CN105622654B - By the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid and preparation method thereof - Google Patents
By the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid and preparation method thereof Download PDFInfo
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- CN105622654B CN105622654B CN201510992049.4A CN201510992049A CN105622654B CN 105622654 B CN105622654 B CN 105622654B CN 201510992049 A CN201510992049 A CN 201510992049A CN 105622654 B CN105622654 B CN 105622654B
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Abstract
By the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid and preparation method thereof, it is related to metal-organic framework material.The rare earth metal organic framework materials belong to hexagonal crystal system, space group P63Mc, molecular formula is：{[Gd4O(OH)3(C5NH4COO)3(OHCH2COO)3(H2O)3](CF3SO3)(H2O)6}n, cell parameter is：
Description
Technical field
The present invention relates to metal-organic framework material, more particularly, to using isonicotinic acid and hydroxyacetic acid as the dilute of mixed ligand
Earth metal organic framework materials and preparation method thereof.
Background technology
Metal-organic framework material is called metal organic coordination polymer, has become a kind of new functionalized crystal material
Material.It is to be connected inorganic metal center by way of coordinate bond by organic bridging ligand to form unlimited extension with week
The network structure crystalline material of phase property.Compared with traditional inorganic porous material, the maximum feature of metal-organic framework material is just
It is that it has the porosity and huge inner ratio surface area of superelevation, 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 cluster with organic bridging ligand,
The characteristics of making it have inorganic material and organic material, it is with a wide range of applications, such as the storage of hydrogen, drug carrier, urge
Change reaction, gas absorption with separate and the exchange of ion in terms of (Zhai Rui, Jiao Fenglong, Lin Hongjun, Hao Feiran, Li Jiabin,
Progress [J] chromatograms of face brightness metal-organic framework materials, 2014,32,107-116.).
However, many metal-organic framework materials reported up to now remain unchanged the problem of existence and stability.Many gold
Belong to organic framework materials in aqueous or in malaria, will gradually dissolve and either decompose or only exist
It can be stabilized in sour environment, it is limited by very large (J.B.DeCoste in application aspect；
G.W.Petersons,Metal-Organic Frameworks for Air Purification of Toxic
Chemicals[J].Chem.Rev.；2014,114,5695-5727).Few document reports, relevant metal organic frame material
What material be able to can be stabilized in the environment of soda acid and water.
The content of the invention
It is an object of the invention to provide using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic frame material of mixed ligand
Material and preparation method thereof.
It is described to belong to hexagonal crystal system using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand,
Space group P63Mc, molecular formula is：{[Gd4O(OH)3(C5NH4COO)3(OHCH2COO)3(H2O)3](CF3SO3)(H2O)6}n, structure cell
Parameter is：A, b, c, respectively structure cell three axial lengths, V
For the volume of structure cell, n is periodicity, takes positive integer.
It is described using isonicotinic acid and hydroxyacetic acid as the preparation method of the rare earth metal organic framework materials of mixed ligand, its have
Body step is as follows：
It is transferred to instead after trifluoromethanesulfonic acid gadolinium, isonicotinic acid and hydroxyacetic acid are dissolved in into the mixed solvent, 30~60min of stirring
Answer in kettle, be warming up to 150~160 DEG C and constant temperature, be then down to room temperature, filtration washing, obtain using isonicotinic acid and hydroxyacetic acid as
The rare earth metal organic framework materials of mixed ligand, are able to isonicotinic acid and hydroxyacetic acid organic for the rare earth metal of mixed ligand
Frame material is colourless bar-shaped crystal.
