CN105622640B - A kind of preparation method of metal-organic framework materials - Google Patents
A kind of preparation method of metal-organic framework materials Download PDFInfo
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- CN105622640B CN105622640B CN201410585339.2A CN201410585339A CN105622640B CN 105622640 B CN105622640 B CN 105622640B CN 201410585339 A CN201410585339 A CN 201410585339A CN 105622640 B CN105622640 B CN 105622640B
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Abstract
The invention discloses a kind of preparation methods of metal-organic framework materials, including：（1）Stirring and dissolving in organic solvent, obtained solution A is added in metal precursor；（2）Stirring and dissolving in organic solvent, obtained solution B is added in organic ligand；（3）Solution A and B are respectively fed to in-situ preparation MOFs crystal seeds in micro passage reaction module I according to certain flow rate, product feed liquid is sent into micro passage reaction module ii by reaction after a certain period of time；（4）When above-mentioned product feed liquid enters in module ii, solution B is sent into according to certain flow rate in module ii and carries out crystal seed induction synthesis MOFs materials；（5）MOFs suspensions obtained are separated by solid-liquid separation, solid is washed with ethyl alcohol, and product is made after dry.The present invention uses Dual module micro passage reaction, the in-situ preparation MOFs crystal seeds in module I to carry out the continuous preparation MOFs materials of crystal seed induction in module ii, have many advantages, such as simple and quick preparation process, product cut size narrowly distributing, good dispersion.
Description
Technical field
The present invention relates to the preparation methods of metal-organic framework materials, and in particular to a kind of to be prepared using micro passage reaction
The method of metal-organic framework materials.
Background technology
Metal-organic framework materials（MOFs）, also known as metal coordinating polymer, refer to inorganic metal or metal cluster with contain
The crystalline material formed by the multiple tooth organic ligand of nitrogen oxygen is keyed by being coordinated is a kind of with high-specific surface area, adjustable variable orifice
Road size, the porous material of organic functional.Metal-organic framework materials have following excellent compared with conventional porous material
Gesture：（1）Regulate and control organic ligand length, size, effectively controls material texture performance（Specific surface area, aperture）；（2）Internal gutter body
System is flourishing, no dead volume；（3）Duct or skeleton surface metal ion content are high, and availability is high.Currently used preparation method
Including the methods of hydro-thermal method, solvent-thermal method, circumfluence method, microwave method, sonic method, electrochemical process.
CN201210050548.8 discloses a kind of preparation method of nano level metal organic framework material, including metal
Salt, organic ligand in a solvent, react metal-organic framework materials are made in the presence of a base, can be made with different-shape
Nanoscale/Subnano-class metal-organic framework materials.
CN201210252943.4 discloses a kind of system of the metal-organic framework materials of adsorbing separation carbon dioxide/methane
Preparation Method includes the following steps：（1）By the equal benzene three of the copper nitrate aqueous solution of 0.46 ~ 1.16mol/L and 0.23 ~ 0.58mol/L
Formic acid ethanol solution mixes, and is added in the stainless steel cauldron with polytetrafluoroethyllining lining and seals after being sufficiently stirred, controlling crystallizing
Temperature is 60 ~ 150 DEG C and crystallization time is to carry out solvent thermal reaction in 12 ~ 24 hours；（2）Stainless steel cauldron is opened, through filtering,
And washed successively with methanol and deionized water, it is dried to obtain blue colored crystal at 80 ~ 105 DEG C；（3）The blue colored crystal is existed
Vacuumize process obtains copper-containing metal organic framework material at 150 ~ 200 DEG C.
CN200780035704.0 discloses a kind of preparation method of the metal-organic framework materials containing copper, by copper sulphate
Methanol solution is added to the N containing terephthalic acid (TPA), in N'- dimethylformamide suspensions, is stirred under certain temperature, obtains blue
Color precipitates.Again by the methanol solution blending and stirring 16h of blue precipitate and triethylenediamine, precipitation repeatedly washed by methanol
It washs, copper-containing metal organic framework material is obtained after vacuum drying.
