CN111087428A - Dissimilar metal substituted polyacid crystalline material and preparation method thereof - Google Patents
Dissimilar metal substituted polyacid crystalline material and preparation method thereof Download PDFInfo
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- 239000002178 crystalline material Substances 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
- -1 rare earth ion Chemical class 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- OKIIEJOIXGHUKX-UHFFFAOYSA-L Cadmium iodide Inorganic materials [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007974 sodium acetate buffer Substances 0.000 claims description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 238000009825 accumulation Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 abstract description 2
- LWXUYQCPFKRHRU-UHFFFAOYSA-N [W].[P].[O] Chemical compound [W].[P].[O] LWXUYQCPFKRHRU-UHFFFAOYSA-N 0.000 abstract 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 abstract 1
- 239000013460 polyoxometalate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001907 polarising light microscopy Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BBHWVKTXEIOYBU-UHFFFAOYSA-K lanthanum(3+) triacetate hexahydrate Chemical compound O.O.O.O.O.O.C(C)(=O)[O-].[La+3].C(C)(=O)[O-].C(C)(=O)[O-] BBHWVKTXEIOYBU-UHFFFAOYSA-K 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
A heterometallic metal substituted polyacid crystalline material and a preparation method thereof belong to the technical field of inorganic chemistry polyoxometalate. The invention uses the vacancy Keggin type phosphotungstic acid as a tungsten-oxygen cluster precursor, and adopts a hydrothermal synthesis technology to obtain a novel supported Cd2+、La3+Heterometallic modified organic-inorganic hybrid phosphorus-tungsten-oxygen cluster compound crystalline material [ Cd (en) ]2(H2O)]2{[Cd(en)2][Cd(en)2(H2O)]2[La(α‑PW11O39)‑(CH3COO)(H2O)]2}·5H2In this compound, dimeric { [ La (α -PW) substituted with acetate ions bridging the monotRE ions11O39)(CH3COO)(H2O)]}2 10‑Between the cluster blocks pass through [ Cd (en)2]2+The cations are connected to form a one-dimensional chain structure. In thatOn the ac plane, the anions of the compound are in a two-dimensional layered-AAA-stacking mode. The La-Cd heterometallic modified polyacid crystalline material is successfully prepared by a simple method.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry polymetallic oxygen clusters, and particularly relates to a preparation method of a heterometallic modified phosphotungstic acid crystalline material.
Background
Rare earth-transition metal complexes have attracted much attention due to their attractive structural types and their important uses in the fields of adsorption materials, fluorescent receptors, magnetic materials, etc. however, compared to organic ligands, polyoxometalates, abbreviated as POMs, have been found to be very promising in the fields of electricity, light, catalysis, and magnetism, etc., due to the fact that a large number of oxygen atoms on the surface can be easily bound to most of transition metals or rare earth metals, forming a series of POMs derivatives with potential application prospects or rare earth metal substitutions in the fields of electricity, light, catalysis, and magnetism, etc., which have been widely researched by polyacid chemists (coord. chem. rev.,2019,392, 49-80; chemcectrochem, 2018,5,823-838), while a large number of transition metal substituted polyacid materials have been widely researched, while rare earth ions themselves have high coordination, oxygen affinity, and chemical modification, 719, 5,823, etc., have been reported to be very promising for rare earth metal substituted polyacid derivatives, such as rare earth metal complexes, fluorescent transition metals, especially rare earth metal complexes, such as mercuric-transition metal complexes, chemical complexes, fluorescent complexes, rare earth complexes, fluorescent receptors, rare earth complexes, fluorescent complexes, organic complexes, rare earth complexes, rare.
Disclosure of Invention
The invention aims to obtain a novel preparation method of a dissimilar metal modified phosphotungstic acid compound, which has the following specific structural formula:
[Cd(en)2(H2O)]2{[Cd(en)2][Cd(en)2(H2O)]2[La(α-PW11O39)(CH3CO2)(H2O)]2}·5H2o, structural formula is shown in figure 1 in the specification.
