CN103992340A - Mono-substituted hexamethyl hexahydric cucurbit urils-rear earth adduct as well as synthetic method and application thereof - Google Patents
Mono-substituted hexamethyl hexahydric cucurbit urils-rear earth adduct as well as synthetic method and application thereof Download PDFInfo
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- CN103992340A CN103992340A CN201410228462.9A CN201410228462A CN103992340A CN 103992340 A CN103992340 A CN 103992340A CN 201410228462 A CN201410228462 A CN 201410228462A CN 103992340 A CN103992340 A CN 103992340A
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- hexamethyl
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Abstract
The invention discloses a mono-substituted hexamethyl hexahydric cucurbit urils-rear earth adduct as well as a synthetic method and application thereof, and belongs to the technical field of metal-organic adducts. In the presence of cadmium chloride, the mono-substituted hexamethyl hexahydric cucurbit urils and heavy rear-earth metal salt can be used for synthesizing the mono-substituted hexamethyl hexahydric cucurbit urils-rear earth adduct in hydrochloric acid liquor, wherein a composing general formula of the adduct is as follows: {[Ln(H2O)8SHMeQ[6]].3Cl.xH2O}, wherein x is not less than 11 and not greater than 21. Under the same condition, the mono-substituted hexamethyl hexahydric cucurbit urils and light rear-earth metal salt cannot be used for synthesizig the solid adduct; according to the characteristic, the mono-substituted hexamethyl hexahydric cucurbit urils-rear earth adduct can be used for separating light-heavy rear-earth metal ions.
Description
Technical field
The present invention utilizes the method for the synthetic hexa-atomic melon ring-rare earth solid adduct of monosubstituted hexamethyl and separated weight rare earth thereof to belong to metal-organic adducts and synthetic method field thereof.Be exactly specifically under Cadmium chloride fine powder existence condition, the hexa-atomic melon ring of monosubstituted hexamethyl and heavy rare earth metal Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu form solid adduct, and the hexa-atomic melon ring of monosubstituted hexamethyl and light rare earths La, Ce, Pr, Nd, Sm, Eu metal can not form solid adduct, and utilize it can form solid adduct and the method for separated weight rare earth.
Background technology
Rare earth element is playing the part of at aspects such as communication information, oil catalysis, colored demonstration, hydrogen storage material and superconducting materials the role who can not be substituted, and has the title of industry " VITAMIN ", is the important strategic element of a class.Separation and Extraction goes out single pure rare earth element, is more complicated and difficulty in chemical technology.Its reason is that physical properties and the chemical property between lanthanon is quite similar, in solution, mainly with three stable valence states, presents, therefore large with the avidity of water, is subject to the protection of hydrate, causes very difficulty of separating-purifying.Rare-earth separating adopts fractional crystallization method in early days, and its principle is to utilize the different solubility of compound in solvent to carry out separation and purification, separated repetitive operation sometimes even nearly 20,000 times.The ion-exchange ratio juris growing up is subsequently also the rare earth compounding that utilize the to form difference to ion exchange resin affinity, rare earth ion absorption, departs from the speed difference that resin moves down and reaches separated object.Its advantage is 1) a plurality of elements separation; 2) purity is high.Shortcoming is 1) can not process continuously; 2) cycle is long; 3) there are the regeneration of resin, switching cost high.Therefore, this was once that the separated main method of rare earths is in a large number resigned from office from main flow separation method, and was replaced by solvent extration.But because ion-exchange chromatography has the outstanding feature that obtains high purity single rare earth product, at present, for producing the separation of ultra-pure single product and some heavy rare earth elements, also need to produce a rare earth with ion-exchange chromatography separation and produce.Utilize cascade extraction technology, Mr. Xu Guangxian proposes to be applicable to the cascade extraction theory of rare earth extraction separation in the world first, set up complete Rare Earth Separation Optimization Technology method of design, thereby Solvent Extraction Separation rare earth becomes the main stream approach of current Rare Earth Separation, its technological process generally can be divided into three main phase: extraction, washing, strip.
