CN106268700A - A kind of method improving metal-organic framework materials carbon dioxide adsorption - Google Patents
A kind of method improving metal-organic framework materials carbon dioxide adsorption Download PDFInfo
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Abstract
The invention discloses a kind of method improving metal-organic framework materials carbon dioxide adsorption, belong to the preparing technical field of inorganic-organic hybrid.Described method is particularly as follows: by the MOF material of the concrete synthetically prepared various porous of method, again by the various adjacent diynyl aromatic compound monomer of the method synthesis of organic synthesis, organic monomer is made to enter in the duct of MOF material by immersion, reacted by simple thermal-initiated polymerization again so that organic monomer occurs polyreaction to obtain MOF composite in MOF material duct.The polymer that the method generates can be divided into the less applicable pore chamber arresting carbon dioxide molecule MOF material duct, thus improves carbon dioxide adsorption ability and the selectivity of MOF material.The polymerization of thermal initiation of the present invention is simple to operate, and machine-shaping speed is fast, and low raw-material cost possesses industrialization advantage.
Description
Technical field
The present invention relates to a kind of method improving metal-organic framework materials carbon dioxide adsorption, belong to inorganic-organic miscellaneous
The preparing technical field changed.
Background technology
The main source of carbon dioxide is the burning of fossil fuel, has caused the biggest environmental problem.Currently for
The most advanced method being also the most ripe of arresting of carbon dioxide is alkanolamine solution, but owing to the carbaminate from generation is to alcohol
The regeneration of amine aqueous solution is an irreversible process, and this method inevitably result in the huge waste of energy.Metal has
Machine framework material (MOF material), as a kind of novel porous polymer material, is to be passed through by metal ion or metal cluster
Organic ligand couples together and forms one-dimensional, two-dimentional or tridimensional network, the advantage therefore having inorganic and organic materials concurrently.By
In having higher porosity, orderly open duct, the multiformity of structure and abundant functional group, metallic organic framework material
Expect gas store with separate, be catalyzed, the field such as membrane material, sensing all plays an important role.
For MOF material, following four method is generally had to increase the adsorbance of carbon dioxide: (1) increases the ratio of MOF material
Surface area and hole dimension, the method is at the highest pressure (> 3-5Mpa) under could significantly increase the adsorbance of carbon dioxide, but
It is that actually abandonment pressure after the burning that chimney is discharged is usually less than 0.3Mpa, so seldom application should in actual applications
Method.(2) MOF material hole functionalisation of surfaces, this method is the method being in daily use.MOF material cell walls modifies pole
The functional group such as-OH ,-NO of property2,-CN ,-SH etc..(3) on the skeleton of MOF material, it is loaded into basic amine function and simulates liquid
The chemisorbed of adsorbent is to improve adsorbance and the selectivity of carbon dioxide.(4) design and the molecular dimension phase separated
Carbon dioxide adsorption is improved in the duct joined, and the method design is more difficult.
But, in actual application, in the flue gas after burning in composition, except containing 75% N2With 15% CO2
Outward, possibly together with the water of 5%-7%, the water of this 5%-7% has a great impact for the absorption of carbon dioxide, because hydrone has
The highest polarity and combination energy, can produce the strongest Competition, and the work of MOF material in the adsorption process of carbon dioxide
Property adsorption site is easy to be occupied by these a small amount of water.Thus make to reduce carbon dioxide in the presence of a small amount of water
Adsorptivity and selectivity.On the other hand, the existence of hydrone also can make the framing structure of MOF material cave in, and this also can reduce
The adsorbance of carbon dioxide and selectivity.
Summary of the invention
For in fossil-fuel-fired rear carbon dioxide in flue gas capture process containing the problem of a small amount of water, the mesh of the present invention
Be a kind of method improving metal-organic framework materials carbon dioxide adsorption is provided, the method is simple to operate, machine-shaping
Speed is fast, low raw-material cost, and the product obtained can improve the carbon dioxide adsorption of MOF material.
The purpose of the present invention is realized by techniques below scheme:
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method is for making adjacent diynyl aromatic series
Compound monomer generates adjacent diynyl aromatic compound polymer by thermal initiation in-situ polymerization in MOF material duct and obtains
A kind of duct is contained within the MOF composite of adjacent diynyl aromatic compound polymer, improves MOF material to dioxy with this
Change the absorbability of carbon.
Wherein, described MOF composite preferably employs following method and prepares:
If a () adjacent diynyl aromatic compound monomer is liquid: the MOF material of activation to be immersed in adjacent diynyl fragrance
In compounds of group monomer, then sucking filtration obtains powder sample 5, and cleans the MOF material surface of removal activation not with organic solvent 6
Enter the adjacent diynyl aromatic compound monomer in duct, obtain powder sample 6, powder sample 6 is taken out under liquid nitrogen atmosphere true
Sky, after sealing at 170-220 DEG C reacting by heating 10-18h, i.e. obtain described MOF composite.
If b () adjacent diynyl aromatic compound monomer is solid: by the most molten for neighbour's diynyl aromatic compound monomer
Solution, in organic solvent 7, obtains adjacent diynyl aromatic compound monomer solution, then the MOF material of activation is immersed in adjacent two
In alkynyl aromatic compound monomer solution, then sucking filtration obtains powder sample 7, and cleans removal activation with organic solvent 7
MOF material surface does not enters the adjacent diynyl aromatic compound monomer in inlet hole road, obtains powder sample 8, by powder sample 8 at liquid
Evacuation under blanket of nitrogen, after sealing at 170-220 DEG C reacting by heating 10-18h, i.e. obtain described MOF composite.
Described, the quality (g) of the MOF material of activation in (a): the volume (mL) of adjacent diynyl aromatic compound monomer
≤ 1:3；The quality of the MOF material of activation in (b): the quality≤20:1 of adjacent diynyl aromatic compound monomer；
Preferably, the MOF material of activation is at adjacent diynyl aromatic compound monomer or adjacent diynyl aromatic compound
The time soaked in monomer solution is 1～8h；
Preferably, described powder sample 6 and 8 operation of evacuation under liquid nitrogen atmosphere is: is loaded into pacifying in times bottle and freezes
Take out more than three times；
Preferably, the operation of described sealing is that sealing is melted in flame gun calcining；
Preferably, at 170 DEG C, heat 12h after described powder sample 6 and 8 seals；In described (a), organic solvent 6 is stone
Oil ether；B in (), organic solvent 7 is dichloromethane.
Preferably, the synthetic method of the MOF material of adjacent diynyl aromatic compound monomer, MOF material and activation is as follows:
(1) synthesis of adjacent diynyl aromatic compound monomer
Weigh aromatic compound and the potassium carbonate of trimethyl silicane protection, join the mixed solution of methanol and dichloromethane
In so that it is it is completely dissolved, stirring reaction 15～25h at 20～70 DEG C.By products therefrom sucking filtration, take filtrate rotation and be evaporated dry, utilize
Column chromatography humid analysis separates, and rotation is steamed and is dried to obtain described adjacent diynyl aromatic compound monomer.
