CN101693168B - Method for preparing metal organic framework film - Google Patents
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- CN101693168B CN101693168B CN 200910187939 CN200910187939A CN101693168B CN 101693168 B CN101693168 B CN 101693168B CN 200910187939 CN200910187939 CN 200910187939 CN 200910187939 A CN200910187939 A CN 200910187939A CN 101693168 B CN101693168 B CN 101693168B
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Abstract
The invention belongs to the technical field of new material, and relates to a method for preparing a novel metal organic framework (MOFs) film and the potential application prospect thereof, in particular to the MOFs film which is continuous, compact, firm and crackles and is prepared on the surface of a porous carrier by a back diffusion method. The invention is characterized in that metal precursor of a synthetic membrane and organic ligand nutrient solution are respectively supplied from the two sides of a carrier tube (as shown); the diffusion of metal precursor nutrient solution is promoted to facilitate metal organic framework compound to crystallize and grow on the surface of the carrier; and finally, the MOFs separating film which is continuous, compact, firm and crackles and has selective permeability for molecular mixture is obtained. The invention has the effect and advantage of solving the difficulty that the binding force between metal framework organic matter and the carrier is weak, so that the continuous and compact film is hardly formed; furthermore, the invention provides the method which is used for preparing the MOFs film as well as simple in operation and easy in control, thus initiating the precedent of preparing the MOFs film with high performance on the tubular carrier.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of method, and be applied to the separation of gas at fine and close continuous crackless metallic organic framework (MOFs) film of tubular support surface preparation.Be particularly related to the synthetic metal organic framework film of inverse diffusion method and to the molecule mixture separating application.
Background technology
Membrane science technology outstanding feature is energy-conservation, and cleaning is efficient, and is compatible strong, is suitable for modern industry to energy-conservation, and raw material utilize and eliminate the needs of environmental pollution again, become the important component part that realizes the sustainable economic development strategy.Inorganic microporous barrier since its good heat, chemical stability and its potential carry out the molecule sieve performance of high separation in the molecule rank; Can be widely used in the medium and high temperature catalytic reaction of petrochemical industry critical operation environment; The separation of biogenetic products, the separation of organic chemical industry's product and the recycling of resource, the fine finishining of beverage and drinking water is handled; Aspects such as electronics industry have become the forward position and the focus of current international scientific research.Before the mid-90 in 20th century, inorganic microporous membrane material is mainly zeolite molecular sieve, molecular sieve carbon sill.And in recent years, (metal-organic frameworks MOFs) is different from preceding two types of materials to transition metal ions and the organic ligand micropore metal organic coordination polymer that self assembly forms through complexing, becomes the 3rd polyporous materials.Compare with preceding two types of materials, this type inorganic-organic hybridization composite polymeric materials has the characteristic of organic and inorganic material concurrently, and (Nature 2003,423; 705), structure is various, excellent performance; As functional material at selectivity catalysis, gas absorption, photoelectric material; Field such as magnetic material and chip development has shown charming application prospect (Microporous and Mesoporous Materials 2004; 7,3), become the research field of the most active forefront in of chemistry after the nineties with the material subject territory.
The duct that the MOFs material not only has special topological structure, internal arrangement rule and has specific dimensions and shape; And its duct has controllability; Can regulate and control the structure and the size in the hole of MOFs through the organic ligand of the stereochemical structure selecting to suit and size; The surface characteristic in duct can be modified through introducing functional group, and these excellent characteristics of MOFs material make MOFs become potential of new generation outstanding membrane material, are separating like H
2/ CH
4, O
2/ N
2, CO
2/ CH
4Has potential using value separate and chiral catalysis separation etc.
At present, the MOFs material has obtained flourish in the research of gas absorption and catalytic field, has obtained the progress of leap, but MOFs becomes the research of membranization just at the early-stage, only several pieces of relevant bibliographical informations.Up to the present the whole world has only several groups of research units to the film forming research of MOFs on chip carrier, and (J.Am.Chem.Soc 2005,127 to have prepared the MOF-5 film respectively; 13744); Cu-BTC film (Microporous Mesoporous Mater 2008,113,132) and Mn (HCO
2)
2Film (Eur.J.Inorg.Chem 2007,60), but have only a research institute to prepare continuous densification, micro-molecular gas is had the MOFs film of certain separating property.Research shows, zero defect, and synthetic and its application of fine and close continuously MOFs film is a brand-new field, the development and application of MOFs film will be the new growth point of MOFs and inoranic membrane subject, need carry out a large amount of deep research.
