Preface to the First Edition |
|
xiii | |
Preface to the Second Edition |
|
xv | |
|
|
xvii | |
|
|
1 | (24) |
|
|
|
|
|
|
1.1 The Importance of Adsorption |
|
|
1 | (1) |
|
|
2 | (4) |
|
1.3 General Definitions and Terminology |
|
|
6 | (5) |
|
1.4 Physisorption and Chemisorption |
|
|
11 | (1) |
|
1.5 Types of Adsorption Isotherms |
|
|
11 | (4) |
|
1.5.1 Classification of Gas Physisorption Isotherms |
|
|
11 | (3) |
|
1.5.2 Chemisorption of Gases |
|
|
14 | (1) |
|
1.5.3 Adsorption from Solution |
|
|
14 | (1) |
|
1.6 Energetics of Physisorption and Molecular Modelling |
|
|
15 | (6) |
|
1.7 Diffusion of Adsorbate |
|
|
21 | (4) |
|
|
22 | (3) |
|
2 Thermodynamics of Adsorption at the Gas/Solid Interface |
|
|
25 | (32) |
|
|
|
|
|
26 | (1) |
|
2.2 Quantitative Expression of Adsorption of a Single gas |
|
|
27 | (6) |
|
2.2.1 Adsorption up to 1 bar |
|
|
27 | (3) |
|
2.2.2 Adsorption Above 1 bar and Much Higher |
|
|
30 | (3) |
|
2.3 Thermodynamic Potentials of Adsorption |
|
|
33 | (5) |
|
2.4 Thermodynamic Quantities Related to the Adsorbed States in the Gibbs Representation |
|
|
38 | (2) |
|
2.4.1 Definitions of the Molar Surface Excess Quantities |
|
|
38 | (1) |
|
2.4.2 Definitions of the Differential Surface Excess Quantities |
|
|
39 | (1) |
|
2.5 Thermodynamic Quantities Related to the Adsorption Process |
|
|
40 | (5) |
|
2.5.1 Definitions of the Differential Quantities of Adsorption |
|
|
40 | (2) |
|
2.5.2 Definitions of the Integral Molar Quantities of Adsorption |
|
|
42 | (1) |
|
2.5.3 Advantages and Limitations of Differential and Integral Molar Quantities of Adsorption |
|
|
43 | (1) |
|
2.5.4 Evaluation of Integral Molar Quantities of Adsorption |
|
|
44 | (1) |
|
2.6 Indirect Derivation of the Quantities of Adsorption from of a Series of Experimental Physisorption Isotherms: The Isosteric Method |
|
|
45 | (3) |
|
2.6.1 Differential Quantities of Adsorption |
|
|
45 | (2) |
|
2.6.2 Integral Molar Quantities of Adsorption |
|
|
47 | (1) |
|
2.7 Derivation of the Adsorption Quantities from Calorimetric Data |
|
|
48 | (2) |
|
2.7.1 Discontinuous Procedure |
|
|
48 | (1) |
|
2.7.2 Continuous Procedure |
|
|
49 | (1) |
|
2.8 Other Methods for the Determination of Differential Enthalpies of Adsorption |
|
|
50 | (1) |
|
2.8.1 Immersion Calorimetry |
|
|
50 | (1) |
|
2.8.2 The Chromatographic Method |
|
|
51 | (1) |
|
2.9 State Equations for High Pressure: Single Gases and Mixtures |
|
|
51 | (6) |
|
|
52 | (2) |
|
2.9.2 Case of Gas Mixtures |
|
|
54 | (1) |
|
|
55 | (2) |
|
3 Methodology of Gas Adsorption |
|
|
57 | (48) |
|
|
|
|
58 | (1) |
|
3.2 Determination of the Surface Excess Amount (and Amount Adsorbed) |
|
|
59 | (29) |
|
3.2.1 Gas Adsorption Manometry (Measurement of Pressure Only) |
|
|
59 | (8) |
|
3.2.2 Gas Adsorption Gravimetry (Measurement of Mass and Pressure) |
|
|
67 | (3) |
|
3.2.3 Gas Adsorption with Gas Flow Control or Monitoring |
|
|
70 | (5) |
|
|
75 | (1) |
|
