CN109336809A - The stable metal-organic framework material and its preparation method and application of performance - Google Patents
The stable metal-organic framework material and its preparation method and application of performance Download PDFInfo
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- CN109336809A CN109336809A CN201811363085.4A CN201811363085A CN109336809A CN 109336809 A CN109336809 A CN 109336809A CN 201811363085 A CN201811363085 A CN 201811363085A CN 109336809 A CN109336809 A CN 109336809A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses a kind of metal-organic framework material and its preparation method and application that performance is stable, which contains complex, and the molecular formula of complex is [Cu2(L)2]∞, L N, N'- bis- (3- carboxyl phenyl) -3,5- pyridine diformamide, the continuity of ∞ expression three-dimensional structure；Wherein, complex contains multiple double-core copper secondary construction unit Cu2(COO)4N2；In each double-core copper secondary construction unit, copper ion carries out coordination composition turbo Mode with the nitrogen in the carboxylic acid and two L in two L respectively.The metal-organic framework material has excellent adsorptivity with excellent thermal stability and to carbon dioxide, so that it can be applied in gas separation, while preparation method has the advantages that process is simply and easy to operate.
Description
Technical field
The present invention relates to organic framework materials, and in particular, to a kind of metal-organic framework material that performance is stable and its
Preparation method and application.
Background technique
Metal-organic framework material has unique pore structure, applies in terms of gas is separated with storage, it has also become when
The research hotspot of modern gas separation storage is [referring to (a) Yaghi O.Nature.2003,423,705. (b) Zhou H.-
C.Adv.Mater., 2018,30,1704303], porosity is 50% of its crystal volume or more, usually this method synthesis
MOFs specific surface area is generally all in 1000m2/ g or more is even higher, and the application study of MOFs is mainly stored in gas,
The absorption of gas with separate；However the soda acid of MOFs and water stability but have it is to be hoisted.
Summary of the invention
The object of the present invention is to provide a kind of metal-organic framework materials and its preparation method and application that performance is stable, should
Metal-organic framework material has excellent adsorptivity with excellent thermal stability and to carbon dioxide, so that it can
It is applied in gas separation, while preparation method has the advantages that process is simply and easy to operate.
To achieve the goals above, the present invention provides a kind of metal-organic framework material that performance is stable, which has
Machine frame frame material contains complex, and the molecular formula of complex is [Cu2(L)2]∞, L N, N'- bis- (3- carboxyl phenyl) -3,5- pyrrole
Pyridine diformamide, ∞ indicate the continuity of three-dimensional structure, i.e. complex is made of the repetitive unit of unlimited similar structures；
Wherein, complex contains multiple double-core copper secondary construction unit Cu2(COO)4N2；It is constructed in each double-core copper secondary
In unit, copper ion carries out coordination composition turbo Mode with the nitrogen in the carboxylic acid and two L in two L respectively.
The present invention also provides a kind of preparation methods of above-mentioned metal-organic framework material, which is characterized in that the preparation
Method includes:
1) in organic solvent, L, mantoquita are heat-treated；
2) reaction system is subjected to crystallisation by cooling, be then separated by solid-liquid separation to obtain metal-organic framework material.
Invention further provides a kind of application of above-mentioned metal-organic framework material in gas separation.
