1. Chapter 18 Introduction to Solid State NMR
18.0 Summary of internal interactions in solid state NMR
18.1 Typical lineshapes for static samples
18.2 Magic-angle-spinning (MAS)
18.3 Cross polarization (CP) and CPMAS
18.4 Homonuclear decoupling pulse sequences
18.5 Recoupling (CSA and dipolar)
18.6 Multi-quantum MAS (MQMAS) of quadrupole spins
18.7 Applications

2. High resolution solid state NMR
Recoupling (Secoupling)
Resolution gap between LSNMR and SSNMR: still large but decreasing
“Solid NMR” in chemistry and condensed matter physics can be very different (the later normally uses conducting samples that contain large Knight shift)

3. Single Crystal or Polycrystalline (Powder) Samples

4. Review of Lecture 9 for the summary of the four major interactions in NMR spectroscopy.

5. Magic Angle Spinning (MAS)
Θ=54.74° B0

7. Coordinate Systems

8. Coordinate Systems 33 11 22 Z X Y

9. Coordinate Systems Lab Frame(XYZ) Molecular frame (may be a PAS of11 22 33 β
Molecular frame (may be a PAS of
certain interaction tensor)
Lab Frame(XYZ)

10. How to calculate a solid NMR spectrum
More generally,

11. Sensitivity
High Fields
Labeled samples CP
CPMAS

12. Cross polarization
CPMAS─one of the most important solid state NMR techniques.
CP contact time: several hundred microseconds to tens of milliseconds.
Purpose: To enhance the sensitivity of the lower γ spins such as carbon-13. maximal enhancement factor: γI/γS
Other advantages: Shorter recycle delay time
Distinguish the interconnectivity of nuclear spins such as the protonation of a certain carbon nucleus.

14. 1H-13C CPMAS spectrum of (a) mixed lactose, (b) -lactose and (c) anhydrous stable -lactose.
The lines marked by asterisks are assigned to the residual amorphous lactose

15. Sodium silicate glasses
Static 17O NMR spectra
bridging (BO) and
non-bridging (NBO)
oxygens
Na2Si2O5
Na2Si3O7
Na2Si4O9
NBO BO
ppm

16. Structure of glasses (I)
NBO BO

17. 29Si NMR spectra for sodium silicate glasses
static MAS Q4
mole %
Na2O 34 37 41 Q3 Q2
Q3 + Q2
ppm

18. Structure of glasses (II)Q4 Q2 Q3 Q1

19. 1H-29Si CPMAS intensity as a function of contact timeQ2 Q3 Q4
Different sites in a Na2Si4O9 glass with 9.1 wt% H2O
contact time (ms)

20. Ramp CP (Matching Condition Satisfied at High Speeds)
Acquisition X CP
decoupling 1H

21. Comparison of standard and ramp-CP
Carbonyl-signal of glycine (nat. abundance), nrot = 20 kHz,
as function of 1H-power
rectangle 10 11 12 13 14 15 16 17 18 19
pl2 in dB
ramp

22. Double-CP
CP 1
Decoupling
Avoid CP 1H
CP 2 Y
Acquisition X

23. H-N-C Double- CPMAS: Spectral Simplification
(A) CP-MAS 13C NMR spectrum and (B) 15N-13C double-
CP/MAS NMR data of the [13C6,15N3]-His labeled LH2 complex,
measured at 220 K by using a wide-bore 750 NMR spectrometer. The
spinning rate around the magic angle was kept at 12 kHz. Each spectrum
represents about scans collected with an acquisition time of 8
ms and a recycle time of 2 s. The spectra are normalized at the α’ peaks.
de Groot et al., JACS 123,4203(2001).

24. Shielding Bloc = B0 – Bi = B0 (1 – s)
electronic shielding induced magnetic field
Bloc = B0 – Bi = B0 (1 – s)

26. Shielding Tensor: Decomposed= xx 1 2 ( xy + yx ) xz zx yy yz zy zz æ è ç ö ø ÷ as - |
Theoretically, CSA tensor contains anti-symmetric components, but the
experimental evidence has been rather weak. It remains an interesting
topic in fundamental NMR research.

