CN103265580A - Method for preparing porous europium-manganese coordination polymer material and application thereof - Google Patents
Method for preparing porous europium-manganese coordination polymer material and application thereof Download PDFInfo
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- CN103265580A CN103265580A CN2013101986598A CN201310198659A CN103265580A CN 103265580 A CN103265580 A CN 103265580A CN 2013101986598 A CN2013101986598 A CN 2013101986598A CN 201310198659 A CN201310198659 A CN 201310198659A CN 103265580 A CN103265580 A CN 103265580A
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Abstract
The invention discloses a method for preparing a porous europium-manganese coordination polymer and an application thereof. The porous europium-manganese coordination polymer is a coordination compound in the following chemical formula: [Eu(CAM)(HCAM)2Mn2(H2O)7].7H2O, wherein CAM and HCAM respectively are obtained from 4-hydroxy-2,6-cinchomeronic acid, from which three hydrogen ions and two hydrogen ions are removed. The preparation method of the coordination polymer comprises the steps of mixing Eu(NO3)3.6H2O with 4-hydroxy-2,6-cinchomeronic acid according to the mol ratio of 1:3 and adding to DEF; reacting for 72 hours at 90 DEG C to obtain the coordination compound, namely Eu(H2CAM)3.5H2O; mixing the Eu(H2CAM)3.5H2O with MnCl2.4H2O according to the mol ratio of 1:3, adding to water to react for 72 hours at 120 DEG C; and cooling, filtering, standing and washing by a program to obtain the product. The coordination polymer contains a one-dimensional duct; the mixture of methanol and ethanol has a good separating effect at normal temperature and normal pressure, and has good cycle performance. The coordination polymer can separate fatty alcohol compounds without activation at normal temperature and normal pressure, and has good cycle performance. The coordination polymer has great significance in the aspects of preparation of separate materials and mechanism research.
Description
Technical field
The invention belongs to the technical field that inorganic chemistry and materials chemistry combine, relate to porous europium-manganese coordination polymer material, particularly a kind of based on europium (III) ion, manganese (II) ion and 4-hydroxyl-2, the coordination polymer material that the 6-cinchomeronic acid is constructed and preparation method and application thereof.
Background technology
Synthetic and the property research of porous ligand polymer is one of important field of research in the inorganic chemistry that grows up in later stage nineteen nineties and the materials chemistry.Because the duct size with ligand polymer of open pore passage structure can be regulated and control, and the duct inwall can modify, so the porous ligand polymer can be finished the separation of a lot of similar mixtures as parting material.Such material has also that specific surface area is big, the bulky characteristics of hole in addition, is a kind of high efficiency separation material therefore.In general, separating mechanism can be divided into the selectivity of duct size and the selectivity in hole wall functional group or empty metal site.After U.S. scientist Yaghi in 2006 etc. had reported that the alkane of porous ligand polymer MOF-508a has good separating effect, correlative study had caused the attention of countries in the world.After people such as U.S. scientist Long had reported that the porous ligand polymer can be separated the polycomponent aliphatic compound in 2013, the separating property of porous ligand polymer research was with its prospects for commercial application and become international emerging advanced subject of 21st century widely.In the research of having reported, the porous ligand polymer needs to carry out earlier the high temperature desorption as before the parting material, removes the ligand solvent molecule, thereby consumes the more energy.At normal temperatures and pressures just can be directly rarely found as the porous ligand polymer of parting material and reusable edible without desorption.
Summary of the invention
Handle the problem that consumes the more energy thereby the objective of the invention is to solve existing porous ligand polymer as needing to carry out the high temperature desorption earlier before the parting material, preparation method and the application thereof of a kind of porous europium-manganese coordination polymer material are provided.
The present invention selects 4-hydroxyl-2 for use, and 6-cinchomeronic acid (chelidamic acid monohydrate) is part, has synthesized the europium-manganese ligand polymer with 1-dimention nano pore space structure.Do not need at normal temperatures and pressures activatedly can separate with ethanol and can recycle liquid phase methyl alcohol.
Technical scheme of the present invention:
Porous europium-manganese coordination polymer material, chemical formula is: [Eu (CAM) (HCAM)
2Mn
2(H
2O)
7] 7H
2O, wherein CAM and HCAM are respectively and slough three hydrogen ions and slough two hydrionic 4-hydroxyls-2,6-cinchomeronic acid (chelidamic acid monohydrate).Crystal of the present invention belongs to oblique system, and spacer is
P2
1/ n, unit cell parameters is:
a=8.9169 (5),
b=24.4814 (5),
c=17.3224 (3),
α=
γ=90 °,
β=99.3878 (15) °.
