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NMRNulcearMagnetic ResonanceNMRNMRNMRNMRNMRNMRNMR
NMRNMR
NMRNMRSiNMRNMRNMRNMR
JEOL RESONANCE IncToshihito Nakai
Solid-state 29Si NMR for Evaluating Microscopic Sites of Glass Materials :29Si Measurements in Multinuclear NMRMost Efficient Measurements
Quantitative MeasurementsAdvanced Measurements
JEOL RESONANCE
Si NMR: NMR
TEL FAX Email : tnakai@jeolcojp
Q1 Q2
Q3 Q4
Na 2O
-O
Si
Si
OSi
O
+Na
Si
Si
O
Si
O
O
O
-O
SiO
SiO O
O
O
O
-O
O
NMRSi
SiIV SiOBONa
NMRMaekawa sodium silicate glassNaOSiNMRSi Maekawa
SiOQQdeconvolutionNaQQNa SiOSi NMRNMRSi
Reprinted from TNanba et alGeochimCosmochimActawith permission from Elsevier
Si NMRReprinted from HMaekawa et alJNon-CrystSolidswith permis-sion from Elsevier
NEW GLASS Vol No
Si|O|
ROSiOR|R
Si|O|
ROSiOSi|R
Si|O|
SiOSiOSi|R
R|O|
ROSiOR|R
R|O|
ROSiOR|O|R
Si|O|
ROSiOR|O|R
Si|O|
ROSiOSi|O|R
Si|O|
SiOSiOSi|O|R
Si|O|
SiOSiOSi|O|Si
R|O|
RSiR|R
Si|O|
RSiR|R
Annotation of All Species of Si(IV) - O Tetrahedral Units with the Second Neighboring -Si / R
R|O|
RSiOR|R
Si|O|
RSiOR|R
Si|O|
RSiOSi|R
M0 : O1, O-Si0 M1 : O1, O-Si1
D0 : O2, O-Si0 D1 : O2, O-Si1 D2 : O2, O-Si2
T0 : O3, O-Si0 T1 : O3, O-Si1 T2 : O3, O-Si2 T3 : O3, O-Si3
Q0 : O4, O-Si0 Q1 : O4, O-Si1 Q2 : O4, O-Si2 Q3 : O4, O-Si3 Q4 : O4, O-Si4
TMS : O0, O-Si0
|RSiR
|R
R
R = CH3
0 50 100 ppm
T3
T2
T1
T0
Q4
Q3 Q2 Q1
Q0
D2 D1
D0
M 1 M 0
TMS
Si Annotation Si NMRNMR
NMRSi
HC NMRSi
SiIVAnnotation
SiIV
NEW GLASS Vol No
OCa NMRSi Na NMR
Spin Quantum Number
NMRXIXIX IXIX
C NMRNMRB Al
NMRNMRLi B NMRSiB Al
NMRNMR FrequencyGyromagnetic RatioNMR
NMRNMR gyromagnetic ra-tioS/NNMRlow-NMRNMR
Li Pb NMROMgTi TNMRTNMRlow- NMRNMR
NMRNMRNMRNMRlow- NMRNMR
Si NMR
NEW GLASS Vol No
Normalizedto 13CRc (X)
Normalizedto 29SiRSi (X)
[ppm][kHz]
at 11.75 Tat 24.20 T
4.69(4.683 - 4.70) (r(29Si-1H) = 1.74 )
99.99(99.985 -99.989) (r(1H-1H) = 1.78 )
7.5(7.42 - 7.59)
92.5(92.41 - 92.5)
19.7(19.58 - 19.9)
80.1
1.11(1.107 - 1.110) (r(13C-1H) = 1.09 )
99.63(99.630 - 99.632)
0.038(0.037 - 0.038)
100
10.1(10.0 - 10.13)
100
0.135
7.4(7.28 - 7.44)
5.5(5.41 - 5.51)
22.8(22.6 - 22.92) (r(207Pb-1H) = 1.88 )
(1H) = 2.675 222 005 ( 0.000 000 063) x 108 [rad/s 1/T] (13C) = 0.672 828 410 x 108 [rad/s 1/T] RA(X) = ( Nabd(X) / Nabd(A) ) | (X) / (A) | 3 D(1H-1H) = (0 / 4) (h2 (1H) 2 / r(1H-1H) 3 ) [kHz/3]* h = 6.626 075 5 [Js] = h/2 [(J s) /rad] = 120.120 3 [kHz/3] (for r(
1H-1H) = 1)0 = 4 x 10-7 [H/m] 0 / 4 = 10-7 [H/(mrad)] D(X-1H) = (0 / 4) (h2 X) 1H) / r(X-1H) 3 [kHz/3]
SpinQuantumNumber
I (X)
Nucleus(Isotope)
X
Receptivity(Relative Sensitivity)
Chemical ShiftAnisotropy (X)
(for Spin-1/2 Nuclei)Magnetic Dipolar
Interaction with 1HD (X-1H) [kHz/ 3]
(for Spin-1/2 Nuclei)
NaturalAbundanceNabd (X) [%]
NMRFrequencyat 24.20 T(X) [MHz]
NMRFrequencyat 11.75 T0 (X) [MHz]
GyromagneticRatio
(X) (= )[MHz/T]
X
Everybodys Playmate
X
Cinderella Nucleus
X
Sleeping Beauty
X
Good Worker
Legend of Nucleus
Spin Quantum Number NMR Frequency Legend of Nucleus Properties
Dipolar Interaction Chemical Shift Anisotropy
X 1/2 Half-integer Integer
> 300 MHz 100 300 50 100 0 50
X
No Problem Can Decouple Challenging
X No Problem Easy Spin-away Can Spin-away Untractable
X
> 80 % 10 80 1 10 0 1
X
Natural Abundance Receptivity High Moderate Low
X
Si NMR
NEW GLASS Vol No
Si Si C NMR
Natural AbundanceNMR
ONMRONMROSi
ReceptivityReceptivityRAXA AX XXA