27. (Static) Powder Patterns

28. Powder spectrum
iso , δ,

29. Magic-Angle-Spinning Spectrum

30. MAS for spin 1/2 nuclei

32. Total Suppression of Spinning Side Bands (TOSS)

33. TOSS Example

34. TOSS Example
Proton NMR spectra of a water and hexadecane mixture in a sample of packed glass beads.

35. The Quadrupolar Majority

36. First and Second Order Quadrupolar Hamiltonains

37. 2H MAS HZ HZ + HQ HZ + HQ (powder)
Experimental (A) and simulated (B and C) 2H MAS NMR
spectra (14.1 T) of KD2PO4 using ωr= 7:0 kHz. The
simulated spectrum in (B) employs the optimized 2H
quadrupole coupling and CSA parameters listed below
whereas the simulation in (C) only considers the quadrupole
coupling interaction. The asterisk indicates the isotropic peak.

38. Half-Integer Quadrupolar Spins: Central Transtion
A few hundred Hz to several kHz

39. Satellite Transitions
Static
MAS
Hundreds kHz to a few MHz!

40. Spin-3/2
23Na ( MHz) NMR spectra of NaN03 recorded using (a) static and
(b) MAS (v, = 4820 Hz) conditions ( 16 scans). The central transition is cut off at (a) 1/4 and (b) 1/13 of its total height.

41. JORGEN SKIBSTED, NIELS CHR. NIELSEN, HENRIK BILDME, HANS J
JORGEN SKIBSTED, NIELS CHR. NIELSEN, HENRIK BILDME, HANS J. JAKOBSEN, JMR, 95, 88(1991)

42. Spin-5/2
27AI ( MHz) MAS NMR spectra of the central and satellite transitions for α-Al2O3. The
ppm scale is referenced to an external sample of 1 .0 M AlCl3, in H2O. (a) Experimental spectrum showing the relative intensities of the central and satellite transitions and observed using a Varian VXR-400 S wideline spectrometer; ωr= 7525 Hz, spectral width SW = 1 .0 MHz, pulse width pw = 1 .0 μs (π /4 solid pulse), and number of transients nt= (b) Spectrum in (a) with the vertical scale expanded by a factor of ten; the inset shows expansion of a region where the second-order quadrupolar shift between the (±5/2, ±3/2) and the (±3/2, ±1/2) satellite transitions is clearly observed (see text). (c) Simulated MAS spectrum for the satellite transitions in (b) obtained using QCC = 2.38 MHz, η = 0.00, ωr= 7525 Hz, and Gaussian linewidths of 900 and I 175 Hz for the (±3/2, ±1/2) and (±5/2, ±3/2) transitions. respectively.
HANS J. JAKOBSEN, JORGEN SKIBSTED, HENRIK BILDSBE, ANDNIELS CHR .NIELSEN,JMR 85,173(1989)

43. 51V MAS (HQ+HCSA) Question: is it possible to suppress the sidebands
of a satellite transition MAS spectrum?
“Answer”: Not done yet, but it’s an interesting topic.

45. Direct Dipole-Dipole Coupling

46. Direct Dipole-Dipole Coupling

47. Dipolar Coupling

48. Direct Dipole-Dipole Coupling
~80 kHz
Many coupled spins
Spin Pair

49. Homogeneous Interaction (Homonuclear Dipolar Interaction): All Spins Are Coupled to Each Other

50. Decoupling Sequences Hetronuclear decoupling: Homonuclear decouplingCW
TPPM
XiX
COMORO
SPINAL
SDROOPY,eDROOPY,DUMBO, eDUMBO, eDUMBOlk
Homonuclear decoupling
WAHUHA
Lee-Goldburg (LG and variants: FSLG, PMLG,wPMLG)
MREV-8
BR-24
BLEW-12
CORY-24
TREV-8
MSHOT-3
DUMBO, eDUMBO, eDUMBOlk,
CNnv, RNnv

51. Decoupling sequences: TPPM
TPPM = Two Pulse Phase Modulation
Pulse length: tp  tp - e: e  0 – 0.6 ms, optimize!
Phaseshift:   15°, evt. optimize!

