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Structural and 31P NMR investigation of Bi(MM')2PO6 statistic solid solutions : Deconvolution of lattice constraints and cationic influences

Identifieur interne : 000158 ( PascalFrancis/Checkpoint ); précédent : 000157; suivant : 000159

Structural and 31P NMR investigation of Bi(MM')2PO6 statistic solid solutions : Deconvolution of lattice constraints and cationic influences

Auteurs : Marie Colmont [France] ; Laurent Delevoye [France] ; EL MOSTAFA KETATNI [Maroc] ; Lionel Montagne [France] ; Olivier Mentre [France]

Source :

RBID : Pascal:06-0397501

Descripteurs français

English descriptors

Abstract

Two solid solutions BiMxMg2-x)PO6 (with M2+ = Zn or Cd) have been studied through 31P MAS NMR. The analysis has been performed on the basis of refined crystal structures through X-ray diffraction and neutron diffraction. The BiZnxMg(2-x)PO6 does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn2+ for Mg2+ substitution. On the other hand, the Cd2+ for Mg2+ substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/lCd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each configuration of the statistical Cd2+/Mg2+ mixed occupancy. The match is further improved when one takes into account the influence of the 2nd cationic sphere that is available from high-field NMR data (18.8T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a2 effective field into two sub-effects: a lattice constraint-only term and a chemical-only term whose effects are directly quantifiable.