The above-mentioned method for preparing metal-organic framework materials is intermittent reaction synthetic method, there is reaction in preparation process
The shortcomings of time is long, product yield is low, properties of product are unstable is unfavorable for the amplification production of product large-scale industrial.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide a kind of preparation of metal-organic framework materials
Method.The present invention uses Dual module micro passage reaction, the in-situ preparation MOFs crystal seeds in micro passage reaction module I, in mould
The continuous preparation MOFs materials of crystal seed induction are carried out in block II, and there is simple and quick preparation process, product cut size narrowly distributing, dispersibility
The advantages that good.
The preparation method of metal-organic framework materials of the present invention, includes the following steps：
（1）Stirring and dissolving in organic solvent, obtained solution A is added in metal precursor；
（2）Stirring and dissolving in organic solvent, obtained solution B is added in organic ligand；
（3）Solution A and B are respectively fed to in-situ preparation MOFs crystalline substances in micro passage reaction module I according to certain flow velocity
Kind, the product feed liquid containing MOFs crystal seeds is sent into micro passage reaction module ii by reaction after a certain period of time；
（4）When above-mentioned product feed liquid enters in micro passage reaction module ii, solution B is sent into according to certain flow velocity
Crystal seed induction synthesis MOFs materials are carried out in micro passage reaction module ii；
（5）By step（4）MOFs suspensions obtained are separated by solid-liquid separation, and solid is washed with ethyl alcohol, at 80~120 DEG C
Dry 8~for 24 hours.
Step of the present invention（1）The metal precursor is the sulfuric acid of copper, iron, zirconium, zinc, magnesium, aluminium, cobalt, chromium, nickel, calcium, titanium
One or more of salt, nitrate, acetate, carbonate, halide salt or its hydrate, preferably zinc nitrate, zinc sulfate, nitre
Sour copper, copper sulphate, magnesium sulfate, more preferably copper nitrate.Step（1）The organic solvent is water, methanol, ethyl alcohol, isopropanol, second
Glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N- diethylformamides, N, in N- diethyl acetamides
One or more, preferably water, methanol, ethyl alcohol, more preferably ethyl alcohol.A concentration of 0.01- of metal precursor in the solution A
5.0mol/L, preferably 0.1-1.0mol/L.
Step of the present invention（2）The organic ligand is multiple tooth organic compound, preferably bidentate, three tooth Carboxylic acid ligand chemical combination
Object and its derivative, including terephthalic acid (TPA), M-phthalic acid, trimesic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids,
2,6- naphthalene dicarboxylic acids etc., preferably trimesic acid；Derivative refers to one or more carboxylic-acid functionals in Carboxylic acid ligand compound
Group is replaced by functional groups such as nitryl group, hydroxyl group, methyl group, cyano groups.Step（2）The organic solvent is first
Alcohol, ethyl alcohol, isopropanol, ethylene glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N- diethylformamides, N, N-
One or more of diethyl acetamide, preferably methanol, ethyl alcohol, isopropanol, more preferably ethyl alcohol.Have in the solution B
A concentration of 0.01-10mol/L of machine ligand, preferably 0.1-2.0mol/L.
Step of the present invention（3）The flow velocity of the solution A is 0.1-2000 μ l/min, preferably 5-200 μ l/min；Solution B
Flow velocity be 0.1-2000 μ l/min, preferably 5-200 μ l/min.After solution A and B enter micro passage reaction module I, reaction
Temperature is 30-80 DEG C, and preferably 40-70 DEG C, reaction pressure 0.1-2.0MPa, preferably 0.1-1.0MPa, the reaction time is
1-600s, preferably 30-180s.
Step of the present invention（4）The flow velocity of the solution B is 0.1-2000 μ l/min, preferably 5-200 μ l/min.Contain
The flow velocity that the feed liquid of MOFs crystal seeds is sent into micro passage reaction module ii is 0.2-2000 μ l/min, preferably 10-400 μ l/
min.Step（4）The reaction temperature of crystal seed induction synthesis MOFs materials is 50-200 DEG C, preferably 80-150 DEG C, reaction pressure
Power is 0.1-2.0MPa, preferably 0.1-1.0MPa, reaction time 1-600s, preferably 60-200s.
Step of the present invention（3）And step（4）The middle acid or the pH value of alkali adjusting reaction system of being added into solution B is 2-7, excellent
It is selected as 4-5.The acid can be hydrochloric acid, acetic acid, citric acid etc.；The alkali can be sodium hydroxide, potassium hydroxide, second two
Amine, triethylamine etc..
