CN101240067A - Micro-pore coordination polymer based on diethylbenzotriazole cuprous and its preparation method and application - Google Patents
Micro-pore coordination polymer based on diethylbenzotriazole cuprous and its preparation method and application Download PDFInfo
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- CN101240067A CN101240067A CNA200810026375XA CN200810026375A CN101240067A CN 101240067 A CN101240067 A CN 101240067A CN A200810026375X A CNA200810026375X A CN A200810026375XA CN 200810026375 A CN200810026375 A CN 200810026375A CN 101240067 A CN101240067 A CN 101240067A
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Abstract
The invention discloses a microporous coordination polymer based on cuprous diethyl triazole, with a formula of [Cu(etz)]<infinity>, wherein Cu is one valent copper ion, etz is anion of 3,5-diethyl -1,2,4-triazole. The polymer is in structure of three-dimentional coordination network of NbO type. The inventive microporous coordination polymer can be used to recycle organic solvent in water, to effectively separate benzene and cyclohexane, to detect toxic organic steam such as small molecular alcohols, acetonitrile and benzene. The inventive microporous coordination polymer is easy to synthesize, suitable for mass production.
Description
Technical field
The present invention relates to the porous material technical field, be specifically related to a kind of based on triazole cuprous microporous coordination polymer material and technology of preparing and application.
Background technology
Microporous coordination polymer is a kind of novel porous material, has advantages such as density is low, specific surface area is big, chemical modifiability strong, structural flexibility, can be widely used in fields such as atmosphere storage, separation, heterogeneous catalyst, Molecular Detection.
This novel porous material can provide some traditional porous materials such as not available specific function such as molecular sieve, gac.For example, because water molecules is littler than the diameter of organic molecule, so the conventional molecular screen material of selecting based on the aperture generally optionally planar water and absorb organic molecule not.On the other hand, though can utilize the porous material absorb organic molecule and reduce the absorption of water optionally with hydrophobic surface, the capillary condensation effect of water makes its adsorptive capacity very fast in the higher rising of humidity.Hydrophobic dynamic microporous polymer then may be up to humidity near the saturated absorption that does not also produce water.
Certainly, with respect to traditional inorganic materials, the stability of ligand polymer is lower, the more high drawbacks limit of cost its widespread use.Existing in addition ligand polymer also lacks special excellent comprehensive performance, so real at present practical microporous coordination polymer is also very rare.
Summary of the invention
The objective of the invention is to deficiency at the prior art existence, a kind of simply scale operation is provided, and the microporous coordination polymer and preparation method thereof with special porous performance and this microporous coordination polymer are in fractionation by adsorption and detect application aspect the organism.
Above-mentioned purpose of the present invention solves by the following technical programs:
Microporous coordination polymer of the present invention is a kind of based on the cuprous polymkeric substance of diethyl triazole, and chemical formula is [Cu (etz)]
∞, wherein Cu is a univalent copper ion, etz takes off 3 of proton, 5-diethyl-1,2,4-triazole negatively charged ion.This compound crystal has the three-dimensional coordinated network structure of NbO type in tripartite spacer.This microporous coordination polymer has higher thermostability and chemical stability, and is insensitive to empty G﹠W, but should use nitrogen atmosphere protection during standing storage.
The preparation method of above-mentioned microporous coordination polymer is as follows:
Under nitrogen atmosphere, express the amount proportioning of requirement by chemical formula, with concentration is 3 of 0.1～0.5mol/L, 5-diethyl-1,2, the methanol solution of 4-triazole slowly joins in the ammoniacal liquor-methanol mixed solution that contains 0.2～0.3mol/L univalent copper ion, ageing, boil off partial solvent, promptly get product with vacuum-drying after filtration.
The another kind of preparation method of above-mentioned ligand polymer is as follows:
Express the amount proportioning of requirement by chemical formula, with 3,5-diethyl-1,2,4-triazole, Red copper oxide or other cupric salt, strong aqua and methanol mixture place the tetrafluoroethylene reactor of sealing to be heated to 80～150 ℃ of insulations 2～3 days, promptly get product with vacuum-drying after filtration.
Microporous coordination polymer of the present invention can be used for the dried up and small molecules organic solvent of branch, and its method can optionally be adsorbed small molecules organic solvent such as methyl alcohol, ethanol and acetonitrile etc. for this microporous coordination polymer, and planar water not.
Microporous coordination polymer of the present invention can be used for high efficiency separation benzene and hexanaphthene, and its method is not adsorbed hexanaphthene for this microporous coordination polymer can optionally adsorb benzene.