Melon ring (Cucurbit[
n] urils, Q[
n]) be that a class is by n glycosides urea unit and 2n the large ring cage compound that methylene bridge links up.Due to two ports of melon ring " inlay " one circle carbonylic oxygen atom, there is the ability that forms title complex or adducts with metallic ion coordination, be used as in recent years organic ligand, in the research field of constructing at metal-organic supermolecular polymkeric substance, receive increasing concern.Our laboratory, having carried out extensive work aspect the coordination of melon ring and rare earth ion and supramolecule self-assembly thereof, found that melon ring has recognition capability to rare earth in recent years.After different melon rings and serial rare-earth effect, can form title complex or adducts and supramolecule self-assembly entity or the ligand polymer of different structure and character; Moreover, same melon ring also can form title complex or adducts and supramolecule self-assembly entity or the ligand polymer of different structure and character under different condition.As we utilize [CdCl
4]
2-the structure-directing effect of negatively charged ion has synthesized a series of seven yuan of melon ring-rare earth metal tubulose supermolecule polymers, and has applied for the linear tubulose supermolecule polymer of seven yuan of melon rings-rare earth metal and the synthetic method (application number: 201110388587.4 > > of the induction of < < Cadmium chloride fine powder for this reason.And under same experiment condition, utilize [CdCl
4]
2-the structure-directing effect of negatively charged ion has synthesized a series of eight yuan of melon ring-rare earth metal Magnetic Properties of Three-Dimensional Supramolecular Complex polymkeric substance, and has applied for mono-kind eight yuan melon ring-rare earth metal supermolecule polymer synthetic methods of < < and application (application number: 201310218642.4 > > for this reason.And for example we adopt ortho position Tetramethyl melon ring as part recently, under cadmium nitrate existence condition with serial rare-earth Action of Metal Ions, find ortho position Tetramethyl melon ring and heavy rare earths Tb, Dy, Ho, Er, Tm, Yb and Lu formation solid complexes, and with light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd can not form solid complexes, utilizes the separable weight rare earth of this characteristic (number of patent application: 201410154607.5 > >.Under similarity condition, do not add cadmium nitrate, ortho position Tetramethyl melon ring and heavy rare earths Tb, Dy, Ho, Er, Tm, Yb and Lu form solid adduct, and with light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd can not form solid adduct, utilizes also separable weight rare earth (number of patent application: 201410154607.5 > > of this characteristic.
Present patent application is chosen in 1.5 molL
-1in hydrochloric acid soln, under Cadmium chloride fine powder existence condition, make the hexa-atomic melon ring of monosubstituted hexamethyl SHMeQ[6] interact with serial rare-earth metal ion, synthesized the hexa-atomic melon ring-rare earth of a series of monosubstituted hexamethyl solid adduct.Utilize the hexa-atomic melon ring of monosubstituted hexamethyl and heavy rare earth metal Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu to form solid adduct, but can not obtain the hexa-atomic melon ring of monosubstituted hexamethyl and form the different of solid adduct from light rare earths La, Ce, Pr, Nd, Sm, Eu metal, can be used for the separation of weight rare earth ion.
Summary of the invention
The object of the invention is to synthesize the hexa-atomic melon ring of a series of monosubstituted hexamethyl and heavy rare earths adducts, disclose its synthetic method.Utilize the hexa-atomic melon ring of monosubstituted hexamethyl and heavy rare earth Gd, Tb, Dy, Ho, Er, Tm, Yb, the formed solid adduct of Lu, but can not form the difference of solid adduct with light rare earths La, Ce, Pr, Nd, Sm, Eu, for the separation of weight rare earth ion.
The hexa-atomic melon ring of the monosubstituted hexamethyl of the present invention SHMeQ[6]-rare earth adducts is at Cadmium chloride fine powder CdCl
2under existence condition, the hexa-atomic melon ring of monosubstituted hexamethyl and rare earth metal salt are at 1.5 molL
-1the hexa-atomic melon ring-heavy rare earth Gd of monosubstituted hexamethyl, Tb, Dy, Ho, Er, Tm, Yb, Lu synthetic in hydrochloric acid soln form solid adduct.The hexa-atomic melon ring of monosubstituted hexamethyl of indication and heavy rare earths form adducts chemical constitution general formula:
{[Ln(H
2O)
8SHMeQ[6]]·3Cl·xH
2O}
Ln represents rare earth ion, and x is crystal water molecular amounts 11≤x≤21.
