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HAL Id: hal-01881898

https://hal.sorbonne-universite.fr/hal-01881898

Submitted on 26 Sep 2018

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Low Temperature NMR Study of Silicophosphate

Materials

Cristina Coelho, Guillaume Laurent, Christian Bonhomme

To cite this version:

Cristina Coelho, Guillaume Laurent, Christian Bonhomme. Low Temperature NMR Study of

Sil-icophosphate Materials. 9ème réunion de travail RMN du solide d’Eveux, Nov 2006, La Baume,

France. �hal-01881898�

(2)

Low Temperature NMR Study of Silicophosphate Materials

C. COELHO, G. LAURENT, C. BONHOMME

Laboratoire de Chimie de la Matière Condensée de Paris, CNRS-Université Pierre et Marie Curie, Paris

TEOS

EtOH

H

3

PO

4

NiCl

2

.6H

2

O (1%)

136°C

298K

278K

258K

238K

31

P MAS

Ro ≈ 8080 Hz

d1= 10s/ NS=128

Bearing= 2160 mB

Drive= 670 mB

ppm

-60

-50

-40

-30

-20

-10

0

10

No effect

signal

signal

Q’

0

Q’

1

Q’

2

Q’

3

Q’

4

Ro ≈ 3822 Hz

d1= 1s/ NS=16

Bearing= 1080 mB

Drive= 200 mB

ppm

-220

-200

-180

-160

-140

-120

-100

-80

-60

-40

-20

0

HETCOR

31

P 

29

Si MAS 238K

Si

5

O(PO

4

)

6

Ro ≈ 3815Hz

d1= 5s/ NS= 480 / 96 slices

t

CP

= 40 ms

Bearing = 1080 mB

Drive = 200 mB

Si(HPO

4

)

2

.H

2

O

Unknown phase

CP

31

P 

29

Si MAS

Ro ≈ 3800-3900Hz

d1= 8s/ NS= 1800

Bearing = 1080 mB

Drive = 200 mB

ppm

-180

-200

-220

-240

-160

-140

-120

-100

298K

238K

t

cp

= 5 ms

t

cp

= 40 ms

Silicophosphate can be used as bioactive materials for the growing of hydroxyapatite, or for protonic conduction.

They are also interesting models for the study of diatoms, organisms containing a biological part with phoshorous

and a shell of silica. The aim of this work is to develop methods to study by NMR interactions between

31

P and

29

Si

nuclei. Due to the mobility, it is difficult to see interactions at ambiant temperature. In order to improve the signal to

noise ratio and to study dynamic properties, we have used low temperature NMR. However, such study needs a

special equipement and a rigorous calibration, which has been done using

207

Pb NMR on Pb(NO

3

)

2

1

. This nucleus

is particulary sensitive to the temperature.

1

H MAS

ppm

-50

-40

-30

-20

-10

0

10

20

30

40

50

60

70

Ro ≈ 8080 Hz

d1= 10s/ NS=128

Bearing= 2160 mB

Drive= 670 mB

P-OH/SiOH

298K

278K

258K

238K

Signal

broadening

CP

1

H

 31

P MAS

Ro ≈ 8080 Hz

d1= 10s/ NS=400/t

CP

= 3ms

Bearing= 2160 mB

Drive= 670 mB

ppm

-60

-50

-40

-30

-20

-10

0

10

-20

-10

0

-50

-45

-40

-35

signal

10

20

30

40

50

60

70

0

2

4

6

8

10

a

im

a

n

ta

tio

n

contact time (ms)

Ro ≈ 3818 Hz

d1= 1s/ NS= 48

Bearing= 1080 mB

Drive= 200 mB

CP

1

H

 31

P MAS 234K

0

5

10

15

20

25

0

2

4

6

8

10

a

im

a

n

ta

tio

n

spin-lock time (ms)

fine peak

T

1rho

H

=0.257 ms +/- 0.009 ms

broad peak

T

1rho

H

=5.9 ms +/- 0.6ms

Ro ≈ 3700 Hz

d1= 1s/ NS=16

Bearing= 1080 mB

Drive= 200 mB

1

H relaxation MAS 234K

0

20

40

60

80

100

0

2

4

6

8

10

a

im

a

n

ta

tio

n

spin-lock time (ms)

fine peak

0.58 ms +/- 0.07 ms

broad peak

7 ms +/- 11ms

1

H

relaxation MAS 298K

Current Data Parameters NAME Pb(NO3)2-triple EXPNO 49 PROCNO 1 F2 - Acquisition Parameters Date_ 20060616 Time 16.52 INSTRUM spect PROBHD 4 mm MAS 1H/13 PULPROG zg TD 8192 SOLVENT D2O NS 4 DS 0 SWH 25000.000 Hz FIDRES 3.051758 Hz AQ 0.1639100 sec RG 4100 DW 20.000 usec DE 20.00 usec TE 233.0 K D1 40.00000000 sec ======== CHANNEL f1 ======== NUC1 207Pb P1 5.20 usec PL1 4.50 dB SFO1 62.5691242 MHz F2 - Processing parameters SI 16384 SF 62.5690027 MHz WDW EM SSB 0 LB 10.00 Hz GB 0 PC 0.80

207Pb mas ~1700Hz - av300 4Tr - Pb(NO3)2

Bp=640mB, Dp=50mB, multi_zgvt 20s

-40

-20

100

80

60

40

20

0

ppm

*

*

*

*

*

*

*

*

*

*

*

*

MAS ~1700Hz

293K

273K

253K

233K

313K (BT)

313K (HT)

333K

353K

373K

393K

207

Pb

-20

-15

-10

-5

0

5

10

15

20

0

500

1000 1500 2000 2500 3000

233 K

293 K

353 K

T

re

a

l

-T

d

es

ire

d

(

K

)

Bp+Dp (mB)

1

.7

k

H

z

8

kH

z

207

Pb MAS

Flow=2000L/h

Ro ≈ 3818 Hz

d1= 1s/ NS= 3600/t

CP

= 400s

Bearing= 1080 mB

Drive= 200 mB

ppm

-60

-50

-40

-30

-20

-10

0

*

*

298K

278K

258K

238K

CP

1

H

 31

P MAS

CP

1

H 

29

Si MAS

Ro ≈ 3.800-3.900 Hz

d1= 10s/ t

CP

= 5ms/ NS= 4000

Bearing = 1080 mB

Drive = 200 mB

ppm

-220

-200

-180

-160

-140

-120

-100

298K

268K

238K

45-60% signal enhancement on Q

3

/Q

4

/Si

5

O(PO

4

)

6

20% signal enhancement on Si(HPO

4

)

2

.H

2

O

T° 20-25% signal enhancement

Si

5

O(PO

4

)

6

Si(HPO

4

)

2

.H

2

O

SiO

2

Q

3

Q

4

1

Temperature Dependence of 207Pb MAS spectra of Solid Lead Nitrate. An accurate, Sensitive

Thermometer for Variable Temperature MAS, A. Bielecki and D. P. Burum, J. Magn. Reson.,

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