Microporous coordination polymer of the present invention can be used for detecting multiple organic steam, and as small molecular alcohol, acetonitrile and benzene etc., its method changes for this ligand polymer can produce corresponding structure when the various different organic steam of absorption, has the feature of intelligent material.
Compared with prior art, the present invention has following beneficial effect: 1. microporous coordination polymer of the present invention can optionally adsorb small molecules organic solvent such as methyl alcohol, ethanol and acetonitrile etc., and planar water not can be used for the organic solvent in the recycle-water; 2. microporous coordination polymer of the present invention can optionally adsorb benzene and not adsorb hexanaphthene, can be used for the high efficiency separation of benzene and hexanaphthene; 3. microporous coordination polymer of the present invention can produce specific thaumatropy when the different organic steams of absorption (as small molecular alcohol, acetonitrile and benzene), thereby can be used for the detection to these poisonous organic steams; 4. its synthetic method of microporous coordination polymer of the present invention is simple and convenient, can be mass-produced, and has filled up the blank of associated materials.
Description of drawings
Fig. 1 (1) is the local coordination structure of microporous coordination polymer;
Fig. 1 (2) is the three-dimensional net structure of microporous coordination polymer;
Fig. 2 is the X-ray diffractogram (CuK) of microporous coordination polymer;
Fig. 3 is the adsorption isotherm line chart (P of microporous coordination polymer to water, methyl alcohol, ethanol and acetonitrile
0Be corresponding saturation vapour pressure under the 298K);
Fig. 4 is the adsorption isotherm line chart (P of microporous coordination polymer to benzene and hexanaphthene
0Be corresponding saturation vapour pressure under the 298K);
Fig. 5 is the X-ray diffractogram (CuK) of microporous coordination polymer behind absorption methyl alcohol, ethanol, acetonitrile and benzene.
Embodiment
Embodiment 1:
Material synthesis method under the nitrogen atmosphere:
50 milliliters of methyl alcohol
0.2mol/L[Cu (NH
3)
2] 50 milliliters of the ammonia solns of OH
0.1mol/L 100 milliliters of the methanol solutions of Hetz
Under nitrogen atmosphere, 50 ml methanol and 100 milliliters of Hetz methanol solutions are joined [Cu (NH successively
3)
2] in the ammonia soln of OH, obtaining white precipitate, 50 ℃ of ageings are after 3～5 hours, and half solvent of pressure reducing and steaming can get product with the white crystalline powder vacuum-drying of filtering gained, and its structure is seen Fig. 1, and X-ray diffractogram is seen Fig. 2.
Embodiment 2:
Material synthesis method under hydro-thermal (solvent thermal) condition:
Cu
2O 0.715 gram
Hetz 1.252 grams
(26%) 30 milliliter of ammoniacal liquor
30 milliliters of methyl alcohol
The mixture of above-mentioned material is enclosed in is heated to 120 ℃ of insulations 3 days in 100 milliliters of tetrafluoroethylene reactors, can get white with vacuum-drying after filtration to crystalline product.
Embodiment 3:
Water separates with the small molecules organic solvent:
To slough the steam that the cuprous material of diethyl triazole behind the object places water, methyl alcohol, ethanol or acetonitrile, this material can just begin to adsorb in a large number organic steam in low-down relative vapour pressure, but under the very large situation of humidity planar water not also.Its adsorption isotherm line chart is seen Fig. 3.
Embodiment 4:
Separating of benzene and hexanaphthene:
To slough the steam that the cuprous material of diethyl triazole behind the object places benzene and hexanaphthene, this material can just begin to adsorb in a large number benzene in low-down relative vapour pressure, but does not also adsorb hexanaphthene water in very high relative vapour pressure.Its adsorption isotherm line chart is seen Fig. 4.
Embodiment 5:
The detection of organic steam:
To slough the steam that the cuprous material of diethyl triazole behind the object places methyl alcohol, ethanol, acetonitrile or benzene, this material produces different structural changess behind the different organic steams of absorption.Its X-ray powder diffraction figure sees Fig. 5.
Claims (6)
1, a kind of microporous coordination polymer is characterized in that the chemical formula of this polymkeric substance is [Cu (etz)]
∞, wherein Cu is a univalent copper ion, and etz takes off 3 of proton, and 5-diethyl-1,2,4-triazole negatively charged ion, this polymkeric substance have the three-dimensional coordinated network structure of NbO type.