According to literature research MOFs material film forming on chip carrier all is to need earlier carrier to be carried out preliminary treatment to modify, and film forming procedure is complicated, and the film of preparing is continuous inadequately.Compare with chip carrier, reasons such as unfavorable are adhered in its surface to film in the field of force that this geometric features of tubulose is brought, and make that synthetic high-quality firm film has more challenge on tubular support surfaces.But the carrier of relative sheet, the surface area of tubulose is big, is prone to be assembled into assembly, has higher industrial use value, does not also see bibliographical information about the MOFs material so far in the tubulose film forming.
Summary of the invention
The technical problem that the present invention will solve is the technical barrier that is difficult for film forming a little less than the nonmetallic materials carrier adhesions such as this material of metallic organic framework and pottery; Provide a kind of simple; Easy operating; The MOFs material load on tubular carrier, prepared the synthetic method of the crackless MOFs film of continuous densification, started at tubular carrier and successfully prepared continuous densification; Micro-molecular gas is had the precedent of the MOFs film of separation function, stepped major step for the MOFs material is applied to the film engineering.
The technical scheme of a kind of MOFs of preparation film provided by the invention comprises:
1) preliminary treatment of carrier.Carrier surface is used 800# and 1200# sand papering outer surface successively; Smooth until carrier surface, respectively soak 24h with soda acid, use residual alkali in the ultrasonic oscillation flush away hole then; Be washed till neutral back with deionized water again and dry naturally, at last dry for standby under the 423K temperature.
2) configuration of casting film solution.With quantitative slaine presoma and organic ligand (organic bridging agent) soluble in water respectively with organic solvent in, be mixed with film forming solution A and B respectively.The slaine presoma comprises Fe
2+, Cu
2+, Zn
2+, Mn
2+, Mg
2+, Al
3+, Cr
3+, Co
2+Etc. various slaines; Organic ligand (organic bridging agent) comprises 1; 3-benzene-dicarboxylic acid (m-BDC), 1; 4-benzene-dicarboxylic acid (p-BDC), triethylamine (TMA), Bromothymol Blue (BTB), 6 '-methoxyl-(8S, 9R)-cinchonan-9-ol-3-carboxylic acid (HQA), formic acid (HCOOH), pyridine (Py), trimesic acid (H
3BTC), four-(4 '-carboxyl benzene) methane (TCPM), fumaric acid (FURM), 2,2 '-bipyridine (2,2 '-bipy), 1,10-Phenanthroline (Phen), piperazine (PRZ), pyridine-2,5-dicarboxylic acids (H
2PDC), 1, the 4-cyclohexane diacid (1,4-chdc), o-phenanthroline (phne), pyridine-1,3,5-tricarboxylic acids (H
3PTC),, 4,4 ', 4 " three carboxyl triphenylamine (H
3(TCA)), 1,4,8; 11-tetraazacyclododecane tetradecane (cyclam), 2,2 '-bipyridyl-5,5 '-dioctyl phthalate (bpyde), sophthalate (ip), imidazole (Him), hexamethylenetetramine (hmt), 4; 4 '; 4 " s-triazine-2,4,6-triyltribenzoic acid (H
3TATB), triphenylene-2,6,10-tricarboxylic acid (H
34,4 TTCA), '-bipyridine (bpy), 1; 4-diazabicyclo [2.2.2] octane (dabco), 4,4 '-biphenyldicarboxylic acid (bpdc) 1,2; 4,5-tetrakis (4-carboxyphenyl)-benzene (TCPB), meso-1,2-bis (4-pyridyl)-1; 2-ethanediol (DPG), naphthalene-2,6-dicarboxylate various organic matters such as (NDC).The MOFs material of being made up of these golden precursors and organic ligand specifically comprises MOF-5, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-10, IRMOF-12, IRMOF-14, IRMOF-16, IRMOF-9, IRMOF-11, IRMOF-13, IRMOF-15, Cu
3(BTC)
2, ZIF-2, ZIF-4, ZIF-10, ZIF-64.Metallic framework compound (the A that the mol ratio of metal ion/organic ligand is greater than or equals to form
xB
y) value of X/Y, be no more than 15: 1.The kind of metallic organic framework compound according to document (Science.2002,295:469-72., Accounts of Chemical Research.1998,, Nature.1999,402:276-9) confirm.
