmental Applications351
- 14.9 Adsorption from Solution: Analytical Applications353
- 14.10 Adsorption from Solution: Colloidal and Biological Systems357
- 14.11 Conclusions359
- Acknowledgments359
- References359
- Chapter 15 Hydrogen Adsorption in Single-Walled Carbon Nanotubes369
- 15.1 Introduction369
- 15.2 Experiment, Simulation, and Theory of Hydrogen Storage370
- 15.2.1 Modeling of Physisorption with Classical Potentials371
- 15.2.2 Ab Initio Modeling of Physisorption379
- 15.2.3 Ab Initio Modeling of Chemisorption384
- 15.3 Quantum Sieving385
- 15.4 Phase Transition Phenomena391
- 15.5 Summary and Conclusions393
- Acknowledgments393
- References394
- Chapter 16 Adsorption on Carbon Nanotubes: Experimental Results403
- 16.1 Introduction403
- 16.2 Hydrogen Storage404
- 16.3 Adsorption of Rare Gases and Simple Molecular Species408
- 16.3.1 Methane409
- 16.3.2 Argon414
- 16.3.3 Helium417
- 16.3.4 Hydrogen419
- 16.3.5 Xenon420
- 16.3.6 Neon422
- 16.3.7 Tetrafluoromethane422
- 16.3.8 Nitrogen424
- 16.4 Conclusions425
- Acknowledgments426
- References426
- Chapter 17 Adsorption on Activated Carbon Fibers431
- 17.1 Introduction431
- 17.2 Preparation of ACFs433
- 17.3 Characterization of ACFs436
- 17.3.1 Adsorption on the ACF and Its Usefulness to Understand Micropore Characterization438
- 17.3.2 Understanding the Activation–Pore Structure Relationship of ACFs: Effect of Activating Agen444
- 17.4 Some Examples of ACF Applications447
- 17.5 Conclusions449
- Acknowledgments449
- References449
- Chapter 18 Adsorption on Ordered Porous Carbons455
- 18.1 Ordered Porous Carbons455
- 18.1.1 Synthesis of Ordered Porous Carbons455
- 18.1.2 Applications of Ordered Porous Carbons457
- 18.2 Characterization of Ordered Porous Carbon by Gas Adsorption458
- 18.2.1 General Features of the Nitrogen Adsorption Isotherms459
- 18.2.2 Determination of the Pore Size Distribution461
- 18.2.3 Adsorption Potential Distribution463
- 18.2.4 Verification of the Presence of Micropores by the α-plot Method469
- 18.2.5 Determination of the Specific Surface Area472
- 18.3 Conclusions474
- Acknowledgments474
- References475
- Chapter 19 Electrochemical Behavior of Carbon Materials479
- 19.1 A Brief Summary of Electrochemical Concepts479
- 19.1.1 The Electrochemical Interface479
- 19.1.2 Adsorption at Electrodes481
- 19.1.3 Relevant Kinetic Parameters482
- 19.2 Thermodynamic Data for Carbon Electrodes484
- 19.3 Relevant Characteristics of Carbon Electrode Materials485
- 19.3.1 Types of Carbons Used in Electrochemistry485
- 19.3.2 Structural Aspects486
- 19.3.3 Surface Free Radical States486
- 19.3.4 Double-layer Properties487
- 19.3.5 Roughness Factor489
- 19.3.6 Fractality490
- 19.3.7 Intercalation of Ions in Graphite490
- 19.4 Chemically Modified Electrodes and Supramolecular Configurations492
- 19.5 Electrochemical Kinetics on Carbon Electrodes in Aqueous Solutions494
- 19.5.1 Direct Electrode Processes494
- 19.5.2 Oxygen Electroreduction on Carbon Electrodes495
- 19.5.3 Oxygen Reduction on Macrocyclic Transition Metal Complexes on Graphite and Carbon Surfaces499
- 19.5.4 Oxygen, Hydrogen, and Chlorine Electrode Reactions499
- 19.6 Organic Electrochemistry at Carbon Electrodes501
- 19.7 Reactions on Biological Active Electrodes502
- 19.8 Corrosion Processes503