In above-mentioned technical proposal, present invention metal-organic framework material as made from simple solvent thermal reaction, the tool
There is excellent thermal stability and there is excellent adsorptivity to carbon dioxide, so that it can be answered in gas separation
With, while preparation method has the advantages that process is simply and easy to operate.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
The alternating temperature X-ray powder diffraction figure of product prepared by Fig. 1 embodiment 1；
The X-ray single crystal diffraction polymerization state figure of product prepared by Fig. 2 embodiment 1
The X-ray single crystal diffraction molecular structure of product prepared by Fig. 3 embodiment 1
The BET figure of product prepared by Fig. 4 embodiment 1；
The pore size test result of product prepared by Fig. 5 embodiment 1；
Product prepared by Fig. 6 embodiment 1 is at 273K and 298K to the absorption behavior of the gases such as carbon dioxide, nitrogen；
The thermogravimetric analysis figure of product prepared by Fig. 7 embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of metal-organic framework material that performance is stable, which contains cooperation
Object, the molecular formula of complex are [Cu2(L)2]∞, L (shown in formula I) is N, N'- bis- (3- carboxyl phenyl) -3,5- pyridine, two formyl
Amine, ∞ indicate the continuity of three-dimensional structure, i.e. complex is made of the repetitive unit of unlimited similar structures；
Wherein, complex contains multiple double-core copper secondary construction unit Cu2(COO)4N2；It is constructed in each double-core copper secondary
In unit, copper ion carries out coordination composition turbo Mode with the nitrogen in the carboxylic acid and two L in two L respectively, and two in L
Nitrogen is in axial position；
In above-mentioned metal-organic framework material, the crystal structure of complex can select in a wide range, but be
Further increase the gas separating capacity of metal-organic framework material, it is preferable that complex belongs to tetragonal crystal system, I41/amd
Space group.
In above-mentioned metal-organic framework material, complex unit cell size can select in a wide range, but in order to
Further increase the gas separating capacity of metal-organic framework material, it is preferable that complex unit cell size are as follows:Crystallographic axis angle α=β=γ=90.0 °,
Unit-cell volume
In above-mentioned metal-organic framework material, energy is separated in order to further increase the gas of metal-organic framework material
Power, it is preferable that also contain organic solvent in metal-organic framework material.Wherein, the content of organic solvent can also be in wide model
Interior selection is enclosed, but in order to further increase the gas separating capacity of metal-organic framework material, it is preferable that organic solvent is in gold
Belonging to the specific gravity in organic framework materials is 5 weight %-8 weight %.
In above-mentioned metal-organic framework material, the type of organic solvent can select in a wide range, it is contemplated that
To cost and with the compatibility of complex, in order to further increase the gas separating capacity of metal-organic framework material, preferably
Ground, organic solvent are selected from least one of n,N-Dimethylformamide, n,N-dimethylacetamide, methanol, ethyl alcohol.
In above-mentioned metal-organic framework material, the hole of metal-organic framework material can select in a wide range,
But in order to further increase the gas separating capacity of metal-organic framework material, it is preferable that metal-organic framework material meets
The following conditions: MOFs specific surface area is 1800-1900cm3/ g, porosity 64-65%.
The present invention also provides a kind of preparation methods of above-mentioned metal-organic framework material, which is characterized in that the preparation
Method includes:
1) in organic solvent, L, mantoquita are heat-treated；
2) reaction system is subjected to crystallisation by cooling, be then separated by solid-liquid separation to obtain metal-organic framework material.
In the above preparation method, the dosage of each material can select in a wide range, but in order to further increase
The gas separating capacity of metal-organic framework material obtained, it is preferable that mantoquita, L molar ratio be 4mmol:0.8-2mmol；
It is highly preferred that the amount ratio of mantoquita, organic solvent is 1mmol:1-20mL.
In the above preparation method, the type of organic solvent can select in a wide range, it is contemplated that cost with
And the compatibility with complex, it is preferable that organic solvent be selected from n,N-Dimethylformamide, n,N-dimethylacetamide, methanol,
At least one of ethyl alcohol, mantoquita are selected from least one of copper chloride, copper nitrate, copper acetate.
In the above preparation method, the condition of heat treatment can select in a wide range, but in order to further increase
The gas separating capacity of metal-organic framework material obtained, it is preferable that heat treatment meets the following conditions: temperature is 65-90 DEG C,
Time is 24-48h.
In the above preparation method, the mode of crystallisation by cooling can select in a wide range, but in order to further mention
Highly crystalline yield, it is preferable that crystallisation by cooling uses program cooling down mode, and cooling rate is 4-6 DEG C/min.
Invention further provides a kind of application of above-mentioned metal-organic framework material in gas separation.
The present invention will be described in detail by way of examples below.
