CN107903401A - A kind of method that metal-organic framework materials are prepared using dielectric barrier discharge plasma - Google Patents
A kind of method that metal-organic framework materials are prepared using dielectric barrier discharge plasma Download PDFInfo
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- CN107903401A CN107903401A CN201711214009.2A CN201711214009A CN107903401A CN 107903401 A CN107903401 A CN 107903401A CN 201711214009 A CN201711214009 A CN 201711214009A CN 107903401 A CN107903401 A CN 107903401A
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- metal
- organic framework
- dielectric barrier
- barrier discharge
- framework materials
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000004888 barrier function Effects 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000005611 electricity Effects 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 40
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000012212 insulator Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000009434 installation Methods 0.000 claims 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 4
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 230000002572 peristaltic effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a kind of method that metal-organic framework materials are prepared using dielectric barrier discharge plasma.Metal salt, organic ligand addition solvent are mixed evenly dissolving and obtain reaction solution, reaction solution is pumped into the inner tube of dielectric barrier discharge plasma reactor, again from the interior tube edges spilling less than outer tube, uniform wall-hanging liquid film is formed between the inner and outer pipe sections and is slowly flowed downward；Working gas is passed through into inner tube at the same time.Driven by high-frequency and high-voltage power supply, liquid film of the action of plasma that liquid electrode and outer tube high-voltage electricity interpolar discharge produce between inner and outer pipes are flowed through, makes reaction solution carry out the reaction of certain time under action of plasma, prepare Organometallic framework material.The present invention have the advantages that aggregate velocity soon, performance stability and high efficiency, controllability be strong, highly practical, non-secondary pollution, there is preferable application prospect.
Description
Technical field
The invention belongs to functional material preparing technical field, relates generally to a kind of dielectric impedance of metal-organic framework materials
Method for preparing discharge plasma.
Background technology
Metal-organic framework materials are a kind of novel porous coordination function nano materials formed by metal and organic ligand,
It is the hot research problem in the fields such as current Coordinative Chemistry, material science and crystal engineering.Metal-organic framework materials have super
High-specific surface area, unique pore structure, the features such as duct geomery and chemical environment are controllable, have to the pollutant in waste water
There are higher adsorption capacity and photocatalysis performance.
Metal-organic framework materials are synthesized using metal salt and organic ligand in certain solvent under middle cryogenic conditions, main
Method is wanted to have solvent-thermal process method, stirring synthetic method, diffusion method, microwave method, ultrasonic method, electrochemical process etc..Solvent-thermal process method
It is to synthesize the most commonly seen method of metal-organic framework materials, has that equipment is simple, crystal growth is perfect, easy to operate etc. excellent
Point, but reaction needs high temperature and pressure, and the reaction time is longer, and energy consumption is big, low production efficiency.Stirring synthetic method can synthesize
Measure it is larger, but synthesize material may contain more impurity.The metal-organic framework materials of diffusion method synthesis are more pure, matter
Amount is preferable, but due to be diffusion under room temperature as motive force, the reaction time is longer, low output.Microwave method and ultrasonic method
It is swift in response, is nucleated easy to rapid crystallization, but reacts not easy to control, product morphology and the more difficult control of stability.Electrochemical process is
A kind of extremely unique metal-organic framework materials preparation method, but technological process is complex, and production intensity is not high.
In view of the above-mentioned problems, Chinese patent CN 105037404A, disclose a kind of based on plasma discharging system in liquid phase
The method of standby metal-organic framework materials, but since liquid is conductive, the ion in liquid will participate in being electrically conductive forming from
Subflow, makes the foundation of liquid plasma more difficult, and this method reaction solution be sufficiently mixed and different topology structure
It is more limited in the regulation and control of metal-organic framework materials.
At present, at home and abroad there is no using dielectric barrier discharge plasma prepare metal-organic framework materials research or
Report.Therefore, a kind of method that metal-organic framework materials are prepared using dielectric barrier discharge plasma how is researched and developed, is solved
Above-mentioned technical problem, has important practical significance.