3) dress still.The pretreated carrier of learning from else's experience with the sealing of polytetrafluoroethylene (PTFE) end socket, is poured A solution the tubulose bottom into pipe in; Then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket; After sealing, pipe is put in the agitated reactor, injected B solution; Then the still sealing is placed under certain temperature mode of operation such as Fig. 1.
4) crystallization.Crystallization after synthetic a period of time with the film for preparing with deionized water/alcohol flushing, dry for standby.Synthetic dry film entire synthesis process will synthesize several times repeatedly, up to the film that synthesizes at room temperature film nitrogen infiltration rate less than 10
-6Molm
-2S
-1Pa
-1-film thinks that film is fine and close, continuous, stops synthesizing film.The film of handling well is installed in the membrane separator, and gas cylinder after sealing, is opened respectively to single gas test with the fluorine glue O type washer sealing of corrosion resistant in two ends, and gas pressure carries out under 1.0MP and room temperature in the operating process.
Effect of the present invention and benefit have provided a kind of simple; Easy operating, on tubular carrier, preparation is the synthetic method of fine and close crackless MOFs film continuously with the MOFs material load; The preparation that this method universality is wide, be applicable to various MOFs films; Solved the technological difficulties that are difficult for film forming a little less than the nonmetallic materials carrier adhesions such as this material of metallic organic framework and pottery, make on tubular carrier preparation continuously the preparation of fine and close crackless MOFs film become possibility, started in the tubular support surfaces preparation fine and close continuously crackless; Micro-molecular gas is had the precedent of the MOFs film of separation function, stepped major step for the MOFs material is applied to the film engineering.
Description of drawings
Accompanying drawing is the sketch map that inverse diffusion method prepares metal organic framework film.
Among the figure: A is the casting solution of metalline precursor;
B is the casting solution that contains organic part.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
Synthesizing of embodiment 1Cu3 (BTC) 2 films
In the beaker of 100ml with 3.75g Cu (NO
3)
2Fully be dissolved in the 12g water and form A solution, in the beaker of another 100ml with 0.08g mesitylene formic acid (1,3,5-tribenzenetricarboxylate, BTC) BTC is dissolved in and forms B solution in the 24g ethanol.The pretreated carrier of learning from else's experience with the sealing of polytetrafluoroethylene (PTFE) end socket, is poured A solution the tubulose bottom into pipe in then; Then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing, pipe is put in the agitated reactor; Inject B solution, then still is sealed under the temperature that is placed on 120 ℃, crystallization is synthesized 12h; The preparation Cu3 (BTC) 2 films with deionized water/alcohol flushing, dry for standby under 40 ℃ of vacuum drying ovens.Entire synthesis process is Synthetic 2 repeatedly, till synthetic film is fine and close, continuous.
Single gas test: the Cu3 that above-prepared is good (BTC) 2 films, be installed in the membrane separator, under the room temperature condition, the pressure reduction at film two ends is controlled at 0.1MPa, test result H
2/ N
2, H
2/ CH
4, H
2/ CO
2Separation factor be respectively 4.67,5.76,8.7, H
2Permeability be 4.03*10
-7Molm
-2s
-1Pa
-1
Synthesizing of embodiment 2MOF-5 film:
In the beaker of 100ml with 0.399g Zn (NO
3)
2Fully be dissolved in 2.846g dimethyl formamide (N; N '-dimethylformamide DMF) forms A solution, in the beaker of another 100ml with 0.0502g phthalic acid (1; 4-benzenedicarboxylate BDC) is dissolved in formation B solution among the 12.33gDMF.(the pretreated carrier of learning from else's experience with the sealing of polytetrafluoroethylene (PTFE) end socket, is poured A solution the tubulose bottom into pipe in then; Then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing, pipe is put in the agitated reactor; Inject B solution, then still is sealed under the temperature that is placed on 100 ℃, crystallization is synthesized 12h; The MOF-5 film of preparation washes dry for standby under 40 ℃ of vacuum drying ovens with DMF.Entire synthesis process is Synthetic 2 repeatedly, till synthetic film is fine and close, continuous.
