Multinuclear Solid-State Nuclear Magnetic Resonance of Inorganic Materials

by MacKenzie; Smith

• ISBN13: 9780080437873
• ISBN10: 0080437877
• Edition: 1st
• Format: Hardcover
• Copyright: 2002-04-26
• Publisher: Elsevier Science

Summary

Techniques of solid state nuclear magnetic resonance (NMR) spectroscopy are constantly being extended to a more diverse range of materials, pressing into service an ever-expanding range of nuclides including some previously considered too intractable to provide usable results. At the same time, new developments in both hardware and software are being introduced and refined. This book covers the most important of these new developments. With sections addressed to non-specialist researchers (providing accessible answers to the most common questions about the theory and practice of NMR asked by novices) as well as a more specialised and up-to-date treatment of the most important areas of inorganic materials research to which NMR has application, this book should be useful to NMR users whatever their level of expertise and whatever inorganic materials they wish to study.

Table of Contents

Preface	v
Introduction
Methodology of Materials Characterization by NMR	3	(3)
Historical Aspects of NMR Spectroscopy	6	(1)
Brief Description of the NMR Experiment	7	(10)
General Principles	7	(3)
Overcoming NMR Spectral Broadening in Solids by MAS	10	(1)
Other NMR Experiments used with Solids	11	(1)
Decoupling	12	(1)
Cross-Polarisation (CP)	12	(1)
Spin-Echo Experiments	12	(1)
Two-Dimensional Experiments	12	(1)
Nuclei Suitable for NMR Spectroscopy	13	(4)
Further Reading	17	(6)
References	18	(5)
Physical Background
Fundamental Interaction with External Magnetic Fields	23	(12)
A Quantum Mechanical Description of the Zeeman Interaction	25	(1)
Bulk Magnetisation	26	(3)
The Rotating Frame and the Application of RF Pulses	29	(5)
Observation of the NMR Signal	34	(1)
Internal Interactions	35	(23)
The Dipolar Interaction	37	(3)
Scalar Coupling	40	(3)
Paramagnetic Coupling	43	(1)
Chemical Shielding	44	(4)
Knight Shift	48	(2)
Quadrupole Interaction	50	(7)
Nature of Interactions	57	(1)
One Dimensional Methods for Improving Resolution	58	(20)
Magic Angle Spinning and First-Order Effects	59	(1)
Physical Principles	59	(2)
Formation of Spinning Sidebands	61	(2)
Magic Angle Spinning and Higher-Order Effects	63	(1)
MAS of Second-Order Quadrupole Effects	64	(7)
Residual Coupling Effects due to Quadrupolar Nuclei in MAS Spectra	71	(3)
Nonequivalent Homonuclear Spins	74	(1)
Variable Angle Spinning	74	(1)
Double Angle Spinning	75	(2)
Multiple Quantum Transitions	77	(1)
Ultrasonically-Induced Narrowing	78	(1)
Dipolar Decoupling	78	(5)
Heteronuclear Dipolar Decoupling	78	(1)
Homonuclear Dipolar Decoupling	79	(4)
Spin-locking	83	(2)
Cross-Polarisation	85	(5)
Two-Dimensional Methods	90	(8)
Dynamic Angle Spinning	92	(1)
2D MQMAS	93	(5)
NMR Relaxation	98	(13)
Introduction to Relaxation	98	(3)
Mechanism for Relaxation Processes	101	(4)
References	105	(6)
Experimental Approaches
Basic Experimental Principles of FT NMR	111	(1)
Instrumentation	112	(15)
Overview of a Pulsed FT NMR Spectrometer	112	(1)
Magnets	113	(2)
Shimming	115	(1)
Transmitters	116	(4)
Probes	120	(2)
Connection of the Probe	122	(2)
Signal Detection	124	(3)
Additional Equipment	127	(1)
Practical Acquisition of NMR Spectra	127	(6)
Processing the FID to Produce a Spectrum	128	(1)
Window Functions	128	(1)
Shifting of the Time Origin and Linear Back Prediction	129	(1)
Zero Filling	129	(1)
Phase Correction	130	(1)