3.2.5 Calibration Procedures and Corrections |
|
|
76 | (10) |
|
3.2.6 Other Critical Aspects |
|
|
86 | (2) |
|
3.3 Gas Adsorption Calorimetry |
|
|
88 | (8) |
|
3.3.1 Equipment Available |
|
|
88 | (5) |
|
3.3.2 Calorimetric Procedures |
|
|
93 | (3) |
|
|
96 | (4) |
|
3.4.1 Aim of the Outgassing |
|
|
96 | (1) |
|
3.4.2 Conventional Vacuum Outgassing |
|
|
96 | (2) |
|
3.4.3 Controlled Vacuum Outgassing by CRTA |
|
|
98 | (2) |
|
3.4.4 Outgassing with a Carrier Gas |
|
|
100 | (1) |
|
3.5 Presentation of Experimental Data |
|
|
100 | (5) |
|
|
101 | (1) |
|
3.5.2 Experimental Conditions |
|
|
101 | (1) |
|
3.5.3 Surface Excess Amounts |
|
|
101 | (1) |
|
|
102 | (3) |
|
4 Adsorption at the Liquid-Solid Interface: Thermodynamics and Methodology |
|
|
105 | (54) |
|
|
|
|
106 | (1) |
|
4.2 Energetics of Immersion of Solid in Pure Liquid |
|
|
107 | (26) |
|
4.2.1 Thermodynamic Background |
|
|
107 | (10) |
|
4.2.2 Experimental Techniques of Immersion Microcalorimetry in Pure Liquid |
|
|
117 | (6) |
|
4.2.3 Applications of Pure Liquid Immersion Microcalorimetry |
|
|
123 | (10) |
|
4.3 Adsorption from Liquid Solution |
|
|
133 | (26) |
|
4.3.1 Quantitative Expression of the Amounts Adsorbed from a Binary Solution |
|
|
134 | (6) |
|
4.3.2 Quantitative Expression of the Energies Involved in Adsorption from Solution |
|
|
140 | (2) |
|
4.3.3 Basic Experimental Methods for the Study of Adsorption from Solution |
|
|
142 | (7) |
|
4.3.4 Applications of Adsorption from Solution |
|
|
149 | (5) |
|
|
154 | (5) |
|
5 Classical Interpretation of Physisorption Isotherms at the Gas-Solid Interface |
|
|
159 | (32) |
|
|
|
|
|
160 | (1) |
|
5.2 Adsorption of a Pure Gas |
|
|
160 | (23) |
|
5.2.1 Equations Related to the Gibbs Adsorption Equation: Description of the Adsorbed Phase on Available Surface or in Micropores |
|
|
160 | (4) |
|
5.2.2 The Langmuir Theory |
|
|
164 | (2) |
|
5.2.3 Multilayer Adsorption |
|
|
166 | (8) |
|
5.2.4 The Dubinin-Stoeckli Theory: Filling of Micropores |
|
|
174 | (3) |
|
5.2.5 Type VI Isotherms: Phase Changes in Physisorbed Layers |
|
|
177 | (4) |
|
5.2.6 Empirical Isotherm Equations |
|
|
181 | (2) |
|
5.3 Adsorption of a Gas Mixture |
|
|
183 | (3) |
|
5.3.1 Extended Langmuir Model |
|
|
183 | (2) |
|
5.3.2 Ideal Adsorbed Solution Theory |
|
|
185 | (1) |
|
|
186 | (5) |
|
|
187 | (4) |
|
6 Modelling of Physisorption in Porous Solids |
|
|
191 | (46) |
|
|
|
192 | (1) |
|
6.2 Microscopic Description of the Porous Solids |
|
|
193 | (1) |
|
6.2.1 Crystalline Materials |
|
|
193 | (1) |
|
6.2.2 Non-Crystalline Materials |
|
|
194 | (1) |
|
6.3 Intermolecular Potential Function |
|
|
194 | (7) |
|
6.3.1 General Expression of the Pairwise Adsorbate/Adsorbent Interactions |
|
|
194 | (3) |
|
6.3.2 Common Strategy for `Simple' Adsorbate/Adsorbent System |
|
|
197 | (2) |
|
6.3.3 Cases of More `Complex' Adsorbate/Adsorbent System |
|
|
199 | (2) |
|
6.4 Characterization Computational Tools |
|
|
201 | (4) |
|
|
201 | (1) |