52. TPPM- decoupling, optimize tp
Ca-signal in Glycine-2-13C-15N, nrot= 30 kHz,  = 15°
2.0
2.5
3.0
3.5
4.0
4.5
tp/ms
ndec = 150 kHz
optimum pulse length: tp = 2.9 ms, (tp = 3.2 ms)

53. XiX - decoupling XiX= X Inverse X ntR t
Pulse length: tp = x ·tR, x  n, but x  n, (recoupling at (n/4)tR ) optimize!

54. XiX- decoupling, optimize tp
Ca-signal of glycine-2-13C-15N, nrot= 30 kHz, 90 95
100
105
110
115
tp/ms
120
ndec = 150 kHz

55. Comparison of decoupling methods
Ca-signal of glycine-2-13C-15N, ndec = 150 kHz
10 kHz
TPPM (15°) CW
XiX
30 kHz

56. Decoupling methods: π-pulse decoupling
Rotorsynchronised train of 180°-pulses
xy-16-phase cycle for large band width tR t
xy-16-phase cycle: 0–90–90–0–0–90–90–0–180–270–270–180–180–270–270–180

57. π-pulse decoupling for 19F
19F: Dipol-Dipol-coupling spun out at fast rotation
but: large chemical shift anisotropy
 large band width important
-2e+04
4e+04
2e+04
0e+00 Hz
1000
19F-spectrum of
teflon at 30 kHz

58. π-pulse-decoupling for 19F
13C{19F}-CP/MAS-spectrum of Teflon, nrot= 30 kHz
100
120
140
ppm CW
TPPM 15°
p-pulse

59. Pulsed (homonuclear) decoupling
WAHUHA
Lee-Goldburg (LG and variants: FSLG, PMLG, wPMLG)
MREV-8
BR-24
BLEW-12
CORY-24
TREV-8
MSHOT-3
DUMBO, eDUMBO, eDUMBOlk,
CNnv, RNnv

60. Lee-Goldburg (LG) Series
LG: Magic-angle-spinning in spin space (Magic Sandwich) X Y Z
54.74o
ωrf Δω [ ] n * [ ] * n
Frequency-Switched LG (windowed) Phase-Modulated LG

61. TREV-8 [ ] n *

62. MSHOT (Magic Sandwich High Order Terms Decoupling)

63. MSHOT Ca(OH)2 Malonic Acid KHSO4
M. Hohwy and N. C. Nielsen, J. Chem. Phys. 106, 7571 (1997).
M. Hohwy, P. V. Bower, H. J. Jakobsen, and N. C. Nielsen, Chem,
Phys. Lett. 273, 297 (1997)
M. Hohwy, J. T. Rasmussen, P. V. Bower, H. J. Jakobsen, and N. C. Nielsen
J. Magn. Reson. 133,374(1998).
Ca(OH)2
Malonic Acid
KHSO4

64. MSHOT-3-CRAMPS (combination of rotation and multi-pulse spectroscopy

65. PMLG, wPMLG

66. wPMLG: Example
The one-dimensional proton spectra of (a) U–15N–DL-alanine, (b) monoethyl fumarate, (c) glycine and (d) U–13C –15N–histidineHClH2O, detected during wPMLG-5 at a spinning frequency of 14.3 kHz and a Larmor frequency of 300 MHz. The length of the detection windows was 3.2μs and that of the PMLG pulses was 1.7 μs.

67. 2D proton–proton correlation spectra of U–13C–histidineHClH2O, obtained using the pulse sequence shown at the top,
with mixing times of (a) 200 μs and (b) 500 μs. The F1 (vertical) and F2 (horizontal) proton spectra are skyline projections of the 2D
spectra. These experiments were performed at a spinning frequency of kHz and a Larmor frequency of 300 MHz. During the
PMLG-9 and wPMLG-5 irradiation the pulse lengths were 1.1 and 1.7 μs, respectively. The length of the detection windows during
wPMLG-5 was 3.2 μs.

68. 2D carbon–proton correlation spectra of U–13C–histidineHClH2O, obtained using the pulse sequence shown at the top,
with Lee–Goldburg CP mixing times of (a) 80 μs and (b) 3 ms. The F1 (vertical) carbon and F2 (horizontal) proton spectra are skyline projections of the 2D spectra. These experiments were performed at a spinning frequency of kHz and a Larmor frequency of 300 MHz. During the wPMLG-5 irradiation the pulse lengths were 1.7 μs and the length of the detection windows was 5.1 μs.