Micro passage reaction module I of the present invention, module ii are cascade, can be with according to needs of production
In parallel several module Is, module ii tandem reactor.Micro passage reaction of the present invention may be used commercially available or homemade
Micro passage reaction.The material of reactor is special glass, ceramics, polytetrafluoroethylene (PTFE), stainless steel or alloy etc., and structure is the heart
The shape that type, diamond shape, rectangle etc. can be mixed with intensified response object, reactor inside diameter are 10-2000 microns.The microchannel plate
It includes at least two feed inlets and a discharge port to answer device module, can be required to change feed inlet quantity and position according to reaction.
Compared with prior art, the method for the present invention has following outstanding advantages：
（1）The reactor that micro passage reaction is made of multiple microchannel modules, the spy with high mass transfer, high heat transfer
Point is used to prepare Organometallic framework material, can not only obtain the high nanometer of narrow particle diameter distribution, good dispersion, specific surface area
Grade MOFs materials, and can significantly shorten the reaction time to tens seconds to a few minutes, substantially increase reaction efficiency and production
Efficiency.Compared with the preparation method of similar product, have preparation process simple, period short feature, more suitable for industrialization batch
Amount production；
（2）Using Dual module micro passage reaction, the in-situ preparation MOFs crystal seeds first in micro passage reaction module I,
Then the continuous preparation MOFs materials of crystal seed induction are carried out in micro passage reaction module ii, do not need plus seed, and make
Standby MOFs properties of product are more preferable；
（3）The pH value for adjusting reaction system in MOFs crystal seeds and crystal seed Induction Process is generated in situ between 2-7, is kept
The pH value of the reaction solution of synthesis contributes to the generation and growth of MOFs crystal in MOFs crystal seeds, module ii in module I.
Description of the drawings
Fig. 1 is the structural schematic diagram for the Dual module micro passage reaction that the method for the present invention uses；
Wherein 1,2 be the feed inlet of module I, and 3 be the discharge port of module I, and 4,5 be the feed inlet of module ii, and 6 be module ii
Discharge port.
Fig. 2 is the XRD diagram of the method for the present invention embodiment 1-4,6-7 and comparative example 1-3 synthetic samples.
Fig. 3 is the SEM figures of 3 synthetic sample of the method for the present invention embodiment.
Specific implementation mode
With reference to embodiment and comparative example, the present invention is further illustrated, but the protection domain of this patent not by
The limitation of embodiment.Reagent and material described in following embodiments and comparative example commercially obtain unless otherwise specified
.
Used in the embodiment of the present invention is Dual module micro passage reaction, as shown in Fig. 1.Detailed process is will be before metal
Drive body, which is dissolved in organic solvent, forms solution A, and organic ligand is dissolved in organic solvent and forms solution B, the two is according to one
Fixed flow velocity enters hybrid reaction in module I by feed inlet 1,2, and the material containing MOFs crystal seeds is formed under certain temperature, pressure
Then liquid flows out from discharge port 3 and enters in micro passage reaction module ii from feed inlet 4 according to certain flow velocity, with feed inlet 5
The B solution hybrid reaction of entrance generates MOFs materials under certain temperature, pressure, is finally discharged from the discharge port of module ii 6.
The embodiment of the present invention adopts used micro passage reaction and is commercially available micro passage reaction, and the material of reactor is stainless
Steel, structure are cardioid, and reactor inside diameter is 10-2000 microns.
The conveying equipment of reaction solution described in the embodiment of the present invention is high pressure pump, using III types of 305SFM01, pressure
Range 0-6000psi, flow control accuracy 0.2%, flow rates 0.001-5ml/min.
