CN104370820B - Preparation method and applications of porous metal organic skeleton material - Google Patents
Preparation method and applications of porous metal organic skeleton material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- C07F1/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
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- C07F5/069—Aluminium compounds without C-aluminium linkages
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
Abstract
The invention relates to a preparation method of a porous metal organic skeleton material. The porous metal organic skeleton material comprises at least a metal ion and at least an organic compound that can be matched with the metal ion. The material can be prepared by dissolving metal compounds, organic ligand, and sustained-released alkali into a solvent and carrying out direct water (solvent) thermal synthesis at a certain temperature under a certain pressure so as to obtain the porous metal organic skeleton material. The operation of the provided preparation method is simple, the preparation method is suitable for massive industrial production and is suitable for the synthesis of porous metal organic skeleton membrane, and the provided porous metal organic skeleton material is used to absorb, separate, and store gas.
Description
Technical field
The invention belongs to chemical material synthesis and application project technical field, and in particular to a kind of porous metal-organic framework
The preparation method and application of material.
Background technology
Porous metal organic frameworks（Metal-organic Frameworks,MOFs）, with specific duct knot
Structure and superhigh specific surface area, and the surface texture that can be fine-tuned, the research of always field of porous materials is hot nearly ten years
Point.
Research team with U.S. professor Yaghi as representative, continuously delivers new structure MOFs on Science in recent years
Synthesis, aperture adjustment and surface property regulation and control method [Science, 2002,295,469;2010,330,650;2012,336,
1018;].Meanwhile, the large-scale international chemical company with German BASF SE as representative also discloses that the organic bone of substantial amounts of porous metals
The technology of preparing of frame material, the metal-organic framework materials of metal and preparation method thereof such as including Al, Mg, Cu, Zn.Current MOFs
Preparation method mainly include：Electrochemical synthesis [CN1886536A, WO2005049892], water or solvent-thermal process
[CN101384537A、Cu-BTC US5648502、US20030078311、US20030148165、US20030222023、
US20040081611, US2004265670], ball-milling method [Angew.Chem.Int.Ed.2006,45,142,2010,49,
712], microwave method [WO2008057140], and diffusion method [US6965026] etc..The preparation skill of comprehensive these MOFs materials
From the point of view of art, hydro-thermal and solvent-thermal process technology are still currently MOFs materials largely one of best-of-breed technology of synthesis.
In general, direct synthesis technique, i.e. metal salt solution and part are used the preparation of metal organic complex in water more
Solution or organic solvent（Such as DMF, methyl alcohol, ethanol, ethylene glycol）In, obtain bridging and match somebody with somebody by hydro-thermal method or solvent-thermal method reaction
Compound.From the point of view of chemically constituting, porous metal organic frameworks are made up of metal ion with anion ligand, similar to gold
Category salt, so theoretically can directly be prepared by displacement or acid-base reaction.However, porous metal organic frameworks
Influence MOFs synthesis has factors, and such as pH value, concentration, temperature, anionic type, hydrogen bond, pi-pi accumulation is interacted, permeated
The factors such as effect, inclusion and guest molecule.Wherein temperature is key factor, but these factors are to the influence that MOFs synthesizes
It is mutually related.
The structure of Metal-organic complex is mainly by part deprotonation degree and auxiliary with what metal center was coordinated
Help the influence of ligand properties.Because expected network structure can be obtained by solvent and organic ligand deprotonation, and simultaneously
Strengthen the heat endurance and rigidity of resulting structures.Porous metal organic frameworks in building-up process, generally using hydroxide
Sodium, potassium hydroxide, pyrimidine, triethylamine, sodium acetate, acetic acid or watery hydrochloric acid etc. adjust pH.Under different pH, organic coordination group energy
Enough deprotonations wholly or in part, so that part shows abundant coordination mode, and the complex structure for being generated
There occurs obvious change.
