Loading...Solid-State NMR in Materials Science – Principles and Applications
Vladimir I Bakhmutov
Contents
Preface xi
Author xv
Chapter 1 General Principles of Pulsed NMR and NMR Techniques 1
1 1 Early History of NMR in the Solid State 2
1 2 Nuclei in the External Magnetic Field 3
1 3 Effects of Radio Frequency Pulses 9
1 4 From Macroscopic Magnetization to Nuclear Relaxation
and Shapes of NMR Signals 12
1 4 1 Common Representations of Molecular Motions
and Their In?uence on NMR 14
1 4 2 Contribution of Molecular Mobility to Spin–Spin
and Spin–Lattice Nuclear Relaxation 17
1 5 Parameters Characterizing Nuclei in the External
Magnetic Field 20
1 5 1 Chemical Shift 20
1 5 2 Spin–Spin Coupling 22
1 5 3 Quadrupolar Coupling 24
1 6 Introducing NMR Equipment and NMR Experiments 26
1 6 1 Magnets and NMR Probes 28
1 6 2 Homogeneity of the External Magnetic Field
and Digital Resolution in NMR Spectra 30
1 6 3 Dead Time of NMR Spectrometers: Intensity
of Signals and Distortion of Baselines
in NMR Spectra 30
1 7 Main Principles of Two-Dimensional NMR 32
1 8 Enhancement of Sensitivity in NMR 34
References 35
Chapter 2 On Amorphous Materials as Potential Objects in Solid-State
NMR Studies: Common and Key Problems 37
2 1 Hybrid Materials 38
2 2 Polymer Solids 40
2 3 Systems Based on Nanostructures 41
2 4 Wood and Wood Components 42
2 5 Glasses 44
2 6 Zeolites 45vi Contents
2 7 Design of Porous and Layered Molecular Systems 47
2 7 1 General Problems in Structural Characterizations
of Amorphous Porous Materials 48
2 7 2 Some Key Structural Issues in Characterizations
of Amorphous Materials Modifed by Metal Ions
and Methods for Structure Solution 50
References 54
Chapter 3 Features of Solid-State NMR: Diamagnetic Materials 57
3 1 From Isotropic Chemical Shifts to Magnetic
Shielding Tensors 57
3 1 1 Visualization of Chemical Shift Tensors
and Determination of Their Orientations 62
3 2 Nuclei with a Spin of 1/2 66
3 3 Quadrupolar Nuclei in Solids 70
3 3 1 Two Categories of Quadrupolar Nuclei 72
3 4 Detection of NMR Signals in Solids: Common Aspects 73
3 4 1 Wide-Line NMR 73
3 4 2 Direct Excitation 74
3 4 3 Cross-Polarization 76
3 4 4 Cross-Polarization with Quadrupolar Nuclei 79
3 5 High-Power Decoupling 81
3 6 Multi-Quantum NMR Experiments 83
3 7 Dipolar Recoupling NMR Techniques 85
3 8 Sideband Manipulations 90
3 9 Zero-Field Solid-State NMR Experiments 92
3 10 Solid-State NMR Imaging 94
References 96
Chapter 4 Practice of Multinuclear NMR in Diamagnetic Solids: General
Information and Examples of Applications 99
4 1 Structural Information by Increasing the Spectral
Resolution in Multinuclear Solid-State NMR 99
4 1 1 Spectral Resolution for Nonquadrupolar Nuclei 100
4 1 2 Signal Assignments 102
4 1 3 Resolving Quadrupolar Nuclei 104
4 2 Probing Proximities of Nuclei and Measurements
of Internuclear Distances in Diamagnetic Solids 106
4 3 31P Solid-State NMR 111
4 4 Solid-State NMR of Halogen Nuclei and Oxygen 116
4 5 Solid-State NMR of Oxide Materials: Nuclei 51V,
93Nb, and 181Ta 123
4 6 Solid-State 13C NMR: Wood and Wood Products 127
4 7 2H NMR in Solids at Deuterium Natural Abundance 129Contents vii
4 8 Between Solution- and Solid-State NMR: Nanoparticles
and Suspensions 131
References 137
Chapter 5 Dynamics in Diamagnetic Materials from Solid-State NMR:
Methods, Measurements, and Analysis 139
5 1 Variable-Temperature Solid-State NMR Experiments