Embodiment 1
12.1g Gerhardites are dissolved in formation A liquid in 500ml ethyl alcohol, 10.5g trimesic acids are dissolved in
B liquid is formed in 500ml ethyl alcohol.The flow velocity of A liquid is 5 μ l/min, is sent into module I by feed inlet 1, while the flow velocity of B liquid is 5 μ
L/min, by 2 injection module I of feed inlet, wherein the temperature of module I is 40 DEG C, and pressure 0.1MPa, A liquid is with B liquid in module I
In uniformly mixing generate the feed liquid containing Cu-MOFs crystal seeds, the residence time is 180s.Feed liquid containing Cu-MOFs crystal seeds by into
Material mouth 4 be sent into micro passage reaction module ii, flow velocity be 10 μ l/min, by remaining B liquid with flow velocity be 5 μ l/min by feeding
Mouthfuls 5 are sent into micro passage reaction module iis, and wherein the temperature of module ii is 80 DEG C, pressure 0.1Mpa, and the residence time is
200s collects product Cu-MOFs suspensions, is centrifuged after reaction, and solid is washed with ethyl alcohol, dry at 100 DEG C
24h.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 8.6 μm, and specific surface area is
1812m2/g。
Embodiment 2
121g Gerhardites are dissolved in formation A liquid in 500ml ethyl alcohol, 210g trimesic acids are dissolved in
B liquid is formed in 500ml ethyl alcohol.The flow velocity of A liquid is 200 μ l/min, is sent into module I by feed inlet 1, while the flow velocity of B liquid is
200 μ l/min, by 2 injection module I of feed inlet, wherein the temperature of module I is 70 DEG C, and pressure 1.0MPa, A liquid exists with B liquid
Uniformly mixing generates the feed liquid containing Cu-MOFs crystal seeds in module I, and the residence time is 30s.Feed liquid containing Cu-MOFs crystal seeds
Micro passage reaction module ii is sent by feed inlet 4, flow velocity is 400 μ l/min, by remaining B liquid with flow velocity for 200 μ l/
Min is sent by feed inlet 5 in micro passage reaction module ii, and wherein the temperature of module ii is 150 DEG C, pressure 1MPa, is stopped
Time is 60s, after reaction, collects product Cu-MOFs suspensions, is centrifuged, solid is washed with ethyl alcohol, at 100 DEG C
Drying is for 24 hours.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 7.3 μm, and specific surface area is
1865m2/g。
Embodiment 3
60.5g Gerhardites are dissolved in formation A liquid in 500ml ethyl alcohol, 105g trimesic acids are dissolved in
B liquid is formed in 500ml ethyl alcohol.The flow velocity of A liquid is 100 μ l/min, is sent into module I by feed inlet 1, while the flow velocity of B liquid is
100 μ l/min, by 2 injection module I of feed inlet, wherein the temperature of module I is 60 DEG C, and pressure 0.5MPa, A liquid exists with B liquid
Uniformly mixing generates the feed liquid containing Cu-MOFs crystal seeds in module I, and the residence time is 120s.Feed liquid containing Cu-MOFs crystal seeds
Micro passage reaction module ii is sent by feed inlet 4, flow velocity is 200 μ l/min, by remaining B liquid with flow velocity for 100 μ l/
Min is sent by feed inlet 5 in micro passage reaction module ii, and wherein the temperature of module ii is 120 DEG C, and pressure 1.0MPa stops
It is 150s to stay the time, after reaction, collects product Cu-MOFs suspensions, is centrifuged, solid is washed with ethyl alcohol, at 100 DEG C
Lower drying is for 24 hours.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 5.2 μm, specific surface area
For 1948m2/g。
Embodiment 4
It is molten that 62.5g Salzburg vitriols are dissolved in formation A liquid, 2, the 6- naphthalene dicarboxylic acids of 108g in 500ml deionized waters
Solution forms B liquid in 500ml methanol.The flow velocity of A liquid is 100 μ l/min, is sent into module I by feed inlet 1, while the stream of B liquid
Speed is 100 μ l/min, by 2 injection module I of feed inlet, wherein the temperature of module I is 60 DEG C, pressure 0.5MPa, A liquid and B
Uniformly mixing generates the feed liquid containing Cu-MOFs crystal seeds to liquid in module I, and the residence time is 120s.Contain Cu-MOFs crystal seeds
Feed liquid is sent into micro passage reaction module ii by feed inlet 4, and flow velocity is 200 μ l/min, by remaining B liquid with flow velocity for 100 μ
L/min is sent by feed inlet 5 in micro passage reaction module ii, and wherein the temperature of module ii is 120 DEG C, pressure 1.0MPa,
Residence time is 150s, after reaction, collects product Cu-MOFs suspensions, is centrifuged, solid is washed with ethyl alcohol, 100
It is dried for 24 hours at DEG C.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 7 μm, specific surface area
For 1754m2/g。
Embodiment 5
74.5g zinc nitrates are dissolved in formation A liquid, 83.1g terephthalic acid (TPA)s in 500ml methanol and are dissolved in 500ml isopropyls
B liquid is formed in alcohol.The flow velocity of A liquid is 100 μ l/min, is sent into module I by feed inlet 1, while the flow velocity of B liquid is 100 μ l/
