CN105541884A - Rare-earth metal organic framework material taking glycolic acid as ligand and preparation method thereof - Google Patents
Rare-earth metal organic framework material taking glycolic acid as ligand and preparation method thereof Download PDFInfo
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- CN105541884A CN105541884A CN201510989610.3A CN201510989610A CN105541884A CN 105541884 A CN105541884 A CN 105541884A CN 201510989610 A CN201510989610 A CN 201510989610A CN 105541884 A CN105541884 A CN 105541884A
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- organic framework
- earth metal
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 48
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title abstract 8
- 239000003446 ligand Substances 0.000 title abstract 3
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 230000004323 axial length Effects 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 63
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910003317 GdCl3 Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 238000002050 diffraction method Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a rare-earth metal organic framework material taking glycolic acid as ligand and a preparation method thereof, and relates to a rare-earth metal organic framework material. The rare-earth metal organic framework material taking the glycolic acid as the ligand belongs to a hexagonal crystal system of which a space group is P63/m; a molecular formula of the material is shown as {[Gd7(CO3)3(OH)8(HOCH2COO)6].Cl}n, wherein n is a cycle number, and is a positive integer; a lattice parameter is shown in the description, wherein a, b and c are three axial lengths of a unit cell respectively, and V is a volume of the unit cell. The preparation method comprises the following steps: dissolving gadolinium chloride and glycolic acid into a mixed solvent; stirring for 30-60 minutes, and transferring into a reaction kettle; heating to 150-160 DEG C and keeping a constant temperature; cooling to the room temperature; filtering and washing to obtain the rare-earth metal organic framework material.
Description
Technical field
The present invention relates to rare earth metal organic framework materials, especially relating to a kind of take oxyacetic acid as rare earth metal organic framework materials of part and preparation method thereof.
Background technology
Metal-organic framework material is metal organic coordination polymer again, has become a kind of novel functionalized crystal material.It to be coupled together at inorganic metal center by the mode of coordinate bond by organic bridgingligand to form unlimited extension and have periodic reticulated structure crystalline material.Compared with traditional inorganic porous material, the maximum feature of metal-organic framework material is exactly that it has the porosity of superelevation and huge inner ratio surface area, especially adjustable aperture and variable functional group.Due to this characteristic that metal-organic framework material is made up of inorganic metal ion or metal ion bunch and organic bridgingligand, make it have the feature of inorganic materials and organic materials, with a wide range of applications, the absorption of the storage of such as hydrogen, drug carrier, catalyzed reaction, gas be separated and the aspect (Zhai Rui such as exchange of ion, Jiao Fenglong, Lin Hongjun, Hao Feiran, Li Jiabin, Yan Hui. the progress [J] of metal-organic framework material. chromatogram, 2014,32,107-116.).
But the many metal-organic framework material reported up to now remain unchanged the problem of existence and stability.Many metal-organic framework material in aqueous or be exposed in malaria, will be dissolved gradually or decompose, or only can stable existence in sour environment, make it be limited by very large (J.B.DeCoste in application aspect; G.W.Petersons, Metal-OrganicFrameworksforAirPurificationofToxicChemical s [J] .Chem.Rev.; 2014,114,5695-5727).Seldom have bibliographical information, metal organic framework materials can stable existence under the environment of soda acid and water.
Summary of the invention
The object of the present invention is to provide a kind of take oxyacetic acid as rare earth metal organic framework materials of part and preparation method thereof.
Described take oxyacetic acid as the rare earth metal organic framework materials of part, belongs to hexagonal system, spacer P6
3/ m, molecular formula is: { [Gd
7(CO
3)
3(OH)
8(HOCH
2cOO)
6] Cl}
n, wherein n is cycle life, gets positive integer, and unit cell parameters is:
wherein a, b, c, be respectively three axial lengths of structure cell, V is the volume of structure cell.