The crystal belongs to monoclinic system, C2/C space group, and the unit cell parameters are as follows:
α＝102.880(2)°，β＝104.63°，γ＝90°，Z＝2，R1＝0.0596，wR2＝0.1471。
the asymmetric molecular structural unit of the tested polyacid-based crystalline material comprises one { [ La (α -PW)11O39)(CH3COO)(H2O)]}2 10Dimeric cluster anion, two free [ Cd (en)2(H2O)]2+Cationic, two pendant [ Cd (en)2(H2O)]2+Cation, a modified [ Cd5(en)2]2+Cationic and 5 free water molecules dimeric { [ La (α -PW)11O39)(CH3COO)(H2O)]}2 10The anion is formed by 2 rare earths La3+Monosubstituted { [ La (α -PW 78 { ]11O39)(H2O)]}4-Subunit passing through 2(η)2,μ-1,1)-CH3COO-Ligand bridged [ La (α -PW)11O39)]4–The subunit is composed of 1 rare earth LaIIIIon embedding to single-vacancy Keggin [ α -PW11O39]7–Formed by the position of the anion defect, [ α -PW11O39]7–The anion is formed by saturated Keggin type [ α -PW12O40]3–Removing one W ═ OdDerived from the group. In the compound, La3+Adopts eight-coordinate tetragonal antiprism configuration, and is respectively connected with a catalyst from [ α -PW11O39]7–The anion is coordinated at 4O atoms in the default position, 3O atoms from two different acetate ligands and one water molecule. In addition, theThere are also five crystallographically independent cadmium ions in this compound, whose coordination patterns differ from each other: supported [ Cd1(en)2(H2O)]2+，[Cd3(en)2(H2O)]2+，[Cd5(en)2]2+The cations all forming N4O2Form an octahedral configuration, all with four nitrogen atoms from two ethylenediamine ligands and from [ α -PW11O39]7–One oxygen coordination of the unit, except that the other coordinated oxygen atom is from a water molecule or an adjacent vacancy polyacid cluster block; but free [ Cd2(en)2(H2O)]2+And [ Cd4(en)2(H2O)]2+In a tetragonal pyramid configuration, coordination is made with four nitrogen atoms from two ethylenediamine ligands and with water molecules (fig. 1).
The rare earth ion substituted dimeric cluster is passed through [ Cd5(en)2]2+The cations are connected to form a one-dimensional chain structure (figure 2). On the ac plane, a two-dimensional layered-AAA-packing structure is formed between anions of the compounds (fig. 3). It is worth noting that the compound is the first hetero La-Cd metal modified phosphotungstic acid compound.
Has the advantages that: the La-Cd heterometallic modified polyacid crystalline material is successfully prepared by a simple method.
Drawings
FIG. 1 is a schematic diagram of an asymmetric unit structure of a cluster compound
FIG. 2 is a one-dimensional chain structure diagram of a cluster compound
FIG. 3 is a stacking diagram of one-dimensional interchain-AAA alignment of clusters
Detailed description of the invention
First, Na is added9[A-α-PW9O34]·7H2O, lanthanum acetate hexahydrate, CdI21-10 phenanthroline is sequentially added into the system, a certain amount of acetic acid-sodium acetate solution is added into the system, stirring is carried out, a small amount of diethylenetriamine is added dropwise into the system, finally, the uniformly mixed reactant system is placed in a drying box, the reaction temperature is 160 ℃, the reactant system is naturally cooled after reacting for several days, then observation is carried out under an optical microscope, and mother liquor is stored.