The present invention is under Cadmium chloride fine powder existence condition, 1.5 mol L
-1the hexa-atomic melon ring-heavy rare earths of the monosubstituted hexamethyl adducts forming in hydrochloric environment is:
(1) {Tb(H
2O)
8SHMeQ[6]}3Cl·14H
2O
(2) {Dy(H
2O)
8SHMeQ[6]}3Cl·12H
2O
(3) {Ho(H
2O)
8SHMeQ[6]}3Cl·21H
2O
(4) {Er(H
2O)
8SHMeQ[6]}[3Cl·18H
2O
(5) {Tm(H
2O)
11SHMeQ[6]}3Cl·11H
2O
The hexa-atomic melon ring of the monosubstituted hexamethyl of above-mentioned indication SHMeQ[6] chemical formula be C
42h
48n
24o
12, crystalline structure is as accompanying drawing 1.
The hexa-atomic melon ring-rare earth of monosubstituted hexamethyl described above adduction synthetic method, its synthetic method follows these steps to carry out:
(1) by SHMeQ[6] use 3 molL
-1hydrochloric acid soln dissolves obtain solution A completely;
(2) by Tb (NO
3)
3with Cadmium chloride fine powder CdCl
28:6 weighs in molar ratio respectively, in mixing and same container, with distilled water, two kinds of materials is dissolved obtain solution B completely;
(3) solution A and B are pressed to SHMeQ[6]: Tb (NO
3)
3: Cadmium chloride fine powder (CdCl
2) equal the mixed in molar ratio of 1:8:6;
(4) standing, for light rare earths La, Ce, Pr, Nd, Sm, Eu cannot grow crystal; And for Gd and the later heavy rare earths of ordination number thereof, larger according to ordination number, crystal grows the faster rule of speed and grows corresponding crystal.
The hexa-atomic melon ring-rare earth of above-described monosubstituted hexamethyl adducts synthetic method, its solution is 1.5 molL
-1hydrochloric acid soln, works as SHMeQ[6], Ln (NO
3)
3, CdCl
21: 6 in molar ratio ~ 9: 4 ~ 6 o'clock, grow the fastest of crystal, productive rate is the highest.
The application of the hexa-atomic melon ring-rare earth of a kind of monosubstituted hexamethyl of the present invention adducts, to utilize the hexa-atomic melon ring of monosubstituted hexamethyl and light rare earth metal (La, Ce, Pr, Nd, Sm, Eu) do not form solid adduct and the hexa-atomic melon ring of monosubstituted hexamethyl can form the different of solid adduct from heavy rare earth metal, can be used for the separation of weight rare earth ion.
In the present invention, the melon cyclic group of synthesized being added to thing adopts the analysis means such as X-ray single crystal diffraction, IR, DSC-TG, ITC to carry out the signs such as structure, character.
Feature 1 of the present invention) synthetic method of using has simple to operate, and productive rate is high; 2) utilize the difference that can form solid adduct, can be used for the separation of weight rare earth ion.
Accompanying drawing explanation
The hexa-atomic melon ring of the monosubstituted hexamethyl of Fig. 1 SHMeQ[6] crystalline structure figure.