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Pascal:06-0397501

Le document en format XML

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<sup>31</sup>
P NMR investigation of Bi(MM')
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PO
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statistic solid solutions : Deconvolution of lattice constraints and cationic influences</title>
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<title xml:lang="en" level="a">Structural and
<sup>31</sup>
P NMR investigation of Bi(MM')
<sub>2</sub>
PO
<sub>6</sub>
statistic solid solutions : Deconvolution of lattice constraints and cationic influences</title>
<author>
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<series>
<title level="j" type="main">Journal of solid state chemistry : (Print)</title>
<title level="j" type="abbreviated">J. solid state chem. : (Print)</title>
<idno type="ISSN">0022-4596</idno>
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<date when="2006">2006</date>
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<idno type="ISSN">0022-4596</idno>
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<keywords scheme="KwdEn" xml:lang="en">
<term>Bismuth phosphates</term>
<term>Chemical shift</term>
<term>Cobalt phosphates</term>
<term>Deconvolution</term>
<term>Experimental study</term>
<term>Lattice parameters</term>
<term>Magnesium phosphates</term>
<term>Multi-element compounds</term>
<term>Neutron diffraction</term>
<term>Nuclear magnetic resonance</term>
<term>Refinement</term>
<term>Solid solutions</term>
<term>XRD</term>
<term>Zinc phosphates</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr">
<term>Etude expérimentale</term>
<term>Résonance magnétique nucléaire</term>
<term>Paramètre cristallin</term>
<term>Déconvolution</term>
<term>Affinement</term>
<term>Diffraction RX</term>
<term>Diffraction neutron</term>
<term>Déplacement chimique</term>
<term>Solution solide</term>
<term>Bismuth phosphate</term>
<term>Magnésium phosphate</term>
<term>Zinc phosphate</term>
<term>Cobalt phosphate</term>
<term>Composé n éléments</term>
<term>BiZnMg2-xPO6</term>
<term>Bi Mg O P Zn</term>
<term>BiCdMg2-xPO6</term>
<term>Bi Cd Mg O P</term>
<term>6166F</term>
<term>7660C</term>
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<div type="abstract" xml:lang="en">Two solid solutions BiM
<sub>x</sub>
Mg
<sub>2-x)</sub>
PO
<sub>6</sub>
(with M
<sup>2+</sup>
= Zn or Cd) have been studied through
<sup>31</sup>
P MAS NMR. The analysis has been performed on the basis of refined crystal structures through X-ray diffraction and neutron diffraction. The BiZn
<sub>x</sub>
Mg
<sub>(2-x</sub>
)PO
<sub>6</sub>
does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn
<sup>2+</sup>
for Mg
<sup>2+</sup>
substitution. On the other hand, the Cd
<sup>2+</sup>
for Mg
<sup>2+</sup>
substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/lCd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each configuration of the statistical Cd
<sup>2+</sup>
/Mg
<sup>2+</sup>
mixed occupancy. The match is further improved when one takes into account the influence of the 2nd cationic sphere that is available from high-field NMR data (18.8T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a
<sup>2</sup>
effective field into two sub-effects: a lattice constraint-only term and a chemical-only term whose effects are directly quantifiable.</div>
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<s1>Structural and
<sup>31</sup>
P NMR investigation of Bi(MM')
<sub>2</sub>
PO
<sub>6</sub>
statistic solid solutions : Deconvolution of lattice constraints and cationic influences</s1>
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<s0>Two solid solutions BiM
<sub>x</sub>
Mg
<sub>2-x)</sub>
PO
<sub>6</sub>
(with M
<sup>2+</sup>
= Zn or Cd) have been studied through
<sup>31</sup>
P MAS NMR. The analysis has been performed on the basis of refined crystal structures through X-ray diffraction and neutron diffraction. The BiZn
<sub>x</sub>
Mg
<sub>(2-x</sub>
)PO
<sub>6</sub>
does not provide direct evidence for sensitive changes in the phosphorus local symmetry. This result is in good agreement with structural data which show nearly unchanged lattices and atomic separations through the Zn
<sup>2+</sup>
for Mg
<sup>2+</sup>
substitution. On the other hand, the Cd
<sup>2+</sup>
for Mg
<sup>2+</sup>
substitution behaves differently. Indeed, up to five resonances are observed, each corresponding to one of the five first-cationic neighbour distributions, i.e. 4Mg/0Cd, 3Mg/lCd, 2Mg/2Cd, 1Mg/3Cd and 0Mg/4Cd. Their intensities match rather well the expected weight for each configuration of the statistical Cd
<sup>2+</sup>
/Mg
<sup>2+</sup>
mixed occupancy. The match is further improved when one takes into account the influence of the 2nd cationic sphere that is available from high-field NMR data (18.8T). Finally, the fine examination of the chemical shift for each resonance versus x allows to de-convolute the mean Z/a
<sup>2</sup>
effective field into two sub-effects: a lattice constraint-only term and a chemical-only term whose effects are directly quantifiable.</s0>
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<s0>Refinement</s0>
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<s5>07</s5>
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<s5>07</s5>
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<s0>Diffraction neutron</s0>
<s5>08</s5>
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<s0>Neutron diffraction</s0>
<s5>08</s5>
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<s0>Déplacement chimique</s0>
<s5>09</s5>
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<s0>Solid solutions</s0>
<s5>15</s5>
</fC03>
<fC03 i1="10" i2="3" l="FRE">
<s0>Bismuth phosphate</s0>
<s2>NK</s2>
<s5>16</s5>
</fC03>
<fC03 i1="10" i2="3" l="ENG">
<s0>Bismuth phosphates</s0>
<s2>NK</s2>
<s5>16</s5>
</fC03>
<fC03 i1="11" i2="3" l="FRE">
<s0>Magnésium phosphate</s0>
<s2>NK</s2>
<s5>17</s5>
</fC03>
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<s0>Magnesium phosphates</s0>
<s2>NK</s2>
<s5>17</s5>
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<s0>Zinc phosphate</s0>
<s2>NK</s2>
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<fC03 i1="13" i2="3" l="FRE">
<s0>Cobalt phosphate</s0>
<s2>NK</s2>
<s5>19</s5>
</fC03>
<fC03 i1="13" i2="3" l="ENG">
<s0>Cobalt phosphates</s0>
<s2>NK</s2>
<s5>19</s5>
</fC03>
<fC03 i1="14" i2="3" l="FRE">
<s0>Composé n éléments</s0>
<s5>20</s5>
</fC03>
<fC03 i1="14" i2="3" l="ENG">
<s0>Multi-element compounds</s0>
<s5>20</s5>
</fC03>
<fC03 i1="15" i2="3" l="FRE">
<s0>BiZnMg2-xPO6</s0>
<s4>INC</s4>
<s5>52</s5>
</fC03>
<fC03 i1="16" i2="3" l="FRE">
<s0>Bi Mg O P Zn</s0>
<s4>INC</s4>
<s5>53</s5>
</fC03>
<fC03 i1="17" i2="3" l="FRE">
<s0>BiCdMg2-xPO6</s0>
<s4>INC</s4>
<s5>54</s5>
</fC03>
<fC03 i1="18" i2="3" l="FRE">
<s0>Bi Cd Mg O P</s0>
<s4>INC</s4>
<s5>55</s5>
</fC03>
<fC03 i1="19" i2="3" l="FRE">
<s0>6166F</s0>
<s2>PAC</s2>
<s4>INC</s4>
<s5>56</s5>
</fC03>
<fC03 i1="20" i2="3" l="FRE">
<s0>7660C</s0>
<s2>PAC</s2>
<s4>INC</s4>
<s5>57</s5>
</fC03>
<fC07 i1="01" i2="3" l="FRE">
<s0>Composé minéral</s0>
<s5>48</s5>
</fC07>
<fC07 i1="01" i2="3" l="ENG">
<s0>Inorganic compounds</s0>
<s5>48</s5>
</fC07>
<fC07 i1="02" i2="3" l="FRE">
<s0>Métal transition composé</s0>
<s5>49</s5>
</fC07>
<fC07 i1="02" i2="3" l="ENG">
<s0>Transition element compounds</s0>
<s5>49</s5>
</fC07>
<fN21>
<s1>261</s1>
</fN21>
<fN44 i1="01">
<s1>PSI</s1>
</fN44>
<fN82>
<s1>PSI</s1>
</fN82>
</pA>
</standard>
</inist>
<affiliations>
<list>
<country>
<li>France</li>
<li>Maroc</li>
</country>
<region>
<li>Hauts-de-France</li>
<li>Nord-Pas-de-Calais</li>
</region>
<settlement>
<li>Villeneuve d'Ascq</li>
</settlement>
</list>
<tree>
<country name="France">
<region name="Hauts-de-France">
<name sortKey="Colmont, Marie" sort="Colmont, Marie" uniqKey="Colmont M" first="Marie" last="Colmont">Marie Colmont</name>
</region>
<name sortKey="Delevoye, Laurent" sort="Delevoye, Laurent" uniqKey="Delevoye L" first="Laurent" last="Delevoye">Laurent Delevoye</name>
<name sortKey="Mentre, Olivier" sort="Mentre, Olivier" uniqKey="Mentre O" first="Olivier" last="Mentre">Olivier Mentre</name>
<name sortKey="Montagne, Lionel" sort="Montagne, Lionel" uniqKey="Montagne L" first="Lionel" last="Montagne">Lionel Montagne</name>
</country>
<country name="Maroc">
<noRegion>
<name sortKey="El Mostafa Ketatni" sort="El Mostafa Ketatni" uniqKey="El Mostafa Ketatni" last="El Mostafa Ketatni">EL MOSTAFA KETATNI</name>
</noRegion>
</country>
</tree>
</affiliations>
</record>

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