Example 1
4mL of acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH ═ 4.8 is prepared, and Na is added9[A-α-PW9O34]·7H2O(0.0906g)，La(CH3CO2)3·6H2O(0.1569g)，CdI2(0.1114g) and 1-10 phenanthroline hydrate (0.0487g) are sequentially added into the system, 3 drops of diethylenetriamine are added dropwise into the system under continuous stirring, the mixture is put into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining after being continuously stirred for 60 minutes, the reaction kettle is sealed and placed in a 160 ℃ oven for heating for 7 days, the mixture is taken out and naturally cooled to room temperature, and the product is filtered, washed with distilled water and dried at room temperature to obtain a brown yellow columnar crystal.
Comparative example 1
The reaction time was shortened to 1,3 days, and other reaction conditions were not changed, and a product having the same structure as in example was not obtained.
Comparative example 2
With La (NO)3)3·6H2O (0.1541g) instead of La (CH)3CO2)3·6H2O, and adjusting the reactant ratio range, a product with the same structure as the example is not obtained. Salt compounds of other rare earth elements Sm, Eu, Tb and Dy are selected to replace La salt of the application, experiments are carried out according to the reaction conditions of the embodiment 1, and products with the same structure as the embodiment 1 are obtained
Comparative example 3
With Na10[A-α-SiW9O34]·19H2O or K8Na2[A-α-GeW9O34]·25H2O instead of Na9[A-α-PW9O34]·7H2O (0.0906g), and adjusting the reactant ratio range, a product having the same structure as in example was not obtained.
Comparative example 4
In the reaction system of example 1, 10-phenanthroline was added, but it did not enter the final crystal structure, but if any one of the four reactants was not added in the reaction system, a product having the same structure as example 1 could not be obtained.
Comparative example 5
Substitution of 2,2 bipyridine and imidazole for 1, 10-phenanthroline failed to provide a product of the same structure as in example 1.
The process parameters and routes of the present invention are not limited to the specific embodiments listed above, which are merely illustrative of the present invention and are not limited to the process parameters and routes described in the examples of the present invention. It should be understood by those skilled in the art that the present invention can be modified or substituted with equivalents in practical applications to achieve the same technical effects. As long as the application requirements are met, the invention is within the protection scope.
Claims (10)
1. The special metal substituted polyacid crystalline material is characterized in that the crystalline material is a La-Cd special metal substituted polyacid crystal, and the molecular formula is as follows: c24H108Cd5La2N20O100P2W22。
2. The heterometallic polyacid crystalline material as claimed in claim 1, wherein the crystal is a single crystal belonging to monoclinic system, group C2/C space, and the structural formula is:
[Cd(en)2(H2O)]2{[Cd(en)2][Cd(en)2(H2O)]2[La(α-PW11O39)(CH3CO2)(H2O)]2}·5H2O。
3. a heterometallic polyacid-substituted crystalline material as claimed in claim 1, wherein the unit cell parameters:
α＝102.880(2)°，β＝104.63°，γ＝90°，Z＝2，R1＝0.0596，wR2＝0.1471。
4. the dissimilar metal according to claim 1The substituted polyacid crystalline material is characterized in that the molecular structural unit of the object to be tested contains { [ La (α -PW 78- ]11O39)(CH3COO)(H2O)]}2 10Dimeric cluster anion, two free [ Cd (en)2(H2O)]2+Cationic, two pendant [ Cd (en)2(H2O)]2+Cation, a modified [ Cd5(en)2]2+Cations and 5 free water molecules. Five crystallographically independent cadmium ions are present in this compound and differ in their coordination pattern: supported [ Cd1(en)2(H2O)]2+，[Cd3(en)2(H2O)]2+，[Cd5(en)2]2+The cations all forming N4O2Form an octahedral configuration, all with four nitrogen atoms from two ethylenediamine ligands and from [ α -PW11O39]7-One oxygen coordination of the unit, except that the other coordinated oxygen atom is from a water molecule or an adjacent vacancy polyacid cluster block; but free [ Cd2(en)2(H2O)]2+And [ Cd4(en)2(H2O)]2+Adopting a tetragonal pyramid configuration, coordinating with four nitrogen atoms from two ethylene diamine ligands and water molecules.