Described, the aromatic compound of trimethyl silicane protection and the mol ratio of potassium carbonate are 1:2.5～1:4, preferably 1:
2.5；
Described, the volume ratio of methanol and dichloromethane is 1:1～2:1, preferably 1:1；
Described, if sucking filtration, it is solid that dried product exhibited is steamed in rotation, then need first to be dissolved in organic solvent 2, then carry out post color
Spectrum humid analysis separates；The preferred dichloromethane of organic solvent 2；
Preferably, column chromatography humid analysis separation eluant is petroleum ether or petroleum ether with methylene chloride volume than for 2:1
～the mixed solution of 3:1；
Preferably, whipping temp is 25 DEG C, and the time is 20h；
Preferably, the synthetic method of the aromatic compound of described trimethyl silicane protection is as follows:
If a () adjacent two iodo aromatic compounds are liquid: weigh Pd catalyst and CuI catalyst, repeat evacuation and fill
Nitrogen to air by emptying；Measure the most aeriferous pure triethylamine and toluene, be added in above-mentioned catalyst, add neighbour
Two iodo aromatic compound and trimethylsilyl acetylenes, at 20～70 DEG C, stirring reaction 15～25h, then takes out products therefrom
Filter, takes filtrate rotation and is evaporated dry, utilize column chromatography humid analysis to separate, and the fragrance being dried to obtain described trimethyl silicane protection is steamed in rotation
Compounds of group.
If b () adjacent two iodo aromatic compounds are solid: weigh Pd catalyst, CuI catalyst and adjacent two iodo fragrance
Compounds of group, repeats vacuum nitrogen filling gas to air by emptying；Measure the most aeriferous pure triethylamine and toluene, be added into
In above-mentioned catalyst and raw material, adding trimethylsilyl acetylene, at 20～70 DEG C, stirring reaction 15～25h, then produces gained
Thing sucking filtration, takes filtrate rotation and is evaporated dry, utilize column chromatography humid analysis to separate, and rotation is steamed and is dried to obtain described trimethyl silicane protection
Aromatic compound.
Described, the volume ratio of triethylamine and toluene is 1:1～1:4；
Described, adjacent two iodo aromatic compounds: trimethylsilyl acetylene, Pd catalyst, the mol ratio of CuI are 1:2.5:
0.03～0.06:0.03～0.06；
Described, if sucking filtration, it is solid that dried product exhibited is steamed in rotation, then need first to be dissolved in organic solvent 1, then carry out post color
Spectrum humid analysis separates；The preferred dichloromethane of organic solvent 1.
Preferably, column chromatography humid analysis separation eluant is petroleum ether or petroleum ether with methylene chloride volume than for 2:1
～the mixed solution of 3:1.
Preferably, described Pd catalyst is: Pd (PPh3)4Or Pd (PPh3)2Cl2；Described repetition vacuum nitrogen filling gas three times；
Described adjacent two iodo aromatic compounds are 1,2-bis-iodo benzene or 1,2-bis-iodo-4,5-dimethoxy benzene；
Preferably, described whipping temp is 25 DEG C, and the response time is 20h.
(2) synthesis of MOF material
Slaine, organic ligand are dissolved completely in organic solvent 3 and water and obtain mixed solution, anti-at 85～120 DEG C
Answer 7～24h, be centrifugally separating to obtain powder sample 1, be MOF material.
Described, slaine, the mol ratio of organic ligand are 8:5～17:5；
Preferably, the mixed solution that organic solvent 3 is DMF or DMF and ethanol in described method；Slaine is six hydrations
Magnesium nitrate, Gerhardite or zinc nitrate hexahydrate；Organic ligand used is p-phthalic acid, trimesic acid or 3,
3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxylic acids.
(3) activation of MOF material
By MOF material organic solvent 4 washing by soaking, it is centrifugally separating to obtain powder sample 2, by powder sample 2 with organic
Solvent 5 washing by soaking, is centrifugally separating to obtain powder sample 3, and powder sample 3 is dried under the vacuum environment of 100～180 DEG C 10
～18h, obtain the MOF material of described activation.
Preferably, organic solvent 4 is DMF, and powder sample 1 soaks three times in organic solvent 4, each 6～10h；Organic
Solvent 5 is chloroform, dichloromethane, methanol or ethanol, and powder sample 2 soaks three times in organic solvent 5, each 6～
10h。
Beneficial effect
(1) the method for the invention, improves MOF material hydrophobic and water stability, reduces carbon dioxide adsorption mistake
The Competition of hydrone in journey, and the hydrone destruction to MOF material framework material in adsorption process.
(2) the method for the invention has certain universality, to most metals MOF material silica carbon adsorption performance
All increase, and the widest model of scope of selected adjacent diynyl aromatic compound monomer.
(3) the method for the invention makes adjacent diynyl aromatic compound monomer carry out thermal initiation in MOF material duct
In-situ polymerization, the polymer of generation is divided into the less applicable duct arresting carbon dioxide molecule MOF material duct, and this gathers
Conjunction operation is simple, and machine-shaping speed is fast, low raw-material cost, and the product obtained can improve the dioxy of MOF material
Change carbon adsorption, and selectivity, possess industrialization advantage.
Accompanying drawing explanation
Fig. 1 is the x-ray powder sample diffraction figure of the MOF-5 material of the MOF-5 material in embodiment 1 and activation；
Fig. 2 is the x-ray powder sample diffraction figure of the MOF-5 composite in embodiment 1；
Fig. 3 is the powder sample 5 in embodiment 1 and the infared spectrum of powder sample 6；
Fig. 4 is the MOF-5 material in embodiment 1 and the scanning electron microscope (SEM) photograph of MOF-5 composite；
Fig. 5 is the MOF-5 material in embodiment 3 and MOF-5 composite nitrogen adsorption curve under 77K；
Fig. 6 is the MOF-5 material in embodiment 3 and the quencher based on the nitrogen adsorption curve under 77K of MOF-5 composite
The pore size distribution figure that density of solid Functional Theory (QSDFT) model calculates；
Fig. 7 is the MOF-5 material in embodiment 3 and the test of MOF-5 composite contact angle；
Fig. 8 is the MOF-5 material in embodiment 3 and MOF-5 composite carbon dioxide adsorption curve under 273K.
Detailed description of the invention
The present invention is described in detail in detail with specific embodiment below in conjunction with the accompanying drawings, but is not limited to this.
The main agents information mentioned in following example is shown in Table 1:
Table 1
Method of testing:
1. nuclear magnetic resonance chemical analyser, INSTRUMENT MODEL: Mercury-Plus 400, apparatus manufacture: Varian company of the U.S..This
The nuclear-magnetism operation that experiment relates to is all liquid nuclear-magnetism, 400M nuclear-magnetism.
