Chapter 7

CHARACTERIZATION METHODS:
Solid State NMR

Dr. rer. nat. I Wayan Karyasa, S.Pd., M.Sc.

 7.4 Solid State NMR
7.4.1 Principle
7.4.2 Solution NMR vs Solid State NMR
7.4.3 Magnetic Interaction in solid State
7.4.4 Methods to Obtain High Resolution
Solid State NMR Spectra
7.4.5 Some Applications
7.4 Solid State NMR
7.4.1 Principle
The behaviour of magnetic moment of certain atomic nuclei under the influence of
external constant and alternating magnetic fields is the basic of NMR technique
(Engelhardt and Michel, 1987). This is also affected by the local fields created by the
surrounding nuclei and by the electronic charge distribution around the nuclei. When
the magnetic field is applied, the nuclear moments orient themselves with only certain
allowed orientations.
The nuclear magnetic moment () is proportional to the nuclear spin () as the
equation (Abraham, et al., 1990):

  h/2
where  = magnetogyric ratio (i.e. a constant for each particular nucleus)

When a nucleus of magnetogyric ratio  is placed in a magnetic field B (in laboratory

1-15 Tesla), the resonant condition for general NMR experiments is satisfied when the
frequency of the applied radiation  (i.e. most atoms are in radio-frequency region, 5-
600 MHz) is given by:

B2
Table: Some common nuclei used in NMR experiments (Lynden-
Bell and Harris, 1971)

 Frequency Spin Isotropic natural

Nucleus (MHz/Tesla) (MHz at field of 4.7 T) (Units of h) abundance (%)

1H 42.57 200.00 ½ 99.98

2H 6.54 30.70 1 0.016
11B 13.66 64.17 3/2 81.2
13C 10.71 50.29 ½ 1.1
14N 3.08 14.45 1 99.64
15N 4.31 20.27 ½ 0.37
17O 5.77 21.11 5/2 0.037
19F 40.06 188.15 ½ 100
27Al 11.09 52.11 5/2 100
29Si 8.46 39.73 ½ 4.7
31P 17.24 80.96 ½ 100
195Pt 9.15 42.00 ½ 33.7
7.4.2 Solution NMR vs Solid State NMR

In Solution NMR, high

resolution spectra due to
averaging of anisotropic NMR
interactions by rapid random
motion on the molecules
imparted on this state.

In Solid State NMR, very

broad spectra, featureless
hump and very little chemical
information provided due to
some effects of magnetic
interaction in the solid.

It is difficult to convert the solid Magnetic interaction in the solid state?

samples to liquids or solution
and to work with a single crystal. To obtain high resolution Solid State NMR spectra?
7.4.3 Magnetic Interaction in the Solid State
1: Zeeman interaction of nuclear spins
2: Direct dipolar spin interaction
3: Indirect spin-spin coupling (J-coupling),
nuclear-electron spin coupling
(paramagnetic), coupling of nuclear spins
with molecular electric field gradients
(quadrupolar interaction)
4: Direct spin-lattice interactions
3-5: Indirect spin-lattice interaction via
electrons
3-6: Chemical shielding and polarization of
nuclear spins by electrons
4-7: Coupling of nuclear spins to sound
fields

To obtain high resolution Solid State NMR, it can be considered to solve three main problems:
 line broadening as a result of dipole-dipole interaction
 chemical shift anisotropy resulting in rather broad and complex patterns
 nuclei in solids possess extremely long relaxation times
7.4.5 Methods to Obtain High Resolution Solid State NMR Spectra
a. Magic Angle Spinning (MAS)

The chemical shifts of solids are contributed by

the anisotropy of possible orientations of
molecules of the solids regarding the applied
field:
  (3cos2 - 1)/R3
Where  = the difference between the parallel
and perpendicular susceptibility,  = angle of
spinning, and R = the distance between the
anisotropy and the nucleus.
MAS can completely remove chemical shift
MAS introduces artificial motion (spinning rate anisotropy and diminish dipolar and
1-35 kHz) by placing the axis of the sample quadrupolar interactions but the latter is not
rotor at the magic angle (54.74°) with respect completely removed. To completely remove
to B0 - the term 3cos2 - 1 = 0 when  = the quadrupolar interaction, spinning the
54.74°. The rate of MAS must be greater than sample about two MAS (so called double
or equal to the magnitude of the anisotropic rotation (DOR) MAS technique) at the
interaction to average it to zero. same times is often applied
b. Dilution

