Sách Hấp thụ và phân tán vật liệu nano

Table of Contents
Chapter 1
Statistical Mechanics 1
1.1 Introduction 1
1.1.1 Thermodynamic Functions and Relationships 1
1.2 Definition of Microstate and Macrostate .2
1.3 Definition of Ensemble 4
1.4 The Canonical Ensemble .5
1.5 Evaluation of
α
and
β
for the Canonical Ensemble .8
1.6 The Grand Canonical Ensemble 9
1.7 Evaluation of
α
,
β
, and
γ
for the Grand Canonical Ensemble .11
1.8 Canonical Partition Function for a System of Noninteracting Particles .13
1.9 Factorization of the Molecular Partition Function 15
1.10 Density Functional Theory (DFT) .16
1.11 Thermodynamics of Irreversible Processes .20
1.12 Statistical Mechanics of Irreversible Processes .23
1.12.1 Correlation Functions and Generalized Susceptibilities .24
1.12.2 Calculation of the Mean Square Displacement and the
Self-Diffusion Coefficient 26
1.12.2.1 Calculation of the Mean Square Displacement with the
Help of the Velocity Autocorrelation Function 26
1.12.2.2 Langevin’s Brownian Motion Model .27
1.12.2.3 The Diffusion Equation 29
References 31
Appendix 1.1 Legendre Transformations .33
Appendix 1.2 The Lagrange Multipliers 33
Appendix 1.3 Methods of Counting .35
Appendix 1.4 Calculus of Variations 36
Chapter 2
General Introduction to Adsorption in Solids .39
2.1 Definitions and Terminology .39
2.1.1 What Is the Meaning of the Term Adsorption 39
2.1.2 Phases and Components Involved in the Adsorption Process 39
2.1.3 Porous Materials 40
2.2 Interfacial Layer, Gibbs Dividing Surface, and Gibbs Adsorption .41
2.3 Thermodynamics of Gas–Solid Adsorption 43
2.3.1 Adsorption Interaction Fields 43
2.3.2 Isosteric and Differential Heats of Adsorption 44
2.3.3 Some Relations between Adsorption Macroscopic and
Microscopic Parameters .46
2.4 Gases and Vapors Adsorption in Porous Materials .47
2.4.1 Measurement of Adsorption Isotherms by the Volumetric
Method .47
2.4.2 Porous Materials Characterization by Vapor Adsorption Methods 49
2.5 Some Examples of the Application of the Volumetric Method 50
2.5.1 Volumetric Automatic Surface Area and Porosity Measurement
Systems .50
2.5.2 Adsorption Isotherms of Nitrogen at 77 K in Zeolites .52
2.5.3 Calorimetry of Adsorption of NH
3
in AlPO
4
-5 and FAPO-5
Molecular Sieves 53
References 54
Chapter 3
Microporosity and Surface Area Evaluation Methods 57
3.1 Introduction 57
3.2 The Dubinin and Osmotic Adsorption Isotherms .57
3.2.1 Dubinin Adsorption Isotherm 57
3.2.2 Osmotic Adsorption Isotherm 61
3.3 Langmuir and Fowler–Guggenheim Type Adsorption Isotherm
Equations 63
3.3.1 Introduction 63
3.3.2 Application of the Grand Canonical Ensemble Methodology to
Describe Adsorption in Zeolites 64
3.3.2.1 Immobile Adsorption 65
3.3.2.2 Mobile Adsorption 68
3.3.3 Some Remarks in Relation with the Langmuir Type and
Fowler–Guggenheim Type Adsorption Isotherm Equations .69
3.4 The t-Plot Method 72
3.5 Additional Comments about the Application of the Dubinin and Osmotic
Isotherms, the LT and the FGT Isotherm Equation Types, and the t-Plot
Method in the Measurement of the Micropore Volume 76
3.6 The BET Method .79
3.7 Horvath-Kawazoe Method .85
References 89
Chapter 4
Nanoporous Materials Mesoporosity Evaluation 93
4.1 Introduction 93
4.2 Capillary Condensation 93
4.3 Macroscopic Theories to Describe Pore Condensation 96
4.3.1 The Kelvin-Cohan Equation 96
4.3.2 The Derjaguin-Broeckhoff-de Boer Theory 102
4.3.3 Some Concluding Remarks about the Macroscopic Theories to
Describe Multilayer Adsorption and Pore Condensation 105
4.4 Density Functional Theory 106
4.4.1 The Density Functional Theory Methodology in General 106
4.4.2 Calculation of the Pore Size Distribution 108
4.4.3 The Nonlocal Density Functional Theory for the Description
of Adsorption in Slit Pores, Cylindrical Pores, and Spherical
Cavities .109
4.4.4 Some Concluding Remarks about the Molecular Models to
Describe Adsorption .117
References 119
Chapter 5
Diffusion in Porous Materials 121
5.1 Introduction 121
5.2 Fick’s Laws 121
5.3 Transport, Self-Diffusion, and Corrected Coefficients 123
5.3.1 Transport Diffusion and Self-Diffusion .123