Fig. 2 is in acidic solution, and the solid adduct that the hexa-atomic melon ring of heavy rare earth metal and monosubstituted hexamethyl forms has similar structures, is homeomorphism crystal, and heavy rare earths is: Gd, Tb, Ho, Er, Tm, Yb, Lu.(a) heavy rare earth metal ionized water compound [Ln (H
2o)
x]
3+, the hexa-atomic melon ring of monosubstituted hexamethyl SHMeQ[6] adducts that forms; (b) SHMeQ[6]/[Ln (H
2o)
x]
3+in adducts, melon ring and metal are by each SHMeQ[6 of the mode of action (c) of water molecules]/[Ln (H
2o)
x]
3+adducts is by six chlorion (Cl
-) around; (d) chlorion (Cl
-) by SHMeQ[6]/[Ln (H
2o)
x]
3+adducts is around pattern; (e) SHMeQ[6]/[Ln (H
2o)
x]
3+adducts and chlorion (Cl
-) the b axonometric drawing of alternate accumulation; (f) SHMeQ[6]/[Ln (H
2o)
x]
3+title complex and chlorion (Cl
-) unidirectional (b axle) accumulation graph.
Fig. 3 SHMeQ[6] the X-ray powder diffraction pattern of/Ln system (represents 8
smeQ[6]/Ln system).
Fig. 4 and SHMeQ[6] SHMeQ[6 relatively] differential thermal (DTA) and the thermogravimetric (TG) of/Ln system analyze collection of illustrative plates.
Fig. 5 and SHMeQ[6] SHMeQ[6 relatively] the IR collection of illustrative plates of/Ln system.Ln is followed successively by: (1) Gd, (2) Tb, (3) Dy(4) Ho, (5) Er, (6) Tm, (7) Yb and (8) Lu.
Fig. 6 is from containing the La that mol ratio is 1:1
3+and Tb
3+, La
3+and Ho
3+, La
3+and Tm
3+, Nd
3+and Tb
3+, Nd
3+and Ho
3+, Nd
3+and Tm
3+in mixing solutions, obtain the electron spectroscopy analysis result of crystal.
specific implementation method
Embodiment 1: at CdCl
2under existence condition, heavy rare earths (nitrate) metal ion and the effect of the hexa-atomic melon ring of monosubstituted hexamethyl form adducts implementation method.With Tm (NO
3)
3for example illustrates:
Take respectively Tm (NO
3)
35H
2o 28.17 mg (0.0633 mmol), CdCl
2in 10.87 mg (0.0475 mmol) and same beaker, add the 1.0 mL aqueous solution, be heated to 70 ℃, make it to be sufficiently uniformly dissolved; Take SHMeQ[6] 10 mg (0.0079 mmol), add 1.0 mL3molL
-1hydrochloric acid soln is heated to 70 ℃, shakes several minutes, makes solution clarification, by SHMeQ[6] solution injects above-mentioned mixing solutions, shakes up; Standing about 1 day, there is colourless transparent crystal, productive rate is 50 ~ 65%.Its structural formula is { Tm (H
2o)
11sHMeQ[6] } 3Cl11H2O.Under similarity condition, it is homeomorphic supermolecule polymer that the hexa-atomic melon ring of monosubstituted hexamethyl and other heavy rare earth metals form structure, and its general structure is { [Ln (H
2o)
8sHMeQ[6]] 3ClxH
2o}.
Embodiment 2: utilize the hexa-atomic melon ring of monosubstituted hexamethyl and heavy rare earth metal to form supramolecule self-assembly polymkeric substance, but cannot form the different of supramolecule self-assembly polymkeric substance from light rare earth metal, the method for separated weight rare earth ion, with separated La
3+with Tm
3+for example illustrates:
Take respectively La (NO
3)
36H
2o 13.74 mg (0.0316 mmol), Tm (NO
3)
35H
2o 14.13 mg (0.0316 mmol), CdCl
2in 10.87 mg (0.0475 mmol) and same beaker, add 1 mL water, be heated to 70 ℃, make it to be sufficiently uniformly dissolved; Take SHMeQ[6] 10 mg (0.0079 mmol), add 1.0 mL 3molL
-1hydrochloric acid soln is heated to 70 ℃, shakes several minutes, makes solution clarification; By SHMeQ[6] solution injects above-mentioned mixing solutions, shakes up, and standing 1 day, the precipitate and separate washing producing is to be measured, and productive rate was 50 ~ 70%.