Single gas test: the MOF-5 film that above-prepared is good, be installed in the membrane separator, under the room temperature condition, the pressure reduction at film two ends is controlled at 0.06MPa, test result H
2/ N
2, H
2/ CH
4, H
2/ CO
2Separation factor be respectively 3.12,2.18,3.15, H
2Permeability be 2.27*10
-6Molm
-2s
-1Pa
-1
Claims (5)
1. the preparation method of a metal organic framework film; Be to supply with from the both sides of support tube respectively through the metallic precursor and the organic ligand nutrient solution that will synthesize film; Thereby the diffusion that promotes the metallic precursor nutrient solution promotes the crystalline growth of metallic organic framework compound at carrier surface; The fine and close continuous firm zero defect of preparation does not have be full of cracks molecule mixture is had the metallic organic framework diffusion barrier of selecting permeability, it is characterized in that:
(1) preliminary treatment of carrier is used 800# and 1200# sand papering outer surface successively with carrier surface; Smooth until carrier surface; Respectively soak 24 h with soda acid; Use residual alkali in the ultrasonic oscillation flush away hole then, be washed till neutral back with deionized water again and dry naturally, at last dry for standby under 423 K temperature;
(2) metal precursor that will synthesize MOFs is dissolved in solvent and forms A solution, and organic ligand is dissolved in solvent and forms B solution, and A solution and B solution are not mixed; Reactant liquor is supplied with from the both sides of pipe respectively, and the pretreated carrier of both having learnt from else's experience seals the tubulose bottom with the polytetrafluoroethylene (PTFE) end socket; A or B solution are added in the pipe, then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing; Pipe is put in the agitated reactor, B or A solution are injected agitated reactor, sealed reactor; The mol ratio of metal ion/organic ligand is greater than or the value of metallic framework compound (AxBy) X/Y that equals to form, is no more than 15:1; Synthetic liquid is supplied with from the both sides of pipe respectively, selects for use solution A in pipe, and outer or A is outside pipe at pipe for B, and a kind of mode of B in pipe makes two kinds of solution in the carrier surface haptoreaction, synthesizes the firm MOFs rete of growing;
(3) agitated reactor in (2) is put into baking oven and carry out crystallization.
2. the preparation method of a kind of metal organic framework film according to claim 1, the drying condition that it is characterized in that film is drying at room temperature or vacuum drying, 20 ℃ to 100 ℃ of temperature, vacuum are 0 to 0.01Mpa.
3. the preparation method of a kind of metal organic framework film according to claim 1 is characterized in that the carrier of synthetic film is the earthenware of porous, porous stainless steel, a kind of in the porous charcoal pipe.
4. the preparation method of a kind of metal organic framework film according to claim 1 is characterized in that choosing of metallic precursor is Fe
2+Or Cu
2+Or Zn
2+Or Mn
2+Or Mg
2+Or Al
3+Or Cr
3+Or Co
2+Metal salt solution, organic ligand are m-BDC or p-BDC or TMA or BTB or HQA or HCOOH or Py or H
3BTC or TCPM or FURM or 2,2 '-bipy or Phen or PRZ or H
2PDC or 1,4-chdc or phne or H
3PTC or H
3(TCA) or cyclam or bpyde or ip or Him or H
3TATB or H
3Among TTCA or bpy or dabco or bpdc or hmt or TCPB or DPG or the NDC one or both.
5. the preparation method of a kind of metal organic framework film according to claim 1; It is characterized in that preparing A and the used solvent of B solution are deionized water, N; Dinethylformamide, N; N-DEF, chloroform, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol, absolute methanol, glacial acetic acid, 1, one or both in 4-dioxane, N-methyl pyrrolidone, acetone, chloroform, oxolane, ether, the dimethyl sulfoxide (DMSO).
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| CN116688243A (en) * | 2022-09-26 | 2023-09-05 | 中国科学院精密测量科学与技术创新研究院 | For hyperpolarization 129 Developable interventional guide wire for Xe MRI and preparation method thereof |
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