CN104262371A - IQ[6]-rare earth complex, as well as synthesis and application thereof - Google Patents
IQ[6]-rare earth complex, as well as synthesis and application thereof Download PDFInfo
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- CN104262371A CN104262371A CN201410530488.9A CN201410530488A CN104262371A CN 104262371 A CN104262371 A CN 104262371A CN 201410530488 A CN201410530488 A CN 201410530488A CN 104262371 A CN104262371 A CN 104262371A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 89
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 50
- 239000007787 solid Substances 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 rare earth metal ions Chemical class 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- 238000010189 synthetic method Methods 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical group N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims description 52
- 241000219112 Cucumis Species 0.000 claims description 18
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 238000013329 compounding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052689 Holmium Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052771 Terbium Inorganic materials 0.000 claims description 7
- 229910052775 Thulium Inorganic materials 0.000 claims description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 238000001941 electron spectroscopy Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003929 acidic solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses an iQ[6]-rare earth complex as well as synthesis and application thereof, and belongs to the field of metal organic complexes and synthetic methods. The iQ[6]-rare earth complex is characterized in that in 3 mol/L of a hydrochloric acid solution, under the presence of [ZnCl4]2<->, enabling iQ[6] and a series of rare earth metal ions to interact with each other to synthesize a series of iQ[6]-rare earth solid complexes. With adoption of the characteristics that the iQ[6] can be reacted with light rare earth metals such as La and Ce to quickly form precipitates, and the speeds for forming solid complexes from the iQ[6] and other rare earth metals are different, the iQ[6]-rare earth complex can be used for the separation of the rare earth metal ions. The synthetic method has the characteristics of simple operation, high yield and the like.
Description
Technical field
The present invention utilizes the method for the hexa-atomic melon ring-rare earth solid complexes of synthesis of trans and separation weight rare earth thereof to belong to Metal-organic complex and synthetic method field thereof.Be exactly tetrachloro zincic acid root ZnCl specifically
4 2-under existence condition, utilize trans hexa-atomic melon ring and light rare earth metal La, Ce comparatively fast to form precipitation in 1-3 days, Sm, Eu grow crystal in mono-month, and can form the different of solid complexes speed from other rare earth metals, can be used for the separation of rare earth ion.
Background technology
Rare earth element plays the role that can not be substituted in communication information, oil catalysis, colored display, hydrogen storage material and superconducting material etc., has the title of industry " VITAMIN ", is the important strategic element of a class.Separation and Extraction goes out single pure rare earth element, chemical technology is more complicated and difficulty.Its reason is that physical properties between lanthanon and chemical property are quite similar, mainly in the solution presents with three stable valence states, therefore large with the avidity of water, by the protection of hydrate, causes separating-purifying very difficult.Rare-earth separating adopts fractional crystallization method in early days, and its principle utilizes compound different solubility in a solvent to carry out isolation andpurification, is sometimes separated repetitive operation even nearly 20,000 times.The ion-exchange ratio juris grown up subsequently is also utilize the rare earth compounding formed to the difference of ion exchange resin affinity, and the speed difference that rare earth ion absorption, disengaging resin move down reaches separation object.Its advantage is 1) multiple element sepatation; 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 main method being separated a large amount of rare earth is resigned from office from main flow separation method, and was replaced by solvent extration.But because ion-exchange chromatography has the outstanding feature obtaining 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 be separated by ion-exchange chromatography to produce a rare earth product.Utilize cascade extraction technology, Mr. Xu Guangxian proposes the countercurrent extraction theory being applicable to rare earth extraction separation in the world first, establish complete Rare Earth Separation Optimization Technology method of design, thus Solvent Extraction Separation rare earth becomes the main stream approach of current Rare Earth Separation, and its technological process generally can be divided into three main phase: extraction, washing, reextraction.