and a Line-Shape Analysis 141
5 1 1 Dynamics in Polymeric Materials
from a Line-Shape Analysis 143
5 2 Molecular Mobility from the Solid-State NMR Relaxation 145
5 2 1 Measurements of Relaxation Times and Errors
of the Measurements 145
5 2 2 How Molecular Motions Affect Nuclear Relaxation 149
5 2 2 1 Correlation Time Distribution
versus Single Correlation Time 151
5 2 3 Relaxation Approaches: Methodology
and Examples 153
5 3 One- and Two-Dimensional Exchange Solid-State
NMR Spectroscopy 156
5 4 Molecular Mobility from the Cross-Polarization
NMR Experiments 158
5 5 Molecular Mobility from Magnetic Relaxation
Dispersion Experiments 160
References 163
Chapter 6 Strategies in Solid-State Multinuclear NMR: Studies
of Diamagnetic Porous Materials 165
6 1 Porosity of Materials from NMR 165
6 1 1 NMR Cryoporometry 168
6 1 2 NMR Relaxometry 171
6 1 3 NMR Behavior of Gases in Pore Spaces 173
6 2 Structural Features of Silica Lattice and Surface
by Solid-State 1H 29Si, 27Al, and 17O NMR Spectra 176
6 2 1 Distribution of Diamagnetic Metal Ions
from Solid-State NMR 181
6 3 Molecular Mobility in Diamagnetic Porous Materials 186
References 189
Chapter 7 Paramagnetic Effects in Solid-State NMR 191
7 1 Theoretical Aspects 193
7 1 1 Chemical Shifts and Magnetic Shielding Tensors
in the Presence of Unpaired Electrons 193viii Contents
7 2 Nuclear Relaxation in the Presence of Unpaired Electrons 197
7 2 1 Spin Diffusion 198
7 2 2 Nuclear Relaxation via Nucleus–Electron
Dipolar and Contact Interactions 199
7 3 Practical Consequences from the Theory
of Paramagnetic Effects 200
7 4 1H, 31P, 13C, 2H, 29Si, 7Li, and 6Li NMR Spectra
of Paramagnetic Solids 205
7 5 51V and 55Mn NMR Spectra of Paramagnetic Solids 210
7 5 1 Analyzing the Nature of Metal Ions by Their
Direct Observation in Solid-State NMR Spectra 212
7 6 Special NMR Techniques for Observations
of “Invisible” Target Nuclei 215
7 7 Relaxation Measurements and Relaxation Times
in Paramagnetic Solids 217
7 7 1 Solid-State T1 Measurements 224
7 7 2 Spin–Spin Relaxation Times and Anomalies
in Solid-State T2 Measurements 225
References 228
Chapter 8 Strategy in NMR Studies of Amorphous Porous
Paramagnetic Materials 231
8 1 Intense Sideband Patterns in MAS NMR Spectra of
Paramagnetic Amorphous Materials and Their Analysis 231
8 2 Direct Detection of the Nuclei Closest to Paramagnetic
Ions in Porous Materials by the Hahn-Echo Mapping
NMR Experiments 236
8 3 NMR Relaxation Approaches to Structure of Porous
Amorphous Paramagnetic Silica-Based Materials:
From Experiments to Models and Interpretations 240
8 3 1 Factors Affecting Relaxation Times in Porous Solids 241
8 3 2 Spin–Lattice Relaxation Times in Porous
Silica-Based Materials and Concentrations
of Paramagnetic Ions 242
8 3 3 29Si Spin–Lattice and Spin–Spin Relaxation
in Static and Spinning Porous Amorphous
Paramagnetic Silica-Based Materials 243
8 3 4 T1 Criteria for Locations of Paramagnetic Ions:
Relaxation of Isotropic Resonances 247
8 3 5 T1 Criteria Based on Relaxation of Sideband
Patterns in MAS Spectra of Porous
Paramagnetic Materials 251
8 3 6 BMS Effects and NMR Relaxation of Sideband
Patterns in MAS Spectra of Porous
Paramagnetic Materials 254Contents ix
8 4 Protocol for Quantifcation of “Invisible Nuclei”
in MAS NMR 255
8 5 Concluding Remarks 256
References
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