2.X ray powder diffractometer, INSTRUMENT MODEL: Bruker Foucus D8, apparatus manufacture: Bruker company of Germany.
The x-ray powder Sample Scan that this experiment relates to is at 298K, and pressure is 40KV, electric current 50mA, and x-ray radiation source is Cu-K α.
3. infrared spectrometer, INSTRUMENT MODEL: Bruker Foucus D8, apparatus manufacture: Bruker company of Germany.Infrared sweep
Scope of retouching is from 400-4000cm-1。
4. specific surface and pore-size distribution analyser, model: ASiQMVH002-5, apparatus manufacture: U.S. Quantachrome
Company.The N of this experimental design2Absorption is measured under liquid nitrogen atmosphere 77K and is obtained.Pore size distribution curve figure is to be surveyed by under 77K
The N obtained2Adsorption curve, calculated by QSDFT model.Carbon dioxide adsorption curve is to be measured under 273K by this instrument
Arrive.
5. scanning electron microscope instrument, INSTRUMENT MODEL: JEOL model S-4800, apparatus manufacture: HIT.This experiment
Concrete operations are by obtained sample, disperse, be placed on silicon chip scanning in ethanol solution.
6. contact angle test instrunment, INSTRUMENT MODEL OCA20, apparatus manufacture: dataphysics company of Germany.This experiment is
At room temperature operate, measure the contact angle of the water of each material.
Embodiment 1
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
(1) 1,2-bis-(trimethylsilyl acetylene base) benzene synthesizes
By 0.2669g Pd (PPh3)4With 0.0440g CuI, join in the three-necked bottle of 100mL, repeat vacuum nitrogen filling
Gas three times.Triethylamine 15mL and toluene 45mL is placed in conical flask and obtains mixed solution, drum nitrogen, mixed solution is injected into
In three-necked bottle, by the 1 of 2.5400g, the trimethylsilyl acetylene of 2-bis-iodo benzene and 1.8905g joins in three-necked bottle, at 25 DEG C
Stirring reaction 20h, obtains the product of black, product sucking filtration, obtains yellow solution, and rotation is evaporated dry, obtains the yellow liquid of oily；
By yellow liquid, utilizing column chromatography humid analysis (petroleum ether is eluant) to separate, rotation is evaporated dry, obtains pale yellowish oil liquid
Body.
Characterized the structure of pale yellowish oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is known that pale yellowish oil liquid is 1,2-bis-
(trimethylsilyl acetylene base) benzene.
The preparation of (2) 1,2-diynyl benzene
Weighing the 1 of 3.1500g, 2-bis-(trimethylsilyl acetylene base) benzene and 4.0231g potassium carbonate, addition volume ratio is 1:1
Methanol and the mixed solution 300mL of dichloromethane, at 25 DEG C stirring reaction 20h.Obtain ruddy liquid, by its sucking filtration,
Filtrate being revolved steaming and obtains red oil, utilize column chromatography humid analysis (petroleum ether is eluant) to separate, rotation is evaporated dry,
To light red oil liquid.
Characterized the structure of light red oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 3.35 (s, 2H), 7.32 (q, 2H), 7.53 (q, 2H), it is known that light red oil liquid is 1,2-diine
Base benzene, vehicle economy B
(3) synthesis of MOF-5 material and activation thereof
4.5000g zinc nitrate hexahydrate, 0.8300g p-phthalic acid are dissolved in the mixed of 10mL ultra-pure water and 490mLDMF
Closing in solution, at 100 DEG C, stirring reaction 7h, centrifugation, obtain powder sample 1, is soaked by powder sample 1 DMF, washing
Three times, washed once every 8h, 300mL DMF is used in washing every time.It is centrifugally separating to obtain powder sample 2, powder sample 2 is placed in
Soaking in chloroform solvent, total immersion is steeped three times, changes a solution every 8h, uses chloroform 300mL every time.Centrifugal point
From obtaining powder sample 3, by powder sample 3 100 DEG C of drying 12h under vacuum conditions, obtain powder sample 4.
Its diffraction spectrogram is obtained, such as Fig. 1, difference by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
With document (Steven, S.K.；Dailly,A.；Yaghi,O.M.；Long,J.R.J.Am.Chem.Soc.2007,129,
14176.) the MOF-5 material reported in and the diffraction pattern of the MOF-5 material of activation coincide, MOF-5 material and activation in document
MOF-5 material diffraction pattern the most consistent, it is known that powder sample 1 is MOF-5 material, powder sample 4 be activation MOF-5 material
Before and after material, and activation, the structure of MOF-5 material does not changes.
(4) preparation of MOF-5 composite
Weigh the MOF-5 material of the activation of 0.2000g, be immersed in light red oil liquid D EB of 0.6mL, leaching
Bubble 2h, then sucking filtration obtains powder sample 5, and obtains powder sample 6, by powder with the petroleum ether powder sample 5 of 250mL
Sample 6 is put in the peace times bottle of 10mL, puts it in the Dewar flask filling liquid nitrogen, after freezing 20min, thaws, more freezing
10min, thaws, more freezing 5min, thaws, seals by flame gun.The peace times bottle sealed is placed in 170 DEG C of baking ovens heating 12h,
Then take out sample, obtain MOF-5 composite.
Its diffraction spectrogram is obtained, such as Fig. 2, with MOF-5 material by x-ray powder diffraction instrument test MOF-5 composite
Diffraction pattern to go out peak position completely the same, illustrate that the structure of MOF-5 material is maintained in heat polymerization process.Carry out infrared
Test, as Fig. 3, MOF-5 composite infrared spectrum and be polymerized before powder sample 6 compare, it is at 3300cm-1Neighbouring alkynes
The C ≡ C-H stretching vibration peak of hydrocarbon disappears, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB is at this
Polyreaction is there occurs under part.By scanning electron microscope analysis, if the plane of crystal of Fig. 4, MOF-5 composite is almost without polymerization
The pattern of thing, and MOF-5 composite maintains the cubic crystal pattern of MOF-5 material, illustrates not occur outside duct
Polyreaction.Inhale with specific surface and pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite nitrogen under 77K
Attached character, finds that the absorbability comparing MOF-5 composite with MOF-5 material substantially reduces, such as Fig. 5, Brunauer-
It is 3300m that Emmett-Telle (BET) specific surface area model calculates the specific surface area of MOF-5 material2g-1, MOF-5 composite
Specific surface area be 2600m2g-1, after polymerization, specific surface area reduces, and illustrates that polyreaction is carried out in duct, and polymer accounts for
Duct according to MOF-5 material so that adsorption capacity for nitrogen reduces.It is distributed by QSDFT model calculated hole diameters, finds MOF-5
Composite pore size distribution intensity at 1.2nm reduces, and the pore size distribution intensity at 0.6nm gradually becomes strong, such as Fig. 6, explanation
Compare for MOF-5 material, MOF-5 composite occurs in that two kinds of pore size distributions, and the polymer segments formed MOF-5
The duct of material.Hydrophobicity is tested: by testing the contact angle of water, the contact angle of MOF-5 material is 0 degree, and after being polymerized
The contact angle of MOF-5 composite becomes big, and after polymerization is described, the hydrophobicity of MOF-5 composite strengthens.With specific surface and aperture
Distribution Analyzer measures MOF-5 material and MOF-5 composite carbon dioxide adsorption property under 273K, it can be seen that
In hole after polymerization, the duct of MOF-5 material is divided into less duct by the polymer of generation so that MOF-5 material is to two
The energy-absorbing power of carbonoxide improves.
