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�
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’
0Q’
1Q’
2Q’
3Q’
4Ro ≈ 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
5O(PO
4)
6Ro ≈ 3815Hz
d1= 5s/ NS= 480 / 96 slices
t
CP= 40 ms
Bearing = 1080 mB
Drive = 200 mB
Si(HPO
4)
2.H
2O
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
T°
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
T°
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= 400s
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°
T° 20-25% signal enhancement
Si
5O(PO
4)
6Si(HPO
4)
2.H
2O
SiO
2Q
3Q
41