The content of the invention
For problems of the prior art, it is an object of the invention to provide one kind using dielectric barrier discharge etc. from
The method that daughter efficiently quickly prepares metal-organic framework materials.Mixed using different operating gas sparging with reaction solution, a side
Face promotes being sufficiently mixed for metal salt and organic ligand, on the other hand, also change electric discharge atmosphere and discharge condition, so as to adjust
Control the structure of metal-organic framework materials.
To achieve these goals, the technical solution of use is the present invention：
A kind of method that metal-organic framework materials are prepared using dielectric barrier discharge plasma, specifically includes following step
Suddenly：
(1) metal salt, organic ligand addition solvent are mixed evenly dissolving and obtain reaction solution, reaction solution is pumped into Jie
In matter barrier discharge plasma reactor；
(2) when reaction solution is entered in plasma reactor, first pass through liquid inlet and be pumped into interior pipe, then from less than outer tube
Interior tube edges overflow, form uniform wall-hanging liquid film between the inner and outer pipe sections and slowly flow downward；
(3) in dielectric barrier discharge plasma reactor, the reaction solution that inner tube comes into full contact with leading electrode is filled with
Form liquid electrode；
(4) working gas is passed through into inner tube by gas access, high-frequency and high-voltage power supply, control input is opened after stablizing
Voltage is 50-100V, frequency 10-20kHz, electric current 1-3A, what the high-voltage electricity interpolar discharge of liquid electrode and outer tube produced
Liquid film of the action of plasma between inner and outer tubes are flowed through, carries out reaction 10-150min in working gas atmosphere is passed through,
High energy electron, the group isoreactivity particle produced by plasma discharge, destroys original chemical bond, makes metal ion and has
Machine ligand binding forms new complex, and metal-organic framework materials are prepared.
(5) metal-organic framework materials will be obtained to stand and centrifuge the reaction solution containing precipitation, be put into after cleaning
Drying box is dried, and to remove solvent, obtains purer material.
Further, the metal salt is zinc nitrate, zinc acetate, iron chloride, aluminium chloride, aluminum nitrate, copper nitrate, chlorination
Any one or more in zirconium, magnesium nitrate or its hydrate.
Further, the organic ligand is terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2,5- dihydroxy terephthaldehydes
Acid or trimesic acid in any one or more.
Further, the solvent is any one in n,N-Dimethylformamide, water, ethanol or N, N- dimethyl sulfoxide (DMSO)
The mixture of kind or two or more compositions.
Further, the mass ratio of the metal salt and organic ligand is (0.3-3):1, metal salt and organic ligand are molten
Concentration in liquid is 1-100mg/mL.
Further, the working gas is any one in air, nitrogen, argon gas, helium, carbon dioxide or hydrogen
Or the gaseous mixture of a variety of compositions, being passed through for gas not only act as immixture, and change discharge condition, strengthen active particle and make
With.
Further, the dielectric barrier discharge plasma reactor includes cylinder, the insulation installed in cylinder body bottom
Base, the cover board being installed at the top of cylinder and the leading electrode for being installed on body centre, the cylinder are arranged to coaxially arrange
Cylindrical upright inner tube and vertical outer tube, inner and outer tubes bottom be respectively arranged with liquid inlet and liquid outlet；Insulation bottom
Gas access is provided with seat；Gas vent is provided with cover board；Parcel is provided with high-field electrode on outer tube excircle side face.
Further, said inner tube and outer tube are using any insulating materials in quartz, ceramics or macromolecule organic
It is made.
Further, it is slightly below outer tube top edge in the inner tube top edge at cover board and forms opening, liquid point
Cloth device is installed in this opening；Gas distributor is provided with the gas access.
Further, the leading electrode is arranged to bar-shaped or acicular texture；The high-field electrode for being wrapped in outer tube is set
For 1 section, 2 sections, 3 sections or multistage metal electrode, it is arranged to one kind in spiral metal wire, metal mesh or metal tape.
Further, supporting rod is provided with the outside of cylinder, the bottom of supporting rod is provided with support footing.
The beneficial effects of the invention are as follows：
Dielectric barrier discharge plasma efficiently can quickly prepare metal-organic framework materials, using different operating gas
Bubbling is mixed with reaction solution, on the one hand promotes being sufficiently mixed for metal salt and organic ligand, on the other hand, also changes electric discharge atmosphere
And discharge condition, strengthen active particle effect, so as to regulate and control the structure of metal-organic framework materials.The present invention, which has, to be prepared
The advantages that process is simple, aggregate velocity is fast, performance stability and high efficiency, controllability are strong, highly practical, non-secondary pollution, have compared with
Good application prospect.