|
6.4.2 Accessible Specific Surface Area |
|
|
202 | (2) |
|
|
204 | (1) |
|
6.5 Modelling of Adsorption in Porous Solids |
|
|
205 | (20) |
|
|
205 | (15) |
|
6.5.2 Quantum Chemical Calculations |
|
|
220 | (5) |
|
6.6 Modelling of Diffusion in Porous Solids |
|
|
225 | (6) |
|
|
225 | (1) |
|
6.6.2 Single Component Diffusion |
|
|
226 | (4) |
|
6.6.3 Gas Mixture Diffusion |
|
|
230 | (1) |
|
6.7 Conclusions and Future Challenges |
|
|
231 | (6) |
|
|
233 | (4) |
|
7 Assessment of Surface Area by Gas Adsorption |
|
|
237 | (32) |
|
|
|
237 | (2) |
|
|
239 | (14) |
|
|
239 | (1) |
|
|
239 | (3) |
|
7.2.3 Validity of the BET Monolayer Capacity |
|
|
242 | (2) |
|
7.2.4 The BET Area of Non-porous and Mesoporous Adsorbents |
|
|
244 | (5) |
|
7.2.5 The BET Area of Microporous Solids |
|
|
249 | (2) |
|
7.2.6 BET Areas - Some Applications |
|
|
251 | (2) |
|
7.3 Empirical Methods for Isotherm Analysis |
|
|
253 | (5) |
|
7.3.1 Standard Adsorption Isotherms |
|
|
253 | (1) |
|
|
254 | (1) |
|
|
255 | (3) |
|
|
258 | (1) |
|
|
258 | (5) |
|
7.5 Conclusions and Recommendations |
|
|
263 | (6) |
|
|
264 | (5) |
|
8 Assessment of Mesoporosity |
|
|
269 | (34) |
|
|
|
|
|
|
269 | (1) |
|
8.2 Mesopore Volume, Porosity and Mean Pore Size |
|
|
270 | (3) |
|
|
270 | (2) |
|
|
272 | (1) |
|
8.2.3 Hydraulic Radius and Mean Pore Size |
|
|
272 | (1) |
|
8.3 Capillary Condensation and the Kelvin Equation |
|
|
273 | (5) |
|
8.3.1 Derivation of the Kelvin Equation |
|
|
273 | (2) |
|
8.3.2 Application of the Kelvin Equation |
|
|
275 | (3) |
|
8.4 Classical Computation of the Mesopore Size Distribution |
|
|
278 | (6) |
|
|
278 | (1) |
|
8.4.2 Computation Procedure |
|
|
279 | (3) |
|
8.4.3 The Multilayer Thickness |
|
|
282 | (1) |
|
8.4.4 Validity of the Kelvin Equation |
|
|
282 | (2) |
|
8.5 DFT Computation of the Mesopore Size Distribution |
|
|
284 | (6) |
|
|
284 | (3) |
|
8.5.2 Nitrogen Adsorption at 77 K |
|
|
287 | (2) |
|
8.5.3 Argon Adsorption at 87 K |
|
|
289 | (1) |
|
|
290 | (7) |
|
8.7 Conclusions and Recommendations |
|
|
297 | (6) |
|
|
298 | (5) |
|
9 Assessment of Microporosity |
|
|
303 | (18) |
|
|
|
|
|
|
303 | (3) |
|
9.2 Gas Physisorption Isotherm Analysis |
|
|
306 | (8) |
|
|
306 | (1) |
|
9.2.2 Dubinin-Radushkevich-Stoeckli Methods |
|
|
307 | (2) |
|
9.2.3 The Horvath-Kawazoe (HK) Method |
|
|
309 | (1) |
|
9.2.4 Density Functional Theory |
|
|
310 | (2) |
|
9.2.5 Nonane Pre-adsorption |
|
|
312 | (1) |
|
9.2.6 Choice of Adsorptive and Temperature |
|
|
313 | (1) |
|
9.3 Microcalorimetric Methods |
|
|
314 | (3) |
|
9.3.1 Immersion Microcalorimetry |
|
|
314 | (3) |
|
9.3.2 Gas Adsorption Microcalorimetry |
|
|
317 | (1) |
|
9.4 Conclusions and Recommendations |
|
|
317 | (4) |
|
|
318 | (3) |
|
10 Adsorption by Active Carbons |
|
|
321 | (72) |
|
|
|
322 | (1) |
|
10.2 Active Carbons: Preparation, Properties and Applications |
|
|
323 | (16) |
|
|
323 | (2) |
|
10.2.2 Fullerenes and Nanotubes |
|
|
325 | (3) |