Melon ring (Cucurbit [
n] urils, Q [
n]) be the large ring cage compound that a class is linked up by n glycosides urea unit and 2n methylene bridge." inlay " due to melon ring two ports and a circle carbonylic oxygen atom, there is the ability forming title complex or adducts with metallic ion coordination, be used as organic ligand in recent years, in the research field that metal-organic supermolecular polymkeric substance is constructed, receive increasing concern.Extensive work has been carried out in our laboratory in the coordination and Supramolecular self assembly thereof of melon ring and rare earth ion in recent years, and topology discovery melon ring has recognition capability to rare earth.The title complex of different structure and character or adducts and Supramolecular self assembly entity or ligand polymer can be formed after different melon rings and serial rare-earth effect; Moreover, same melon ring, also can form the title complex of different structure and character or adducts and Supramolecular self assembly entity or ligand polymer at different conditions.As we utilize [CdCl
4]
2-the structure-directing effect of negatively charged ion synthesized a series of seven yuan of melon rings-rare earth metal tubulose supermolecule polymer, and applies for " seven yuan of melon ring-rare earth metal linear, tubular supermolecule polymers of Cadmium chloride fine powder induction and synthetic method (application number: 201110388587.4 " for this reason.And under same experiment condition, utilize [CdCl
4]
2-the structure-directing effect of negatively charged ion synthesized a series of eight yuan of melon rings-rare earth metal Magnetic Properties of Three-Dimensional Supramolecular Complex polymkeric substance, and applies for " a kind of eight yuan of melon ring-rare earth metal supermolecule polymer synthetic methods and application (application number: 201310218642.4 " for this reason.And for example we adopt ortho position Tetramethyl melon ring as part recently, with serial rare-earth Action of Metal Ions under cadmium nitrate existence condition, find that ortho position Tetramethyl melon ring and heavy rare earths Tb, Dy, Ho, Er, Tm, Yb and Lu form solid complexes, and with light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd then can not form solid complexes, utilize 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 then form solid adduct, and with light rare earths La, Ce, Pr, Nd, Sm, Eu, Gd then can not form solid adduct, utilize this characteristic also separable weight rare earth (number of patent application: 201410154607.5 ".
Present patent application is selected at 3 molL
-1in hydrochloric acid soln, at tetrachloro zincic acid root ZnCl
4 2-under existence condition, trans hexa-atomic melon ring iQ [6] and serial rare-earth metal ion are interacted, has synthesized a series of trans hexa-atomic melon ring-rare earth solid complexes.Utilization utilizes trans hexa-atomic melon ring and light rare earth metal La, and Ce comparatively fast forms precipitation, and can form the different of solid complexes speed from other rare earth metals, can be used for the separation of rare earth ion.
Summary of the invention
The object of the invention is to synthesize a series of trans hexa-atomic melon ring and rare earth compounding, disclose its synthetic method.Utilize trans hexa-atomic melon ring and light rare earth metal La, Ce comparatively fast forms precipitation, and can form the different of solid complexes speed from other rare earth metals, can be used for the separation of rare earth ion.
The trans hexa-atomic melon ring iQ [6] of the present invention-rare earth metal forms title complex, is at tetrachloro zincic acid root ZnCl
4 2-under existence condition, at 3 molL
-1in hydrochloric acid soln, trans hexa-atomic melon ring and rare earth metal salt La, Ce form white precipitate, form solid complexes with Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the trans hexa-atomic melon ring of indication and rare earth form coordination chemistry and form general formula and be:
(1) {Ln(H
2O)
5iQ[6]} [ZnCl
4] x(H
2O) （Ln=Pr、Nd,10≤ x ≤11）
(2) {Ln
2(H
2O)
10(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Gd、Tb、Dy、Ho, 41≤ x ≤49）
(3) {Ln
2(H
2O)
13(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Er、Tm、Yb，39≤ x ≤49）
(4) {Ln
2(H
2O)
12(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Lu,x=46）
Ln represents rare earth ion, and x is crystalline water molecules quantity, and iQ [6] is trans hexa-atomic melon ring.