Claims (5)
1. the hexa-atomic melon ring of monosubstituted hexamethyl SHMeQ[6]-rare earth adducts, it is characterized in that at Cadmium chloride fine powder CdCl
2under existence condition, the hexa-atomic melon ring of monosubstituted hexamethyl and heavy rare earth metal salt are at 1.5 molL
-1the hexa-atomic melon ring-heavy rare earth Gd of monosubstituted hexamethyl, Tb, Dy, Ho, Er, Tm, Yb, the formed solid adduct of Lu that in hydrochloric acid soln, synthesize; The hexa-atomic melon ring of monosubstituted hexamethyl of indication and heavy rare earths form adducts chemical constitution general formula:
{[Ln(H
2O)
8SHMeQ[6]]·3Cl·xH
2O}
Ln represents rare earth ion, and x is crystal water molecular amounts 11≤x≤21;
Its crystalline structure is
。
2. the hexa-atomic melon ring-rare earth of monosubstituted hexamethyl according to claim 1 adducts, is characterized in that under Cadmium chloride fine powder existence condition 1.5 molL
-1the hexa-atomic melon ring-heavy rare earths of the monosubstituted hexamethyl adducts forming in hydrochloric environment is:
(1) {Tb(H
2O)
8SHMeQ[6]}3Cl·14H
2O
(2) {Dy(H
2O)
8SHMeQ[6]}3Cl·12H
2O
(3) {Ho(H
2O)
8SHMeQ[6]}3Cl·21H
2O
(4) {Er(H
2O)
8SHMeQ[6]}[3Cl·18H
2O
(5) {Tm(H
2O)
11SHMeQ[6]}3Cl·11H
2O。
3. the hexa-atomic melon ring-rare earth of the monosubstituted hexamethyl as described in one of claim 1-2 adducts synthetic method, is characterized in that synthetic method follows these steps to carry out:
(1) by SHMeQ[6] use 3 molL
-1hydrochloric acid soln dissolves obtain solution A completely;
(2) by Ln (NO
3)
3with Cadmium chloride fine powder CdCl
28:6 weighs in molar ratio respectively, in mixing and same container, with distilled water, two kinds of materials is dissolved obtain solution B completely;
(3) solution A and B are pressed to SHMeQ[6]: Ln (NO
3)
3: Cadmium chloride fine powder CdCl
2equal the mixed in molar ratio of 1:8:6;
(4) standing, for light rare earths La, Ce, Pr, Nd, Sm, Eu does not form crystal; And for Gd, Tb, Dy, Ho, Er, Tm, Yb, eight kinds of heavy rare earths of Lu, larger according to ordination number, crystal grows the faster rule of speed and grows corresponding crystal.
4. the hexa-atomic melon ring-rare earth of monosubstituted hexamethyl according to claim 3 adducts synthetic method, is characterized in that: work as SHMeQ[6], Ln (NO
3)
3, Cadmium chloride fine powder (CdCl
2) in molar ratio 1: during 8:6, grow the fastest of crystal, productive rate is the highest.
5. the application of the hexa-atomic melon ring-rare earth of the monosubstituted hexamethyl as described in one of claims 1 to 3 adducts, it is characterized in that utilizing the hexa-atomic melon ring of monosubstituted hexamethyl and light rare earth metal La, Ce, Pr, Nd, Sm, Eu can not form solid adduct and the hexa-atomic melon ring of monosubstituted hexamethyl can form the different of solid adduct from heavy rare earth metal, can be used for the separation of weight rare earth ion.
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| CN105153206A (en) * | 2015-10-10 | 2015-12-16 | 贵州大学 | Two HMeQ[6] microporous supermolecular frame materials as well as preparation and application thereof |
| US11762721B2 (en) | 2020-08-20 | 2023-09-19 | Inspur Electronic Information Industry Co., Ltd. | Method for realizing nGraph framework supporting FPGA rear-end device |
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| US11762721B2 (en) | 2020-08-20 | 2023-09-19 | Inspur Electronic Information Industry Co., Ltd. | Method for realizing nGraph framework supporting FPGA rear-end device |
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