|
|
328 | (2) |
|
|
330 | (4) |
|
10.2.5 Superactive Carbons |
|
|
334 | (1) |
|
10.2.6 Carbon Molecular Sieves |
|
|
335 | (1) |
|
|
336 | (1) |
|
|
337 | (1) |
|
10.2.9 Carbon Aerogels and OMCs |
|
|
338 | (1) |
|
10.3 Physisorption of Gases by Non-Porous Carbons |
|
|
339 | (10) |
|
10.3.1 Adsorption of Nitrogen and Carbon Dioxide on Carbon Blacks |
|
|
339 | (6) |
|
10.3.2 Adsorption of the Noble Gases |
|
|
345 | (3) |
|
10.3.3 Adsorption of Organic Vapours |
|
|
348 | (1) |
|
10.4 Physisorption of Gases by Porous Carbons |
|
|
349 | (25) |
|
10.4.1 Adsorption of Argon, Nitrogen and Carbon Dioxide |
|
|
349 | (12) |
|
10.4.2 Adsorption of Organic Vapours |
|
|
361 | (5) |
|
10.4.3 Adsorption of Water Vapour |
|
|
366 | (6) |
|
10.4.4 Adsorption of Helium |
|
|
372 | (2) |
|
10.5 Adsorption at the Carbon-Liquid Interface |
|
|
374 | (4) |
|
10.5.1 Immersion Calorimetry |
|
|
374 | (2) |
|
10.5.2 Adsorption from Solution |
|
|
376 | (2) |
|
10.6 LPH and Adsorbent Deformation |
|
|
378 | (4) |
|
|
378 | (1) |
|
|
379 | (1) |
|
10.6.3 Low-Pressure Hysteresis |
|
|
380 | (1) |
|
10.6.4 Expansion and Contraction |
|
|
381 | (1) |
|
10.7 Characterization of Active Carbons: Conclusions and Recommendations |
|
|
382 | (11) |
|
|
383 | (10) |
|
11 Adsorption by Metal Oxides |
|
|
393 | (74) |
|
|
|
|
|
394 | (1) |
|
|
394 | (21) |
|
11.2.1 Pyrogenic and Crystalline Silicas |
|
|
394 | (9) |
|
11.2.2 Precipitated Silicas |
|
|
403 | (2) |
|
|
405 | (10) |
|
11.3 Aluminas: Structure, Texture and Physisorption |
|
|
415 | (14) |
|
11.3.1 Introduction to Activated Aluminas |
|
|
415 | (1) |
|
11.3.2 Starting Materials |
|
|
416 | (3) |
|
11.3.3 Thermal Decomposition of Hydrated Aluminas |
|
|
419 | (6) |
|
11.3.4 Resulting Activated Aluminas |
|
|
425 | (4) |
|
11.4 Titanium Dioxide Powders and Gels |
|
|
429 | (9) |
|
11.4.1 Titanium Dioxide Pigments |
|
|
429 | (2) |
|
11.4.2 Rutile: Surface Chemistry and Gas Adsorption |
|
|
431 | (5) |
|
11.4.3 The Porosity of Titania Gels |
|
|
436 | (2) |
|
|
438 | (6) |
|
11.5.1 Physisorption of Non-polar Gases on Non-porous MgO |
|
|
438 | (2) |
|
11.5.2 Physisorption by Porous Forms of MgO |
|
|
440 | (4) |
|
11.6 Miscellaneous Oxides |
|
|
444 | (13) |
|
11.6.1 Chromium Oxide Gels |
|
|
444 | (3) |
|
11.6.2 Ferric Oxide: Thermal Decomposition of FeOOH |
|
|
447 | (2) |
|
11.6.3 Micro-crystalline Zinc Oxide |
|
|
449 | (2) |
|
11.6.4 Hydrous Zirconia Gels |
|
|
451 | (2) |
|
|
453 | (2) |
|
|
455 | (2) |
|
11.7 Applications of Adsorbent Properties of Metal Oxides |
|
|
457 | (10) |
|
11.7.1 Applications as Gas Adsorbents and Desiccants |
|
|
457 | (1) |
|
11.7.2 Applications as Gas Sensors |
|
|
458 | (1) |
|
11.7.3 Applications as Catalysts and Catalyst Supports |
|
|
458 | (1) |
|
11.7.4 Applications as Pigments and Fillers |
|
|
459 | (1) |
|
11.7.5 Applications in Electronics |
|
|
459 | (1) |
|
|
460 | (7) |
|
12 Adsorption by Clays, Pillared Clays, Zeolites and Aluminophosphates |