Embodiment 2
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
The synthesis of (1) 1,2-bis-(trimethylsilyl acetylene base) benzene
1 is prepared, 2-bis-(trimethylsilyl acetylene base) benzene according to the method for embodiment 1 step (1)
The volume of triethylamine used and toluene is respectively 60mL, 60mL；1,2-bis-iodo benzene, trimethylsilyl acetylene, Pd
(PPh3)4, the quality of CuI be respectively 2.5400g, 1.8905g, 0.3559g, 0.0587g；Whipping temp is 20 DEG C, the response time
For 15h.
Characterized the structure of pale yellowish oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is known that pale yellowish oil liquid is 1,2-bis-
(trimethylsilyl acetylene base) benzene.
(2) preparation of DEB
DEB is synthesized according to the method for embodiment 1 step (2).1,2-bis-(trimethylsilyl acetylene base) benzene and the matter of potassium carbonate
Amount is respectively 3.1500g, 4.8277g；Add methanol and the mixed solution 300mL of dichloromethane that volume ratio is 1.5:1；Stirring
Temperature is 25 DEG C, and the time is 15h.
Characterized the structure of light red oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 3.35 (s, 2H), 7.32 (q, 2H), 7.53 (q, 2H), it is known that light red oil liquid is DEB.
(3) synthesis of MOF-5 material and activation thereof
Method according to embodiment 1 step (3) prepares the MOF-5 material of activation.
Its diffraction spectrogram is obtained, with document by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
(Steven,S.K.；Dailly,A.；Yaghi,O.M.；Long, J.R.J.Am.Chem.Soc.2007,129,14176.) middle report
The diffraction pattern of the MOF-5 material in road and the MOF-5 material of activation coincide, the MOF-5 material of MOF-5 material and activation in document
Diffraction pattern is the most consistent, it is known that powder sample 1 is MOF-5 material, before and after powder sample 4 is the MOF-5 material of activation, and activation
The structure of MOF-5 material does not changes.
(4) preparation of MOF-5 composite
Weigh the MOF-5 material of the activation of 0.2000g, be immersed in light red oil liquid D EB of 0.8mL, leaching
Bubble 3h, then sucking filtration obtains powder sample 5, and obtains powder sample 6, by powder with the petroleum ether powder sample 5 of 150mL
Sample 6 is put in the peace times bottle of 10mL, puts it in the Dewar flask filling liquid nitrogen, after freezing 20min, thaws, more freezing
10min, thaws, more freezing 5min, thaws, seals by flame gun.The peace times bottle sealed is placed in 200 DEG C of baking ovens heating 10h,
Then take out sample, obtain MOF-5 composite.
Its diffraction spectrogram is obtained, this spectrogram and MOF-5 material by x-ray powder diffraction instrument test MOF-5 composite
Diffraction pattern completely the same, illustrate that the structure of MOF-5 material is maintained in heat polymerization process.Carry out infrared test,
The infrared spectrum of MOF-5 composite is compared with the powder sample 6 before polymerization, and it is at 3300cm-1The C ≡ C-H of neighbouring alkynes
Stretching vibration peak disappears, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB there occurs with this understanding
Polyreaction.By scanning electron microscope analysis, the plane of crystal of MOF-5 composite is almost without the pattern of polymer, and MOF-5
Composite maintains the cubic crystal pattern of MOF-5 material, illustrates not occur polyreaction outside duct.Use specific surface
The nitrogen adsorption character under 77K with pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite, finds and MOF-5
Material is compared the absorbability of MOF-5 composite and is substantially reduced, and BET specific surface area model calculates the specific surface of MOF-5 material
Amass as 3250m2g-1, the specific surface area of MOF-5 composite is 1700m2g-1, after polymerization, specific surface area reduces, and illustrates that polymerization is anti-
Should carry out in duct, polymer occupies the duct of MOF-5 material so that adsorption capacity for nitrogen reduces.Pass through QSDFT
Model calculated hole diameters is distributed, and finds that MOF-5 composite pore size distribution intensity at 1.2nm reduces, and the hole at 0.6nm is divided
Cloth intensity gradually becomes strong, and for the MOF-5 material that illustrates to compare, MOF-5 composite occurs in that two kinds of pore size distributions, and is formed
The polymer segments duct of MOF-5 material.Hydrophobicity is tested, by testing the contact angle of water, the contact angle of MOF-5 material
Being 0 degree, and after being polymerized, the contact angle of MOF-5 composite becomes big, after polymerization is described, the hydrophobicity of MOF-5 composite increases
By force.With specific surface and pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite carbon dioxide under 273K
Adsorption property, it can be seen that in hole after polymerization, the duct of MOF-5 material is divided into less duct by the polymer of generation,
The energy-absorbing power of carbon dioxide is improve by MOF-5 material.
Embodiment 3
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
(1) 1,2-bis-(trimethylsilyl acetylene base) benzene synthesizes
1 is prepared, 2-bis-(trimethylsilyl acetylene base) benzene according to the method for embodiment 1 step (1).Triethylamine used and first
The volume of benzene is respectively 15mL, 60mL；1,2-bis-iodo benzene, trimethylsilyl acetylene, Pd (PPh3)4, CuI quality be respectively
2.5400g, 1.8905g, 0.5338g, 0.0880g；Whipping temp is 70 DEG C, and the time is 25h.
Characterized the structure of pale yellowish oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is known that pale yellowish oil liquid is 1,2-bis-
(trimethylsilyl acetylene base) benzene.
(2) preparation of DEB
DEB is synthesized according to the method for embodiment 1 step (2).1,2-bis-(trimethylsilyl acetylene base) benzene and the matter of potassium carbonate
Amount is respectively 3.1500g, 6.4370g；Add methanol and the mixed solution 300mL of dichloromethane that volume ratio is 2:1；Stirring temperature
Degree is 70 DEG C, and the time is 25h.
Characterized the structure of light red oil liquid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR
(400MHz,CDCl3): δ 3.35 (s, 2H), 7.32 (q, 2H), 7.53 (q, 2H), it is known that light red oil liquid is DEB.
(3) synthesis of MOF-5 material and activation thereof
Method according to embodiment 1 step (3) prepares the MOF-5 material of activation.
