1. 核磁共振光譜與影像導論
Introduction to NMR Spectroscopy and Imaging Lecture 09 Applications of Solid State NMR (Spring Term, 2011) Department of Chemistry National Sun Yat-sen University

2. Applications of Solid State NMR
Polymers
Glasses
Porous materials
Liquid crystals

3. Schematic of a typical semicrystalline linear polymer

4. Stereochemical issue in substituted polymers

5. Signature of stereoregularity in the solid state spectrum

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

7. 3D static 13C exchange spectra of polyethyleneoxide polyvinylacetate

8. Applications
Polymers
Glasses
Porous materials
Liquid crystals

9. 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

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

11. Structure of glasses (I)
NBO BO

12. 29Si NMR spectra for sodium silicate glasses
static MAS Q4
mole %
Na2O 34 37 41 Q3 Q2
Q3 + Q2
ppm

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

14. 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)

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

16. 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

17. 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

18. 31P MAS NMR spectra for sodium phosphate glasses
mol % Na2O 56 53 40 30 15 5
Q1 Q2 Q3
ppm

19. 31P double-quantum NMR spectrum
-60
2-2
Double-quantum dimension (ppm)
1-2
2-1
1-1
0 -30
Single-quantum dimension

20. 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)

21. 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)

22. 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)

23. 11B-{27Al} CP-HETCOR NMR spectrum
BO4
BO3
-80 80
AlO6
AlO5
AlO4
ppm

24. Applications
Polymers
Glasses
Porous materials
Liquid crystals

25. Porous materials
Zeolite A
Sodalite

26. Porous materials
Faujasite
Cancrinite

27. Porous materials
Zeolite ZK-5
Zeolite Rho

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

29. 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

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

31. 29Si MAS NMR spectrum of highly siliceous mordenite3 2
29Si MAS NMR spectrum of highly siliceous mordenite 1
Intensities
ppm

32. 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 °

33. 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 °

34. 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

35. 29Si MAS NMR spectra of ultrastabilized and hydrothermally realuminated zeolites1
Si/Al = 2.56 3
ppm

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

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

38. 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

39. 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

40. 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

41. 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

42. 13C MAS NMR spectrum of H-ZSM-5 with 50 torr of adsorbed MeOH heated to 300 °C for 35 mins
ppm

43. 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

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

45. 13C NMR spin diffusion spectrum of products of methanol conversion over zeolite ZSM-5
ppm

46. 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

47. Methylated aromatic products* CO * * * *
ppm

48. 129Xe NMR as a sensitive tool for materials
0: reference
S: surface collisions
Xe: Xe-Xe collisions
E: electric field effect
M: paramagnetic species

49. 129Xe as a sensitive probe for various zeolites
ZK4
ZSM-5
1021
NaY
ZSM-11
K - L
Xe atoms /g
omega
1020
ppm

50. Applications
Polymers
Glasses
Porous materials
Liquid crystals

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

52. HBC monolayer on HOPG

53. Phase transitions of alkyl substituted HBC

54. Temperature dependence of the one dimensional charge carrier mobility

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

56. Charge carrier mobility in HHTT

57. 1H DQ MAS NMR spectra of HBC-C12
a-deuterated fully protonated

59. Proposed stacking model based on solid state NMR

60. „Graphitic“ stacking

61. 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

62. Homonuclear correlation between I = 1/2 spins

63. 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

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

67. Space filling model for HBC-PhC1

68. X-ray diffraction patterns of the mesophases