From in terms of current patented technology, it is harsh to there is low yield, synthesis condition in the MOFs synthetic technologys under mild alkaline conditions
The shortcomings of；MOFs synthetic technologys under strong basicity environment usually using a large amount of severe corrosives alkali（Such as NaOH, US2012/
0082864）Carry out the deprotonation of organic ligand.The use of deep-etching alkali can be realized synthesizing in a low temperature of MOFs materials, but
The danger of corrosion with the operation of equipment is will also result in, and the difficulty of material subsequent purification can be caused, it is also possible to because alkali metal
The presence of ion influences some performances of porous MOFs materials.
In view of shortcoming present in existing MOFs materials hydro-thermal or solvent-thermal process technology, it is an object of the invention to provide
It is a kind of simple, practical, it is easy to the porous MOFs material synthesis methods of a large amount of productions.
The content of the invention
It is an object of the invention to provide a kind of preparation method and application of porous metal organic frameworks.
The invention provides a kind of preparation method of porous metal organic frameworks, by the metallization containing metal ion
The organic ligand of compound and metallic ion coordination, sustained release alkali, are sufficiently mixed in a solvent, under certain temperature and pressure, lead to
Cross ligand complex to act on and be self-assembly of with supramolecular network structure compound, then by filtering, washing, dry, live
Porous metal organic frameworks are formed after change；
The metal ion is CuII、AlIII、MgII、MnII、FeIII、NiII、CoII、ZnIIIn one or more；
The organic ligand be with least one it is independent selected from oxygen, sulphur, nitrogen atom, and the organic ligand passes through
They can ligand complex in the metal ion.
The metal ion that porous metals framework material of the present invention is included need not all be two or more, comprising
Organic ligand also need not all be two or more, but comprising metal ion and organic ligand must at least a pair can be mutual
Mutually coordination forms porous metal-organic framework structure.
The preparation method of the porous metal organic frameworks that the present invention is provided, the organic ligand includes organic carboxylic acids
Appointing in compound, organic sulfonic acid compound, glyoxaline compound, pyridine compounds and their, aminated compounds and its derivative
A kind of or arbitrarily several mixing of meaning.
The present invention provide porous metal organic frameworks preparation method, the organic ligand selected from succinic acid,
Fumaric acid, l,2,3 benzene tricarboxylic acid, 1,2,4 benzenetricarboxylic acid, 1,3,5- benzenetricarboxylic acids, 1,4- phthalic acids, 2,5- dihydroxy-
1,4- phthalic acids, 1,3- phthalic acids, 1,4- naphthalenes diacid, 2,6- naphthalenes diacid, isonicotinic acid, acidum nicotinicum, 3,4- pyridines two
Formic acid, 2,5- pyridinedicarboxylic acids, 2,6- naphthalene disulfonates, 3- pyridine-sulfonic acids, 4,5- dihydroxy -1,3- DAADBSAs, imidazoles, 2-
Methylimidazole, 4-methylimidazole, 2- nitroimidazoles, benzimidazole, 4,4 '-bipyridyl, ethylenediamine, triethylene diamine.It is especially excellent
The organic ligand of choosing selected from fumaric acid, 1,3,5- benzenetricarboxylic acids, 1,4- phthalic acids, 2,5- dihydroxy -1,4- phthalic acids,
1,3- phthalic acids, isonicotinic acid, imidazoles, 2-methylimidazole, 4,4 '-bipyridyl, triethylene diamine.It is especially particularly preferred organic
Part have fumaric acid, 1,3,5- benzenetricarboxylic acids, 1,4- phthalic acids, 1,3- phthalic acids, isonicotinic acid, imidazoles, 2-methylimidazole,
Triethylene diamine.