Described take oxyacetic acid as the preparation method of the rare earth metal organic framework materials of part, and concrete steps are as follows:
Gadolinium trichloride, oxyacetic acid are dissolved in mixed solvent, be transferred in reactor after stirring 30 ~ 60min, be warming up to 150 ~ 160 DEG C and constant temperature, then room temperature is down to, filtration washing, be able to the rare earth metal organic framework materials that oxyacetic acid is part, described take oxyacetic acid as the rare earth metal organic framework materials of part is colourless bar-shaped crystal.
Described mixed solvent can be the mixed solvent of acetonitrile, second alcohol and water;
The consumption proportion of described Gadolinium trichloride, oxyacetic acid, acetonitrile, ethanol, water can be 0.5mmol: 0.5mmol: 6mL: 5mL: 4mL, and wherein Gadolinium trichloride, oxyacetic acid are with a mole calculating, and acetonitrile, ethanol, water are calculated by volume; Described water can adopt deionized water; Described reactor can adopt the withstand voltage stainless steel cauldron of inner liner polytetrafluoroethylene; The speed of described intensification can be 65 DEG C/h; The time of described constant temperature can be 48h; Described speed of being down to room temperature can be 4.3 DEG C/h.
X-ray single crystal diffraction instrument can be utilized to carry out single crystal structure test to the rare earth metal organic framework materials taking oxyacetic acid as part, and probe temperature is 100K.By the immersion in soda acid and the aqueous solution, powdery diffractometry show described with oxyacetic acid be part rare earth metal organic framework materials can stable existence wherein.
Be the rare earth metal organic framework materials of part with oxyacetic acid described in soaking in soda acid and the aqueous solution, and verify its stability by powdery diffractometry, concrete grammar is as follows:
1) the concentrated hydrochloric acid 8.3mL that commercial concentration is 37% is got, with deionized water dilution, at 100mL volumetric flask constant volume, be mixed with the dilute hydrochloric acid solution of 1.0mol/L, then get this dilute hydrochloric acid solution 1mL, dilute with deionized water, constant volume in 10mL volumetric flask, is mixed with the hydrochloric acid soln of pH=1.Getting with oxyacetic acid is that the rare earth metal organic framework materials of part is immersed in the hydrochloric acid soln of this pH=1 after 12h, verifies its stability by powdery diffractometry;
2) get commercially available sodium hydroxide 1g, with deionization dilution, at 25mL volumetric flask constant volume, be mixed with the sodium hydroxide solution of pH=14.Getting with oxyacetic acid is that the rare earth metal organic framework materials of part is immersed in the sodium hydroxide solution of this pH=14 after 12h, verifies its stability by powdery diffractometry;
3) getting with oxyacetic acid is that the rare earth metal organic framework materials of part soaks in deionized water, and heat 12h at 100 DEG C after, verifies its stability by powdery diffractometry.
The present invention chooses oxyacetic acid as part, chooses rare-earth Gd
3+as inorganic metal ion, by solvent structure be the rare earth metal organic framework materials of part with oxyacetic acid.And demonstrate this metal-organic framework material by XRD, in soda acid and the aqueous solution, there is fabulous stability.
Remarkable advantage of the present invention is:
1, be that the synthesizer of rare earth metal organic framework materials of part is simple with oxyacetic acid, preparation method is quick, and easy handling, productive rate is high, has larger synthesis application prospect.
2, take oxyacetic acid as the rare earth metal organic framework materials of part, from strong acid to highly basic and under boiling water environment, all there is extremely strong stability, thermostability.
To sum up show, the present invention is that the rare earth metal organic framework materials of part has extremely strong stability in strong acid, highly basic and boiling water with oxyacetic acid, in metal organic frame stability, have potential application prospect.
Accompanying drawing explanation
Fig. 1 is the minimum repeat unit structure figure of the rare earth metal organic framework materials taking oxyacetic acid as part.
Fig. 2 is the three-dimensional frame structure figure of the rare earth metal organic framework materials taking oxyacetic acid as part.
Fig. 3 is the XRD figure of the rare earth metal organic framework materials taking oxyacetic acid as part.