69. FSLG for Heteronuclear Decoupling
CH2 CH

70. Pulsed (homonuclear) decoupling (WAHUHA (WHH4), MREV-8)[ ] n *
J. S. WAUGH, L. HUBER, AND U. HAEBERLEN, Phys. Rev. Lett. 20, 180 (1968).
P. MANSFIELD, M. J. ORCHARD, D. C. STALKER, AND K. H. B. RICHARDS, Phys. Rev. B 7, 90 (1973).
W. K. RHIM, D. D. ELLEMAN, AND R. W. VAUGHAN, .I. Chem. Phys. 59, 3740 (1973).
W. K. RHIM, D. D. ELLEMAN, L. B. SCHREIBER, AND R. W. VAUGHAN, J. Chem. Phys. 60, 4595 ( 1974).

71. BR-(24,48,52) [ ] n *
D. P. BURUM AND W. K. RHIM, J. Chem. Phys. 71, 944 (1979).

72. BLEW-(12,48) [ ] n *
D. P. BURUM,* M. LINDER, AND R. R. ERNST, J. MAGN. RESON. 4, (1981)

73. CORY-24 [ ] n *

74. Hrf =ω1[Ixcosψ(t)+Iysinψ(t)]
eDUMBO (experimental Decoupling Using Mind-Boggling Optimization)
Hrf =ω1[Ixcosψ(t)+Iysinψ(t)]
MAS rate = 22 kHz

75. DUMBO and eDUMBO
Flow diagrams illustrating (a) the DUMBO and (b) the eDUMBO approaches to developing improved decoupling schemes.

76. Symmetry Based Decoupling Pulse Sequences[ ] n *

77. Indirect Spin-Spin Coupling  

79. Dipolar-Chemical Shift NMR (1D)
The interplay of chemical shift anisotropy and spin-spin coupling interactions results in complex line shapes.
The dipolar-chemical shift method is useful in the case of isolated spin pairs.
Many other cases where more than one interaction are involved.

80. Multidimensional Approaches
Separation of Local Fields (Correlation)
MQC-SQC Correlation

81. Separation of Local Fields
Chemical shift correlation
Chemical shift -dipolar correlation
Chemical shift-quadrupolar correlation
Interaction A
Interactions B(+A)
Mixing I t1 t2 tm S

82. Homonuclear correlation : establishing connectivities

83. Dipolar - Chemical Shift Correlation

84. Dipolar Coupling

85. Measuring dipolar coupling constants

86. Homonuclear correlation between I = 1/2 spins

87. Double/single quantum correlation

88. Homonuclear double/single-quantum correlation

89. MQMAS

90. Under rapid magic angle spinning (MAS):

91. Lineshape of half-integer quadropolar nuclei
static
MAS

92. Dig EFGs From This Spectrum!
Multiple Sites
Quadrupolar Coupling May Be Very Strong!
Dig EFGs From This Spectrum! m
3/2
1/2
-1/2
-3/2
In A Powder
Zeeman
Quadrupolar (first-order)
Quadrupolar (second-order)
Energy Levels of a Spin-3/2 Nucleus in a Static Magnetic Filed

93. Second Order Quadrupolar Frequency
2D Solution:Keep AND Remove
Both The EFG Information And High Resolution Can Be Achieved.

94. Magic Angle (54.7 ) Spinning
Multi-Quantum Magic-Angle Spinning (MQMAS)
          
Magic Angle
(54.7 ) Spinning
MQC SQC o
θM θM

95. Multiple quantum selection : phase cycles
(i) direct method (ii) indirect method

96. L.Frydman, J.S.Harwood, JACS, 1995.

97. 17O-MQMAS spectrum of the silicate coesite

98. MQMAS Signal Enhancement
RIACT
QCPMG
Shaped Pulses
FASTER
SPAM + STMAS …

100. What MQMAS Tells And Does Not Tell
Three Principal Values—Yes! Plus Isotropic Chemical Shift Z
Orientation—No For Powder Samples Used
V11
V33
V22 Y X

101. What MQMAS May Tell
The Relative Orientation Between Two Quadrupolar Tensors ZA
V33,A ZB
V11,B
V11,A YA
V33,B
V22,A
V22,B YB XA XB