At tetrachloro zincic acid root ZnCl
4 2-under existence condition, 3molL
-1the trans hexa-atomic melon ring-rare earth compounding formed in hydrochloric environment is:
(1) ｛Pr(H
2O)
5(NO
3@iQ[6])｝[ZnCl
4] 11(H
2O)
(2) ｛Nd(H
2O)
5(NO
3@iQ[6])｝[ZnCl
4] 10(H
2O)
(3) ｛Gd
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 43(H
2O)
(4) ｛Tb
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 41(H
2O)
(5) ｛Dy
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 45(H
2O)
(6) ｛Ho
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 49(H
2O)
(7) ｛Er
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 49(H
2O)
(8) ｛Tm
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 39(H
2O)
(9) ｛Yb
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 43(H
2O)
(10)｛Lu
2(H
2O)
12(NO
3@iQ[6])
2｝2[ZnCl
4] 46(H
2O)
The chemical formula of the trans hexa-atomic melon ring iQ [6] of above-mentioned indication is C
36h
36n
24o
12, crystalline structure is as accompanying drawing 1.
Trans hexa-atomic melon ring-rare earth metal supermolecule polymer synthetic method described above, its synthetic method follows these steps to carry out:
(1) iQ [6] is used 3 molL
-1hydrochloric acid soln dissolves obtain solution A completely;
(2) by Ln (NO
3)
3with zinc nitrate Zn (NO
3)
2respectively 12:5-10 weighs in molar ratio, and two kinds of materials, with same container, to dissolve with distilled water and obtain solution B by mixing completely;
(3) solution A and B are pressed iQ [6]: Ln (NO
3)
3: zinc nitrate Zn (NO
3)
2equal the mixed in molar ratio of 1:12:5-10;
(4) leave standstill, formed precipitation for the nearly 1-3 of light rare earths La, Ce days; Other rare earth metals can grow crystal in 1-2 week except Sm, Eu, and Sm, Eu grow crystal about January.
As iQ [6], Ln (NO
3)
3, Zn (NO
3)
2in molar ratio 1: 12:10 time, grow the fastest of crystal, productive rate is the highest.
Utilize trans hexa-atomic melon ring and light rare earth metal La, Ce comparatively fast to form precipitation in 1-3 days, Sm, Eu grow crystal in mono-month, and can form the different of solid complexes speed from other rare earth metals, can be used for the separation of rare earth ion.
Above-described trans hexa-atomic melon ring-rare earth compounding synthetic method, its solution is 3 molL
-1hydrochloric acid soln.As iQ [6], Zn (NO
3)
2, Ln (NO
3)
3in molar ratio 1: 12:10 time, grow the fastest of crystal, productive rate is the highest.
The application of a kind of trans hexa-atomic melon ring-rare earth compounding of the present invention, utilize trans hexa-atomic melon ring and light rare earth metal La, Ce 1-3 days comparatively fast forms precipitation, Sm, Eu grow crystal in mono-month, and the different of solid complexes speed can be formed from other rare earth metals, can be used for the separation of rare earth ion.The analysis means such as X-ray single crystal diffraction, IR, DSC-TG, XRD is adopted to carry out the sign such as structure, character to synthesized melon ring title complex in the present invention.
Feature of the present invention: 1) the present invention has synthesized a series of trans hexa-atomic melon ring-rare earth compounding; 2) synthetic method used has simple to operate, productive rate high; 3) utilize the difference forming precipitation and solid complexes speed, can be used for the separation of rare earth ion.
Accompanying drawing explanation
The crystalline structure figure of the trans hexa-atomic melon ring iQ [6] of Fig. 1.Left figure is vertical view, and right figure is side-view.
In an acidic solution, the solid complexes crystalline structure figure that rare earth metal Pr and trans hexa-atomic melon ring iQ [6] are formed, Pr, Nd have similar structures to Fig. 2, and be homeomorphism crystal, a is Pr
3+the title complex formed with iQ [6], b is that each iQ [6] is by four [ZnCl
4]
2-the vertical view surrounded, c is Pr
3+and the interaction between the oversubscription subchain that iQ [6] is formed and oversubscription subchain, d is at [ZnCl
4]
2-under existence, Pr
3+the solid complexes formed with iQ [6].
