CN105237583A - Preparation method of three-dimensional super-molecule framework coordination polymer - Google Patents
Preparation method of three-dimensional super-molecule framework coordination polymer Download PDFInfo
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Abstract
The invention relates to a preparation method of a three-dimensional super-molecule framework coordination polymer, and belongs to the technical field of material chemistry. A two-dimensional metal-organic framework coordination polymer {[Co(azdc)(bbtz)(H2O)2].2DMF}n is synthesized by adopting a simple solution method, two-dimensional metal-organic frameworks are further formed into an amphimorphic interpenetrating three-dimensional super-molecule framework coordination polymer through hydrogen bond effects. In the amphimorphic interpenetrating framework coordination polymer, nitrogen atoms which are not coordinated exist in ligands azdc2- and bbtz, so that the framework coordination polymer presents favorable reversible adsorption-desorption characteristic for carbon dioxide, methane, nitrogen and the like, and excellent selectivity for carbon dioxide.
Description
Technical field
The invention belongs to material chemistry technical field, particularly the preparation method of metal-organic framework supramolecule ligand polymer.
Background technology
Metal-organic framework supramolecule ligand polymer (metal-organicframeworks, be called for short MOFs), it is a kind of novel class zeolite porous material with supramolecule microporous network structure utilizing the coordination self-assembly between organic ligand and metal ion to be formed, because of this kind of material there is high permeability, specific surface area is large, synthesis is convenient, framework scale is variable and can make the advantage such as chemically modified, structure-rich according to target call, now there is extremely wide application prospect in fields such as gas adsorption, get more and more people's extensive concerning.
Metal-organic framework complex type porous material has compared following advantage with gac with zeolitic material: pore structure high-sequential, and hole dimension is controlled, the functional group of hole surface and the controlled system of surperficial potential energy.After the nineties in last century, along with increasing sharply of studying Porous coordination polymer, the poromerics with special adsorption function also occurs in succession.Constitutionally stable MOFs can keep permanent cell size, and in crystal, free volume percentage is generally considerably beyond any zeolite.There is the MOFs of regular pore texture, in the storage of gas, have potential application.At present for the storage applied research of MOFs, mainly concentrate on the fuel gas such as carbonic acid gas, methane, hydrogen and nitrogen.By the absorption in MOF material of carbonic acid gas, methane, hydrogen and nitrogen with show in the absorption comparative study of other conventional porous materials [as zeolite, MCM-41, carbon nanotube, molecule side (molecularsquares) etc.], MOF material really shows the excellent properties being different from traditional material in atmosphere storage.MOFs shows great potential storing in the gas such as a large amount of carbonic acid gas, methane, hydrogen and nitrogen, lays a solid foundation becoming novel gas storage material for MOFs.
Comprehensive achievement in research is in recent years known, and the MOFs synthetic method mainly that people's synthesis has excellent absorption property to gases such as carbonic acid gas, methane and nitrogen is solvent-thermal method.And solvent-thermal method needs to consume more energy, and the product obtained often purity is not high, need hand, this just needs to consume a large amount of manpower and materials.It should be noted that the MOFs with excellent gas storage performance of current bibliographical information is generally the three-dimensional framework ligand polymer be connected by covalent linkage.And rarely have report by the Magnetic Properties of Three-Dimensional Supramolecular Complex framework ligand polymer with excellent gas storage performance that hydrogen bond action is formed.
Summary of the invention
The object of the invention is to propose a kind of preparation method at normal temperatures carbonic acid gas to the Magnetic Properties of Three-Dimensional Supramolecular Complex framework material of selective adsorption.
Technical solution of the present invention is: at normal temperatures, first by the aqueous solution of soluble cobalt and 1,4-bis-(1H-1,2,4-triazole-methylene radical) N of benzene (be called for short bbtz), dinethylformamide (being called for short DMF) solution mixing, and then add nitrogen benzide-3,3-dicarboxylic acid (abbreviation H
2and the DMF solution of NaOH azdc), after reaction terminates, filter, get solid phase, i.e. framework ligand polymer { [Co (azdc) (bbtz) (H
2o)
2] 2DMF}
n.