The preparation method of the porous metal organic frameworks that the present invention is provided, the metal ion is preferably selected from CuII、
AlIII、FeIII、NiII、CoII、ZnII.Particularly preferred metal ion is selected from CuII、AlIII、CoII、ZnII。
The preparation method of the porous metal organic frameworks that the present invention is provided, the metallic compound is metal ion pair
One kind or many in nitrate, sulfate, chloride, acetate, oxalates, hydroxide, carbonate, the subcarbonate answered
Plant combination.
The preparation method of the porous metal organic frameworks that the present invention is provided, the solvent is water, methyl alcohol, ethanol, second
One or more mixing in glycol, DMF.Particularly preferred solvent is selected from a kind of or many in water, methyl alcohol, ethanol
The mixing planted.Especially particularly preferred solvent is water.
The preparation method of the porous metal organic frameworks that the present invention is provided, the sustained release alkali is urea, hexa-methylene
One kind or its mixture in tetramine, preferably urea.
Metal ion of the present invention and the design basis of organic ligand use ratio be metal total electrical charge number with it is organic
The total gear ratio of part is 1, it is contemplated that actual water（Solvent）Thermal process, one of metallic compound or organic ligand raw material are excessively made
With.In porous metal organic frameworks synthesis of the present invention, the use ratio of the metallic compound and organic ligand
It is the ratio between metal total electrical charge number and the total number of teeth of organic ligand between 0.5~2；The metallic compound makes with organic ligand
It is that the ratio between metal total electrical charge number and the total number of teeth of organic ligand are preferably between 0.8~1.2 with ratio.
In porous metal organic frameworks synthesis of the present invention, the use ratio of the sustained release alkali and organic ligand
Be sustained release the ratio between alkali molal quantity and the total number of teeth of organic ligand between 0.1~10；Sustained release alkali molal quantity and the organic ligand
The ratio between total number of teeth is preferably between 0.2~2.One of feature of the invention is that the use of sustained release alkali is required, if do not examined
Consider production cost problem, be sustained the usage amount of alkali（Molal quantity）Can be more than 10 with the ratio between the total number of teeth of organic ligand.But, it is considered to
To real cost of production and subsequent wash problem, sustained release alkali usage amount should be as far as possible reduced.
The preparation method of the porous metal organic frameworks that the present invention is provided, the temperature is 40-180 DEG C, preferably
80-150℃。
In a kind of some embodiments of porous metal organic frameworks preparation method of the present invention, use
Reaction temperature is at 90 DEG C~150 DEG C.
The preparation method of the porous metal organic frameworks that the present invention is provided, the synthesis pressure is corresponding solution anti-
Saturated vapour pressure at a temperature of answering（Preferably normal pressure）.
Synthesis under normal pressure is carried out in synthesis under normal pressure container, such as glass round bottom flask, normal-pressure reaction kettle；Reaction under high pressure is in high pressure
Carried out in reactor, such as the autoclave with polytetrafluoroethyllining lining.
In some embodiments of involved porous metal organic frameworks preparation method of the invention, use
Reaction vessel is with the poly- four 150ml autoclaves for flying ethene liner.
Reaction temperature is the affecting parameters of most critical in metal-organic framework materials synthesis.It is exactly the characteristics of of the invention maximum
It is organic to meet different ligands and metal formation metal using the controllability that alkali deprotonation performance changes with reaction temperature is sustained
Growing environment required for skeleton.
The second largest feature of the present invention is exactly the sustained release alkali, both can water as solvent porous metal-organic framework material
It is used as deprotonation alkali in the synthesis of material, it is also possible in synthesis of the organic solvent as the porous metal organic frameworks of solvent
As deprotonation alkali.
A kind of method for preparing porous metal organic frameworks that the present invention is provided, in porous metals of the present invention
In some embodiments prepared by organic framework material, the reaction time of use is between 30 minutes to 48 hours.
The porous metal organic frameworks preparation method that the present invention is provided, the filter process can be using naturally heavy
Drop is separated, vacuum filtration, press filtration, or is centrifugally separating to obtain described porous metal organic frameworks.
