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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