Baseline Correction	130	(1)
Complications in Recording Spectra	130	(3)
Static Broad Line Experiments	133	(5)
Pulsed Echo Experiments	133	(3)
Stepped Experiments	136	(2)
One-Dimensional High Resolution Techniques	138	(15)
Magic Angle Spinning (MAS)	138	(5)
Extraction of Parameters from MAS NMR Spectra	143	(1)
Suppression of Spinning Sidebands	143	(1)
Special Considerations for MAS of Quadrupolar Nuclei	144	(5)
Magic Angle Spinning Observation of Satellite Transitions	149	(1)
Double Angle Rotation of Quadrupolar Nuclei	150	(2)
Practical Implementation of CRAMPS	152	(1)
Two-Dimensional Experiments	153	(19)
Nutation NMR	153	(1)
Off-Resonance Nutation	154	(1)
Order-Resolved Sideband Spectra	155	(1)
Dynamic Angle Spinning (DAS)	156	(1)
Two-Dimensional Sequences Developed from Solution NMR	157	(3)
Multiple Quantum Experiments in Dipolar Coupled Systems	160	(1)
Multiple Quantum NMR Experiments of Non-Integer Spin Quadrupolar Nuclei	161	(7)
2D XY Correlation Methods	168	(2)
Correlation of Tensor Information - Separated Local Field Experiments	170	(2)
Summary of Approaches for Examining Quadrupole Nuclei	172	(1)
Multiple Resonance	172	(11)
Cross-Polarisation (CP)	173	(5)
SEDOR, REDOR and TEDOR	178	(4)
TRAPDOR and REAPDOR	182	(1)
Techniques for Determining Relaxation Times and Motional Parameters	183	(4)
Measurement of T1	183	(1)
Other Spin-Lattice Relaxation Times (T1p, T1D)	184	(1)
Transverse Relaxation Times (T2)	185	(1)
Molecular Motion	186	(1)
Diffusion Measurements	187	(1)
NMR Under Varying Physical Conditions	187	(14)
Variable Temperature NMR	187	(2)
High Pressure Experiments	189	(1)
References	190	(11)
29 SI NMR
General Considerations	201	(4)
Broadening Effects in 29Si Spectra	201	(1)
Relaxation Effects in 29Si Spectra	202	(2)
Effect of Structure on 29Si Spectra	204	(1)
Si-O Compounds	205	(3)
Relationships between 29Si NMR Spectra and Structure/Bonding	205	(1)
Four-Coordinated Si-O-Compounds	205	(1)
Tetrahedral 29Si Chemical Shifts in Silicates	205	(1)
29Si Chemical Shifts in Aluminosilicates	206	(2)
Effects of Other Nearest Neighbours on the 29Si Shift	208	(1)
Order-Disorder Effects in Minerals	208	(4)
Identification of Silicate Minerals	212	(2)
Thermal Decomposition of Silicate Minerals	214	(3)
Relationships between 29Si Chemical Shift (d) and Structure	217	(8)
Relationships between δ and the Si-O Bond Length	218	(1)
Relationships between δ and the Si-O-Si Bond Angle	219	(4)
More Complex Relationships between δ and the Structure	223	(2)
Five and Six-Coordinated Si-O Compounds	225	(2)
Cross-Polarisation (CPMAS) Experiments	227	(3)
Cross-Polarisation between 1H and 29Si	227	(2)
Cross-Polarisation between 19F and 29Si	229	(1)
Other Cross-Polarisation Experiments with 29Si	229	(1)
Glasses, Gels and Other Amorphous Materials	230	(14)
Silicate Glasses	231	(4)
Deconvolution of 29Si NMR Spectra	235	(1)
Connectivities in Glass	236	(2)
Chalcogenide Glasses	238	(2)
Gels	240	(2)
Other Amorphous Materials	242	(2)
Si-N and Si-N-O Compounds	244	(3)
Si-Al-O-N Compounds	247	(6)
β-Sialon, Si6-zAlzOzN8-z	247	(3)
O-Sialon, Si2-xAlxO1+xN2-x	250	(1)
X-Sialon, nominally Si12Al18O39N8	251	(2)
Polytypoid Sialons, (Si,Al)m,(O,N)m+1	253	(1)
α-Sialons, MxSi12-(m+n)Alm+nOnN16-n	253	(1)
Other Metal Silicon Nitrides and Oxynitrides	253	(2)
Si-C, Si-C-O and Si-C-N Compounds	255	(2)
Silicon Oxycarbide Species	256	(1)
Silicon Carbonitride Species	257	(1)
Other Materials	257	(14)
Biologically Compatible Glasses	257	(1)
Cements	257	(2)
Inorganic Polymers	259	(1)
References	260	(11)
27AL NMR
General Considerations	271	(1)