In some embodiments of porous metal organic frameworks preparation method involved in the present invention, use point
It is vacuum filtration or centrifugation from the mode of precipitation solid.
The porous metal organic frameworks preparation method that the present invention is provided, the filter process is carried out with solvents upon solids
Washing.On the one hand solid washing needs to be removed unreacted organic ligand and slaine with solvent, on the other hand needs with molten
The solvent that the organic ligand and reaction that agent will be trapped in hole need is replaced away with " extraction mode ".Especially work as organic ligand
When the solvent needed with reaction is higher-boiling compound, the solvent as needed for reaction is DMF, DEF, during NMP, can use low boiling
Solvent cement out.Preferred extractant is water, methyl alcohol, ether, acetone.
The preparation method of the porous metal organic frameworks that the present invention is provided, the porous metals skeleton material after the washing
Material forms porous metal organic frameworks after generally going through dry, activation.
There is specific surface high according to the porous metal organic frameworks that method provided by the present invention synthesizes, often inhale
Attached water, air, organic matter etc. could be used for the separation of mixed gas, it is necessary to further activate.Typically, using supercritical CO2Put
Change or long-time high temperature high vacuum carrys out activated metal organic framework material.
The porous metal organic frameworks preparation method that the present invention is provided, involved metal-organic framework materials activation
Some embodiments in, activation process is carried out using vacuum.But, vacuum condition activates metal involved in the present invention to be had
Machine framework material is not required.Due to solvent for use and part in different porous MOFs material synthesis processes physical property not
Together, so the activation temperature used in the present invention is also different.The porous metal organic frameworks provided in the present invention are lived
During change, between 60-200 DEG C, between 0-1bar, soak time is generally situated between activation pressure the activation temperature of use
Between 2-72 hours.Some embodiments of the present invention, the activation temperature selection for being used is 100-160 DEG C, and soak time is pushed away
It is 2-8 hours to recommend, and is typically employed under the vacuum condition of 0.1-0.2bar to improve efficiency and activates.If additionally, metal has
Its washing caused by washing difficulty or cost factor of machine framework material is insufficient or incomplete, can be by improving activation temperature
Method improves performance of the adsorbent, and highest activation temperature can reach more than 300 DEG C.
The present invention provide porous metal organic frameworks preparation method, methods described be particularly well-suited to glass,
Porous metal-organic framework film is grown on any solid matrix such as ceramics, Carbon Materials, organic polymer, silica, silicon.
Present invention also offers porous metal organic frameworks prepared by a kind of methods described, the organic bone of the porous metals
Frame material contain at least one metal ion with it is at least one can be with the organic ligand of metallic ion coordination.
The preparation method of the porous metal organic frameworks that the present invention is provided, the porous metal organic frameworks,
It is more than 10m with the specific surface area determined by Langmuir methods2/g.Preferred specific surface area is more than 100m2/g.Compare excellent
The specific surface area of choosing is more than 500m2/ g, preferred specific surface area is more than 1000m2/g。
The preparation method of the porous metal organic frameworks that the present invention is provided, the porous metal organic frameworks bag
Apertures, especially micropore and（Or）Mesopore.According to IUPAC（IUPAC）The classification of device to hole, micropore
It is that there is the hole less than or equal to 2nm, mesopore is that have more than 2nm, the hole less than or equal to 50nm.
Had according to the porous metals prepared by a kind of method for preparing porous metal organic frameworks that the present invention is provided
Machine framework material, described porous metal organic frameworks are used for gas storage, gas and separate, used as catalyst, sensor
Or ion conductor, for light or magnetic application, the absorption point of natural gas, air, inert gas is particularly well-suited to as porous material
From with storage.
Porous metal-organic framework prepared by the present invention and/or prepared in accordance with the present invention and comprising at least one basis
Can be used in many ways on the formed body of porous metal-organic framework prepared by the present invention, such as sensor or ion are led
Body, for light or magnetic application.