102. Relative Orientation Is The Same For All Crystallites In A Powder Sample
EFG Tensor of Spin A
EFG Tensor of Spin B

103. MQMAS Spin Diffusion/Exchange Pulse Sequence
P t P2 tm P3 t2
SQC of Spin B(A)
MQC of Spin A(B)
A(3/2,-3/2)B(1/2,-1/2) Scheme

104. Two Spin-3/2 MQMAS-Spin Diffusion Spectrum
(3/2,-3/2)(1/2,-1/2)
Ding Lab
MQMAS Peaks
Cross Peaks

105. Ding Lab

106. 3D CSA-D Correlation (with One Quadrupolar Spin)
Six nonequivalent Na sites are resolved.
J. Grinshtein, C. V. Grant, L. Frydman,
J Am Chem Soc 124,13344(2002).

107. Recoupling
High resolution achieved with MAS sacrifices information on anisotropy.
Anisotropy can be recovered with recoupling
Selective and broadband recoupling
CSA recoupling and dipolar recoupling

108. CSA Recoupling Off magic angle spinning Stop and go (STAG)
Magic-angle-hopping (MAH)
Switching-angle-spinning (SAS) or Dynamic-angle-spinning (DAS)
Magic-angle-turning (MAT)
(SPEED)

109. Dipolar Recoupling
SEDOR
REDOR
DRAMA
(DRAW)
TRAPDOR
REAPDOR C7

110. Dipolar recovery at the magic angle (DRAMA)

111. Full DRAMA sequence

112. Zero and double quantum coherence

113. Double quantum filtered experiments

114. The C7 recoupling sequence

115. Rotational resonance experiment

116. Data resulting from rotational resonance

117. Heteronuclear correlation : general spin-echo sequence

118. Spin-echo double resonance experiment (SEDOR)

119. The REDOR experiment

120. Transfer of population in double resonance (TRAPDOR )

121. Adiabatic zero crossing

122. REAPDOR sequence for measuring dipolar couplings between I ≥ 1 and I = 1/2 spins

123. Example of relaxation: dipolar relaxation

124. How does the magnetization relax back to equilibrium after applying a
radiofrequency pulse?

128. How does the spectra density J depend on the correlation time?

130.   
In the extreme narrowing limit (very fast motion and very short correlation time), the following holds.

134. Other Topics
Multiple pulse for homonuclear decoupling (WAHUHA, MREV, HR, CORY etc)
Combination of rotation and multiple pulses (CRAMP)
Recoupling (Rotational Resonance, REDOR, RFDR etc)
Other multi-dimensional solid state NMR (HETCOR, CSA/Q correlation, D/Q correlation, 3D correlation spectra)
Single-Crystal NMR

135. Applications
Polymers
Glasses
Porous materials
Liquid crystals

136. Schematic of a typical semicrystalline linear polymer

137. Stereochemical issue in substituted polymers

138. Signature of stereoregularity in the solid state spectrum

139. Static 2D exchange spectrum for polyethyleneoxide (PEO)
Experiment Simulation

140. 3D static 13C exchange spectra of polyethyleneoxide polyvinylacetate

141. Applications
Polymers
Glasses
Porous materials
Liquid crystals

142. Static whole-echo 207Pb NMR spectra in Pb-silicate glasses
mol %
PbO 66
50.5 31
Linewidth ~ T
—> signals of 6 experiments summed up
ppm

143. Sodium silicate glasses
Static 17O NMR spectra
bridging (BO) and
non-bridging (NBO)
oxygens
Na2Si2O5
Na2Si3O7
Na2Si4O9
NBO BO
ppm

144. Structure of glasses (I)
NBO BO

145. 29Si NMR spectra for sodium silicate glasses
static MAS Q4
mole %
Na2O 34 37 41 Q3 Q2
Q3 + Q2
ppm

146. Structure of glasses (II)Q4 Q2 Q3 Q1

147. 1H-29Si CPMAS intensity as a function of contact timeQ2 Q3 Q4
Different sites in a Na2Si4O9 glass with 9.1 wt% H2O
contact time (ms)

148. Efficiency for (1H 29Si)-CP
Acquisition
29Si CP
decoupling 1H t

149. 29Si MAS NMR spectra for a CaSi2O5 glass
SiO4 SiO SiO6
x 8
glass
crystal
quenched from a 10 GPa pressure melt isotopically enriched
high pressure phase normal isotopes
ppm

