CN101693168A - Method for preparing metal organic framework film - Google Patents
Method for preparing metal organic framework film Download PDFInfo
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- CN101693168A CN101693168A CN 200910187939 CN200910187939A CN101693168A CN 101693168 A CN101693168 A CN 101693168A CN 200910187939 CN200910187939 CN 200910187939 CN 200910187939 A CN200910187939 A CN 200910187939A CN 101693168 A CN101693168 A CN 101693168A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 235000015097 nutrients Nutrition 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- 230000035699 permeability Effects 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000013384 organic framework Substances 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- RTSZQXSYCGBHMO-UHFFFAOYSA-N 1,2,4-trichloro-3-prop-1-ynoxybenzene Chemical compound CC#COC1=C(Cl)C=CC(Cl)=C1Cl RTSZQXSYCGBHMO-UHFFFAOYSA-N 0.000 claims description 2
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000002904 solvent Substances 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- JKMPXGJJRMOELF-UHFFFAOYSA-N 1,3-thiazole-2,4,5-tricarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)S1 JKMPXGJJRMOELF-UHFFFAOYSA-N 0.000 claims 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- UXFSPRAGHGMRSQ-UHFFFAOYSA-N 3-isobutyl-2-methoxypyrazine Chemical compound COC1=NC=CN=C1CC(C)C UXFSPRAGHGMRSQ-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- 229960000583 acetic acid Drugs 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 239000012362 glacial acetic acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 229910021426 porous silicon Inorganic materials 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 206010011376 Crepitations Diseases 0.000 abstract description 7
- 208000037656 Respiratory Sounds Diseases 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
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- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
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- 238000007789 sealing Methods 0.000 description 6
- 238000000280 densification Methods 0.000 description 5
- 239000013132 MOF-5 Substances 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 238000011010 flushing procedure Methods 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ODEKVGFMXNUYKH-YYKCRFIFSA-N (3S,4S,6S)-3-ethenyl-6-[(R)-hydroxy-(6-methoxyquinolin-4-yl)methyl]-1-azabicyclo[2.2.2]octane-3-carboxylic acid Chemical compound O(C)C1=CC=C2N=CC=C([C@H]([C@@H]3C[C@H]4[C@](CN3CC4)(C=C)C(=O)O)O)C2=C1 ODEKVGFMXNUYKH-YYKCRFIFSA-N 0.000 description 1
- SYNOTUYVMZZAAQ-UHFFFAOYSA-N 1-pyridin-4-ylethane-1,2-diol Chemical compound OCC(O)C1=CC=NC=C1 SYNOTUYVMZZAAQ-UHFFFAOYSA-N 0.000 description 1
- ZEGFMCQPAMLDCS-UHFFFAOYSA-N 2-(n-phenylanilino)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ZEGFMCQPAMLDCS-UHFFFAOYSA-N 0.000 description 1
- XQCVMONLSHHNMB-UHFFFAOYSA-N 2H-pyridine-1,3,5-tricarboxylic acid Chemical class N1(CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O XQCVMONLSHHNMB-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- SRTQKANXPMBQCX-UHFFFAOYSA-N 4-[2,4,5-tris(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=C(C=2C=CC(=CC=2)C(O)=O)C=C1C1=CC=C(C(O)=O)C=C1 SRTQKANXPMBQCX-UHFFFAOYSA-N 0.000 description 1
- MSFXUHUYNSYIDR-UHFFFAOYSA-N 4-[4,6-bis(4-carboxyphenyl)-1,3,5-triazin-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=NC(C=2C=CC(=CC=2)C(O)=O)=NC(C=2C=CC(=CC=2)C(O)=O)=N1 MSFXUHUYNSYIDR-UHFFFAOYSA-N 0.000 description 1
- SQBTUTKHVNQGBF-UHFFFAOYSA-N C(=O)O.C1(=CC(=CC(=C1)C)C)C Chemical compound C(=O)O.C1(=CC(=CC(=C1)C)C)C SQBTUTKHVNQGBF-UHFFFAOYSA-N 0.000 description 1
- ZOFZSXGOSAPAAV-UHFFFAOYSA-N C1=C(C=CC=2C3=CC(=CC=C3C3=CC(=CC=C3C12)C(=O)O)C(=O)O)C(=O)O Chemical compound C1=C(C=CC=2C3=CC(=CC=C3C3=CC(=CC=C3C12)C(=O)O)C(=O)O)C(=O)O ZOFZSXGOSAPAAV-UHFFFAOYSA-N 0.000 description 1
- NMSIUONIJZCLNU-UHFFFAOYSA-N CCCCCCCCCCCCCC.N1CCNCCCNCCNC1 Chemical compound CCCCCCCCCCCCCC.N1CCNCCCNCCNC1 NMSIUONIJZCLNU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
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- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical class OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-L naphthalene-2,6-dicarboxylate Chemical compound C1=C(C([O-])=O)C=CC2=CC(C(=O)[O-])=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-L 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
