Diffusion in Nanoporous Materials, 2 Volumes

Atoms and molecules in all states of matter are subject to continuous irregular movement. This process, referred to as diffusion, is among the most general and basic phenomena in nature and determines the performance of many technological processes. This book provides an introduction to the fascinating world of diffusion in microporous solids. Jointly written by three well-known researchers in this field, it presents a coherent treatise, rather than a compilation of separate review articles, covering the theoretical fundamentals, molecular modeling, experimental observation and technical applications. Based on the book Diffusion in Zeolites and other Microporous Solids, originally published in 1992, it illustrates the remarkable speed with which this field has developed since that time. Specific topics include: new families of nanoporous materials, micro-imaging and single-particle tracking, direct monitoring of transient profiles by interference microscopy, single-file diffusion and new approaches to molecular modeling.

Table of Contents:
Volume 1 PART I: Introduction ELEMENTARY PRINCIPLES OF DIFFUSION Fundamental Definitions Driving Force for Diffusion Diffusional Resistances in Nanoporous Media Experimental Methods PART II: Theory DIFFUSION AS A RANDOM WALK Random Walk Model Correlation Effects Boundary Conditions Macroscopic and Microscopic Diffusivities Correlating Self-Diffusion and Diffusion with a Simple Jump Model Anomalous Diffusion DIFFUSION AND NON-EQUILIBRIUM THERMODYNAMICS Generalized Forces and Fluxes Self-Diffusion and Diffusive Transport Generalized Maxwell - Stefan Equations Application of the Maxwell - Stefan Model Loading Dependence of Self- and Transport Diffusivities Diffusion at High Loadings and in Liquid-Filled Pores DIFFUSION MECHANISMS Diffusion Regimes Diffusion in Macro- and Mesopores Activated Diffusion 99 Diffusion in More Open Micropore Systems SINGLE-FILE DIFFUSION Infinitely Extended Single-File Systems Finite Single-File Systems Experimental Evidence SORPTION KINETICS Resistances to Mass and Heat Transfer Mathematical Modeling of Sorption Kinetics Sorption Kinetics for Binary Mixtures PART III: Molecular Modeling CONSTRUCTING MOLECULAR MODELS AND SAMPLING EQUILIBRIUM PROBABILITY DISTRIBUTIONS Models and Force Fields for Zeolite - Sorbate Systems Monte Carlo Simulation Methods Free Energy Methods for Sorption Equilibria Coarse-Graining and Potentials of Mean Force MOLECULAR DYNAMICS SIMULATIONS Statistical Mechanics of Diffusion Equilibrium Molecular Dynamics Simulations Non-Equilibrium Molecular Dynamics Simulations INFREQUENT EVENT TECHNIQUES FOR SIMULATING DIFFUSION IN MICROPOROUS SOLIDS Statistical Mechanics of Infrequent Events Tracking Temporal Evolution in a Network of States Example Applications of Infrequent Event Analysis and Kinetic Monte Carlo for the Prediction of Diffusivities in Zeolites PART IV: Measurement Methods MEASUREMENT OF ELEMENTARY DIFFUSION PROCESSES NMR Spectroscopy Diffusion Measurements by Neutron Scattering Diffusion Measurements by Light Scattering DIFFUSION MEASUREMENT BY MONITORING MOLECULAR DISPLACEMENT Pulsed Field Gradient (PFG) NMR: Principle of Measurement The Complete Evidence of PFG NMR Experimental Conditions, Limitations, and Options for PFG NMR Diffusion Measurement Different Regimes of PFG NMR Diffusion Measurement Experimental Tests of Consistency Single-Molecule Observation IMAGING OF TRANSIENT CONCENTRATION PROFILES Different Options of Observation Monitoring Intracrystalline Concentration Profiles by IR and Interference Microscopy New Options for Experimental Studies DIRECT MACROSCOPIC MEASUREMENT OF SORPTION AND TRACER EXCHANGE RATES Gravimetric Methods Piezometric Method 433 Macro FTIR Sorption Rate Measurements Rapid Recirculation Systems Differential Adsorption Bed 441 Analysis of Transient Uptake Rate Data Tracer Exchange Measurements Frequency Response Measurements CHROMATOGRAPHIC AND PERMEATION METHODS OF MEASURING INTRAPARTICLE DIFFUSION Chromatographic Method Deviations from the Simple Theory Experimental Systems for Chromatographic Measurements Analysis of Experimental Data Variants of the Chromatographic Method Chromatography with Two Adsorbable Components Zero-Length Column (ZLC) Method TAP System Membrane Permeation Measurements Volume 2 PART V: Diffusion in Selected Systems AMORPHOUS MATERIALS AND EXTRACRYSTALLINE (MESO/MACRO) PORES Diffusion in Amorphous Microporous Materials Effective Diffusivity Diffusion in Ordered Mesopores Surface Diffusion Diffusion in Liquid-Filled Pores Diffusion in Hierarchical Pore Systems Diffusion in Beds of Particles and Composite Particles More Complex Behavior: Presence of a Condensed Phase EIGHT-RING ZEOLITES Eight-Ring Zeolite Structures Diffusion in Cation-Free Eight-Ring Structures Diffusion in 4A Zeolite Diffusion in 5A Zeolite General Patterns of Behavior in Type A Zeolites Window Blocking Variation of Diffusivity with Carbon Number Diffusion of Water Vapor in LTA Zeolites Deactivation, Regeneration, and Hydrothermal Effects Anisotropic Diffusion in CHA Concluding Remarks 17 LARGE PORE (12-RING) ZEOLITES Structure of X and Y Zeolites Diffusion of Saturated Hydrocarbons Diffusion of Unsaturated and Aromatic Hydrocarbons In NaX Other Systems PFG NMR Diffusion Measurements with Different Probe Nuclei Self-diffusion in Multicomponent Systems MEDIUM-PORE (TEN-RING) ZEOLITES MFI Crystal Structure Diffusion of Saturated Hydrocarbons Diffusion of Aromatic Hydrocarbons Adsorption from the Liquid Phase Microscale Studies of other Guest Molecules Surface Resistance and Internal Barriers Diffusion Anisotropy Diffusion in a Mixed Adsorbed Phase Guest Diffusion in Ferrierite METAL ORGANIC FRAMEWORKS (MOFS) A New Class of Porous Solids MOF-5 and HKUST-1: Diffusion in Pore Spaces with the Architecture of Zeolite LTA Zeolitic Imidazolate Framework 8 (ZIF-8) Pore Segments in Single-File Arrangement: Zn(tbip) Breathing Effects: Diffusion in MIL-53 Surface Resistance Concluding Remarks PART VI: Selected Applications ZEOLITE MEMBRANES Zeolite Membrane Synthesis Single-Component Permeation Separation of Gas Mixtures Modeling Permeation of Binary Mixtures Membrane Characterization Membrane Separation Processes DIFFUSIONAL EFFECTS IN ZEOLITE CATALYSTS Diffusion and Reaction in a Catalyst Particle Determination of Intracrystalline Diffusivity from Measurements of Reaction Rate Direct Measurement of Concentration Profiles during a Diffusion-Controlled Catalytic Reaction Diffusional Restrictions in Zeolite Catalytic Processes Coking of Zeolite Catalysts