Its diffraction spectrogram is obtained, with document by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
(Steven,S.K.；Dailly,A.；Yaghi,O.M.；Long, J.R.J.Am.Chem.Soc.2007,129,14176.) middle report
The diffraction pattern of the MOF-5 material in road and the MOF-5 material of activation coincide, the MOF-5 material of MOF-5 material and activation in document
Diffraction pattern is the most consistent, it is known that powder sample 1 is MOF-5 material, before and after powder sample 4 is the MOF-5 material of activation, and activation
The structure of MOF-5 material does not changes.
(4) preparation of MOF-5 composite
Weigh the MOF-5 material of the activation of 0.2000g, be immersed in light red oil liquid D EB of 2mL, soak
4h, then sucking filtration obtains powder sample 5, and obtains powder sample 6 by the petroleum ether of 100mL.Powder sample 6 is put into
In the peace times bottle of 10mL, put it in the Dewar flask filling liquid nitrogen, after freezing 20min, thaw, more freezing 10min, thaw,
Freezing 5min, thaws, seals by flame gun again.The peace times bottle sealed is placed in 220 DEG C of baking ovens heating 18h, then takes out sample
Product, obtain MOF-5 composite.
Its diffraction spectrogram is obtained, with the diffraction of MOF-5 material by x-ray powder diffraction instrument test MOF-5 composite
It is completely the same that pattern goes out peak position, illustrates that the structure of MOF-5 material is maintained in heat polymerization process.Carry out infrared test,
The infrared spectrum of MOF-5 composite is compared with the powder sample 6 before polymerization, and it is at 3300cm-1The C ≡ C-H of neighbouring alkynes
Stretching vibration peak disappears, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB there occurs with this understanding
Polyreaction.By scanning electron microscope analysis, the plane of crystal of MOF-5 composite is almost without the pattern of polymer, and MOF-5
Composite maintains the cubic crystal pattern of MOF-5 material, illustrates not occur polyreaction outside duct.Use specific surface
The nitrogen adsorption character under 77K with pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite, finds and MOF-5
Material is compared the absorbability of MOF-5 composite and is substantially reduced, and BET specific surface area model calculates the specific surface of MOF-5 material
Amass as 3280m2g-1, the specific surface area of MOF-5 composite is 1200m2g-1, after polymerization, specific surface area reduces, and illustrates that polymerization is anti-
Should carry out in duct, polymer occupies the duct of MOF-5 material so that adsorption capacity for nitrogen reduces.Pass through QSDFT
Model calculated hole diameters is distributed, and finds that MOF-5 composite pore size distribution intensity at 1.2nm reduces, and the hole at 0.6nm is divided
Cloth intensity gradually becomes strong, and for the MOF-5 material that illustrates to compare, MOF-5 composite occurs in that two kinds of pore size distributions, and is formed
The polymer segments duct of MOF-5 material.Hydrophobicity is tested, by testing the contact angle of water, the contact angle of MOF-5 material
It is 0 degree, and after being polymerized, the contact angle of MOF-5 composite becomes 135 degree, such as Fig. 7, MOF-5 composite after polymerization is described
Hydrophobicity strengthen.With specific surface and pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite under 273K two
Carbon oxide gas adsorption property, such as Fig. 8, it can be seen that in hole after polymerization, the duct of MOF-5 material is divided by the polymer of generation
It is slit into less duct so that the energy-absorbing power of carbon dioxide is improve by MOF-5 material.
Embodiment 4
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
(1) 1,2-bis-(trimethylsilyl acetylene bases)-4,5-dimethoxy benzene synthesizes
By 0.0678g Pd (PPh3)4Cl2, the 1 of 0.0184g CuI and 1.2558g, 2-bis-iodo-4,5-dimethoxy benzene adds
Enter in the three-necked bottle of 100mL, repeat vacuum nitrogen filling gas three times.Triethylamine 15mL and toluene 45mL is placed in conical flask
To mixed solution, drum nitrogen, mixed solution is injected in three-necked bottle, 0.7908g trimethylsilyl acetylene is joined three-necked bottle
In, 25 DEG C of heating 20h, obtain black product, by black product sucking filtration, obtain yellow solution, rotation is evaporated dry, obtains yellow solid
Body；Yellow solid is dissolved in a small amount of dichloromethane, utilizes column chromatography humid analysis (petroleum ether: the volume of dichloromethane
The mixed solution of ratio=2:1 is eluant) separate, rotation is evaporated dry, obtains white solid.
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is appreciated that white solid is 1,2-bis-(trimethyl silicane second
Alkynyl)-4,5-dimethoxy benzene.
(2) 1,2-diynyl-4, the preparation of 5-dimethoxy benzene
The 1 of weighing 1.6800g, 2-bis-(trimethylsilyl acetylene base)-4,5-dimethoxy benzene and 1.7561g potassium carbonate, add
Enter methanol and the mixed solution 300mL of dichloromethane that volume ratio is 1:1, at 25 DEG C, stir 15h.Obtain product light red to produce
Thing, by product sucking filtration, takes filtrate rotation and is evaporated dry, obtain light yellow solid, be dissolved in a small amount of dichloromethane, utilize post
Chromatograph humid analysis (petroleum ether: the mixed solution of the volume ratio=12:5 of dichloromethane is eluant) separates, and rotation is evaporated dry,
To white solid.
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 3.28 (s, 2H), 3.85 (s, 6H), 6.93 (s, 2H), it is known that white solid is 1,2-diynyl-4,5-dimethoxy
Base benzene, vehicle economy B-OMe.
(3) synthesis of MOF-5 material and activation thereof
Method according to embodiment 1 step (3) synthesizes the MOF-5 material of activation.
Its diffraction spectrogram is obtained, with document by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
(Steven,S.K.；Dailly,A.；Yaghi,O.M.；Long, J.R.J.Am.Chem.Soc.2007,129,14176.) middle report
The diffraction pattern of the MOF-5 material in road and the MOF-5 material of activation coincide, the MOF-5 material of MOF-5 material and activation in document
Diffraction pattern is the most consistent, it is known that powder sample 1 is MOF-5 material, before and after powder sample 4 is the MOF-5 material of activation, and activation
The structure of MOF-5 material does not changes.
(4) preparation of MOF-5 composite
Weigh the MOF-5 material of activation of 0.2000g, be immersed in that to be dissolved with the dichloromethane of 10mg DEB-OMe molten
In liquid, soaking 2h, then sucking filtration obtains powder sample 7, and obtains powder-like with the dichloromethane washing powder sample 7 of 250mL
Product 8, put into powder sample 8 in the peace times bottle of 10mL, put it in the Dewar flask filling liquid nitrogen, after freezing 20min, solve
Freeze, more freezing 10min, thaw, more freezing 5min, thaw, seal by flame gun.The peace times bottle sealed is placed in 170 DEG C of baking ovens
Middle heating 12h, then takes out sample, obtains MOF-5 composite.