Fig. 4 take oxyacetic acid as XRD figure after the rare earth metal organic framework materials of part soaks in acid.
Fig. 5 take oxyacetic acid as XRD figure after the rare earth metal organic framework materials of part soaks in alkali.
Fig. 6 take oxyacetic acid as XRD figure after the rare earth metal organic framework materials of part soaks in water.
Embodiment
Following examples will the invention will be further described by reference to the accompanying drawings.
Embodiment 1
Take oxyacetic acid as the preparation process of the rare earth metal organic framework materials of part: 0.5mmol Gadolinium trichloride, 0.5mmol oxyacetic acid are dissolved in 6mL acetonitrile, 5mL ethanol and 4mL water mixed solvent, after stirring at normal temperature 30 ~ 60min, solution is transferred in the withstand voltage stainless steel cauldron of 23mL inner liner polytetrafluoroethylene, with the ramp to 160 of 65 DEG C/h DEG C and constant temperature 48h, then slowly room temperature is down to the speed of 4.3 DEG C/h, filtration washing, obtains colourless rhabdolith.
Embodiment 2
Sample characterization:
1, monocrystalline test:
Be that the single crystal samples structure of the rare earth metal organic framework materials of part adopts AgilentSuperNovaDiffractometerX ray single crystal diffraction instrument to collect under 100K to obtain with oxyacetic acid.Fig. 1, Fig. 2 are the crystalline structure figure of the rare earth metal organic framework materials taking oxyacetic acid as part.
2, take oxyacetic acid as the rare earth metal organic framework materials of part: belong to hexagonal system, spacer P6
3/m, molecular formula is: { [Gd
7(CO
3)
3(OH)
8(HOCH
2cOO)
6] Cl}
n(n is cycle life, gets infinity), unit cell parameters is:
(a, b, c, be respectively three axial lengths of structure cell, V is the volume of structure cell).Fig. 1 is its minimum repeating unit, and as shown in Figure 2, each minimum repeating unit comprises 7 Gd to its structural coordinates pattern
3+ion, 3 unordered CO
3 2-, 6 oxyacetic acid and 8 μ
3-OH
-.Wherein there are seven kinds of crystallography independently Gd
3+ion (Gd1, Gd2, Gd3, Gd1 ', Gd2 ', Gd3 ' and Gd4), Gd1, Gd2, Gd3, Gd1 ', Gd2 ' and Gd3 ' has identical coordination mode, all with O and three μ on the carboxyl in eight-coordinate mode and three oxyacetic acids, the hydroxyl on an oxyacetic acid, a carbonate
3-OH
-coordination forms dodecahedron configuration, and Gd4 is then with O and six μ in the mode of nine coordinations and three carbonates
3-OH
-coordination forms tetrakaidecahedron configuration.Respectively by the carboxyl on an oxyacetic acid and a μ between Gd1, Gd2 and Gd3
3-OH
-bridging is got up, and Gd1, Gd2, Gd3 and Gd1 ', Gd2 ', Gd3 ' they are centrosymmetric about Gd4, Gd4 is then by three carbonates and six μ
3-OH
-with Gd1, Gd2, Gd3, Gd1 ', Gd2 ', Gd3 ' bridging get up.Wherein Gd1, Gd2, Gd3 are by oxyacetic acid and Gd1 ', Gd2 ', Gd3 ' bridging, constitute three-dimensional frame structure, as shown in Figure 2.The bond distance of Gd-O exists
in scope, the bond angle of Gd-O-Gd is 101.4 ~ 113.5 °, and the spacing of GdGd is
Structural characterization:
RigakuVltimaIV type x-ray powder diffraction instrument is adopted to carry out structural characterization to powdered sample.Fig. 3 is the XRD figure of the rare earth metal organic framework materials taking oxyacetic acid as part, as can be seen from Figure 3, its XRD experimental diffraction peak (AsSynthesized) (curve a) with basically identical according to the XRD data (Simulated) (curve b) of single crystal structure matching.Each characteristic diffraction peak peak shape is better, and baseline is relatively more steady, and interpret sample is without dephasign, and purity is higher, and crystalline phase is good.