Embodiment 1
First by 10mg ligand L (C21H15N3O6, 0.025mmol) and it is dissolved in DMF in the n,N-Dimethylformamide of 2mL, so
Gained mixed solution in the above solution, it is anti-to be finally put into polytetrafluoroethylene (PTFE) by 14.1mg copper chloride (0.1mmol) dissolution afterwards
It answers and is heated to 70 DEG C in kettle and keeps the temperature 36 hours, can finally be obtained with the crystallization of rate program cooling down, the centrifuge separation of 5 DEG C/min
Target compound.
Embodiment 2
Carry out according to the method for embodiment 1, it is described unlike, the dosage of ligand L is 0.05mmol.
Embodiment 3
Carry out according to the method for embodiment 1, it is described unlike, the dosage of ligand L is 0.02mmol.
Embodiment 4
Carry out according to the method for embodiment 1, it is described unlike, reaction temperature be 90 DEG C, the reaction time be for 24 hours.
Embodiment 5
Carry out according to the method for embodiment 1, it is described unlike, reaction temperature be 65 DEG C, reaction time 48h.
Detect example 1
Product made from embodiment 1 is subjected to XRD analysis, shown in the result is shown in Figure 1:
Under the conditions of room temperature (25 DEG C), the material 29.29,28.62,23.08,21.86,19.58,19.24,18.28,
17.79, have diffraction maximum at 17.52,14.49,12.15,11.01,7.22,6.46 °, it is more typical 29.29,28.62,
28.37、26.75、25.31、24.51、23.08、21.86、20.29、19.58、19.24、18.28、17.79、17.52、
16.64, there is diffraction maximum at 16.25,15.07,14.49,13.02,12.15,11.01,7.22,6.46 °.
Under the conditions of 50 DEG C and 80 DEG C, by XRD spectra it is found that sample diffraction peak angle degree and the diffraction tested under room temperature
Peak angle degree is almost the same.
At 100 DEG C/120 DEG C, sample crystal form changes, 21.86,19.58,19.24,18.28,17.79,17.52,
14.49, have diffraction maximum at 12.15,11.01,8.27,7.22 °, it is more typical 21.86,20.29,19.58,19.24,
18.28, have at 17.79,17.52,16.64,16.25,15.07,14.49,13.02,12.15,11.01,8.27,7.22 ° and spread out
Penetrate peak.
At 140 DEG C, there is a stronger diffraction maximum at only 7.22.
In above-mentioned XRD spectra, the relative intensity of the angle of diffraction of obtained sample may be because partial size/crystallization condition or its
The difference of its test condition and generate the angle of diffraction relative intensity variation.So the obtained sample diffraction peak of this test example
Relative intensity be not it is characteristic, when whether the synthesized complex of judgement identical as known crystal form, it should be further noted that
Be peak the opposite angle of diffraction position rather than the size of their relative intensities.Since 2 angles θ and incidence X are penetrated in XRD spectrum
The wavelength of line is related, and the transformational relation of interplanar distance d and 2 angles θ are as follows: the wavelength that d=λ/2sin θ, λ represent incident X-rays is (right
In Cu-K α,), therefore indicate more representative away from d with crystal face.For the crystal form of the same race of same compound,
Its XRD spectra has similitude on the whole, characterizes the d value error of peak position generally within ± 2%, most of error does not surpass
Cross ± 1%；Relative intensity error can be larger, but variation tendency is consistent.
Detect example 2
Product made from embodiment 1 is subjected to single crystal diffraction analysis, X-ray single crystal diffraction polymerization state figure is shown in that Fig. 2, X are penetrated
Line single crystal diffraction molecular structure is shown in Fig. 3, and detection data is shown in Table 1:
Table 1
The carboxyl of ligand and copper ion form turbine type coordination mode known to Fig. 2-3, and the axial position of turbine is matched
Occupied by the pyridine nitrogen of body, the double-core copper of turbine forms three-D space structure to extending out to prolong by ligand.