Its diffraction spectrogram is obtained, with the diffraction of MOF-5 material by x-ray powder diffraction instrument test MOF-5 composite
Pattern is completely the same, illustrates that the structure of MOF-5 material is maintained in heat polymerization process.Carrying out infrared test, MOF-5 is combined
The infrared spectrum of material is compared with the powder sample 8 before polymerization, and it is at 3300cm-1The C ≡ C-H stretching vibration peak of neighbouring alkynes
Disappear, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB-OMe there occurs that polymerization is anti-with this understanding
Should.By scanning electron microscope analysis, the plane of crystal of MOF-5 composite is almost without the pattern of polymer, and MOF-5 composite wood
Material maintains the cubic crystal pattern of MOF-5 material, illustrates not occur polyreaction outside duct.With specific surface and aperture
Distribution Analyzer measures MOF-5 material and MOF-5 composite nitrogen adsorption character under 77K, finds and MOF-5 material phase
Substantially reducing than the absorbability of MOF-5 composite, BET specific surface area model calculates the specific surface area of MOF-5 material and is
3260m2g-1, the specific surface area of MOF-5 composite is 2000m2g-1, after polymerization, specific surface area reduces, and illustrates that polyreaction is
Carrying out in duct, polymer occupies the duct of MOF-5 material so that adsorption capacity for nitrogen reduces.By QSDFT model
Calculated hole diameters is distributed, and finds that MOF-5 composite pore size distribution intensity at 1.2nm reduces, and the pore size distribution at 0.6nm is strong
Degree gradually becomes strong, and for the MOF-5 material that illustrate to compare, MOF-5 composite occurs in that two kinds of pore size distributions, and gathering of being formed
Compound has split the duct of MOF-5 material.Hydrophobicity is tested, and by testing the contact angle of water, the contact angle of MOF-5 material is 0
Degree, and after being polymerized, the contact angle of MOF-5 composite becomes big, after polymerization is described, the hydrophobicity of MOF-5 composite strengthens.With
The carbon dioxide absorption under 273K of specific surface and pore-size distribution analysis-e/or determining MOF-5 material and MOF-5 composite
Character, it can be seen that in hole after polymerization, the duct of MOF-5 material is divided into less duct by the polymer of generation so that
The energy-absorbing power of carbon dioxide is improve by MOF-5 material.
Embodiment 5
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
(1) 1,2-bis-(trimethylsilyl acetylene bases)-4,5-dimethoxy benzene synthesizes
1 is prepared according to the method for embodiment 4 step (1), 2-bis-(trimethylsilyl acetylene base)-4,5-dimethoxy benzene.
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is appreciated that white solid is 1,2-bis-(trimethyl silicane second
Alkynyl)-4,5-dimethoxy benzene.
(2) preparation of DEB-OMe
DEB-OMe is synthesized according to the method for embodiment 4 step (2).
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 3.28 (s, 2H), 3.85 (s, 6H), 6.93 (s, 2H), it is known that white solid is DEB-OMe.
(3) synthesis of MOF-199 material and activation thereof
Weigh 11.8000g trimesic acid, 21.9000g Gerhardite be dissolved in 150mL DMF, 200mL ethanol,
In the mixed solution of 100mL water, then it is positioned under 85 DEG C of baking ovens heating 24h.Centrifugation, obtains powder sample 1, by powder-like
Product 1 DMF washs, and washs three times, washed once every 6h, and 100mL DMF is used in washing every time.It is centrifugally separating to obtain powder sample
2, powder sample 2 is placed in ethanol immersion, total immersion is steeped three times, changes a solution every 6h, uses ethanol 300mL every time.
It is centrifugally separating to obtain powder sample 3, by powder sample 3 180 DEG C of drying 10h under vacuum conditions, obtains powder sample 4.
Its diffraction spectrogram is obtained, with document by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
(Katz,M.J.；Brown,Z.J.；Colon,Y.J.；Siu,P.W.；Scheidt,K.A.；Snurr,R.Q.；Hupp,J.T.；
Farha, O.K.Chem Commun.2013,49,9449.) the MOF-199 material of report reported and the MOF-199 material of activation
The diffraction pattern of material coincide, and in document, MOF-199 material is the most consistent with the MOF-199 material diffraction pattern of activation, it is known that powder
Sample 1 is MOF-199 material, powder sample 4 be activation MOF-199 material, and activation before and after MOF-199 material structure not
Change.
(4) preparation of MOF-199 composite
Weigh the MOF-199 material of the activation of 0.2000g, be immersed in the dichloromethane being dissolved with 20mg DEB-OMe
In solution, soaking 2h, then sucking filtration obtains powder sample 7, and obtains powder with the dichloromethane washing powder sample 7 of 250mL
Sample 8, puts into powder sample 8 in the peace times bottle of 10mL, puts it in the Dewar flask filling liquid nitrogen, after freezing 20min,
Thaw, more freezing 10min, thaw, more freezing 5min, thaw, seal by flame gun.The peace times bottle sealed is placed in 170 DEG C of bakings
Case heats 12h, then takes out sample, obtain MOF-199 composite.
Its diffraction spectrogram is obtained, with MOF-199 material by x-ray powder sample diffraction instrument test MOF-199 composite
It is completely the same that the diffraction pattern of material goes out peak position, illustrates that the structure of MOF-199 material is maintained in heat polymerization process.Carry out
Powder sample 8 before infrared test, the infrared spectrum of MOF-199 composite and polymerization is compared, and it is at 3300cm-1Neighbouring alkynes
The C ≡ C-H stretching vibration peak of hydrocarbon disappears, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB-OMe exists
Polyreaction is there occurs under the conditions of this.By scanning electron microscope analysis, MOF-199 composite plane of crystal is almost without polymer
Pattern, and MOF-199 composite maintains the cubic crystal pattern of MOF-199 material, illustrates not send out outside duct
Raw polyreaction.With specific surface and pore-size distribution analysis-e/or determining MOF-199 material and MOF-199 composite under 77K
Nitrogen adsorption character, finds that the absorbability comparing MOF-199 composite with MOF-199 material substantially reduces, BET model meter
The specific surface area calculating MOF-199 material is 1500m2g-1, the specific surface area of MOF-199 composite is 800m2g-1, compare after polymerization
Surface area reduces, and illustrates that polyreaction is carried out in duct, and polymer occupies the duct of MOF-199 material so that nitrogen
Gas absorbability reduces.Hydrophobicity is tested: by testing the contact angle of water, the contact angle of MOF-199 composite after polymerization
The MOF-199 material itself that compares becomes big, and after polymerization is described, the hydrophobicity of MOF-199 composite strengthens.With specific surface and hole
Footpath Distribution Analyzer measures MOF-199 material and MOF-199 composite carbon dioxide adsorption property under 273K, can
After seeing cohesion conjunction of portalling, the duct of MOF-199 material is divided into less duct by the polymer of generation so that MOF-
The energy-absorbing power of carbon dioxide is improve by 199 materials.