By setting gas distributor, change gas flow rate so that reaction solution and the solid produced in reaction process are effective
Mixing, by controlling solid in the residence time of heating region, and then controls crystal growth processes, controls its crystal grain
Degree.Meanwhile different operating gas is passed through the discharge condition also changed in reactor, and then influence MOF material structures and property
Energy.
Preparation method in the present invention cooperates with dielectric barrier discharge plasma reactor, easy to rapid crystallization into
Core, and reaction is easy to control, the reaction time is relatively short, and energy consumption is small, and the amount that can be synthesized is larger, and production efficiency is high, tool
Have the advantages of control crystal growth is perfect, and do not contain impurity, the metal-organic framework materials of synthesis are more pure, quality compared with
Good, product morphology and stability are easier to control.
Brief description of the drawings
Fig. 1 is the overall structure diagram of dielectric barrier discharge plasma reactor in the present invention.
In Fig. 1,1, leading electrode；2nd, high-field electrode；3rd, gas vent；4th, cover board；5th, liquid distribution trough；6th, reaction solution；
7th, supporting rod；8th, liquid outlet；9th, liquid inlet；10th, gas distributor；11st, insulator foot；12nd, gas access；13rd, support
Footing.
Fig. 2 is the XRD diagram of ferrous metal organic framework material made from embodiment 1.
Fig. 3 adsorbs methyl orange design sketch for obtained ferrous metal organic framework material under different electric discharge atmosphere.
In Fig. 3, methyl orange initial concentration is 100mg/L.
Embodiment
The invention will be further elaborated with reference to the accompanying drawings and examples.
As shown in Figure 1, dielectric barrier discharge plasma reactor includes cylinder, installed in the insulation bottom of cylinder body bottom
Seat, the cover board being installed at the top of cylinder and the leading electrode for being installed on body centre, cylinder use sealing structure, cylinder
Outside is provided with supporting rod, and the bottom of supporting rod is provided with support footing, plays firm supporting role；The cylinder is arranged to
The cylindrical upright inner tube coaxially arranged and vertical outer tube, inner and outer tubes are using in quartz, ceramics or macromolecule organic
Any insulating materials is made, and inner and outer tubes bottom is respectively arranged with liquid inlet and liquid outlet, in outer wall of inner tube and outer tube
Electric discharge spacing between wall is adjustable；Gas access is provided with insulator foot；Gas vent is provided with cover board；Outer tube excircle
Parcel is provided with high-field electrode on side face.
It is slightly below outer tube top edge in the inner tube top edge at cover board and forms opening, liquid distribution trough is installed herein
In opening, easy to form the effect of uniform cloth stream to the reaction solution of entrance；
Gas distributor is provided with gas access, easy to form the effect of uniform gas distribution to gas；
Leading electrode is arranged to bar-shaped or acicular texture；
The high-field electrode for being wrapped in outer tube is arranged to 1 section, 2 sections, 3 sections or multistage metal electrode, it is arranged to spiral metal
One kind in silk, metal mesh or metal tape, is in close contact with the outer surface of outer tube.
When dielectric barrier discharge plasma reactor is specifically used：
By the mixed solution of metal salt, organic ligand and solvent, inner tube is pumped into by liquid inlet, out of less than outer tube
Tube edges are overflowed, and are formed uniform wall-hanging liquid film between the inner and outer pipe sections and are slowly flowed downward；Pass through gas access at the same time
Working gas is passed through into inner tube, high-frequency and high-voltage power supply is opened after stablizing, discharging between liquid electrode and cylindrical pipe electrode produces
Liquid film of the action of plasma between inner and outer pipes are flowed through, control source 50-100V, frequency 10-20kHz, electric current 1-3A,
Metal-organic framework materials are made in reaction 10-150min.