Particularly preferably wherein using framework high-specific surface area application.The purifying or separation of such as gas or liquid,
Catalyst or catalyst carrier, and liquid or gas storage with release.
The metal-organic framework materials being prepared by the method for the present invention are particularly well-suited to gas separation.Especially as new
Efficient adsorbent, has good application effect, by CO in the field of purification of natural gas2/CH4, CH4/N2, CO2/N2/CH4's
Separate, carry out the decarburization and denitrogenation of natural gas.
The organic framework material being prepared by the method for the present invention is applied to catalyst or catalyst carrier.
The beneficial effects of the invention are as follows：The preparation method of the porous metal organic frameworks that the present invention is provided, using slow
Alkali is released as deprotonation alkali, its deprotonation property can be adjusted according to reaction temperature, so operating method of the present invention is simple, condition
Relatively mild, suitable large-scale industrial production, involved porous metal organic frameworks are applied to the absorption point of gas
From with storage.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Unless otherwise noted, all numerals for occurring in description of the invention and claims, should not be managed
It is absolute exact value to solve, numerical value those of ordinary skill in the art the is understood, mistake that known technology is allowed
In difference scope.The accurate numerical value occurred in description of the invention and claims should be understood that composition is of the invention
Section Example.
Term " A, B, C ... and combinations thereof " refers to the combination comprising following element：A, B, C ..., and it is wherein any 2 kinds
Or two or more is with the combination of arbitrary proportion.
Embodiment 1：Synthesis Zn- methylimidazole frameworks
By the ZnSO of 26g4·7H2O is dissolved in 150g water；16g urea and 15g2- methylimidazoles are dissolved in 50g water and 100g
In the mixed liquor of methyl alcohol；Then solution of zinc sulfate is mixed with 2-methylimidazole solution, stirring 20min after well mixed,
The autoclave of 500ml is transferred to, is reacted 5 hours under the conditions of 110 DEG C.Temperature fall, filters white precipitate, Ran Houyong
100ml water washings 2 times.Filter cake is dried 6 hours at 100 DEG C, then in 130 DEG C and vacuum（0.2 bar）Under the conditions of dry live
Change 8 hours, obtain 21g products；
N2Specific surface area is 1476m2/g（Langmuir methods determine）.
Embodiment 2：Synthesis Zn- methylimidazole frameworks
By 26g ZnSO4·7H2O, 20g urea are dissolved in 300g water with 15g2- methylimidazoles, under agitation, 100
DEG C backflow 7 hours.White precipitate is formed, then with 100ml water washings 1 time, 50ml water washings three times.By filter cake at 100 DEG C
Dry 6 hours, then in 130 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 12 hours, obtain 20.2g products；
N2Specific surface area is 876m2/g（Langmuir methods determine）.
Embodiment 3：Synthesis Zn- methylimidazole frameworks
By 27g ZnNO3·6H2O, is dissolved in 150g water；12g hexas and 15g2- methylimidazoles are dissolved in 50g
In the mixed liquor of water and 100g methyl alcohol；Then zinc nitrate solution is mixed with 2-methylimidazole solution, stirring 20min is until mixing
After uniform, the autoclave of 500ml is transferred to, is reacted 6 hours under the conditions of 120 DEG C.Temperature fall, filters white precipitate, so
Use 100ml water washings 2 times afterwards.Filter cake is dried 6 hours at 100 DEG C, then in 130 DEG C and vacuum（0.2 bar）Under the conditions of do
Dry activation 8 hours, obtains 22g products；
N2Specific surface area is 1346m2/g（Langmuir methods determine）.
Embodiment 4：Atmospheric synthesis Al- fumaric acid aluminium chassis
By the Al of 35g2(SO4)3·18H2O, 20g urea are dissolved in 12g fumaric acid and 100 DEG C, backflow are heated in 300g water
6 hours, form white precipitate.Filtering, then with 50ml water washings 5 times.Filter cake is dried 2 hours at 100 DEG C, Ran Hou
130 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 12 hours, obtain 15g products.