The mixed solvent can use acetonitrile, the mixed solvent of second alcohol and water；
The trifluoromethanesulfonic acid gadolinium, isonicotinic acid, hydroxyacetic acid, acetonitrile, ethanol, the consumption proportion of water are 0.2mmol:
0.4mmol: 0.2mmol: 6mL: 5mL: 4mL, wherein trifluoromethanesulfonic acid gadolinium, isonicotinic acid, hydroxyacetic acid is calculated in mol, solvent second
Nitrile, ethanol, water are in terms of volume；The water can use deionized water；The reactor can be pressure-resistant using inner liner polytetrafluoroethylene
Stainless steel cauldron；The speed of the heating can be 60 DEG C/h；The time of the constant temperature is 48h；The speed for being down to room temperature
For 4 DEG C/h.
Using X-ray single crystal diffractometer to using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic frame of mixed ligand
Material carries out mono-crystalline structures test, and test temperature is 100K.By the immersion in soda acid and the aqueous solution, powder diffraction shows
It is described to be stabilized wherein by the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid.
There is machine frame by the rare earth metal of mixed ligand of isonicotinic acid and hydroxyacetic acid described in immersion in soda acid and the aqueous solution
Frame material, and its stability is verified by powder diffraction, specific method is as follows：
1) the concentrated hydrochloric acid 8.3mL for taking commercial concentration to be 37%, is diluted with deionized water, in 100mL volumetric flask constant volumes, is prepared
Into 1.0mol/L dilute hydrochloric acid solution, then dilute hydrochloric acid solution 1mL is taken, is diluted with deionized water, the constant volume in 10mL volumetric flasks,
It is configured to pH=1 hydrochloric acid solution.Take a certain amount of has machine frame by the rare earth metal of mixed ligand of isonicotinic acid and hydroxyacetic acid
Frame material is immersed in the hydrochloric acid solution of the pH=1 after 12h, and its stability is verified by powder diffraction；
2) commercially available sodium hydroxide 1g is taken, is diluted with 25mL deionizations, is configured to pH=14 sodium hydroxide solution, then take pH
=14 sodium hydroxide solution 1mL, is diluted with deionized water, and the constant volume in 100mL volumetric flasks is configured to pH=12 hydroxide
Sodium solution.Take and a certain amount of be immersed in the pH by the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid
In=12 sodium hydroxide solution after 12h, its stability is verified by powder diffraction；
3) take and a certain amount of be immersed in by the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid
In deionized water, and heated at 100 DEG C after 12h, its stability is verified by powder diffraction.
In view of analyzing above, the isonicotinic acid being coordinated with nitrogen is chosen as part, hydroxyacetic acid is chosen as assistant ligand
Rare-earth Gd3+As inorganic metal ion, by solvent structure using isonicotinic acid and hydroxyacetic acid as the rare earth of mixed ligand
Metal-organic framework material.And the metal-organic framework material is demonstrated in soda acid and the aqueous solution with fabulous by XRD
Stability.
The remarkable advantage of the present invention is：
1st, it is simple by the synthesizer of the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid, system
Preparation Method is quick, it is easy to operate, and has larger synthesis application prospect.
2nd, using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand, from strong acid to highly basic with
And extremely strong stability, heat endurance are respectively provided with boiling water environment.
To sum up show, the present invention using isonicotinic acid and hydroxyacetic acid be the rare earth metal organic framework materials of mixed ligand strong
There is extremely strong stability in acid, highly basic and boiling water, there is potential application prospect in terms of metal organic frame stability.
Brief description of the drawings
Fig. 1 is using isonicotinic acid and hydroxyacetic acid as the three-dimensional frame structure of the rare earth metal organic framework materials of mixed ligand
Figure.
Fig. 2 is using isonicotinic acid and hydroxyacetic acid as the minimum repeat unit of the rare earth metal organic framework materials of mixed ligand
Structure chart.
Fig. 3 is using isonicotinic acid and hydroxyacetic acid as the one-dimensional catenary structure of the rare earth metal organic framework materials of mixed ligand
Figure.
Fig. 4 is using isonicotinic acid and hydroxyacetic acid as the XRD of the rare earth metal organic framework materials of mixed ligand.
Fig. 5 is after being soaked using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand in acid
XRD.
Fig. 6 is after being soaked using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand in alkali
XRD.