Embodiment 3
Be that the rare earth metal organic framework materials of part is at pH=1 acid solution, pH=14 alkaline solution and detect at 100 DEG C of water stabilities with oxyacetic acid.
Fig. 4 shows, and after soaking 12h, is that the rare earth metal organic framework materials of part is with basically identical according to the XRD data of single crystal structure matching with oxyacetic acid in pH=1 hydrochloric acid soln.Each characteristic diffraction peak peak shape is better, and baseline is relatively more steady, and interpret sample still keeps crystal formation, and crystalline phase is still good.More than show that this material can stable existence in acid solution.
Fig. 5 shows, and after soaking 12h, is that the rare earth metal organic framework materials of part is with basically identical according to the XRD data of single crystal structure matching with oxyacetic acid in pH=14 sodium hydroxide solution.Each characteristic diffraction peak peak shape is better, and baseline is relatively more steady, and interpret sample still keeps crystal formation, and crystalline phase is still good.More than show that this material can stable existence in alkaline solution.
Fig. 6 shows, and after soaking 12h, is that the rare earth metal organic framework materials of part is with basically identical according to the XRD data of single crystal structure matching with oxyacetic acid in 100 DEG C of water.Each characteristic diffraction peak peak shape is better, and baseline is relatively more steady, and interpret sample still keeps crystal formation, and crystalline phase is still good.More than show that this material in aqueous can stable existence.
Claims (8)
1. be the rare earth metal organic framework materials of part with oxyacetic acid, it is characterized in that it belongs to hexagonal system, spacer P6
3/ m, molecular formula is: { [Gd
7(CO
3)
3(OH)
8(HOCH
2cOO)
6] Cl}
n, wherein n is cycle life, gets positive integer, and unit cell parameters is:
wherein a, b, c, be respectively three axial lengths of structure cell, V is the volume of structure cell.
2. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 1 with oxyacetic acid, it is characterized in that its concrete steps are as follows:
Gadolinium trichloride, oxyacetic acid are dissolved in mixed solvent, are transferred in reactor after stirring 30 ~ 60min, be warming up to 150 ~ 160 DEG C and constant temperature, be then down to room temperature, filtration washing, be able to the rare earth metal organic framework materials that oxyacetic acid is part.
3. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 1 with oxyacetic acid, it is characterized in that described mixed solvent is the mixed solvent of acetonitrile, second alcohol and water.
4. be the preparation method of the rare earth metal organic framework materials of part with oxyacetic acid as described in claim 1 and 2, it is characterized in that the consumption proportion of described Gadolinium trichloride, oxyacetic acid, acetonitrile, ethanol, water is 0.5mmol: 0.5mmol: 6mL: 5mL: 4mL, wherein Gadolinium trichloride, oxyacetic acid are with a mole calculating, and acetonitrile, ethanol, water are calculated by volume.
5. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 3 with oxyacetic acid, it is characterized in that described hydromining deionized water.
6. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 1 with oxyacetic acid, it is characterized in that described reactor adopts the withstand voltage stainless steel cauldron of inner liner polytetrafluoroethylene.
7. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 1 with oxyacetic acid, it is characterized in that the speed of described intensification is 65 DEG C/h, the time of described constant temperature is 48h.
8. be the preparation method of the rare earth metal organic framework materials of part as claimed in claim 1 with oxyacetic acid, the speed of being down to room temperature described in it is characterized in that is 4.3 DEG C/h.
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Cited By (1)
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| CN109092361A (en) * | 2018-07-18 | 2018-12-28 | 嘉兴学院 | Organolanthanide complexes and its preparation method and application based on chalcones dicarboxylates |
| CN109092361B (en) * | 2018-07-18 | 2021-08-13 | 嘉兴学院 | Rare earth metal organic complex based on chalcone dicarboxylic acid ligand and preparation method and application thereof |
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Application publication date: 20160504 |
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| RJ01 | Rejection of invention patent application after publication |