Embodiment 6
A kind of method improving metal-organic framework materials carbon dioxide adsorption, described method specifically comprises the following steps that
(1) 1,2-bis-(trimethylsilyl acetylene bases)-4,5-dimethoxy benzene synthesizes
1 is prepared according to the method for embodiment 4 step (1), 2-bis-(trimethylsilyl acetylene base)-4,5-dimethoxy benzene.
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 0.27 (s, 18H), 7.24 (q, 2H), 7.47 (q, 2H), it is appreciated that white solid is 1,2-bis-(trimethyl silicane second
Alkynyl)-4,5-dimethoxy benzene.
(2) preparation of DEB-OMe
DEB-OMe is synthesized according to the method for embodiment 4 step (2).
Characterized the structure of white solid by nuclear magnetic resonance chemical analyser, corresponding data are as follows:1H NMR(400MHz,
CDCl3): δ 3.28 (s, 2H), 3.85 (s, 6H), 6.93 (s, 2H), it is known that white solid is DEB-OMe.
(3) synthesis of MOF-74 material and activation thereof
Weigh magnesium nitrate hexahydrate and 0.2600g 3,3'-dihydroxy-[1,1'-biphenyl]-4,4'-dicarboxyl of 0.8000g
Acid is dissolved in the DMF of 75mL, in the mixed solution of 5mL ethanol and 5mL water.120 DEG C of baking oven for heating 24h.Centrifugation, obtains powder
End sample 1, is immersed in powder sample 1 and washs with DMF, wash three times, washed once every 10h, every time washing 100mL
DMF.Being centrifugally separating to obtain powder sample 2, powder sample 2 is placed in methanol immersion, total immersion is steeped three times, changes one every 10h
Secondary solution, uses methanol 300mL every time.It is centrifugally separating to obtain powder sample 3, by powder sample 3 120 DEG C of bakings under vacuum conditions
Dry 18h, obtains powder sample 4.
Its diffraction spectrogram is obtained, with document by x-ray powder diffraction instrument test powders sample 1 and powder sample 4
(Hexiang Deng,Sergio Grunder,Kyle E.Cordova,Cory Valente,Hiroyasu Furukawa,
Mohamad Hmadeh,Felipe Gándara,Adam C.Whalley,Zheng Liu,Shunsuke Asahina,
Hiroyoshi Kazumori,Michael O’Keeffe,Osamu Terasaki,J.Fraser Stoddart,Omar
M.Yaghi.Science.2012,336,1019) the MOF-74 material reported and the diffraction pattern kiss of the MOF-74 material of activation
Closing, in document, MOF-74 material is the most consistent with the MOF-74 material diffraction pattern of activation, it is known that powder sample 1 is MOF-74 material
Material, powder sample 4 be the MOF-74 material of activation, and the structure of MOF-74 material does not changes before and after activating.
(4) preparation of MOF-74 composite
Weigh the MOF-74 material of the activation of 0.2000g, be immersed in the dichloromethane being dissolved with 30mg DEB-OMe
In solution, soaking 2h, then sucking filtration obtains powder sample 7, and obtains powder with the dichloromethane washing powder sample 7 of 250mL
Sample 8, puts into powder sample 8 in the peace times bottle of 10mL, puts it in the Dewar flask filling liquid nitrogen, after freezing 20min, solves
Freeze, more freezing 10min, thaw, more freezing 5min, thaw, seal by flame gun.The peace times bottle sealed is placed in 170 DEG C of baking ovens
Middle heating 12h, then takes out sample, obtains MOF-74 composite.
Its diffraction spectrogram is obtained, with spreading out of MOF-74 material by x-ray powder diffraction instrument test MOF-74 composite
Penetrating pattern, to go out peak position completely the same, illustrates that the structure of MOF-74 material is maintained in heat polymerization process.Carry out infrared survey
Powder sample 8 before examination, the infrared spectrum of MOF-74 composite and polymerization is compared, and it is at 3300cm-1The C ≡ of neighbouring alkynes
C-H stretching vibration peak disappears, at about 700cm-1The bending vibration peak of place C ≡ C-H disappears, and illustrates, DEB-OMe is with this understanding
There occurs polyreaction.By scanning electron microscope analysis, the plane of crystal of MOF-74 composite almost without the pattern of polymer,
And MOF-74 composite maintains the cubic crystal pattern of MOF-74 material, illustrate not occur polymerization anti-outside duct
Should.By specific surface and pore-size distribution analysis-e/or determining MOF-74 material and MOF-74 composite nitrogen adsorption under 77K
Matter, finds that the absorbability comparing MOF-74 composite with MOF-74 material substantially reduces, and BET model calculates MOF-74 material
Specific surface area be 2400m2g-1, the specific surface area of MOF-74 composite is 980m2g-1, polymerization specific surface area reduces, explanation
Polyreaction is carried out in duct, and polymer occupies the duct of MOF-74 material so that adsorption capacity for nitrogen reduces.Dredge
Aqueous nature is tested: by testing the contact angle of water, after polymerization, the contact angle of MOF-74 composite compares MOF-74 material
Material itself becomes big, and after polymerization is described, the hydrophobicity of MOF-74 composite strengthens.With specific surface and pore-size distribution analysis-e/or determining
MOF-74 material and the MOF-74 composite carbon dioxide adsorption property under 273K, it can be seen that polymerization in hole
After, the duct of MOF-74 material is divided into less duct by the polymer of generation so that MOF-74 material is to carbon dioxide
Energy-absorbing power improves.
The present invention includes but not limited to above example, every any equivalent carried out under the principle of spirit of the present invention
Replace or local improvement, all will be regarded as within protection scope of the present invention.