Min, by 2 injection module I of feed inlet, wherein the temperature of module I is 60 DEG C, and pressure 0.5MPa, A liquid is with B liquid in module I
Uniformly mixing generates the feed liquid containing Zn-MOFs crystal seeds, and the residence time is 120s.Feed liquid containing Zn-MOFs crystal seeds is by feeding
Mouthfuls 4 are sent into micro passage reaction module iis, and flow velocity is 200 μ l/min, by remaining B liquid with flow velocity be 100 μ l/min by into
Material mouth 5 is sent into micro passage reaction module ii, and wherein the temperature of module ii is 120 DEG C, pressure 1.0MPa, and the residence time is
150s collects product Zn-MOFs suspensions, is centrifuged after reaction, and solid is washed with ethyl alcohol, dry at 100 DEG C
24h.Show that the sample is Zn-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 9 μm, and specific surface area is
1590m2/g。
Embodiment 6
Process flow and operating condition are same as Example 1, the difference is that：Hydrochloric acid is added into solution B to adjust instead
It is 4 to answer the pH value of system.After reaction, Cu-MOFs suspensions are collected, are centrifuged, solid is washed with ethyl alcohol, at 100 DEG C
Lower drying is for 24 hours.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 7.5 μm, specific surface area
For 1870m2/g。
Embodiment 7
Process flow and operating condition are same as Example 2, the difference is that：Acetic acid is added into solution B to adjust instead
It is 5 to answer the pH value of system.After reaction, Cu-MOFs suspensions are collected, are centrifuged, solid is washed with ethyl alcohol, at 100 DEG C
Lower drying is for 24 hours.Show that the sample is Cu-MOFs materials through XRD characterization, the product average grain diameter of acquisition is 6.8 μm, specific surface area
For 1905m2/g。
Comparative example 1
Process flow and operating condition are same as Example 3, the difference is that：It is answered using an individual microchannel plate
Device module, reaction temperature are 90 DEG C, pressure 0.5MPa, residence time 270s.After reaction, collect product, carry out from
The heart, solid are washed with ethyl alcohol, and for 24 hours, the product average grain diameter of acquisition is 7.8 μm, and specific surface area is for drying at 100 DEG C
1180m2/g。
Comparative example 2
Process flow and operating condition are same as Example 3, the difference is that：Micro passage reaction module I and module
Reaction condition in II is identical, and reaction temperature is 60 DEG C, pressure 0.5MPa.After reaction, collect product, carry out from
The heart, solid are washed with ethyl alcohol, and for 24 hours, the product average grain diameter of acquisition is 45nm, specific surface area 526m for drying at 100 DEG C2/
g。
Comparative example 3
Process flow and operating condition are same as Example 3, the difference is that：Micro passage reaction module I and module
Reaction condition in II is identical, and reaction temperature is 120 DEG C, pressure 1.0MPa.After reaction, collect product, carry out from
The heart, solid are washed with ethyl alcohol, and for 24 hours, the product average grain diameter of acquisition is 8.5 μm, and specific surface area is for drying at 100 DEG C
1215m2/g。
Claims (11)
1. a kind of preparation method of metal-organic framework materials, it is characterised in that include the following steps：
（1）Stirring and dissolving in organic solvent or/and water, obtained solution A is added in metal precursor；
（2）Stirring and dissolving in organic solvent, obtained solution B is added in organic ligand；The organic ligand is bidentate, three tooth carboxylic acids
Ligand compound and its derivative, Carboxylic acid ligand compound are terephthalic acid (TPA), M-phthalic acid, trimesic acid, Isosorbide-5-Nitrae-naphthalene
Dicarboxylic acids, 1,5- naphthalene dicarboxylic acids or 2,6- naphthalene dicarboxylic acids, derivative refer to one or more carboxylic acid officials in Carboxylic acid ligand compound
It can roll into a ball and be replaced by nitryl group, hydroxyl group, methyl group, cyano group functional group；
（3）Solution A and B are respectively fed to in-situ preparation MOFs crystal seeds in micro passage reaction module I according to certain flow velocity, instead
It is 30-70 DEG C, reaction pressure 0.1-2.0MPa to answer temperature, and reaction after a certain period of time send the product feed liquid containing MOFs crystal seeds
Enter in micro passage reaction module ii；
（4）When above-mentioned product feed liquid enters in micro passage reaction module ii, solution B is sent into micro- lead to according to certain flow velocity
Crystal seed induction synthesis MOFs materials are carried out in road reactor module II, reaction temperature is 80-200 DEG C, reaction pressure 0.1-
2.0MPa；
（5）By step（4）MOFs suspensions obtained are separated by solid-liquid separation, and solid is washed with ethyl alcohol, dry at 80~120 DEG C
8~for 24 hours.