Detect example 3
Product made from embodiment 1 is activated into 10h under the conditions of high vacuum grade (vacuum degree is lower than 10 μm of mHg), 100 DEG C,
The nitrogen adsorption row of sample is measured at 77K using the surface ASAP 2020M+C instrument Micromeritics and Porosimetry
For BET the performance test results are shown in Fig. 4, and pore size testing result is shown in Fig. 5；The metal organic framework compound as seen from the figure
Specific surface area is 1872cm3/ g, aperture are divided into two kinds, and most aperture is distributed in 1.0nm.
Detect example 4
Product made from embodiment 1 is activated into 10h under the conditions of high vacuum grade (vacuum degree is lower than 10 μm of mHg), 100 DEG C,
Its dioxy is measured respectively at 273K/298K using the surface ASAP 2020M+C instrument Micromeritics and Porosimetry
Change the gas adsorption behavior of carbon and nitrogen, test result is shown in Fig. 6；As seen from the figure at the same pressure, compared with absorption nitrogen
The metal organic framework compound can adsorb more carbon dioxide in 273K and 298K.
Detect example 5
Product made from embodiment 1 is subjected to thermogravimetric analysis detection, testing result is shown in Fig. 7；The metal is organic as seen from the figure
Contain less solvent molecule, preferable thermal stability in frame compound, thus the absorption that can be used for gas molecule is deposited
Storage.
The product of embodiment 2-5 is detected in the same manner, the detection of the product of testing result and embodiment 1
As a result almost the same.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of metal-organic framework material that performance is stable, which is characterized in that the metal-organic framework material contains cooperation
Object, the molecular formula of the complex are [Cu2(L)2]∞, L N, N'- bis- (3- carboxyl phenyl) -3,5- pyridine diformamide, ∞ table
Show the continuity of three-dimensional structure；
Wherein, the complex contains multiple double-core copper secondary construction unit Cu2(COO)4N2；It is constructed in each double-core copper secondary
In unit, copper ion carries out coordination composition turbo Mode with the nitrogen in the carboxylic acid and two L in two L respectively.
2. metal-organic framework material according to claim 1, wherein the complex belongs to tetragonal crystal system, I41/amd
Space group.
3. metal-organic framework material according to claim 1, wherein the complex unit cell size are as follows:Crystallographic axis angle α, β, γ are 90.0 °, unit-cell volume
4. metal-organic framework material according to claim 1, wherein also have in the metal-organic framework material
Solvent；
Preferably, specific gravity of the organic solvent in the metal-organic framework material is 5 weight %-8 weight %；
It is highly preferred that the metal-organic framework material meets the following conditions: MOFs specific surface area is 1800-1900cm3/ g, hole
Gap rate is 64-65%.
5. metal-organic framework material according to claim 4, wherein the organic solvent is selected from N, N- dimethyl formyl
At least one of amine, DMAC N,N' dimethyl acetamide, methanol, ethyl alcohol.
6. a kind of preparation method of metal-organic framework material described in any one of -5 according to claim 1, feature exist
In the preparation method includes:
1) in organic solvent, L, mantoquita are heat-treated；
2) reaction system is subjected to crystallisation by cooling, be then separated by solid-liquid separation to obtain the metal-organic framework material.
7. preparation method according to claim 6, wherein the mantoquita, L molar ratio be 4mmol:0.8-2mmol；
Preferably, the mantoquita, organic solvent amount ratio be 1mmol:1-20mL；
It is highly preferred that the organic solvent is in n,N-Dimethylformamide, n,N-dimethylacetamide, methanol, ethyl alcohol
At least one, the mantoquita is selected from least one of copper chloride, copper nitrate, copper acetate.
8. preparation method according to claim 6, wherein the heat treatment meets the following conditions: temperature is 65-90 DEG C,
Time is 24-48h.
9. preparation method according to claim 6, wherein the crystallisation by cooling uses program cooling down mode, cooling
Rate is 4-6 DEG C/min.
10. a kind of application of metal-organic framework material described in any one of -5 according to claim 1 in gas separation.
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| CN112851593A (en) * | 2021-01-07 | 2021-05-28 | 湖南科技大学 | Amino-bridged hexacarboxylic acid ligand, metal organic framework material, and preparation methods and applications thereof |
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