Claims (9)
1. the method improving metal-organic framework materials carbon dioxide adsorption, it is characterised in that: described method is for making adjacent two
Alkynyl aromatic compound monomer generates adjacent diynyl aromatic compound by thermal initiation in-situ polymerization in MOF material duct
Polymer obtains a kind of duct and is contained within the MOF composite of adjacent diynyl aromatic compound polymer, improves MOF with this
The material absorbability to carbon dioxide.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 1, its feature exists
In: the concrete synthetic method of described MOF composite is as follows:
If a () adjacent diynyl aromatic compound monomer is liquid: the MOF material of activation is immersed in adjacent diynyl aromatic series
In monomer adduct, then sucking filtration obtains powder sample 5, and cleans the MOF material surface of surface removal activation not with organic solvent 6
Enter the adjacent diynyl aromatic compound monomer in duct, obtain powder sample 6, powder sample 6 is taken out under liquid nitrogen atmosphere true
Sky, after sealing at 170-220 DEG C reacting by heating 10-18h, obtain described MOF composite；
If b () adjacent diynyl aromatic compound monomer is solid: be dissolved completely in by neighbour's diynyl aromatic compound monomer
In organic solvent 7, obtain adjacent diynyl aromatic compound monomer solution, then the MOF material of activation is immersed in adjacent diynyl
In aromatic compound monomer solution, then sucking filtration obtains powder sample 7, and cleans the MOF material removing activation with organic solvent 7
Material surface is introduced into the adjacent diynyl aromatic compound monomer in duct and obtains powder-like 8, by powder sample 8 under liquid nitrogen atmosphere
Evacuation, after sealing at 170-220 DEG C reacting by heating 10-18h, obtain described MOF composite；
Described, the quality (g) of the MOF of activation in (a): volume (the mL)≤1:3 of adjacent diynyl aromatic compound monomer；
The quality of the MOF material of activation in (b): the quality≤20:1 of adjacent diynyl aromatic compound monomer.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 2, its feature exists
In: the MOF material of activation soaks in adjacent diynyl aromatic compound monomer or adjacent diynyl aromatic compound monomer solution
The time of bubble is 1～8h；Described powder sample 6 and 8 operation of evacuation under liquid nitrogen atmosphere is: is loaded into pacifying in times bottle and freezes
Take out more than three times；The operation sealed is that sealing is melted in flame gun calcining；Powder sample 6 and 8 heats 12h after sealing at 170 DEG C；
Organic solvent 6 is petroleum ether；Organic solvent 7 is dichloromethane.
4. according to a kind of side improving metal-organic framework materials carbon dioxide adsorption according to any one of claims 1 to 3
Method, it is characterised in that: the synthetic method of described adjacent diynyl aromatic compound monomer is as follows:
Weigh aromatic compound and the potassium carbonate of trimethyl silicane protection, join in the mixed solution of methanol and dichloromethane,
It is made to be completely dissolved, stirring reaction 15～25h at 20～70 DEG C, by products therefrom sucking filtration, take filtrate rotation and be evaporated dry, utilize post color
Spectrum humid analysis separates, and rotation is steamed and is dried to obtain described adjacent diynyl aromatic compound monomer；
Described, the aromatic compound of trimethyl silicane protection and the mol ratio of potassium carbonate are 1:2.5～1:4；
Described, the volume ratio of methanol and dichloromethane is 1:1～2:1；
Described, if sucking filtration, it is solid that dried product exhibited is steamed in rotation, then need first to be dissolved in organic solvent 2, then it is wet to carry out column chromatography
Method analytical separation.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 4, its feature exists
In: in described method, the aromatic compound of trimethyl silicane protection and the mol ratio of potassium carbonate are 1:2.5；Methanol and dichloromethane
Volume ratio be 1:1；Whipping temp is 25 DEG C, and the time is 20h；Organic solvent 2 is dichloromethane；Column chromatography humid analysis separates
Eluant be petroleum ether or petroleum ether with methylene chloride volume than the mixed solution for 2:1～3:1.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 4, its feature exists
In: the synthetic method of the aromatic compound of described trimethyl silicane protection is as follows:
If a () adjacent two iodo aromatic compounds are liquid: weigh Pd catalyst and CuI catalyst, repeat vacuum nitrogen filling gas
To air by emptying；Measure the most aeriferous pure triethylamine and toluene, be added in above-mentioned catalyst, add adjacent diiodo-
Base aromatic compound and trimethylsilyl acetylene, at 20～70 DEG C, stirring reaction 15～25h, then by products therefrom sucking filtration, takes
Filtrate rotation is evaporated dry, utilizes column chromatography humid analysis to separate, and the aromatic series being dried to obtain described trimethyl silicane protection is steamed in rotation
Compound；
If b () adjacent two iodo aromatic compounds are solid: weigh Pd catalyst, CuI catalyst and adjacent two iodo aromatic series
Compound, repeats vacuum nitrogen filling gas to air by emptying；Measure the most aeriferous pure triethylamine and toluene, be added into above-mentioned
In catalyst and raw material, adding trimethylsilyl acetylene, at 20～70 DEG C, stirring reaction 15～25h, then takes out products therefrom
Filter, takes filtrate rotation and is evaporated dry, utilize column chromatography humid analysis to separate, and the fragrance being dried to obtain described trimethyl silicane protection is steamed in rotation
Compounds of group；
Described, the volume ratio of triethylamine and toluene is 1:1～1:4；
Described, adjacent two iodo aromatic compounds: trimethylsilyl acetylene, Pd catalyst, the mol ratio of CuI are 1:2.5:0.03
～0.06:0.03～0.06；
Described, if sucking filtration, it is solid that dried product exhibited is steamed in rotation, then need first to be dissolved in organic solvent 1, then it is wet to carry out column chromatography
Method analytical separation.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 6, its feature exists
In: Pd catalyst used in described method is Pd (PPh3)4Or Pd (PPh3)2Cl2；Repeat vacuum nitrogen filling gas three times；Used
Neighbour two iodo aromatic compound be 1,2-bis-iodo benzene or 1,2-bis-iodo-4,5-dimethoxy benzene；Whipping temp is 25 DEG C,
Response time is 20h；Described organic solvent 1 is dichloromethane；Column chromatography humid analysis separation eluant is petroleum ether or oil
Ether and methylene chloride volume are than the mixed solution for 2:1～3:1.
8. according to a kind of method improving metal-organic framework materials carbon dioxide adsorption described in any one of claims 1 to 3,
It is characterized in that: synthesis and the activation method of described MOF material are as follows:
(1) synthesis of MOF material
Slaine, organic ligand are dissolved completely in organic solvent 3 and water and obtain mixed solution, at 85～120 DEG C react 7～
24h, is centrifugally separating to obtain powder sample 1, is MOF material；
Described, slaine, the mol ratio of organic ligand are 8:5～17:5；
(2) activation of MOF material
By MOF material organic solvent 4 washing by soaking, it is centrifugally separating to obtain powder sample 2, by powder sample 2 organic solvent 5
Washing by soaking, is centrifugally separating to obtain powder sample 3, powder sample 3 is dried under the vacuum environment of 100～180 DEG C 10～
18h, obtains the MOF material of described activation.
A kind of method improving metal-organic framework materials carbon dioxide adsorption the most according to claim 8, its feature exists
In: in (1), organic solvent 3 is the mixed solution of DMF or DMF and ethanol；Slaine is magnesium nitrate hexahydrate, Gerhardite
Or zinc nitrate hexahydrate；Organic ligand used is p-phthalic acid, trimesic acid or 3,3'-dihydroxy-[1,1'-connection
Benzene]-4,4'-dicarboxylic acids；
(2) in, organic solvent 4 is DMF, and powder sample 1 soaks three times in organic solvent 4, each 6～10h；Organic solvent 5 is
Chloroform, dichloromethane, methanol or ethanol, powder sample 2 soaks three times in organic solvent 5, each 6～10h.
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