The leading electrode of body centre is low-field electrode, and the electrode of outer barrel outer surface is high-field electrode, and reaction solution first passes through
Heating region between high-field electrode and leading electrode, obtains a degree of processing, since reaction solution is led in inner tube
Electrically, fill with the reaction solution that inner tube and leading electrode come into full contact with and form liquid electrode, treat that the water surface exceedes liquid distribution trough, wait from
Daughter is formed in the annular space between two pipes, and reaction solution passes through the heating region of the annular space between two pipes again,
So that inner tube, the reaction solution of outer tube outer surface obtain further advanced treating, pass through the continuous flowing of reaction solution and cylinder
Double-layer sleeve structure, dexterously realize electrode discharge and reaction solution continuous processing, its ingehious design is also effectively improved
Space availability ratio, increases the contact area of plasma and reaction solution.In addition, reactor uses sealing structure, make to discharge
The active material and ultraviolet radiation energy produced in journey accesses sufficient utilization, improves the treatment effect of reaction solution.
Embodiment 1：Prepare ferrous metal organic framework material
Weigh 0.8gFeCl3·6H2O and 1.6g terephthalic acid (TPA)s, are dissolved in 150mLDMF, stirring 10min to uniform dissolution,
Beaker is poured into after adding the mixing of 150mL absolute ethyl alcohols, is pumped into peristaltic pump in plasma reactor, in discharge voltage 60V, electricity
19min is reacted under conditions of stream 1.5A.Stand simultaneously by containing precipitation reaction solution centrifuge, be put into after cleaning drying box in
Dry 4h at 160 DEG C, carries out precipitation X-ray diffraction (XRD) test, is specifically shown in attached drawing 2, in fig. 2, main diffraction peak is in 2 θ
=9.7,12.6,19 and 22, opposite diffracted intensity and the MOF-235 standards of crystal are identical, it was demonstrated that crystalline material MOF-
235。
Embodiment 2：Argon gas discharging prepares ferrous metal organic framework material
Weigh 0.8gFeCl3·6H2O and 1.6g terephthalic acid (TPA)s, are dissolved in 150mLDMF, stirring 10min to uniform dissolution,
Beaker is poured into after adding the mixing of 150mL absolute ethyl alcohols, is pumped into peristaltic pump in plasma reactor, in discharge voltage 60V, electricity
Stream 1.5A, be passed through under conditions of argon gas and react 19min.Stand and centrifuge the reaction solution containing precipitation, be put into after cleaning
Drying box dry 4h at 160 DEG C.
Embodiment 3：Nitrogen discharge prepares ferrous metal organic framework material
Weigh 0.8gFeCl3·6H2O and 1.6g terephthalic acid (TPA)s, are dissolved in 150mLDMF, stirring 10min to uniform dissolution,
Beaker is poured into after adding the mixing of 150mL absolute ethyl alcohols, is pumped into peristaltic pump in plasma reactor, in discharge voltage 60V, electricity
Stream 1.5A, be passed through under conditions of nitrogen and react 19min.Stand and centrifuge the reaction solution containing precipitation, be put into after cleaning
Drying box dry 4h at 160 DEG C.
By the ferrous metal organic framework material in 10mg embodiments 1-3, the methyl orange for adsorbing 100mL100mg/L is molten
Liquid, methyl orange concentration versus time curve are as shown in Figure 3.
Embodiment 4：Prepare aluminum metal organic framework material
Weigh 11.65gAl (NO3)3·9H2O and 7.98g terephthalic acid (TPA)s, are dissolved in 200mLDMF, are stirred until homogeneous dissolving
After pour into beaker, be pumped into plasma reactor with peristaltic pump, reacted under conditions of discharge voltage 60V, electric current 1.5A
15min.Stand and centrifuge the reaction solution containing precipitation, drying box dry 4h at 160 DEG C is put into after cleaning, obtains aluminium
Metal-organic framework materials.
Embodiment 5：Helium discharge prepares zinc metal-organic framework materials
Weigh 0.6gZn (NO3)2·6H2O and 0.2g 2- amino terephthalic acid (TPA)s, are dissolved in 200mL DMF, are stirred until homogeneous
Beaker is poured into after dissolving, is pumped into peristaltic pump in plasma reactor, helium is passed through in discharge voltage 50V, electric current 1.0A
Under the conditions of react 10min.Stand and centrifuge the reaction solution containing precipitation, drying box is put into after cleaning and is done at 160 DEG C
Dry 4h, obtains zinc metal-organic framework materials.