This ligand polymer is the three-dimensional frame structure that is connected into by hydrogen bond by a kind of two-dimentional ligand polymer.There is one-dimensional channels in this ligand polymer, and the duct cross section is 12.201 * 5.121.Two kinds of coordinated water molecules are arranged in the duct of this ligand polymer, and a kind of is coordinated water molecule towards the duct; Another kind is the coordinated water molecule towards hole wall.In this ligand polymer towards the water molecules in duct can with methyl alcohol generation permutoid reaction, discord ethanol reacts, and can separate with ethanol methyl alcohol; This ligand polymer does not need to add heat extraction ligand solvent molecule before separation, can separate with ethanol methyl alcohol and have an excellent cycle performance at normal temperature and pressure.This material is 0.7mmol/g to liquid phase methyl alcohol adsorptive capacity at normal temperatures and pressures, to the almost not absorption of liquid phase ethanol.Because the selectivity of coordinated water molecule, this material has the performance of separation of methanol and ethanol.This material stable existence in water and air, and have good circulation separation performance.
The present invention provides the preparation method of a kind of porous europium-manganese coordination polymer material simultaneously, and this method comprises the steps:
(1) with Eu (NO
3)
36H
2O and 4-hydroxyl-2,6-cinchomeronic acid mix for 1:3 in molar ratio and add DEF, put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, react 72 h at 90 ° of C, obtain Eu (H
2CAM)
35H
2O, wherein H
2CAM is for sloughing a hydrionic 4-hydroxyl-2,6-cinchomeronic acid; DEF is N, the N-diethylformamide;
(2) Eu (H that (1) step was obtained
2CAM)
35H
2O and MnCl
24H
2O 1:3 in molar ratio mixes, and puts into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after adding water, and reacts 72 h at 120 ° of C;
(3) again through the 1.0 ° of C/h that lower the temperature up to 30 ° of C, filter, water washing, get product porous europium-manganese coordination polymer material;
(4) this product stable existence in water, thermogravimetric analysis and ultimate analysis show that this porous europium-manganese coordination polymer material has seven dissociating water molecules.
Porous europium provided by the invention-manganese coordination polymer material can be applied in the parting material in material field, specifically is applied in the alcohols homologue separation field.
Advantage of the present invention and positively effect:
Porous europium of the present invention-manganese coordination polymer material obtains under hydrothermal condition, has good water stability, and the more most of existing parting materials of this point are more superior.Bao Dao the ligand polymer with centrifugation mostly need be carried out desorption and handled under the high-temperature vacuum condition up to now, removing the ligand solvent molecule as far as possible, for the ligand solvent molecule to the Study on Selectivity of adsorbate seldom.Preparation method's technology of the present invention is simple, the yield height.Porous europium provided by the invention-manganese ligand polymer contains the 1-dimention nano duct, has the performance of separation of methanol and ethanol.Circulation experiment proves that this material still has good separation performance after a plurality of circulations.
[description of drawings]
[Eu (CAM) (HCAM) for Fig. 1
2Mn
2(H
2O)
7] 7H
2The structure iron of the asymmetric cell of O.
[Eu (CAM) (HCAM) for Fig. 2
2Mn
2(H
2O)
7] 7H
2The one-dimensional tunnel structure figure of O.
Fig. 3 porous europium-manganese coordination polymer material under 298 K to the adsorption curve of gas-phase methanol and ethanol.
Fig. 4 porous europium-manganese coordination polymer material under 298 K to the adsorption curve of liquid phase methyl alcohol and ethanol.
The circulation experiment figure of Fig. 5 porous europium-manganese coordination polymer material separation of methanol and ethanol under 298K.
[embodiment]
Embodiment 1
With Eu (NO
3)
36H
2O and 4-hydroxyl-2,6-cinchomeronic acid mix for 1:3 in molar ratio and add 3 mL DEF, put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, react 72 h at 90 ° of C, obtain Eu (H
2CAM)
35H
2O; Again with Eu (H
2CAM)
35H
2O and MnCl
24H
2O 1:3 in molar ratio mixes, and adds the polytetrafluoroethylliner liner of putting into hydrothermal reaction kettle behind the 5 mL water, reacts 72 h at 120 ° of C; Up to 30 ° of C, filtration, water washing obtain colourless strip crystal through the 1.0 ° of C/h that lower the temperature.The productive rate that calculates based on Eu is 36%.
The sign of porous europium-manganese coordination polymer material:
(1) structure determination of porous europium-manganese coordination polymer material
Supernova type X-ray single crystal diffractometer is adopted in crystal structure determination, use the Mo-K alpha-ray (λ=0.71073) through the graphite monochromatization to be incident radiation, collect point diffraction with ω-φ scan mode, obtain unit cell parameters through least-squares refinement, utilize the SHELXL-97 direct method to solve crystalline structure from the difference Fourier electron density map, and through Lorentz and polarizing effect correction.All H atoms are synthetic and definite through desirable position calculation by difference Fourier.Detailed axonometry data see Table 1.Structure is seen Fig. 1 and Fig. 2.