2. according to the method described in claim 1, it is characterized in that：Step（1）The metal precursor be copper, iron, zirconium, zinc,
Magnesium, aluminium, cobalt, chromium, nickel, calcium, the sulfate of titanium, nitrate, acetate, carbonate, halide salt or one kind in its hydrate or
It is several；Organic solvent is methanol, ethyl alcohol, isopropanol, ethylene glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N-
Diethylformamide, N, one or more of N- diethyl acetamides；A concentration of 0.01- of metal precursor in solution A
5.0mol/L。
3. according to the method described in claim 2, it is characterized in that：The metal precursor is zinc nitrate, zinc sulfate, nitric acid
Copper, copper sulphate or magnesium sulfate, organic solvent are methanol or ethyl alcohol；A concentration of 0.1-1.0mol/L of metal precursor in solution A.
4. according to the method described in claim 1, it is characterized in that：Step（2）The organic solvent is methanol, ethyl alcohol, isopropyl
Alcohol, ethylene glycol, isobutanol, glycerine, N,N-dimethylformamide, N, N- diethylformamides, N, N- diethyl acetamides
One or more of；A concentration of 0.01-10mol/L of organic ligand in solution B.
5. method according to claim 1 or 4, it is characterised in that：The organic ligand is trimesic acid, organic solvent
For methanol, ethyl alcohol or isopropanol；A concentration of 0.1-2.0mol/L of organic ligand in solution B.
6. according to the method described in claim 1, it is characterized in that：Step（3）The flow velocity of the solution A is 0.1-2000 μ l/
The flow velocity of min, solution B are 0.1-2000 μ l/min；After solution A and B enter micro passage reaction module I, reaction time 1-
600s。
7. according to the method described in claim 6, it is characterized in that：The flow velocity of the solution A is 5-200 μ l/min, solution B
Flow velocity is 5-200 μ l/min；After solution A and B enter micro passage reaction module I, reaction temperature is 40-70 DEG C, reaction pressure
For 0.1-1.0MPa, reaction time 30-180s.
8. according to the method described in claim 1, it is characterized in that：Step（4）The flow velocity of the solution B is 0.1-2000 μ l/
Min, the flow velocity that product feed liquid is sent into micro passage reaction module ii are 0.2-2000 μ l/min, crystal seed induction synthesis MOFs materials
Reaction time be 1-600s.
9. according to the method described in claim 8, it is characterized in that：The flow velocity of the solution B is 5-200 μ l/min, product material
The flow velocity that liquid is sent into micro passage reaction module ii is 10-400 μ l/min, and the reaction temperature of crystal seed induction synthesis MOFs materials is
80-150 DEG C, reaction pressure 0.1-1.0MPa, reaction time 60-200s.
10. according to the method described in claim 1, it is characterized in that：Step（3）And step（4）It is middle into solution B be added acid or
The pH value that alkali adjusts reaction system is 2-7.
11. according to the method described in claim 1, it is characterized in that：The micro passage reaction is commercially available microchannel plate
Device or homemade micro passage reaction are answered, the material of reactor is special glass, ceramics, polytetrafluoroethylene (PTFE), stainless steel or conjunction
Gold, structure are cardioid, diamond shape or rectangle, and reactor inside diameter is 10-2000 microns.
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