2, a kind of method for preparing the described microporous coordination polymer of claim 1 is characterized in that comprising the steps:
Under nitrogen atmosphere, express the amount proportioning of requirement by chemical formula, with 3 of 0.1～0.5mol/L, 5-diethyl-1,2, the methanol solution of 4-triazole slowly joins in the ammoniacal liquor-methanol mixed solution that contains 0.2～0.3mol/L univalent copper ion, ageing, boil off partial solvent, promptly get product with vacuum-drying after filtration.
3, a kind of method for preparing the described microporous coordination polymer of claim 1 is characterized in that comprising the steps:
Express the amount proportioning of requirement by chemical formula, with 3,5-diethyl-1,2,4-triazole, Red copper oxide or other cupric salt, strong aqua and methanol mixture place the tetrafluoroethylene reactor of sealing to be heated to 80～150 ℃ of insulations 2～3 days, promptly get product with vacuum-drying after filtration.
4, the application of the described microporous coordination polymer of claim 1 in dividing dried up and small molecules organic solvent.
5, the application of the described microporous coordination polymer of claim 1 in Separation of Benzene and hexanaphthene.
6, the application of the described microporous coordination polymer of claim 1 in detecting multiple organic steam.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830918A (en) * | 2010-04-30 | 2010-09-15 | 中山大学 | Synthetic method of polynitrogen azole zinc/cadmium framework material |
| CN102286007A (en) * | 2011-07-04 | 2011-12-21 | 中山大学 | Solventless synthesis method for metal polynitrogen azole framework material |
| CN106397785A (en) * | 2016-09-12 | 2017-02-15 | 广西师范大学 | 3-carboxyl-1, 2, 4-triazole copper coordination polymer and in-situ synthesis method thereof |
| CN109030802A (en) * | 2018-06-08 | 2018-12-18 | 中山大学 | A kind of integration granular pattern immobilised enzymes biosensor and its preparation method and application |
| CN111333854A (en) * | 2020-04-01 | 2020-06-26 | 中山大学 | Super-hydrophobic porous coordination polymer based on partial fluoro organic ligand and preparation method and application thereof |
| CN112661972A (en) * | 2020-12-23 | 2021-04-16 | 汕头大学 | MAF-stu-8 material with ultramicropore pcu-h network topology structure and synthesis and application thereof |
| CN114395136A (en) * | 2022-01-19 | 2022-04-26 | 合肥工业大学 | Preparation method and application of furyl 1,2, 4-tolyltriazole iron or copper coordination polymer |
-
2008
- 2008-02-20 CN CNA200810026375XA patent/CN101240067A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830918A (en) * | 2010-04-30 | 2010-09-15 | 中山大学 | Synthetic method of polynitrogen azole zinc/cadmium framework material |
| CN101830918B (en) * | 2010-04-30 | 2012-05-30 | 中山大学 | Synthetic method of polynitrogen azole zinc/cadmium framework material |
| CN102286007A (en) * | 2011-07-04 | 2011-12-21 | 中山大学 | Solventless synthesis method for metal polynitrogen azole framework material |
| CN102286007B (en) * | 2011-07-04 | 2014-04-23 | 中山大学 | Solventless synthesis method for metal polynitrogen azole framework material |
| CN106397785A (en) * | 2016-09-12 | 2017-02-15 | 广西师范大学 | 3-carboxyl-1, 2, 4-triazole copper coordination polymer and in-situ synthesis method thereof |
| CN109030802A (en) * | 2018-06-08 | 2018-12-18 | 中山大学 | A kind of integration granular pattern immobilised enzymes biosensor and its preparation method and application |
| CN109030802B (en) * | 2018-06-08 | 2021-07-27 | 中山大学 | Integrated particle type immobilized enzyme biosensor and preparation method and application thereof |
| CN111333854A (en) * | 2020-04-01 | 2020-06-26 | 中山大学 | Super-hydrophobic porous coordination polymer based on partial fluoro organic ligand and preparation method and application thereof |
| CN111333854B (en) * | 2020-04-01 | 2022-03-22 | 中山大学 | Super-hydrophobic porous coordination polymer based on partial fluoro organic ligand and preparation method and application thereof |
| CN112661972A (en) * | 2020-12-23 | 2021-04-16 | 汕头大学 | MAF-stu-8 material with ultramicropore pcu-h network topology structure and synthesis and application thereof |
| CN114395136A (en) * | 2022-01-19 | 2022-04-26 | 合肥工业大学 | Preparation method and application of furyl 1,2, 4-tolyltriazole iron or copper coordination polymer |
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