Chemical Shifts in 27Al Spectra	272	(9)
27Al Chemical Shifts in Al-O Environments	273	(1)
27Al Chemical Shifts in Aluminosilicates	274	(5)
Relationships between 27Al Chemical Shift (δiso) and Structure	279	(2)
Five-Coordinated Al-O	281	(10)
Al(v) in Well-Defined (Crystalline) Environments	281	(2)
Al(v) in Non-Crystalline Environments	283	(4)
Al(v) in Zeolites	287	(4)
Aluminium Oxides	291	(3)
Amorphous Aluminium Compounds	294	(10)
Aluminate Gels	294	(5)
Glasses	299	(4)
Other Amorphous Systems	303	(1)
Aluminophosphates	304	(3)
Aluminium Borate and Molybdate	307	(1)
Aluminium Borate	307	(1)
Aluminium Molybdate	307	(1)
Aluminium Fluorides	308	(2)
Thermal Decomposition Reactions	310	(3)
Cements	313	(3)
Nitride and Oxynitride Compounds	316	(1)
Sialon Compounds	317	(16)
Polytypoid Sialons	317	(1)
β-Sialons	318	(2)
O-Sialons	320	(1)
X-Sialons	321	(1)
α-Sialons	322	(1)
Sialon Glasses	323	(1)
References	324	(9)
17O NMR
Introduction	333	(1)
Background	334	(15)
Enrichment Schemes	334	(3)
Experimental NMR Methodology	337	(9)
Relationships between NMR Parameters and Structure	346	(3)
Binary Oxides	349	(6)
Crystalline Materials	349	(3)
Sol-Gel Produced Samples	352	(3)
Crystalline Ternary Ionic Systems	355	(4)
Silicates and Germanates	359	(13)
Crystalline Materials	359	(1)
Silica and Germania	359	(2)
Ternary Silicates	361	(4)
Silicates and Germanates of Zirconium and Titanium	365	(1)
Amorphous Materials	366	(1)
Silica and Germania	366	(1)
Metal Silicate and Germanate Glasses	367	(2)
Gel-Based Silicates	369	(3)
Aluminium- and Gallium-Containing Systems	372	(9)
Alumina and Aluminates	372	(3)
Crystalline Alumino- and Gallosilicates	375	(4)
Amorphous Aluminosilicates	379	(2)
Boron-Containing Systems	381	(3)
Borates	381	(1)
Ternary and Quaternary Systems	382	(2)
Other Systems	384	(2)
Hydrogen-Containing Samples	386	(2)
Crystalline Hydroxides and Other Hydrogen-Containing Materials	386	(1)
Hydrous Gels and Glasses	387	(1)
High Temperature Ceramic Superconductors	388	(11)
References	390	(9)
NMR of Other Commonly Studies Nuclei
23Na NMR	399	(21)
General Considerations	399	(1)
23Na NMR Spectra of Sodium Compounds	399	(4)
Relationships between the 23Na Chemical Shift and Structural Parameters	403	(3)
23Na NMR of Crystalline Materials	406	(6)
23Na NMR Studies of Thermal Reactions	412	(1)
23Na NMR of Glasses	413	(1)
Silicate and Aluminosilicate Glasses	413	(1)
Sodium Borosilicate Glasses	414	(1)
Sodium Borate, Germanate and Tellurite Glasses and Melts	415	(1)
Phosphate Glasses	415	(1)
Miscellaneous Glass Studies	416	(2)
23Na NMR of Zeolites	418	(2)
11B NMR	420	(12)
General Considerations	420	(1)
11B NMR of Crystalline Compounds	421	(3)
11B NMR of Glasses	424	(7)
11B NMR of Zeolites	431	(1)
31 P NMR	432	(29)
Relationships between 31P NMR Parameters and Structure	438	(3)
31P NMR of Glasses	441	(1)
Binary Phosphate Glasses	441	(2)
Phosphosilicate Glasses	443	(2)
Alkali Borophosphate Glasses	445	(1)
Borosilicophosphate Glasses	445	(1)
Phosphoaluminosilicate Glasses	446	(1)
Alkali Phosphoalurninoborosilicate Glasses	447	(1)
Phosphorus Chalcogenide Glasses	447	(1)
31P NMR of AlPO4 Molecular Sieves	448	(2)
31P NMR of Biomaterials	450	(2)
References	452	(9)
NMR of Low-γ Nuclides
General Considerations	461	(1)
Problems Associated with Low-γ Nuclei	461	(1)
NMR of Spin-1/2 Nuclei	462	(13)
89Y NMR	462	(7)
107Ag and 109Ag NMR	469	(4)
183W NMR	473	(2)
Quadrupolar Nuclei	475	(60)
14N NMR	475	(4)
25Mg NMR	479	(9)
33S NMR	488	(3)
35Cl and 37Cl NMR	491	(4)
39K NMR	495	(7)
43Ca NMR	502	(3)