Fig. 3 in an acidic solution, the solid complexes crystalline structure figure that rare-earth metal Tb and trans hexa-atomic melon ring iQ [6] are formed.Gd, Tb, Dy, Ho have similar structures, are homeomorphism crystal.A is Tb
3+the title complex formed with iQ [6], b and c is that each iQ [6] is by [ZnCl
4]
2-the vertical view surrounded, d is Tb
3+and the interaction between the oversubscription subchain that iQ [6] is formed and oversubscription subchain, e is at [ZnCl
4]
2-under existence, Tb
3+the solid complexes formed with iQ [6].
Fig. 4 in an acidic solution, the solid complexes crystalline structure figure that rare earth metal Tm and trans hexa-atomic melon ring iQ [6] are formed.Er, Tm, Yb have similar structures, are homeomorphism crystal.A is Tm
3+the title complex formed with iQ [6], b and c is that each iQ [6] is by [ZnCl
4]
2-the vertical view surrounded, d is Tm
3+and the interaction between the oversubscription subchain that iQ [6] is formed and oversubscription subchain, e is at [ZnCl
4]
2-under existence, Tm
3+the solid complexes formed with iQ [6].
Fig. 5 in an acidic solution, the solid complexes crystalline structure figure that rare earth metal Lu and trans hexa-atomic melon ring iQ [6] are formed.A is Lu
3+the title complex formed with iQ [6], b and c is that each iQ [6] is by [ZnCl
4]
2-the vertical view surrounded, d is Lu
3+and the interaction between the oversubscription subchain that iQ [6] is formed and oversubscription subchain, e is at [ZnCl
4]
2-under existence, Lu
3+the solid complexes formed with iQ [6].
Fig. 6 is from the electron spectroscopy analysis result containing mol ratio being the solid complexes that the iQ [6] obtained two kinds of rare earth metal mixing solutionss of 1:1 is formed.The electron spectroscopy analysis result of a to be La-Sm mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of b to be La-Gd mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of c to be La-Dy mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of d to be La-Ho mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of e to be La-Lu mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of f to be Ce-Eu mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed, the electron spectroscopy analysis result of g to be Pr-Sm mol ratio the be solid complexes that the iQ [6] obtained in two kinds of rare earth metal mixing solutionss of 1:1 is formed.
The iQ [6] that Fig. 7 and iQ [6] compares forms the IR collection of illustrative plates of title complex.A is the comparison diagram of the IR of La-iQ [6] title complex and iQ [6], b is the comparison diagram of the IR of Tb-iQ [6] title complex and iQ [6], c is the comparison diagram of the IR of Tb-iQ [6] title complex and iQ [6], d is the comparison diagram of the IR of Tm-iQ [6] title complex and iQ [6], and e is the comparison diagram of the IR of Lu-iQ [6] title complex and iQ [6].
The thermogravimetric (TG) that the iQ [6] that Fig. 8 and iQ [6] compares forms title complex analyzes collection of illustrative plates.A is the comparison diagram of the TG of La-iQ [6] title complex and iQ [6], b is the comparison diagram of the TG of Tb-iQ [6] title complex and iQ [6], c is the comparison diagram of the TG of Tb-iQ [6] title complex and iQ [6], d is the comparison diagram of the TG of Tm-iQ [6] title complex and iQ [6], and e is the comparison diagram of the TG of Lu-iQ [6] title complex and iQ [6].
The differential thermal (DTA) that the iQ [6] that Fig. 9 and iQ [6] compares forms title complex analyzes collection of illustrative plates.A is the comparison diagram of the DTA of La-iQ [6] title complex and iQ [6], b is the comparison diagram of the DTA of Tb-iQ [6] title complex and iQ [6], c is the comparison diagram of the DTA of Tb-iQ [6] title complex and iQ [6], d is the comparison diagram of the DTA of Tm-iQ [6] title complex and iQ [6], and e is the comparison diagram of the DTA of Lu-iQ [6] title complex and iQ [6].