The present invention adopts simple solution method to synthesize two-dimensional metallic-organic frame ligand polymer { [Co (azdc) (bbtz) (H of a novel structure
2o)
2] 2DMF}
n, the Magnetic Properties of Three-Dimensional Supramolecular Complex framework ligand polymer of two-fold penetration between two-dimensional metallic-organic frame, is formed further by hydrogen bond action.In the framework ligand polymer of this two-fold penetration, part azdc
2-and the nitrogen-atoms that there is non-coordination in bbtz that this framework ligand polymer is shown is good in the reversible adsorption-desorption performance of carbonic acid gas, methane, nitrogen etc. and the excellent selectivity to carbonic acid gas.
The feature of present invention process is:
1) in the process of synthetic compound, by bbtz and H
2it is increase solubleness that azdc is dissolved in the main object of DMF, increases the polarity of solvent simultaneously, is conducive to the formation of the title complex with good crystal formation, and the purity of title complex is improved greatly.
2) the framework ligand polymer made belongs to triclinic(crystalline)system, and structure is comparatively homogeneous, better crystallinity degree, and there is interspersed pore passage structure inside, and have the nitrogen-atoms having neither part nor lot in coordination, chemical stability is high.
3) temperature of reaction condition of the present invention is normal temperature, and product form structure can be made better, and product purity height very.
In addition, in present invention process, the mixing quality ratio of soluble cobalt, Isosorbide-5-Nitrae-two (1H-1,2,4-triazole-methylene radical) benzene and nitrogen benzide-3,3-dicarboxylic acid is 1: 1: 1.This amount of substance ratio, be the amount ratio of the key substance synthesizing title complex, the title complex product purity synthesized is high, and pattern is homogeneous, good dispersion degree.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of the framework ligand polymer adopting the present invention to make.
Fig. 2 is the steric bulk figure of the framework ligand polymer adopting the present invention to make.
Fig. 3 is the x-ray diffractogram of powder of the framework ligand polymer adopting the present invention to make.
The framework ligand polymer that Fig. 4 adopts the present invention to make is to the adsorption-desorption figure of carbonic acid gas, methane and nitrogen.
Embodiment
One, in order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1
Prepare target framework ligand polymer: under normal temperature, first by 0.023gCoCl
26H
2the 5mL deionized water solution of O joins in the 5mLDMF aqueous solution of Isosorbide-5-Nitrae-two (1H-1,2,4-triazole-methylene radical) benzene (bbtz) of 0.024g, then 0.027g nitrogen benzide-3,3-dicarboxylic acid (is called for short H
2azdc) and the 5mLDMF solution of 0.004gNaOH join in above-mentioned mixing solutions, after about 20min reaction, through leaving standstill and filtering, get solid phase, be target framework ligand polymer.
Embodiment 2
Prepare target framework ligand polymer: under normal temperature, first by 0.046gCoCl
26H
2the 8mL deionized water solution of O joins in the 8mLDMF aqueous solution of 0.048gbbtz, then by 0.054gH
2the 8mLDMF solution of azdc and 0.008gNaOH joins in above-mentioned mixing solutions, after about 20min reaction, through leaving standstill and filtering, gets solid phase, is target framework ligand polymer.
Embodiment 3
Prepare target framework ligand polymer: under normal temperature, first by 0.069gCoCl
26H
2the 12mL deionized water solution of O joins in the 13mLDMF aqueous solution of 0.072gbbtz, then by 0.080gH
2the 13mLDMF solution of azdc and 0.012gNaOH joins in above-mentioned mixing solutions, after about 20min reaction, through leaving standstill and filtering, gets solid phase, is target framework ligand polymer.
Two, product property:
Fig. 1 is the central metal ion coordination environment figure of title complex.As seen from Figure 1, central cobalt atom has 6 ligating atoms, is in the octahedral coordination environment distorted a little.