Embodiment 6：Carbon dioxide electric discharge prepares copper metal organic framework material
Weigh 0.9gCu (NO3)2·2H2O and 3g 2,5-Dihydroxyterephthalic acids, are dissolved in 200mL ethanol, stir to equal
Beaker is poured into after even dissolving, is pumped into peristaltic pump in plasma reactor, dioxy is passed through in discharge voltage 60V, electric current 2A
15min is reacted under conditions of change carbon gas.Stand simultaneously by containing precipitation reaction solution centrifuge, be put into after cleaning drying box in
Dry 4h, obtains copper metal organic framework material at 160 DEG C.
Embodiment 7：Argon gas and hydrogen discharge prepare magnesium metal-organic framework materials
Weigh 3gMg (NO3)2·6H2O and 3g trimesic acids, are dissolved in 200mLN, N- dimethyl sulfoxide (DMSO)s, are stirred until homogeneous
Beaker is poured into after dissolving, is pumped into peristaltic pump in plasma reactor, argon gas is passed through in discharge voltage 100V, electric current 3A and lacks
150min is reacted under conditions of amount hydrogen.Stand simultaneously by containing precipitation reaction solution centrifuge, be put into after cleaning drying box in
Dry 4h, obtains magnesium metal-organic framework materials at 160 DEG C.
The organic framework material that above-described embodiment 1-7 is obtained is that porous material has superhigh specific surface area, its specific surface area
Relatively larger than common metal-organic framework materials, have unique pore structure, duct geomery and the chemical environment controllable etc.
Feature, has higher adsorption capacity and photocatalysis performance to the pollutant in waste water.And obtained metal-organic framework materials
More pure, free from admixture, quality is preferable, and yield is high, has a vast market application prospect.
The above is not limitation of the present invention, it should be pointed out that：Come for those skilled in the art
Say, on the premise of essential scope of the present invention is not departed from, some variations, modifications, additions or substitutions can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (10)
- A kind of 1. method that metal-organic framework materials are prepared using dielectric barrier discharge plasma, it is characterised in that specific Include the following steps：(1) metal salt, organic ligand addition solvent are mixed evenly dissolving and obtain reaction solution, reaction solution is pumped into medium resistance Keep off in discharging plasma reactor；(2) when reaction solution is entered in plasma reactor, first pass through liquid inlet and be pumped into interior pipe, then out of less than outer tube Tube edges are overflowed, and are formed uniform wall-hanging liquid film between the inner and outer pipe sections and are slowly flowed downward；(3) in dielectric barrier discharge plasma reactor, fill with inner tube and formed with the reaction solution that leading electrode comes into full contact with Liquid electrode；(4) working gas is passed through into inner tube by gas access, high-frequency and high-voltage power supply, control input voltage is opened after stablizing For 50-100V, frequency 10-20kHz, electric current 1-3A, grade that the high-voltage electricity interpolar discharge of liquid electrode and outer tube produces from Daughter acts on the liquid film flowed through between inner and outer tubes, and reaction 10-150min is carried out in working gas atmosphere is passed through, and prepares Obtain metal-organic framework materials.(5) metal-organic framework materials will be obtained to stand and centrifuge the reaction solution containing precipitation, drying is put into after cleaning Case is dried.
- 2. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the metal salt is zinc nitrate, zinc acetate, iron chloride, aluminium chloride, aluminum nitrate, copper nitrate, zirconium chloride, magnesium nitrate Or any one or more in its hydrate.
- 3. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the organic ligand is terephthalic acid (TPA), 2- amino terephthalic acid (TPA), 2,5-Dihydroxyterephthalic acid or equal benzene Any one or more in tricarboxylic acid.
- 4. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the solvent is any one or two kinds in n,N-Dimethylformamide, water, ethanol or N, N- dimethyl sulfoxide (DMSO) The mixture of composition described above.
- 5. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the mass ratio of the metal salt and organic ligand is (0.3-3):1, metal salt and organic ligand in the solution dense Spend for 1-100mg/mL.