Fig. 7 is after being soaked using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand in water
XRD.
Embodiment
Below by embodiment combination accompanying drawing, the invention will be further described.
Embodiment 1
Using isonicotinic acid and hydroxyacetic acid as the preparation process of the rare earth metal organic framework materials of mixed ligand：Will
0.2mmol trifluoromethanesulfonic acids gadolinium, 0.4mmol isonicotinic acid and 0.2mmol hydroxyacetic acids are dissolved in 6mL acetonitriles, 5mL ethanol and 4mL
In water mixed solvent, after 30~60min of stirring at normal temperature, solution is transferred to the pressure-resistant stainless steel reaction of 23mL inner liner polytetrafluoroethylenes
In kettle, 150 DEG C and constant temperature 48h are warming up to 60 DEG C/h speed, room temperature is then slowly dropped to 4 DEG C/h speed, diafiltration is crossed
Wash, obtain colourless rhabdolith.
Embodiment 2
Sample characterization：
1st, monocrystalline is tested：
Used by the single crystal samples structure of the rare earth metal organic framework materials of mixed ligand of isonicotinic acid and hydroxyacetic acid
Agilent Super Nova Diffractometer X-rays single crystal diffractometers are collected under 100K to be obtained.Fig. 1 is with different cigarette
Acid and the rare earth metal organic framework materials crystal structure figure that hydroxyacetic acid is mixed ligand.
2nd, using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand：Belong to hexagonal crystal system, it is empty
Between group P63Mc, molecular formula is：{[Gd4O(OH)3(C5NH4COO)3(OHCH2COO)3(H2O)3](CF3SO3)(H2O)6}n(n is week
Issue, takes infinity), cell parameter is：(a, b, c, point
Not Wei structure cell three axial lengths, V be structure cell volume).Fig. 2 is its minimum repeat unit, its structural coordinates pattern such as Fig. 3 institutes
Show, each minimum repeat unit includes 4 Gd3+Ion, 3 isonicotinic acid, 3 hydroxyacetic acids, 1 O2-Ion, 3 OH-Ion
With 3 hydrones.Wherein there is the Gd of four kinds of crystallography independence3+Ion (Gd1, Gd2, Gd3 and Gd4), Gd1, Gd2 and Gd3 have
Identical coordination mode, with the carboxyl on two isonicotinic acid in the way of eight-coordinate, carboxyl on a hydroxyacetic acid, one
Hydroxyl, three μ on hydroxyacetic acid3-OH-With a μ3-O2-Coordination forms dodecahedron configuration, and Gd4 is then with the side of seven coordinations
Formula and the carboxyl on three hydroxyacetic acids, three μ3-OH-With a μ3-O2-Coordination forms decahedron configuration.Gd1, Gd2 and Gd3
Between pass through the carboxyl on an isonicotinic acid and a μ respectively3-OH-Bridging is got up, and Gd4 is then by three hydroxyacetic acids
Carboxyl and a μ3-O2-Get up to form one-dimensional catenary structure with Gd1, Gd2, Gd3 bridging, such as Fig. 3.In adjacent one-dimentional structure
Isonicotinic acid is accumulated by pi-pi bond, constitutes three-dimensional structure.Gd-O bond distance 2.267~ In the range of, Gd-O-Gd's
Bond angle be 106.1~112.6 °, between GdGd distance be 3.655~
Structural characterization：
Structural characterization is carried out to powder sample using Rigaku Vltima IV types x-ray powder diffraction instruments.Fig. 4 is with different
Nicotinic acid and hydroxyacetic acid for the rare earth metal organic framework materials of mixed ligand XRD, figure 4, it is seen that its XRD
Experimental diffraction peak (As Synthesized) (curve a) and XRD data (the Simulated) (curve being fitted according to mono-crystalline structures
B) it is basically identical.Preferably, baseline is more steady, illustrates sample without dephasign, purity is higher, and crystalline phase is good for each characteristic diffraction peak peak shape
It is good.