150. 11B MAS NMR spectra for a sodium borate glass
(with 5 mole% Na2O)
data
fit
slow cooled
fast cooled R
BO4 NR
ppm
data
fit R
BO4 NR

151. 31P MAS NMR spectra for sodium phosphate glasses
mol % Na2O 56 53 40 30 15 5
Q1 Q2 Q3
ppm

152. 31P double-quantum NMR spectrum
-60
2-2
Double-quantum dimension (ppm)
1-2
2-1
1-1
0 -30
Single-quantum dimension

153. 1H MAS NMR spectrum for a GeO2-doped silica glass
loaded with H2 and UV-irradiated
after subtraction
of intense back-
ground signal
SiOH + GeOH
GeH
9.4 T, 10 kHz spinning
ppm
Sample contains ~8 ´1019 H atoms/cm3 (corresponding to about 500 ppm of H2O)

154. 17O 3QMAS NMR spectrum for a glass on the NaAlO2-SiO2 join with Si/Al = 0.7
-50 50
100
MAS dimension (ppm)
Al-O-Al
Si-O-Al
Isotropic dimension (ppm)

155. 17O 3QMAS NMR spectrum for a borosilicate
-100
-50 50
100
B-O-B
MAS dimension (ppm)
Si-O-Si
Si-O-B
Isotropic dimension (ppm)

156. 11B-{27Al} CP-HETCOR NMR spectrum
BO4
BO3
-80 80
AlO6
AlO5
AlO4
ppm

157. Applications
Polymers
Glasses
Porous materials
Liquid crystals

158. Porous materials
Zeolite A
Sodalite

159. Porous materials
Faujasite
Cancrinite

160. Porous materials
Zeolite ZK-5
Zeolite Rho

161. Zeolite framework projections
AlPO4-5
along [001]
AlPO4-11
along [100]
VPI-5
along [001]

162. 2
High-resolution 29Si MAS NMR spectra of synthetic Na-X and Na-Y zeolites
(Si/Al) = 1.03
1.19
1.35
1.59
1.67
1.87 3
2.00
2.35
2.56
2.61
2.75 1 4 4
Si(nAl) lines
n = 3 2 1

163. Possible ordering schemes for zeolite Y
Si/Al = 1.67
Intensity ratios:
Si(4Al):Si(3Al):Si(2Al):Si(1Al):Si(0Al) Si Al

164. 29Si MAS NMR spectrum of highly siliceous mordenite3 2
29Si MAS NMR spectrum of highly siliceous mordenite 1
Intensities
ppm

165. Mordenite structure along [001]
T-site No. per unit cell Neighbouring sites Mean T-O-T bond angle
T1 16 T1, T1, T2, T °
T2 16 T1, T2, T2, T °
T3 8 T1, T1, T3, T °
T4 8 T2, T2, T3, T °

166. Mordenite structure along [001]
T1/T3/T2+T4 : 3 cross peaks
T1/T4/T2+T3 : 2 cross peaks
T2/T3/T1+T4 : 2 cross peaks
T2/T4/T1+T3 : 3 cross peaks
T-site No. per unit cell Neighbouring sites Mean T-O-T bond angle
T1 16 T1, T1, T2, T °
T2 16 T1, T2, T2, T °
T3 8 T1, T1, T3, T °
T4 8 T2, T2, T3, T °

167. 29Si MAS NMR spectrum of highly siliceous mordenite
T2 + T4 T1
29Si MAS NMR spectrum of highly siliceous mordenite T3
J-scaled COSY spectrum
T1/T3/T2+T4 : 3 cross peaks
T1/T4/T2+T3 : 2 cross peaks
T2/T3/T1+T4 : 2 cross peaks
T2/T4/T1+T3 : 3 cross peaks
ppm

168. 29Si MAS NMR spectra of ultrastabilized and hydrothermally realuminated zeolites1
Si/Al = 2.56 3
ppm

169. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)

170. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)
……. + x O2 (n-x) CO + n H2 + x CO2 (water gas shift)

171. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)
……. + x O2 (n-x) CO + n H2 + x CO2 (water gas shift)
CO H2 CH3OH (conversion of synthesis gas)
catalyst

172. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)
……. + x O2 (n-x) CO + n H2 + x CO2 (water gas shift)
CO H2 CH3OH (conversion of synthesis gas)
CH3OH CH3OH + CH3OCH3
catalyst
Zeolites
150 °C

173. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)
……. + x O2 (n-x) CO + n H2 + x CO2 (water gas shift)
CO H2 CH3OH (conversion of synthesis gas)
CH3OH CH3OH + CH3OCH3
…….. complex mixture of hydrocarbons
catalyst
Zeolites
150 °C
Zeolites
300 °C

174. Chemical reactions in zeolites
{C} + H2O CO + H2 (water gas reaction)
……. + x O2 (n-x) CO + n H2 + x CO2 (water gas shift)
CO H2 CH3OH (conversion of synthesis gas)
CH3OH CH3OH + CH3OCH3
…….. complex mixture of hydrocarbons
catalyst
Zeolites
150 °C
Zeolites
300 °C

175. 13C MAS NMR spectrum of H-ZSM-5 with 50 torr of adsorbed MeOH heated to 300 °C for 35 mins
ppm

176. 13C MAS NMR spectrum of H-ZSM-5 with 50 torr of adsorbed MeOH heated to 300 °C for 35 mins
scalar coupling
1JCH = 125 Hz
a quintet with ratio 1:4:6:4:1 is expected for methane
ppm

177. Heteronuclear 2D J-resolved 13C MAS NMR spectrum
300
200
100
0 Hz
-100
-200
-300
ppm

178. 13C NMR spin diffusion spectrum of products of methanol conversion over zeolite ZSM-5
ppm

179. 13C MAS NMR spectrum of H-ZSM-5 with 50 torr of adsorbed MeOH heated to 300 °C for 35 mins
Methane
Ethane
Propane
Cyclopropane
n-Butane
Isobutane
(n-Pentane)
Isopentane
n-Hexane
n-Heptane
ppm

180. Methylated aromatic products* CO * * * *
ppm

181. 129Xe NMR as a sensitive tool for materials
0: reference
S: surface collisions
Xe: Xe-Xe collisions
E: electric field effect
M: paramagnetic species

182. 129Xe as a sensitive probe for various zeolites
ZK4
ZSM-5
1021
NaY
ZSM-11
K - L
Xe atoms /g
omega
1020
ppm

183. Applications
Polymers
Glasses
Porous materials
Liquid crystals

184. Graphitic nanowires
Hexa-peri-hexabenzocoronene (HBC)

185. HBC monolayer on HOPG

186. Phase transitions of alkyl substituted HBC

187. Temperature dependence of the one dimensional charge carrier mobility

188. Liquid crystalline (dichotic) behaviour of alkyl substituted HBC‘s
R = C12H25
Hexadodecyl-hexa-peri-hexabenzocoronene (HBC-C12)

189. Charge carrier mobility in HHTT

190. 1H DQ MAS NMR spectra of HBC-C12
a-deuterated fully protonated

192. Proposed stacking model based on solid state NMR

193. „Graphitic“ stacking

194. Spinning side band simulation in the DQ time domain
For an isolated spin pair, using N cycles of the recoupling sequence for both the excitation and reconversion of DQCs, the DQ time domain signal is given by:
b and g are Euler angles relating the PAF of the diploar coupling tensor to the rotor fixed reference frame
with
-> distance information in a rigid system, or indication of mobility:
Ref.: Graf et al. J. Chem. Phys. 1997, 106, 885

195. Homonuclear correlation between I = 1/2 spins

196. DQ spinning side band patterns
aromatic protons at 8.3 ppm
(crystalline phase)
DQ spinning side band patterns
wR = 35 kHz
aromatic protons at 6.2 ppm (LC phase)
wR = 10 kHz
aliphatic protons at 1.2 ppm
(crystalline phase)
wR = 35 kHz
fitted dipolar coupling constants

197. Effect of additional phenyl spacers
R = -C12H25 or -C6H4-C12H25

200. Space filling model for HBC-PhC1

201. X-ray diffraction patterns of the mesophases

202. Let us have a tour of solid state NMR following Professor Malcolm H
Let us have a tour of solid state NMR following Professor Malcolm H. Levitt.