47Ti and 49Ti NMR	505	(6)
67Zn NMR	511	(3)
91Zr NMR	514	(2)
95Mo and 97Mo NMR	516	(6)
135Ba and 137Ba NMR	522	(3)
Other Miscellaneous Low-γ Nuclei	525	(1)
References	526	(9)
NMR of Other Spin-1/2 Nuclei
Introduction	535	(1)
Abundant High-γ Nuclei	536	(14)
1H NMR	536	(1)
Background to Proton Studies in Inorganic Materials	536	(3)
Studies of Stoichiometric Protons in Crystalline Materials	539	(3)
Non-Stoichiometric Proton Environments in Crystalline and Glassy Materials	542	(3)
1H NMR of Hydrous Glasses	545	(5)
Biomineral-Related Materials	550	(1)
19F NMR	550	(13)
Introduction	550	(1)
Simple Inorganic Fluorides	551	(3)
More Complex Fluorides	554	(1)
Applications to Fluoroapatite Studies	555	(1)
Fluorine in Aluminosilicate Minerals and Related Materials	556	(1)
Surface Interaction of Fluorine with Silica-and Alumina-Based Materials	557	(2)
Fluorine in Alumino- and Gallophosphates	559	(1)
Fluorine in Oxygen-Containing Glasses	559	(1)
Fluoride Glasses	560	(2)
Fluorine in Other Materials	562	(1)
Fluorine as a Source of Cross-Polarisation	562	(1)
Summary of 19F Shift Trends and Other NMR Properties	562	(1)
Dilute or Medium-γ Nuclei	563	(76)
13C NMR	563	(1)
13C NMR of Elemental Carbon	563	(5)
Silicon Carbide	568	(2)
Other Binary Carbides	570	(2)
Ternary and Quaternary Carbides	572	(1)
Carbonates	572	(2)
15N NMR	574	(1)
Nitrides	575	(1)
Silicon Aluminium Oxynitride Ceramics and Glasses	576	(3)
Nitride Ceramics from Polymeric Precursors	579	(3)
Nitrates and Nitrites	582	(1)
77Se NMR	583	(4)
111Cd and 113Cd NMR	587	(4)
115Sn, 117Sn and 119Sn NMR	591	(1)
Crystalline Oxygen-Containing Materials	591	(3)
Oxide Solid Solutions and Glasses	594	(1)
Non-oxide Materials	595	(3)
123Te and 125Te NMR	598	(1)
Crystalline Tellurides	598	(1)
Crystalline Tellurites and Tellurates	599	(2)
Glassy Tellurium-Containing Materials	601	(1)
129Xe NMR	601	(2)
195Pt NMR	603	(1)
199Hg NMR	604	(1)
203Tl and 205Tl NMR	604	(3)
207Pb NMR	607	(1)
Correlations between 207Pb Chemical Shifts and Structure	607	(2)
207Pb NMR of Crystalline Lead Compounds	609	(4)
207Pb NMR of Lead-Containing Glasses	613	(2)
207Pb in Sol-Gel Prepared Ceramics	615	(1)
References	616	(13)
NMR of Other Quadrupolar Nuclei
6Li and 7Li NMR	629	(1)
General Considerations	629	(1)
6,7Li NMR of Crystalline Solids	629	(5)
Relation between 6Li Chemical Shifts and Structure	634	(2)
6,7Li NMR of Fast Lithium Ion Conductors	636	(2)
6,7Li NMR of Glasses	638	(1)
9Be NMR	639	(3)
51V NMR	642	(7)
General Considerations	642	(1)
51V NMR of Vanadium Oxides and the Vanadates	642	(4)
51V NMR of Zeolites and Catalysts	646	(3)
63Cu and 65Cu NMR	649	(4)
63Cu NMR of Superconductors and Superfast Ionic Conductors	650	(3)
69Ga and 71Ga NMR	653	(5)
General Considerations	655	(2)
69,71Ga NMR of Crystalline Compounds	657	(1)
69,71Ga NMR of Other Compounds	657	(1)
87Rb NMR	658	(4)
General Considerations	658	(1)
87Rb NMR of Crystalline Compounds	658	(3)
87Rb NMR of Rubidium Fullerides	661	(1)
93Nb NMR	662	(3)
133Cs NMR	665	(9)
General Considerations	665	(1)
133Cs NMR of Crystalline Caesium Compounds	666	(3)
133Cs NMR of Minerals and Zeolitea	669	(4)
133Cs NMR of Fullerides, Superionic Conductors and Semiconductors	673	(1)
139La NMR	674	(13)
References	678	(9)
Solid State NMR of Metals and Alloys
Introduction	687	(2)
Experimental Approaches	689	(2)
Metallic Elements	691	(2)
Intermetallic Alloys	693	(3)
Phase Transformations, Ordering and Defect Sites	696	(2)
Phase Composition and Precipitation	698	(2)
Atomic Motion	700	(3)
References	701	(2)
Subject Index	703	(18)
Mineral Index	721