Embodiment 3
It is the rare earth metal organic framework materials of mixed ligand in pH=1 acid solutions, pH=using isonicotinic acid and hydroxyacetic acid
12 aqueous slkalis and in the detection of 100 DEG C of water stabilities.
Fig. 5 is shown, is soaked in pH=1 hydrochloric acid solutions after 12h, using isonicotinic acid and hydroxyacetic acid as the rare earth of mixed ligand
Metal-organic framework material and the XRD data being fitted according to mono-crystalline structures are basically identical.Each characteristic diffraction peak peak shape is preferable, baseline
Compare steady, illustrate that sample still keeps crystal formation, and crystalline phase remains unchanged well.The material indicated above can be stablized in acid solution to be deposited
.
Fig. 6 is shown, is soaked in pH=12 sodium hydroxide solutions after 12h, using isonicotinic acid and hydroxyacetic acid as mixed ligand
Rare earth metal organic framework materials and the XRD data that are fitted according to mono-crystalline structures it is basically identical.Each characteristic diffraction peak peak shape compared with
Good, baseline is more steady, illustrates that sample still keeps crystal formation, and crystalline phase remains unchanged well.Material energy in aqueous slkali indicated above
Enough it is stabilized.
Fig. 7 is shown, soaks after 12h, has by the rare earth metal of mixed ligand of isonicotinic acid and hydroxyacetic acid in 100 DEG C of water
Machine frame frame material and the XRD data being fitted according to mono-crystalline structures are basically identical.Each characteristic diffraction peak peak shape preferably, relatively put down by baseline
Surely, illustrate that sample still keeps crystal formation, and crystalline phase remains unchanged well.The material indicated above can be stabilized in aqueous.
Claims (9)
1. using isonicotinic acid and hydroxyacetic acid as the rare earth metal organic framework materials of mixed ligand, it is characterised in that belong to hexagonal crystal
System, space group P63Mc, molecular formula is：{[Gd4O(OH)3(C5NH4COO)3(OHCH2COO)3(H2O)3](CF3SO3)(H2O)6}n,
Cell parameter is：A, b, c, respectively structure cell three axles
Long, V is the volume of structure cell, and n is periodicity, takes positive integer.
2. as claimed in claim 1 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that it is comprised the following steps that：
Reactor is transferred to after trifluoromethanesulfonic acid gadolinium, isonicotinic acid and hydroxyacetic acid are dissolved in into the mixed solvent, 30~60min of stirring
In, 150~160 DEG C and constant temperature are warming up to, room temperature is then down to, filtration washing is obtained using isonicotinic acid and hydroxyacetic acid as mixing
The rare earth metal organic framework materials of part.
3. as claimed in claim 2 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the mixed solvent uses acetonitrile, the mixed solvent of second alcohol and water.
4. as claimed in claim 2 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the trifluoromethanesulfonic acid gadolinium, isonicotinic acid, the consumption proportion of hydroxyacetic acid are 0.2mmol: 0.4mmol:
0.2mmol, wherein trifluoromethanesulfonic acid gadolinium, isonicotinic acid, hydroxyacetic acid are calculated in mol.
5. as claimed in claim 3 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the acetonitrile, ethanol, the consumption proportion of water are 6mL: 5mL: 4mL, and solvent acetonitrile, ethanol, water are with volume
Calculate.
6. as claimed in claim 3 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the water uses deionized water.
7. as claimed in claim 2 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the reactor uses the pressure-resistant stainless steel cauldron of inner liner polytetrafluoroethylene.
8. as claimed in claim 2 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the speed of the heating is 60 DEG C/h, and the time of the constant temperature is 48h.
9. as claimed in claim 2 using isonicotinic acid and hydroxyacetic acid as the preparation of the rare earth metal organic framework materials of mixed ligand
Method, it is characterised in that the speed for being down to room temperature is 4 DEG C/h.
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