- 6. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the working gas is any one or more group in air, nitrogen, argon gas, helium, carbon dioxide or hydrogen Into gaseous mixture.
- 7. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 1, its It is characterized in that, the dielectric barrier discharge plasma reactor includes cylinder, the insulator foot installed in cylinder body bottom, installation Cover board at the top of cylinder and the leading electrode for being installed on body centre, the cylinder are arranged to the cylinder coaxially arranged Vertical inner tube and vertical outer tube, inner and outer tubes bottom are respectively arranged with liquid inlet and liquid outlet；Set on insulator foot There is gas access；Gas vent is provided with cover board；Parcel is provided with high-field electrode on outer tube excircle side face.
- 8. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 7, its It is characterized in that, said inner tube and outer tube are made of any insulating materials in quartz, ceramics or macromolecule organic.
- 9. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 7, its It is characterized in that, is slightly below outer tube top edge in the inner tube top edge at cover board and forms opening, liquid distribution trough is installed on In this opening；Gas distributor is provided with the gas access.
- 10. the method for metal-organic framework materials is prepared using dielectric barrier discharge plasma according to claim 7, its It is characterized in that, the leading electrode is arranged to bar-shaped or acicular texture；Be wrapped in outer tube high-field electrode be arranged to 1 section, 2 sections, 3 Section or multistage metal electrode, it is arranged to one kind in spiral metal wire, metal mesh or metal tape.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161027A (en) * | 2018-08-06 | 2019-01-08 | 四川大学 | The method of low temperature plasma induction synthesis and regulation covalent organic frame material |
| CN110572923A (en) * | 2019-07-19 | 2019-12-13 | 中国石油大学(华东) | Recyclable coaxial DBD plasma reactor for liquid modification |
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN111437795A (en) * | 2020-02-25 | 2020-07-24 | 浙江大学 | Zirconium-based metal organic framework material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1493311A1 (en) * | 2002-04-10 | 2005-01-05 | Dow Corning Ireland Limited | Gel and powder making |
| US20060244386A1 (en) * | 2005-05-02 | 2006-11-02 | Hooke William M | Pulsed dielectric barrier discharge |
| CN103331455A (en) * | 2013-07-19 | 2013-10-02 | 四川大学 | Method for continuously preparing metallic nano material with assistance of discharging micro plasma |
| CN104370346A (en) * | 2014-11-04 | 2015-02-25 | 青岛科技大学 | Novel two-stage dielectric barrier discharge plasma wastewater treatment device |
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
-
2017
- 2017-11-28 CN CN201711214009.2A patent/CN107903401B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1493311A1 (en) * | 2002-04-10 | 2005-01-05 | Dow Corning Ireland Limited | Gel and powder making |
| US20060244386A1 (en) * | 2005-05-02 | 2006-11-02 | Hooke William M | Pulsed dielectric barrier discharge |
| CN103331455A (en) * | 2013-07-19 | 2013-10-02 | 四川大学 | Method for continuously preparing metallic nano material with assistance of discharging micro plasma |
| CN104370346A (en) * | 2014-11-04 | 2015-02-25 | 青岛科技大学 | Novel two-stage dielectric barrier discharge plasma wastewater treatment device |
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161027A (en) * | 2018-08-06 | 2019-01-08 | 四川大学 | The method of low temperature plasma induction synthesis and regulation covalent organic frame material |
| CN109161027B (en) * | 2018-08-06 | 2021-07-13 | 四川大学 | Method for synthesizing and regulating covalent organic framework material by low-temperature plasma induction |
| CN110572923A (en) * | 2019-07-19 | 2019-12-13 | 中国石油大学(华东) | Recyclable coaxial DBD plasma reactor for liquid modification |
| CN110951088A (en) * | 2019-12-13 | 2020-04-03 | 安徽大学 | Zirconium-based metal organic framework material, preparation and application as chromium removal agent |
| CN111437795A (en) * | 2020-02-25 | 2020-07-24 | 浙江大学 | Zirconium-based metal organic framework material and preparation method thereof |
| CN111437795B (en) * | 2020-02-25 | 2021-06-15 | 浙江大学 | Zirconium-based metal organic framework material and preparation method thereof |
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