|
|
467 | (62) |
|
|
|
|
|
468 | (1) |
|
12.2 Structure, Morphology and Adsorbent Properties of Layer Silicates |
|
|
469 | (16) |
|
12.2.1 Structure and Morphology of Layer Silicates |
|
|
469 | (4) |
|
12.2.2 Physisorption of Gases by Layer Silicates |
|
|
473 | (12) |
|
12.3 Pillared Clays: Structures and Properties |
|
|
485 | (5) |
|
12.3.1 Formation and Properties of Pillared Clays |
|
|
485 | (2) |
|
12.3.2 Physisorption of Gases by Pillared Clays |
|
|
487 | (3) |
|
12.4 Zeolites: Synthesis, Pore Structures and Molecular Sieve Properties |
|
|
490 | (19) |
|
12.4.1 Zeolite Structure, Synthesis and Morphology |
|
|
490 | (4) |
|
12.4.2 Adsorbent Properties of Molecular Sieve Zeolites |
|
|
494 | (15) |
|
12.5 Phosphate-Based Molecular Sieves: Background and Adsorbent Properties |
|
|
509 | (9) |
|
12.5.1 Background of Phosphate-Based Molecular Sieves |
|
|
509 | (1) |
|
12.5.2 Adsorbent Properties of Phosphate-Based Molecular Sieves |
|
|
510 | (8) |
|
12.6 Applications of Clays, Zeolites and Phosphate-Based Molecular Sieves |
|
|
518 | (11) |
|
12.6.1 Applications of Clays |
|
|
518 | (1) |
|
12.6.2 Applications of Zeolites |
|
|
519 | (2) |
|
12.6.3 Applications of Phosphate-Based Molecular Sieves |
|
|
521 | (1) |
|
|
522 | (7) |
|
13 Adsorption by Ordered Mesoporous Materials |
|
|
529 | (36) |
|
|
|
529 | (1) |
|
13.2 Ordered Mesoporous Silicas |
|
|
530 | (18) |
|
|
530 | (11) |
|
|
541 | (4) |
|
13.2.3 Large Pore Ordered Mesoporous Silicas |
|
|
545 | (3) |
|
13.3 Effect of Surface Functionalisation on Adsorption Properties |
|
|
548 | (9) |
|
13.3.1 Incorporation of Metal Oxides into the Walls |
|
|
548 | (5) |
|
13.3.2 Occlusion of Metal Nanoparticles into the Pores |
|
|
553 | (2) |
|
13.3.3 Grafting of Organic Ligands on the Surface |
|
|
555 | (2) |
|
13.4 Ordered Organosilica Materials |
|
|
557 | (1) |
|
|
557 | (3) |
|
|
560 | (5) |
|
|
561 | (4) |
|
14 Adsorption by Metal-Organic Frameworks |
|
|
565 | (46) |
|
|
|
|
|
565 | (3) |
|
14.2 Assessment and Meaning of the BET Area of MOFs |
|
|
568 | (4) |
|
14.2.1 Assessment of the BET Area of MOFs |
|
|
568 | (3) |
|
14.2.2 Meaning of the BET Area of MOFs |
|
|
571 | (1) |
|
14.3 Effect of Changing the Nature of the Organic Ligands |
|
|
572 | (6) |
|
14.3.1 Changing the Ligand Length |
|
|
572 | (4) |
|
14.3.2 Changing the Ligand Functionalisation |
|
|
576 | (2) |
|
14.4 Effect of Changing the Metal Centre |
|
|
578 | (7) |
|
14.5 Effect of Changing the Nature of Other Surface Sites |
|
|
585 | (4) |
|
14.6 Influence of Extra-Framework Species |
|
|
589 | (3) |
|
14.7 Special Case of the Flexibility of MOFs |
|
|
592 | (9) |
|
|
594 | (3) |
|
|
597 | (2) |
|
|
599 | (2) |
|
14.8 Towards Application Performances |
|
|
601 | (10) |
|
|
602 | (1) |
|
14.8.2 Gas Separation or Purification |
|
|
602 | (1) |
|
|
603 | (1) |
|
|
603 | (1) |
|
|
604 | (1) |
|
14.8.6 Comparing MOFs with Other Adsorbents |
|
|
604 | (1) |
|
|
605 | (6) |
Index |
|
611 | |