Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1...

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Advanced NMR spectroscopy Advanced NMR spectroscopy of of quadrupolar quadrupolar nuclei nuclei Aut Aut h h o o r: r: Libor Libor Kobera Kobera

Transcript of Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1...

Page 1: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Advanced NMR spectroscopy Advanced NMR spectroscopy

of of quadrupolarquadrupolar nuclei nuclei

AutAuthhoor:r: Libor Libor KoberaKobera

Page 2: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

NMR active nuclei – problem of inorganic systems; I>1/2

22 spins I=1/2

77 spins I=3/2, 5/2,9/21 spin I=1

Spectrum: narrow signal

0,1-100 Hz

Spectrum: broad signal

1000-100000 Hz

I=1/2

- /2

m

-1 2

/21

2

I=1/2

- /2

m

-1 2

/21

2

Zeemanova

interakce

I=3/2

3/2

m

1/2

-1/2

-3/2

ν0

ν0

ν0

3Q

Zeemanova

interakce

I=3/2

3/2

m

1/2

-1/2

-3/2

ν0

ν0

ν0

3Q

Page 3: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Quadrupolar broadening

( ) ( )

( ) ( )3cos30cos358

1cos

1cos32

1cos

24

4

2

2

+−=

−=

θθθ

θθ

P

P

= 0

=−7/18

θ = 54.74°MAS narrows 2nd order broadening by

a factor 3 to 4

1st order quadrupolar coupling

2nd order quadrupolar coupling

ν0-νQ1-νSTQ

2

Zeeman

interaction

1st order

quadrupolar

coupling

2nd order

quadrupolar

coupling

I=3/2

3/2

m

1/2

-1/2

-3/2

ν0

ν0

ν0

ν0

ν0-νQ1

ν0+νQ1 ν0+νQ

1+νSTQ2

ν0-νCTQ2

3Q

ν0-νQ1-νSTQ

2

Zeeman

interaction

1st order

quadrupolar

coupling

2nd order

quadrupolar

coupling

I=3/2

3/2

m

1/2

-1/2

-3/2

ν0

ν0

ν0

ν0

ν0-νQ1

ν0+νQ1 ν0+νQ

1+νSTQ2

ν0-νCTQ2

3Q

54.7°

Page 4: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

NMR techniques for quadrupolar nuclei DOR/DAS/MQMAS

DOR NMR DAS NMR MQ/MAS NMR

1D spectrum 2D spectrum 2D spectrum

Page 5: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

DOR: DOuble Rotation

In practice:

ν0 7-8 kHz

v1 1-2 kHzAdvantages

quantitative

high sensitivity

low rf field requirement

fast 1D experiment

Disadvantages

special and expensive probes

required

low spinning frequency

stable spinning is difficult

Only for crystalline

compounds

23Na Static(top),

MAS(middle),

DOR(bottom)

NMR spectra of sodium oxalate

π/2π/2

Page 6: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

ω1

ω2

ω1

ω2

ω1

ω2

ω1

ω2

ω1

ω2

ω1

ω2

Shear

DAS: Dynamic Angle Spinning

Advantages

quantitative

high sensitivity

low rf field requirement

For amorphous compounds

π/2π/2

π/2

Switch

37,38° 79,19°π/2

π/2π/2

Switch

37,38° 79,19°

Disadvantages

special and expensive

probes required

nuclei with long T1

Impossible decoupling

(β1 and β2≠ 54.7°)

Page 7: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

MQ/MAS: Multi Quantum Magic Angle Spinning

Avantages

Easy to implement and no

special probe required

Good for abundant nuclei

Good for nuclei with short T1

17O NMR spectra of hydroxyapatite

Disadvantages

Not quantitative

High rf field required for

the excitation pulse

Poor sensivity for large CQ

57.238

49.071

44.480

t1 t2

z-filter

π/227Al

t1 t2

z-filter

π/227Al

ppm-500

01020304050607080ppm

0

0 CS

QIS

ppm-500

01020304050607080ppm

0

0 CSCS

QISQIS

ppm-500

-20-10010203040ppm

0

0

A

CSQIS

ppm-500

-20-10010203040ppm

0

0

AA

CSQIS

Shear

Page 8: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

MQ/MAS spectrum - analysis

A

CSQIS

Information about

Number of species

Orderliness

Local geometry

determine of CQ, ηQ by simulation

MQ-MAS NMR spectra exhibit a higher resolutionthan DAS or DOR spectra

Chemical shift

27

1017 cs 21 FF

δδδ

+=

Quadrupolar coupling

constant

6

0

2

10])12(4[

3)1(4

10

3

3121

⋅−

−+⋅=

+=−

=

ν

ηδδ

II

IIk

CPk

PQQ

FF

Q

Page 9: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Amorphous materials –glasses, cements, AIPs etc…

Sodium /

Potasium

H2 0

H 20

H 20

H 20

H20

H 20 H 2

0H 2

0 H 20H2

0H

2 0

H20H

20

H20

H20

H20H

20 H20H20

H20

H20

H20

H2 0

H2 0

H2 0

H2 0

H2 0

H2 0

H20

H20

H20

H20

H 20

H20 H20

H2 0

H20

H 20

H2 0

H2 0

H2 0

H20H20H20H20

aluminum

oxygen

oxygen

Sodium /

Potasium

silicon

Amorphous alumino-silicate polymers AIP`s

Boron glasses

crystalline

amorphous

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Preparation and properties of AIP`s