(2) porous europium-manganese coordination polymer material is to the absorption test of gas-phase methanol and ethanol
Porous europium-manganese coordination polymer material to the adsorption curve of gas-phase methanol and ethanol as shown in Figure 3.As can be seen from Figure 3, under the low-temperature activation condition, this material has higher selectivity to methyl alcohol and ethanol absorption.By powdery diffractometry, ultimate analysis and thermogravimetric analysis, we can determine that this higher selectivity is to derive from the coordinated water molecule of not removing in this material.Because coordinated water molecular energy and methanol molecules generation coordination permutoid reaction in this material do not react with ethanol molecule, thereby in the low-temperature activation condition absorption of methyl alcohol and ethanol has been shown selectivity preferably.
(3) porous europium-manganese coordination polymer material is to the absorption test of liquid phase methyl alcohol and ethanol
Porous europium-manganese coordination polymer material to the adsorption curve of liquid phase methyl alcohol and ethanol as shown in Figure 4.As can be seen from the figure, this material reaches 0.7mmol/g to the adsorptive capacity of methyl alcohol at normal temperatures and pressures, to then almost not absorption of ethanol.This this material of test proof can be used for methyl alcohol and separate with ethanol.
(4) circularity test that the porous europium-the manganese coordination polymer material separates with ethanol liquid phase methyl alcohol
The cyclicity that porous europium-manganese coordination polymer material separates with ethanol liquid phase methyl alcohol as shown in Figure 5.As can be seen from the figure, through after the three-wheel circulation, the adsorptive capacity of its methyl alcohol no longer reduces and can repeatedly recycle this material, illustrates that this material is with a wide range of applications at normal temperatures and pressures.
The crystallographic data of table 1 ligand polymer
Claims (4)
1. porous europium-manganese coordination polymer material, [Eu (CAM) (HCAM)
2Mn
2(H
2O)
7] 7H
2O, wherein CAM and HCAM are respectively and slough three hydrogen ions and slough two hydrionic 4-hydroxyls-2,6-cinchomeronic acid; Crystal belongs to oblique system, and spacer is
P2
1/ n, unit cell parameters is:
a=8.98163 (14),
b=24.489 (2),
c=17.1674 (14),
α=
γ=90 °,
β=99.158 (7) °; This ligand polymer is the three-dimensional frame structure that is connected into by hydrogen bond by a kind of two-dimentional ligand polymer; There is one-dimensional channels in this ligand polymer, and the duct cross section is 12.201 * 5.121; Two kinds of coordinated water molecules are arranged in the duct of this ligand polymer, and a kind of is coordinated water molecule towards the duct; Another kind is the coordinated water molecule towards hole wall; In this ligand polymer towards the water molecules in duct can with methyl alcohol generation permutoid reaction, discord ethanol reacts, and can separate with ethanol methyl alcohol; This ligand polymer does not need to add heat extraction ligand solvent molecule before separation.
2. the preparation method of the described porous europium of claim 1-manganese coordination polymer material is characterized in that it comprises the steps:
(1) with Eu (NO
3)
36H
2O and 4-hydroxyl-2,6-cinchomeronic acid mix and add among the 3mL DEF for 1:3 in molar ratio, put into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, react 72 h at 90 ° of C, obtain Eu (H
2CAM)
35H
2O;
(2) Eu (H that (1) step was obtained
2CAM)
35H
2O and MnCl
24H
2O 1:3 in molar ratio mixes, and puts into the polytetrafluoroethylliner liner of hydrothermal reaction kettle behind the adding 5mL water, reacts 72 h at 120 ° of C;
(3) again through the 1.0 ° of C/h that lower the temperature up to 30 ° of C, filter, water washing, get product porous europium-manganese coordination polymer material;
(4) this product stable existence in water, thermogravimetric analysis and ultimate analysis show that this porous europium-manganese coordination polymer material has seven dissociating water molecules.
3. the described porous europium of the claim 1-application of manganese coordination polymer material in alcohols homologue separation field.
4. application according to claim 3, this application specifically are the methods of utilizing the differential liberation alcohols homologue of coordinated water molecule exchange interaction in alkanol molecule and the porous europium-manganese ligand polymer.
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Citations (7)
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| KR100964507B1 (en) * | 2008-04-18 | 2010-06-21 | 포항공과대학교 산학협력단 | Ionic or molecular channel, sensor and antibacterial agent comprising metal-organic polyhedra |
| JP2011068631A (en) * | 2009-08-24 | 2011-04-07 | Kuraray Co Ltd | Metal complex, and material for separation comprising the same |
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2013
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Patent Citations (7)
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| CN1590501A (en) * | 2004-05-26 | 2005-03-09 | 南开大学 | Rare earth transition mixed metal compounding material type zine ion fluorescent probe and its preparation method |
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