5. The heterometallic polyacid-substituted crystalline material of claim 1, wherein the polyacid-based crystalline material tested comprises dimeric { [ La (α -PW 78-PW) substituted with a single rare earth ion and bridged by an acetate ion11O39)(CH3COO)(H2O)]}2 10Between the clusters is a [ Cd5(en) ]2]2+The cations are connected to form a one-dimensional chain structure, and a two-dimensional layered-AAA-accumulation mode is formed between chains.
6. The method for preparing a polymetallic substituted polyacid crystalline material as claimed in claim 1, wherein [ α -PW9O34]7-Precursor and La-containing3+Rare earth and Cd2+Transition goldDissolving salt in distilled water, adding 1, 10-phenanthroline organic ligand, and adding H2NCH2CH2NHCH2CH2NH2And regulating the pH value by weak acid, and heating in a closed container for reaction.
7. The method for preparing a different metal substituted polyacid crystalline material according to claim 6, wherein the reaction time is 7 days, the reaction is synthesized by hydrothermal method, the reactants are placed in a stainless steel reaction kettle with polytetrafluoroethylene lining, and sealed and heated.
8. A method for preparing a crystalline material of a different metal-substituted polyacid as claimed in claim 6, wherein the pH of the system is maintained at 4.8 by adding acetic acid-sodium acetate buffer solution.
9. The method according to claim 6, wherein the reaction temperature is 160 ℃.
10. The method for preparing a crystalline material of a different metal-substituted polyacid as claimed in claim 6, wherein [ α -PW is used9O34]7-Is Na9[A-α-PW9O34]·7H2O precursor, rare earth and transition metal salt are La (CH)3CO2)3·6H2O and CdI2The weak acid for adjusting the pH value is CH3COOH。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342620A (en) * | 2020-09-14 | 2021-02-09 | 大连民族大学 | Dissimilar metal substituted Dawson type polyacid-based crystal material and preparation method thereof |
| CN113831546A (en) * | 2021-10-21 | 2021-12-24 | 河南大学 | Double-heteroatom-regulated polyoxometallate material and preparation method and application thereof |
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| CN103007888A (en) * | 2012-10-30 | 2013-04-03 | 河南大学 | Organic-inorganic hybridization transition-rare earth dissimilar metal substituted germanium tungstate crystal hydrogen storage material and preparation method thereof |
| CN109021032A (en) * | 2018-10-11 | 2018-12-18 | 北京理工大学 | A kind of monocrystalline and preparation method of rare earth interlayer type omission Keggin polyacid |
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- 2019-12-05 CN CN201911235571.2A patent/CN111087428A/en active Pending
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| CN1173394A (en) * | 1997-02-27 | 1998-02-18 | 大连理工大学 | Prepn. and application of heteropolyacid salt modified skeletal nickel catalyst |
| CN103007888A (en) * | 2012-10-30 | 2013-04-03 | 河南大学 | Organic-inorganic hybridization transition-rare earth dissimilar metal substituted germanium tungstate crystal hydrogen storage material and preparation method thereof |
| CN109021032A (en) * | 2018-10-11 | 2018-12-18 | 北京理工大学 | A kind of monocrystalline and preparation method of rare earth interlayer type omission Keggin polyacid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112342620A (en) * | 2020-09-14 | 2021-02-09 | 大连民族大学 | Dissimilar metal substituted Dawson type polyacid-based crystal material and preparation method thereof |
| CN113831546A (en) * | 2021-10-21 | 2021-12-24 | 河南大学 | Double-heteroatom-regulated polyoxometallate material and preparation method and application thereof |
| CN113831546B (en) * | 2021-10-21 | 2022-06-03 | 河南大学 | Double-heteroatom-regulated polyoxometallate material and preparation method and application thereof |
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