N2Specific surface area is 1176m2/g（Langmuir methods determine）.
Embodiment 5：High-pressure synthesis Al- fumaric acid aluminium chassis
By the Al of 35g2(SO4)3·18H2O, 12g hexa are dissolved in 300g water with 12g fumaric acid, are stirred
Then 30min is transferred to the autoclave of 500ml until well mixed, without stirring reaction 5 hours under the conditions of 130 DEG C, is formed
White precipitate.Temperature fall, filtering, then with 50ml water washings 5 times.Filter cake is dried 2 hours at 100 DEG C, then 130
DEG C and vacuum（0.2 bar）Under the conditions of dry activation 12 hours, obtain 15g products.
N2Specific surface area is 931m2/g（Langmuir methods determine）.
Embodiment 6：Synthesis Cu-2- methylimidazole frameworks
Weigh 9g copper acetates（Cu(CH3COO)2·H2O）, 8g2- methylimidazoles and 10g urea, be dissolved in 100ml methyl alcohol with
The mixed solution of 200ml water, 30min is until uniform for stirring, obtains mixed solution；Mixed solution is transferred to polytetrafluoroethyl-ne
Seal tight in the 500ml autoclaves of alkene liner, be placed in and 48h is reacted in 140 DEG C of baking oven, then Temperature fall.Centrifugation
The solid for obtaining；Methyl alcohol is used respectively（100ml）, water（100ml）Solid is washed successively；By solid at 110 DEG C dried overnight, so
Afterwards in 160 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 12 hours, obtain 11g.
N2Specific surface area is 183.2m2/g（Langmuir methods determine）.
Embodiment 7：Synthesis Cu-BTC frameworks
Weigh 11g nitrate trihydrates copper and 12g trimesic acids (H3BTC) it is dissolved in 240ml water-ethanols（Water:Ethanol=1:1 weight
Amount ratio）In, 3.5g urea is added, 30min is until uniform for stirring；It is transferred to 500ml autoclaves and is heated to 110 DEG C, instead
Answer 18h, Temperature fall, the solid being centrifugally separating to obtain；Ethanol 150ml washings solid 1 time.By solid in 80 DEG C of dryings, then
In 130 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 4 hours, obtain 12g solids.
N2Specific surface area is 2435m2/g（Langmuir methods determine）.
Embodiment 8：Synthesis Co-2- methylimidazole frameworks
By the Co (NO of 26g3)2·6H2O is dissolved in 150g water；16g urea and 15g2- methylimidazoles are dissolved in 150g methyl alcohol
In；Then cobalt nitrate solution is mixed with 2-methylimidazole solution, stirring 20min is transferred to the height of 500ml after well mixed
Pressure reactor, reacts 24 hours under the conditions of 120 DEG C.Temperature fall, filtering precipitation, then with 100ml water washings 2 times.Will filter
Cake is dried 6 hours at 100 DEG C, then in 160 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 8 hours, obtain 18.6g produce
Thing.
N2Specific surface area is 1986m2/g（Langmuir methods determine）.
Embodiment 9：Synthesis Co- imidazoles frameworks
By the Co (NO of 26g3)2·6H2O is dissolved in 150g water；16g urea and 13g imidazoles are dissolved in 100g methyl alcohol and 50g
In the mixed liquor of butanol；Then cobalt nitrate solution is mixed with imidazole solution, stirring 20min is transferred to after well mixed
The autoclave of 500ml, reacts 36 hours under the conditions of 140 DEG C.Temperature fall, filtering precipitation, then uses 100ml water washings
2 times.Filter cake is dried 6 hours at 100 DEG C, then in 130 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 8 hours, obtain
17g products.