- 19.9 Carbon Electrodes in Molten Salts504
- 19.9.1 Cryolite-Al2O3 Melts504
- 19.9.2 Halides-containing Melts505
- 19.9.3 Oxygen-containing Melts506
- 19.10 Carbon Electrode Manufacturing Techniques506
- Acknowledgments507
- References507
- Chapter 20 Self-Assembled Monolayers on C(0001)513
- 20.1 Introduction513
- 20.2 Characteristic of the HOPG Substrate514
- 20.2.1 General Considerations514
- 20.2.2 Nanoscopy Characterization of HOPG516
- 20.3 Self-Assembled Submonolayers and Monolayers521
- 20.3.1 Alkane Adsorption on C(0001)521
- 20.3.2 Sulfur Atom Submonolayers on HOPG522
- 20.3.3 Alkanethiol Adsorption on C(0001)522
- Acknowledgments527
- References527
- Part 4 Applications of Adsorption by Carbons531
- Chapter 21 Removal of Inorganic Gases and VOCs on Activated Carbons533
- 21.1 Introduction533
- 21.2 Adsorption of Inorganic Gases534
- 21.2.1 Removal of Hydrogen Sulfide534
- 21.2.2 Removal of Sulfur Dioxide542
- 21.2.3 Adsorption of Hydrogen Cyanide545
- 21.2.4 Adsorption of NOx546
- 21.3 Adsorption of Volatile Organic Compounds549
- 21.4 Choice of Proper Carbon for a Desired Application553
- References556
- Chapter 22 Gas Separation and Storage by Activated Carbons565
- 22.1 Introduction565
- 22.2 Activated Carbons for Gas Separation and Purification567
- 22.3 Mechanisms of Gas Separation by Activated Carbons569
- 22.4 Examples of Gas Separation Processes570
- 22.4.1 Trace or Dilute Impurity Removal570
- 22.4.2 Production of Nitrogen from Air572
- 22.4.3 Production of Hydrogen and Carbon Dioxide from Reformer Off-Gas573
- 22.4.4 Nanoporous Carbon Membranes for Gas Separation578
- 22.4.5 Sorption–Reaction Process for Removal of Trace VOC581
- 22.4.6 Chemically Modified Activated Carbons for Gas Separation583
- 22.5 Adsorptive Process Design585
- 22.6 Storage of Natural Gas on Activated Carbons587
- 22.7 Conclusions589
- References590
- Chapter 23 Electrochemical Energy Storage593
- 23.1 Introduction593
- 23.2 Lithium Insertion in Carbon Materials595
- 23.2.1 Principle of a Li-ion Battery595
- 23.2.2 Properties of Nanostructured Carbon Anodes597
- 23.2.3 Mechanism of Reversible Li Insertion/Deinsertion in Disordered Carbons605
- 23.2.4 Conclusion607
- 23.3 Nanostructured Carbons as Components of Supercapacitor Electrodes607
- 23.3.1 General Properties of Supercapacitors607
- 23.3.2 Activated Carbons for Supercapacitor Application609
- 23.3.3 Mesoporous Carbons as Supercapacitor Electrodes613
- 23.3.4 Carbon Nanotubes – A Unique Electrode Component616
- 23.3.5 Conclusion621
- 23.4 General Conclusion and Perspectives621
- References623
- Chapter 24 Adsorption of Inorganic Species from Aqueous Solutions631
- 24.1 Introduction631
- 24.2 Metal Ion Removal632
- 24.2.1 Adsorption of Metal Ions by Virgin Activated Carbon633
- 24.2.2 Adsorption of Metal Ions onto Activated Carbon Preloaded with Organic Matter638
- 24.2.3 Saturation of Activated Carbon by Organic Matter and Metal Hydroxides639
- 24.3 Anion and Cation Removal640
- 24.4 Reaction Between Activated Carbon and Oxidants641
- 24.4.1 Direct Reaction with High Concentration Oxidants642
- 24.4.2 Reaction with Free Chlorine or Chlorine Dioxide642
- 24.4.3 Dechlorination–dechloramination644
- 24.5 Catalytic Reactions with Modified Activated Carbon645
- 24.5.1 Catalytic Reactions in the Presence of an Oxidant645
