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