Kaolin650°C

Metakaolin

Al4(OH)8Si4O10

1. Calcination

activation @ RT

Primary units2.Activation

Si2O5.Al2O2

Metakaolin

Si2O5.Al2O2 + 5H2O+2NaOH

Si

OH

OHOH

OH

Si

OH

OHOH

OH

Al-

OH

OHOH

OH Na+

Al-

OH

OHOH

OH Na+

polycondensation @ RT

Primary building units

3. Polycondensation

-4H2O

Amorphous network

Si

OH

OHOH

OH

Si

OH

OHOH

OH

Al-

OH

OHOH

OH Na+

Al-

OH

OHOH

OH Na+

PropertiesProperties

excellent mechanical strength

resistance to high

temperatures

easy recycling

low production of CO2

long-time stability

Q4

(4Al)

Q4

(3 Al)

Q4

(2 Al)

Q4

(1 Al )

Q4

(0 Al)

Si O4

AlO4

Building unitsBuilding units

Si

OH

O

OOH

Al-

OH

OOH

Si

OHO

OH

Al-

OHOH

Na+

Na+

OH

2

OH

2 OH

2

OH 2

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Preparation and basic characterization

29Si MAS NMR

0

1

2

3

4

5

ppm-130-120-110-100-90-80-70

ppm-130-120-110-100-90-80-70

0

1

2

3

4

5

Q3(nAl); 2%

Q4(4Al); 28%

Q4(3Al); 35%

Q4(2Al); 22%

Q4(0Al); 8%

Q4(1Al); 5%

Q3(nAl); 1%

Q4(4Al); 27%

Q4(3Al); 36%

Q4(2Al); 22%

Q4(1Al); 5%

Q4(0Al); 9%

ppm01020304050607080

ppm01020304050607080

27Al MAS NMR

Al(IV) Al(IV)

Al(VI) Al(VI)

ppm-40-30-20-10010203040

ppm-40-30-20-10010203040

23Na MAS NMR

stable vs. unstable

Page 12: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Characterization after accelerated aging

ppm-130-120-110-100-90-80-70

0

1

2

3

4

5

Q3(nAl); 3%

Q4(4Al); 23%

Q4(3Al); 27% Q4(2Al); 36%

Q4(1Al); 10%

Q4(0Al); 1%

ppm-130-120-110-100-90-80-70

0

1

3

4

5

Q3(nAl); 11%

Q4(4Al); 16%

Q4(3Al); 30%Q4(2Al); 29%

Q4(1Al); 9%

Q4(0Al); 5%

ppm-130-120-110-100-90-80-70

0

1

2

3

4

5

Q3(nAl); 3%

Q4(4Al); 23%

Q4(3Al); 27% Q4(2Al); 36%

Q4(1Al); 10%

Q4(0Al); 1%

ppm-130-120-110-100-90-80-70

0

1

3

4

5

Q3(nAl); 11%

Q4(4Al); 16%

Q4(3Al); 30%Q4(2Al); 29%

Q4(1Al); 9%

Q4(0Al); 5%

stable vs. unstable

27Al MAS NMR

ppm01020304050607080

ppm01020304050607080

27Al MAS NMR

ppm01020304050607080

ppm01020304050607080

Al(IV)Al(IV)

Al(VI) Al(VI)

23Na MAS NMR

ppm-40-30-20-10010203040 ppm

-40-30-20-10010203040

29Si MAS NMR

Page 13: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

23Na MQ/MAS of AIP systems

stable vs. unstableCompression

strength70 MPa

Compression strength70 MPa

Compression strength70 MPa

Compression strength30 MPa

ppm-20-1001020

-20

-10

0

10

20ppm

0

0 CS

A

QIS

ppm-20-1001020

-20

-10

0

10

20ppm

0

0 CS

A

QIS

ppm-20-1001020

-20

-10

0

10

20ppm

0

0 CS

A

QIS

ppm-20-1001020

-20

-10

0

10

20ppm

0

0 CS

A

QIS

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27Al MQ/MAS of AIP systems

ppm45.050.055.060.065.070.075.0

50

60

70

80ppm

0

0

A

CSQIS

ppm45.050.055.060.065.070.075.0

50

60

70

80ppm

0

0

A

CSQIS

A

CSQIS

ppm45.050.055.060.065.070.075.0

50

60

70

80ppm

0

0

A

CSQIS

stable vs. unstable

Accelerated aging

Compression strength70 MPa

Compression strength70 MPa

Compression strength70 MPa

Compression strength30 MPa

Al-

O+

O

O

OSi

Si

Si

Si

H

Al-

O+

O

O

OSi

Si

Si

Si

Na

ppm45.050.055.060.065.070.075.0

50

60

70

80ppm

0

0

Al-

O

O

O

O

Si

Si

Si

Si

Al

OHOH

OH

Page 15: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

stable vs. unstable

Accelerated aging

1H-1H MAS NMR correlation spectra

ppm

20 15 10 5 0 ppm

-5

20

15

10

5

0

ppm

20 15 10 5 0 ppm

-5

20

15

10

5

0

ppm

20 15 10 5 0 ppm

-5

20

15

10

5

0

ppm

20 15 10 5 0 ppm

-5

20

15

10

5

0

Page 16: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Summary

Since 74% of all magnetically active naturally occurring isotopes

are quadrupolar nuclei

Suitable for descriptions of local geometry to long distance

Combination of high magnetic field and 2D MQ/MAS NMR

experiments allow obtaining high-resolution spectra with usual

MAS probe

Possible for all types of materials (crystalline or amorphous)

Page 17: Advanced NMR spectroscopy of quadrupolar nuclei · 22 spins I= 1/2 77 spins I=3 /2 , 5/2 ,9/2 1 spin I= 1 Spectrum: narrow ... DOR/DAS/MQMAS DOR NMR DAS NMR MQ ... DOR: DOubleRotation

Thanks for your attention Thanks for your attention