RAXXANabdXNabdAIXIXIAIAC NMRC RCXXC Si Si NMRC NMR
HMagnetic Dipolar InteractionNMR
NMRH
HNMRHHC 1H-1H HHHHH
Si NMRH
Chemical Shift Ani-sotropyNMR
NMRCppmSi ppmMagic Angle
SpinningMASHzTC kHzSi kHz
NEW GLASS Vol No
abun
danc
e0
10.0
20.0
30.0
40.0
X : parts per Million : Silicon290 -100.0
S/N = 59
Exp. time: 4.5 h
Rep. time: 120 s
Number of scans: 128
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
X : parts per Million : Silicon290 -100.0
S/N = 128
Exp. time: 9 h
Nunmber of scans: 400
Rep. time : 80 s = 1.2564 * T1_max(63 s)
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
X : parts per Million : Silicon290 -100.0
S/N = 142
Exp. time: 34h
Number of scans: 400
Rep. time: 300 s = 5 * T1_max(63 s)
a b c
SiNMR
NMRSi NMRaSi NMR
T S/NNMRSiNMR
mm
mmSi NMRS/Namm
NMRa
NEW GLASS Vol No
NMRNMRNMRNMRS/NSi NMR
TSiTT S/NT S/N
S/NT
TT S/NTTTSi
aSi NMRss doubleexponential Si TTSi
ssS/NbaS/NS/N S/N
x Sx TSi
NEW GLASS Vol No
TTT x
cos =e-xxoptx Ernst xopt Sx Sx Sx
xSx
S/NNMR Si sTSisSiTSisNMRT
T
cssbssNMR
S/NmmSi NMR
PASS
NMRHzSSB : Spinning Side-bandSSB SSBNMR
kHz SSBNMR
SSBPASSPhase-Adjusted Spinning Sideband
NEW GLASS Vol No
PASS
PASS SSBshearingSSBSSB PASS
Si NMRQQPASSSi NMR
NMR Pb PASS SSBTOSSTOtal Spinning SidebandSSBPb
CPMGCPMGDQMAS
Si NMR
Si PASS
PASS Si NMR
PASS Pb PASS
NEW GLASS Vol No
X : parts per Million : Silicon29-106.0-107.0 -108.0 -109.0 -110.0 -111.0 -112.0 -113.0 -114.0 -115.0 -116.0 -117.0 -118.0 -119.0 -120.0 -121.0-122.0
:p
arts
perM
illio
n:S
ilico
n29
-220
.0-2
30.0
-240
.0 2D DQMAS
X : parts per Million : Silicon29-10.0-20.0 -30.0 -40.0 -50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0 -180.0
1D DQMAS
1D DQMASwith CPMG
SNR = 7
SNR = 40
5.71 time S/N,1/33 time saving !
X : parts per Million : Silicon29-50.0 -60.0 -70.0 -80.0 -90.0 -100.0 -110.0 -120.0 -130.0 -140.0 -150.0 -160.0 -170.0
0[s]
29Si CPMAS with CPMG detection(48 echoes per scan are detected)
4 scansSNR: 16
4 scans
SNR: 92
5.75 time S/N,1/33 time saving !
CPMGCarrPur-cellMeiboomGillNMRNMR S/NSi
NMR S/N
CPMG
NMR INADEQUATEDQMASSi connectivity
CPMG
CPMGSi NMR
Si CPMGDQMAS
NEW GLASS Vol No
NMRNMRNMR
TNanbaMNishimuraand YMiuraGeochimCosmochimActa
HMaekawaTMaekawaKKawamuraand TYokokawaJNon-CrystSolids
RKHarris and BEMannNMR and the Peri-odic TableAcademic Press
PLaszloNMR of Newly Accesible NucleiAcadmic Press
RFreemanA Handbook of Nuclear MagneticResonancend EditionAdison Wesley LongmanLtd
KDMacKenzie and MESmithMultinuclearSolidstate NMR of Inorganic MaterialsFergamonNMR
TNakaiRecent Progress in High-field Low-gamma Solid-state NMR and Its Applications toCatalysts and BiomoleculesA series of invited lec-tures in National Sun Yat-sen UniversityNationalChung Cheng Universityand National Taiwan Uni-versityJune
NMRDCApperleyRKHarrisand PHodgkinsonSolid-state NMR : Basic Principles & PracticeMo-mentum Press
RRErnstGBodenhausenand AWokaunPrinciples of Nuclear Magnetic Resonance in Oneand Two DimensionsClarendon PressNMR
WTDixonJMagnReson.,ONAntzukinSCShekarand MHLevittA
ONAntzukinProgNuclMagnReson.,
WTDixonJChemPhys.,HYCarr and EMPurcellPhysRev.,
SMeiboom and DGillRevSciInstrum.,
FHLarsenHJJakobsenPDEllisand NCNielsenJMagnReson.,
FHLarsen and IFarnanChemPhysLett.,
SSHouFLBeyerand KSchmidt-RohrSolidstate NuclMagnReson.,
JWWienchVS-YLinand MPruskiJMagnReson.,
ABaxRFreemanand SPKempsellJAmChemSoc.,
NEW GLASS Vol No