- 24.5.2 Metal or Metal Oxide Impregnation645
- 24.5.3 Applications of Photocatalysis646
- 24.5.4 Specific Treatment of Sulfide or Hydrogen Sulfide646
- 24.6 Conclusions and Trends647
- References647
- Chapter 25 Adsorption of Organic Solutes from Dilute Aqueous Solutions653
- 25.1 Introduction653
- 25.2 Factors that Control the Adsorption Process655
- 25.3 Adsorption of Nonelectrolytes658
- 25.4 Adsorption of Electrolytes660
- 25.5 Adsorption of Natural Organic Matter668
- 25.6 Adsorption of Bacteria671
- 25.7 Conclusions673
- References674
- Chapter 26 Adsorption from Aqueous Solutions: Water Purification679
- 26.1 Introduction679
- 26.1.1 Conventional Water Treatment Processes679
- 26.1.2 Adsorption Processes680
- 26.2 Factors Influencing the Application of Activated Carbon in Drinking Water Treatment681
- 26.2.1 Characteristics of the Adsorbent and Adsorbate681
- 26.2.2 Prediction of Adsorption Behavior684
- 26.2.3 Biological Removal687
- 26.2.4 Natural Organic Material688
- 26.3 Removal of Microcontaminants of Concern to the Drinking Water Industry689
- 26.3.1 Pesticides690
- 26.3.2 Industrial Chemicals693
- 26.3.3 Pharmaceuticals and Personal Care Products695
- 26.3.4 Algal Metabolites696
- 26.4 Removal of Natural Organic Material702
- 26.5 Conclusions703
- Acknowledgments704
- References704
- Chapter 27 Sorption of Viscous Organics by Macroporous Carbons711
- 27.1 Introduction711
- 27.2 Macropore Structure of Carbon Materials712
- 27.3 Sorption Capacity for Viscous Organics716
- 27.3.1 Heavy Oils716
- 27.3.2 Various Oils Other than Heavy Oils720
- 27.3.3 Biomedical Fluids721
- 27.4 Kinetics of Sorption722
- 27.5 Recovery of Heavy Oils727
- 27.6 Discussion731
- 27.7 Conclusions732
- Acknowledgments732
- References732
- Author Index735
- Subject Index737
This book covers the most significant aspects of adsorption by carbons, attempting to fill the existing gap between the fields of adsorption and carbonaceous materials. Both basic and applied aspects are presented. The first section of the book introduces physical adsorption and carbonaceous materials, and is followed by a section concerning the fundamentals of adsorption by carbons. This leads to development of a series of theoretical concepts that serve as an introduction to the following section in which adsorption is mainly envisaged as a tool to characterize the porous texture and surface chemistry of carbons. Particular attention is paid to some novel nanocarbons, and the electrochemistry of adsorption by carbons is also addressed. Finally, several important technological applications of gas and liquid adsorption by carbons in areas such as environmental protection and energy storage constitute the last section of the book.
- the first book to address the interplay between carbonaceous materials and adsorption
- includes important environmental applications, such as the removal of volatile organic compounds from polluted atmospheres
- covers both gas-solid and liquid-solid adsorption
- the first book to address the interplay between carbonaceous materials and adsorption
- includes important environmental applications, such as the removal of volatile organic compounds from polluted atmospheres
- covers both gas-solid and liquid-solid adsorption