This occurs naturally for many nuclei in the periodic table, as the NMR active isotope may
have a low natural abundance (e.g., 13C, 1.108% n.a.), and the dipolar interactions.
However, this only leads to “high-resolution” spectra if there are no heteronuclear dipolar
interactions (i.e. with protons, fluorine)!

c. Multiple-pulse Sequence (MPS)

MPS NMR technique is primarily used to eliminate both the heteronuclear (very
common) and homonuclear (less common) dipolar couplings. A combination of MPS with
MAS in strong magnetic field (called as combined rotation and multiple-pulse sequence,
CRAMPS) serves as special decoupling schemes for investigating rare spins in solid
samples. MPS part removes 1H-1H couplings and MAS part removes chemical shift
anisotropies.

d. High-power Dipolar Decoupling (DD)

DD is used to suppress the influence of the heteronuclear dipolar Hamiltonian which

corresponds to heteronuclear coupling interactions between rare spins (i.e. such as 29Si,
13C and 15N) and abundant spins (1H). The particular dipolar interaction is often not

completely removed by MAS NMR. DD applies a strong continuous or pulsed radio-

frequency field.
e. Cross-polarization (CP)
In CP technique, polarization from abundant spins such as 1H or 19F is transferred to dilute
spins such as 13C or15N. CP technique consists of three steps (Engelhardt, 1991):
 (1) excitation of the  spins by a 90° pulse.
 (2) polarization transfer from  to S spins by simultaneous irradiation of radio-frequency
fields B1 and B1S of  and S spins respectfully according to the Hartmann-Hahn conditions:
 B1 = S B1S
 (3) acquisition of the free induction decay (FID) of S spins with continued irradiation of the
1H field for heteronuclear dipolar decoupling.

CP requires that nuclei are dipolar coupled to one another, and surprisingly, it even works
while samples are being spun rapidly at the magic angle (though not if the spinning rate is
greater than the anisotropic interaction)  CPMAS NMR
7.4.6 Some Applications
Most of the NMR active nuclei
in the periodic table are
available for investigation by
solids NMR, due to higher
magnetic fields, innovative
pulse sequences, and
improved electronics, computer
and probe technology.

Some applications of Solid State NMR:

organic complexes inorganic complexes
zeolites mesoporous solids
microporous solids aluminosilicates/phosphates
minerals biological molecules
glasses cements
food products wood
ceramics bones
semiconductors metals and alloys
archaelogical specimens polymers
resins surfaces
 American Mineralogist, Volume 85, pages 1030–1037, 2000
Solid state NMR study of oxygen site exchange and Al-O-Al site concentration in analcime

XING CHENG, PEIDONG ZHAO, AND JONATHAN F. STEBBINS*

Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305-2115, U.S.A.

Oxygen isotope exchange between natural analcime and water vapor at low pressure is studied by 17O NMR, which can
distinguish Si-O-Si and Si-O-Al sites and provide information on site specific exchange kinetics and mechanisms. Si-O-Al
sites in analcime are found to exchange faster than Si-O-Si sites at lower temperature (400 °C). At higher temperature (500
°C), the exchange rates for the two types of site are similar, suggesting that the exchange process for Si-O-Si has a higher
activation energy, as predicted by published theoretical calculations. The overall exchange reaction appears to be controlled
largely by reaction at sites, not diffusion. Static 17O spectra show an anomalously high ratio of Si-O-Si to Si-O-Al sites,
suggesting the presence of a few percent of Al-O-Al sites, which are indeed resolved and observed in triple quantum magic-
angle spinning (3QMAS) spectra.
7.4.7 Conclusion
Solid State NMR is very powerful method in characterizing and
analyzing phases and structures of solid state materials. However, it
can be applied complimentary and routinely as a solid state chemistry
laboratory infrastructure, particularly powder XRD.