N2Specific surface area is 113m2/g（Langmuir methods determine）.
Comparative example 10：Synthesis Zn-2- methylimidazoles framework-CN101830918A
The ZnO of 40.7g, the methylimidazole with 82.1g are added to 200ml methyl alcohol with the ammoniacal liquor composition of 50ml25%
In mixed liquor, it is stirred vigorously at room temperature in the flask of 500ml 24 hours.Filtering, filter cake washs three times, 120 with 100ml methyl alcohol
DEG C drying obtains product 110g.Then in 120 DEG C and vacuum（0.2 bar）Under the conditions of activate 6 hours
N2Specific surface area is 1076m2/g（Langmuir methods determine）.
Comparative example 11：Synthesis fumaric acid aluminium-BASF patents US2012/0082864Al
By the Al of 70g2(SO4)3·18H2O is heated to 60 DEG C in being dissolved in 300g water；25.32g NaOH and 24.47g is rich
Horse acid is heated to 60 DEG C in being dissolved in 362g water；Then fumaric acid and the solution of NaOH are pumped into aluminum sulfate under conditions of stirring molten
In liquid, the time is pumped into for 30 minutes, form white precipitate, then with 100ml water washings 1 time, 50ml water washings three times.By filter cake
Dried 12 hours at 100 DEG C, then in 130 DEG C and vacuum（0.2 bar）Under the conditions of dry activation 12 hours, obtain 30g products；
N2Specific surface area is 1076m2/g（Langmuir methods determine）.
Claims (7)
1. a kind of preparation method of porous metal organic frameworks, it is characterised in that：By the metal compound containing metal ion
The organic ligand of thing and metallic ion coordination, sustained release alkali, are sufficiently mixed in a solvent, under certain temperature and pressure, pass through
Ligand complex is acted on and is self-assembly of with supramolecular network structure compound, then by filtering, washing, dry, activation
After form porous metal organic frameworks；The temperature is 40-180 DEG C；The pressure be corresponding solution at the reaction temperatures
Saturated vapour pressure；
The metal ion is CuII、AlIII、MgII、MnII、FeIII、NiII、CoII、ZnIIIn one or more；
The organic ligand have at least one it is independent selected from fumaric acid, l,2,3 benzene tricarboxylic acid, 1,2,4 benzenetricarboxylic acid,
1,3,5- benzenetricarboxylic acids, imidazoles, 2-methylimidazole；And the organic ligand by they can ligand complex in the metal from
Son；
The sustained release alkali is one kind or its mixture in urea, hexa.
2. according to the preparation method of porous metal organic frameworks described in claim 1, it is characterised in that：The metal ion
It is CuII、AlIII、FeIII、NiII、CoII、ZnIIIn one or more.
3. according to the preparation method of porous metal organic frameworks described in claim 1, it is characterised in that：The metal compound
Thing is the corresponding nitrate of metal ion, sulfate, chloride, acetate, oxalates, hydroxide, carbonate, basic carbonate
One or more combination in salt.
4. according to the preparation method of porous metal organic frameworks described in claim 1, it is characterised in that：The solvent is
One or more mixing in water, methyl alcohol, ethanol, ethylene glycol, DMF.
5. according to the preparation method of porous metal organic frameworks described in claim 1, it is characterised in that：Sustained release alkali with it is organic
The use ratio of part is sustained release the ratio between alkali molal quantity and the total number of teeth of organic ligand between 0.1~10.
6. the porous metal organic frameworks that prepared by a kind of claim 1 methods described, it is characterised in that：The porous metals have
Machine framework material contain at least one metal ion with it is at least one can be with the organic ligand of metallic ion coordination.
7. the application of porous metal organic frameworks described in claim 6, it is characterised in that：The porous metal-organic framework material
Expect as catalyst, sensor or ion conductor, for light or magnetic application；As porous material, it is adaptable to air, inert gas
Adsorbing separation with storage.
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