5.3.2 Interdiffusion and the Frame of Reference for Porous Materials .124
5.3.3 Relation between the Transport,
D
, the Corrected, D
0
, and the
Diffusion Coefficients 125
5.3.4 Relation between the Transport,
D
, the Corrected, D
0
, and the
Self-Diffusion Coefficients in Zeolites 126
5.4 Mean Square Displacement, the Random Walker, and Gaseous
Diffusion .127
5.4.1 The Mean Square Displacement (MSD) .127
5.4.2 Gaseous Diffusion and the Random Walker .128
5.5 Transport Mechanisms in Porous Media .130
5.6 Viscous, Knudsen, and Transition Flows 132
5.7 Viscous and Knudsen Flows in Model Porous Systems .134
5.7.1 Viscous Flow in a Straight Cylindrical Pore .134
5.7.2 Knudsen Flow in a Straight Cylindrical Pore .135
5.8 Transport in Real Porous Systems: Membranes .136
5.8.1 Membranes .136
5.8.2 Permeation Mechanisms in Porous Membranes .137
5.8.3 Viscous Flow in Membranes .139
5.8.4 Knudsen Flow in Membranes 140
5.8.5 Transition Flow 141
5.8.6 Surface Flow in the Adsorbed Phase .142
5.8.7 Experimental Permeation Study of Zeolite-Based Porous
Ceramic Membranes 143
5.9 Diffusion in Microporous Materials: Zeolites and Related Materials 146
5.9.1 Model Description of Molecular Diffusion in Zeolites and
Related Materials .147
5.9.2 Anomalous Diffusion .152
5.9.3 Experimental Methods for the Study of Diffusion in Zeolites .155
References 163
Chapter 6
The Plug-Flow Adsorption Reactor .167
6.1 Dynamic Adsorption 167
6.2 The Plug-Flow Adsorption Reactor Model .169
References 175
Appendix 6.1 Laplace Transforms .176
Chapter 7
Amorphous Porous Adsorbents: Silica and Active Carbon 181
7.1 Basic Features of Amorphous Silica .181
7.2 Amorphous Silica Morphology and Surface Chemistry .182
7.3 Precipitated Amorphous Silica Synthesis 185
7.4 Silica Modification .188
7.5 Fundamental Characteristics of Active Carbon .190
7.6 Active Carbon Morphology, Surface Chemistry, and Surface
Modification .191
7.7 Active Carbon Production Methods 193
7.8 Some Applications of Precipitated Silica in Gas Phase Adsorption
Processes 195
7.8.1 Adsorption of NH
3
, H
2
O, CO, N
2
O, CO
2
, and SH
2
in
Precipitated Silica 195
7.8.2 Application of Precipitated Silica in Hydrogen Storage .197
7.8.3 Adsorption of Volatile Organic Compounds (VOCs) in
Precipitated Silica 198
7.9 Some Applications of Activated Carbons and Other Carbonaceous
Materials in Gas-Phase Adsorption Processes 199
7.9.1 Adsorption of H
2
O and CO
2
and Removal of SH
2
and SO
2
with Active Carbon 199
7.9.2 Hydrogen Storage with Active Carbon and Other Carbonaceous
Materials .202
7.9.3 Methane Storage in Activated Carbon and Other Carbonaceous
Materials .202
7.9.4 Adsorption of Volatile Organic Compounds (VOCs) in Activated
Carbon 203
7.9.5 Air-Conditioning with Activated Carbon 204
References 204
Chapter 8
Crystalline and Ordered Nanoporous Materials 211
8.1 Introduction 211
8.2 Fundamental Characteristics of Zeolites and Mesoporous Molecular
Sieves 212
8.3 Structure .213
8.3.1 Crystalline Microporous Materials 213
8.3.2 Ordered Mesoporous Materials .216
8.4 Synthesis and Modification 219
8.4.1 Zeolite Synthesis 219
8.4.2 Zeolite Modification .222
8.4.3 Synthesis of Ordered Silica Mesoporous Materials 223
8.4.4 Modification of Ordered Silica Mesoporous Materials .225
8.5 Some Applications of Crystalline and Ordered Nanoporous Materials
in Gas Separation and Adsorption Processes 227
8.5.1 Gas Cleaning 227
8.5.1.1 Zeolites 227
8.5.1.2 Mesoporous Molecular Sieves 230
8.5.2 Pressure Swing Adsorption 232
8.5.3 Other Separation Applications .233
8.5.4 Air-Conditioning 234
References 235
Chapter 9
Adsorption from Liquid Solution 243
9.1 Introduction 243
9.2 Surface Excess Amount and Amount of Adsorption for Liquid–Solid
Adsorption Systems .244
9.3 Empirical Adsorption Isotherms Applied for the Correlation of
Liquid–Solid Adsorption Equilibria in Systems Containing One
Dissolved Component 247
9.4 Model Description of Adsorption from the Liquid Phase on Solids 250
9.5 Some Applications of Liquid–Solid Adsorption .252
9.5.1 Activated Carbons 252
9.5.2 Precipitated Silica 253
9.5.3 Zeolites .255
References 255
Index 259