Embodiment
Embodiment 1: at ZnCl
4 2-under existence condition, rare earth (nitrate) metal ion and the effect of trans hexa-atomic melon ring form title complex implementation method.With Tb (NO
3)
3for example illustrates:
Take Tb (NO respectively
3)
35H
2o 77.00 mg (0.17 mmol), Zn (NO
3)
360.7 mg (0.20mmol), with same beaker, add the 1.0 mL aqueous solution, are heated to 70 DEG C, make it to be sufficiently uniformly dissolved; Take iQ [6] 20 mg (0.017 mmol), add 1.0 mL 6molL
-1hydrochloric acid soln is heated to 70 DEG C, shakes several minutes, and solution is clarified.I [6] solution is injected above-mentioned mixing solutions, shakes up; Leave standstill about 10 days, occur colourless transparent crystal, calculate productive rate 50 ~ 75% by iQ [6].Its structural formula is { Tb
2(H
2o)
10(NO
3@iQ [6])
22 [ZnCl
4] 41 (H
2o).Under similarity condition, trans hexa-atomic melon ring and rare earth metal (Gd
3+, Tb
3+, Dy
3+, Ho
3+) formed structure be homeomorphic supermolecule polymer, its general structure is { Ln
2(H
2o)
10(NO
3@iQ [6])
22 [ZnCl
4] x (H
2o).
Embodiment 2: utilize trans hexa-atomic melon ring and light rare earth metal La
3+, Ce
3+quick formation precipitation, and except Sm
3+, Eu
3+rare earth metal form the difference of crystal, the method for separating rare-earth metal ion.To be separated La
3+with Gd
3+for example illustrates:
Take La (NO respectively
3)
36H
2o 36.8 mg (0.085 mmol), Tb (NO
3)
35H
2o 38.4 mg (0.085 mmol), Zn (NO
3)
360.7 mg (0.20mmol), with same beaker, add 1 mL water, are heated to 70 DEG C, make it to be sufficiently uniformly dissolved.Take iQ [6] 20 mg (0.017 mmol), add 1.0 mL 6molL
-1hydrochloric acid soln is heated to 70 DEG C, shakes several minutes, and solution is clarified.IQ [6] solution is injected above-mentioned mixing solutions, shakes up, leave standstill 3 days, by be measured for the precipitate and separate washing produced, calculate productive rate 40 ~ 60% by iQ [6].
Claims (5)
1. trans hexa-atomic melon ring-rare earth metal forms title complex, it is characterized in that at tetrachloro zincic acid root ZnCl
4 2-under existence condition, at 3 molL
-1in hydrochloric acid soln, trans hexa-atomic melon ring and rare earth metal salt La, Ce form white precipitate, form solid complexes with Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the trans hexa-atomic melon ring of indication and rare earth form coordination chemistry and form general formula and be:
(1) {Ln(H
2O)
5iQ[6]} [ZnCl
4] x(H
2O) （Ln=Pr、Nd,10≤ x ≤11）
(2) {Ln
2(H
2O)
10(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Gd、Tb、Dy、Ho, 41≤ x ≤49）
(3) {Ln
2(H
2O)
13(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Er、Tm、Yb，39≤ x ≤49）
(4) {Ln
2(H
2O)
12(NO
3@iQ[6])
2} 2[ZnCl
4] x(H
2O) （Ln=Lu,x=46）
Ln represents rare earth ion, and x is crystalline water molecules quantity, and iQ [6] is trans hexa-atomic melon ring.