Fig. 2 is the Magnetic Properties of Three-Dimensional Supramolecular Complex framework ligand polymer steric bulk figure of the two-fold penetration adopting the inventive method gained to be formed by hydrogen bond action.The Magnetic Properties of Three-Dimensional Supramolecular Complex skeleton construction of expansion is formed by the weak effect of hydrogen bond, further by the Magnetic Properties of Three-Dimensional Supramolecular Complex framework ligand polymer of weak effect IPN formation two-fold penetration between Magnetic Properties of Three-Dimensional Supramolecular Complex framework between face two-dimentional as seen from Figure 2.
Fig. 3 is the PXRD figure of target product, as seen from the figure: this product P XRD figure spectrum is consistent with the standard spectrum obtained from single crystal structure matching, illustrates that product purity is very high, inclusion-free.With acetone after the time of three days exchanges the DMF molecule in title complex, then the PXRD figure peak type of the gained dewatered product that dewaters at 185 DEG C is better, and desolventizing product is put in DMF/H again
2in the mixed solvent of O, the structure of title complex is recovered again, illustrates that the framework of this title complex has good thermostability.
Fig. 4 is the reversible adsorption-desorption figure of framework ligand polymer to carbonic acid gas, methane and nitrogen, at room temperature shows good desorption-absorption property from this figure this title complex known to these three kinds of gases.And selective adsorption is shown to carbonic acid gas.Be 35mg at room temperature normal pressure to the adsorptive capacity of carbonic acid gas, and 8mg and 2mg is respectively to the adsorptive capacity of methane and nitrogen.And be 80mg when 38atm to the adsorptive capacity of carbonic acid gas, 25mg and 24mg is respectively to the adsorptive capacity of methane and nitrogen.So show selective adsorption to carbonic acid gas at ambient pressure.
Claims (2)
1. the preparation method of a Magnetic Properties of Three-Dimensional Supramolecular Complex framework ligand polymer, it is characterized in that: at normal temperatures, first by the aqueous solution of soluble cobalt and Isosorbide-5-Nitrae-two (1H-1,2,4-triazole-methylene radical) the DMF solution mixing of benzene, and then add the DMF solution of nitrogen benzide-3,3-dicarboxylic acid and NaOH, after reaction terminates, filter, get solid phase, i.e. framework ligand polymer { [Co (azdc) (bbtz) (H
2o)
2] 2DMF}
n.
2. preparation method according to claim 1, is characterized in that the mixing quality ratio of soluble cobalt, Isosorbide-5-Nitrae-two (1H-1,2,4-triazole-methylene radical) benzene and nitrogen benzide-3,3-dicarboxylic acid is 1: 1: 1.
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Cited By (3)
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| CN108384020A (en) * | 2018-03-09 | 2018-08-10 | 河海大学 | It is a kind of novel containing the metal organic framework for not being coordinated tetrazole group and its synthetic method and application |
| CN111621026A (en) * | 2019-02-28 | 2020-09-04 | 南京农业大学 | Preparation method of bifunctional cobalt complex material and electrochemical performance application thereof |
| CN113659137A (en) * | 2021-08-17 | 2021-11-16 | 广东工业大学 | Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384020A (en) * | 2018-03-09 | 2018-08-10 | 河海大学 | It is a kind of novel containing the metal organic framework for not being coordinated tetrazole group and its synthetic method and application |
| CN108384020B (en) * | 2018-03-09 | 2020-09-11 | 河海大学 | Metal organic framework containing uncoordinated tetrazole group and synthesis method and application thereof |
| CN111621026A (en) * | 2019-02-28 | 2020-09-04 | 南京农业大学 | Preparation method of bifunctional cobalt complex material and electrochemical performance application thereof |
| CN113659137A (en) * | 2021-08-17 | 2021-11-16 | 广东工业大学 | Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof |
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Application publication date: 20160113 |