2. trans hexa-atomic melon ring-rare earth compounding according to claim 1, is characterized in that at tetrachloro zincic acid root ZnCl
4 2-under existence condition, 3 molL
-1the trans hexa-atomic melon ring-rare earth compounding formed in hydrochloric environment is:
(1) ｛Pr(H
2O)
5(NO
3@iQ[6])｝[ZnCl
4] 11(H
2O)
(2) ｛Nd(H
2O)
5(NO
3@iQ[6])｝[ZnCl
4] 10(H
2O)
(3) ｛Gd
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 43(H
2O)
(4) ｛Tb
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 41(H
2O)
(5) ｛Dy
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 45(H
2O)
(6) ｛Ho
2(H
2O)
10(NO
3@iQ[6])
2｝2[ZnCl
4] 49(H
2O)
(7) ｛Er
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 49(H
2O)
(8) ｛Tm
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 39(H
2O)
(9) ｛Yb
2(H
2O)
13(NO
3@iQ[6])
2｝2[ZnCl
4] 43(H
2O)
(10)｛Lu
2(H
2O)
12(NO
3@iQ[6])
2｝2[ZnCl
4] 46(H
2O)。
3. the trans hexa-atomic melon ring-rare earth compounding as described in one of claim 1-2, is characterized in that synthetic method follows these steps to carry out:
(1) iQ [6] is used 3 molL
-1hydrochloric acid soln dissolves obtain solution A completely;
(2) by zinc nitrate Zn (NO
3)
2with Ln (NO
3)
3respectively 12:5-10 weighs in molar ratio, and two kinds of materials, with same container, to dissolve with distilled water and obtain solution B by mixing completely;
(3) solution A and B are pressed iQ [6]: zinc nitrate Zn (NO
3)
2: Ln (NO
3)
3equal the mixed in molar ratio of 1:12:5-10;
(4) leave standstill, formed precipitation for the nearly 1-3 of light rare earths La, Ce days; Other rare earth metals can grow crystal in 1-2 week except Sm, Eu, and Sm, Eu grow crystal about January.
4. trans hexa-atomic melon ring-rare earth compounding synthetic method according to claim 3, is characterized in that: as iQ [6], zinc nitrate Zn (NO
3)
2, Ln (NO
3)
3in molar ratio 1: 12:10 time, grow the fastest of crystal, productive rate is the highest.
5. the application of the trans hexa-atomic melon ring-rare earth compounding as described in one of claims 1 to 3, it is characterized in that utilizing trans hexa-atomic melon ring and light rare earth metal La, Ce 1-3 days comparatively fast forms precipitation, Sm, Eu grow crystal in mono-month, and the different of solid complexes speed can be formed from other rare earth metals, can be used for the separation of rare earth ion.
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|---|---|---|---|---|
| CN105924458A (en) * | 2016-04-22 | 2016-09-07 | 贵州大学 | Separation method of dicyclohexanocucurbiturils-light and heavy rare earths |
| CN106243363A (en) * | 2016-07-31 | 2016-12-21 | 贵州大学 | The full cyclopenta hexa-atomic melon ring rare earth that replaces forms supermolecule polymer and preparation method thereof |
| CN107064199A (en) * | 2017-01-23 | 2017-08-18 | 贵州大学 | A kind of trans cucurbit(7)uril recognizes the application of biogenic amine |
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| CN102936259A (en) * | 2012-11-15 | 2013-02-20 | 贵州大学 | Method for synthesizing cucurbit [6] uril, Q[6]-rear earth linear polymer and separating light rear earth from heavy rear earth |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936259A (en) * | 2012-11-15 | 2013-02-20 | 贵州大学 | Method for synthesizing cucurbit [6] uril, Q[6]-rear earth linear polymer and separating light rear earth from heavy rear earth |
| CN103351399A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Synthesis and separation method for trans cucurbit[6]uril |
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|---|---|---|---|---|
| CN105924458A (en) * | 2016-04-22 | 2016-09-07 | 贵州大学 | Separation method of dicyclohexanocucurbiturils-light and heavy rare earths |
| CN106243363A (en) * | 2016-07-31 | 2016-12-21 | 贵州大学 | The full cyclopenta hexa-atomic melon ring rare earth that replaces forms supermolecule polymer and preparation method thereof |
| CN106243363B (en) * | 2016-07-31 | 2019-07-05 | 贵州大学 | It is complete that the hexa-atomic melon ring of cyclopenta-rare earth is replaced to form supermolecule polymer and preparation method thereof |
| CN107064199A (en) * | 2017-01-23 | 2017-08-18 | 贵州大学 | A kind of trans cucurbit(7)uril recognizes the application of biogenic amine |
| CN107201223A (en) * | 2017-06-02 | 2017-09-26 | 贵州大学 | A kind of preparation method of white fluorescent solid material |
| CN107201223B (en) * | 2017-06-02 | 2019-08-02 | 贵州大学 | A kind of preparation method of white fluorescent solid material |
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