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 molecule mixture and separate 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 class materials to transition metal ions and the organic ligand micropore metal organic coordination polymer that self assembly forms by complexing, becomes the 3rd polyporous materials.Compare with preceding two class materials, this class 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 in selectivity catalysis, gas absorption, photoelectric material, fields such as magnetic material and chip development have shown charming application prospect (Microporous and Mesoporous Materials 2004,7,3), become the most active research field with the forefront of chemistry and material subject territory after the nineties.
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 by the organic ligand of the stereochemical structure selecting to suit and size, the surface characteristic in duct can be modified by introducing functional group, these excellent characteristics of MOFs material make MOFs become potential of new generation outstanding membrane material, are separating as 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 at 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 (MicroporousMesoporous 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.Studies show that, zero defect, 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, the film forming procedure complexity, 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, easily is assembled into assembly, has higher industrial use value, yet there are no bibliographical information about the MOFs material so far in the tubulose film forming.
Summary of the invention
The technical problem to be solved in the present invention 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, with the MOFs material load on tubular carrier, the synthetic method that has prepared 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) is soluble in water respectively and 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
3TTCA), 4,4 '-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).
3) dress still.The pretreated carrier of learning from else's experience, the tubulose bottom is sealed with the polytetrafluoroethylene (PTFE) end socket, A solution is poured in the pipe, then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing, pipe is put in the 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, with the MOFs material load on tubular carrier, preparation is the synthetic method of fine and close crackless MOFs film continuously, this method universality is wide, be applicable to the preparation of various MOFs films, 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 have been solved, make the preparation of the continuous fine and close crackless MOFs film of preparation on tubular carrier 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 schematic diagram 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 1 Cu3 (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, the tubulose bottom is sealed with the polytetrafluoroethylene (PTFE) end socket, then A solution is poured in the pipe, then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing, pipe is put in the reactor, inject B solution, then still is sealed under the temperature that is placed on 120 ℃, crystallization is synthesized 12h, Cu3 (BTC) 2 films of preparation deionized water/alcohol flushing, dry for standby under 40 ℃ of vacuum drying ovens.Entire synthesis process is Synthetic 2 time repeatedly, up to synthetic film densification, continuously till.
Single gas test: Cu3 (BTC) 2 films that will prepare above, 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 2 MOF-5 films:
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, the tubulose bottom is sealed with the polytetrafluoroethylene (PTFE) end socket, then A solution is poured in the pipe, then the other end is sealed with the polytetrafluoroethylene (PTFE) end socket, after sealing, pipe is put in the 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 time repeatedly, up to synthetic film densification, continuously till.
Single gas test: the MOF-5 film that will prepare above, 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 (7)
1. the preparation method of a metal organic framework film, be to supply with from the both sides of support tube respectively by 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 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) 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, and joins the both sides of film pipe respectively, sealed reactor;
(3) 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, it is characterized in that synthesizing liquid supplies with from the both sides of pipe respectively, select for use solution A in pipe, B the pipe outside or A outside pipe, a kind of mode of B in pipe makes two kinds of solution in the carrier surface haptoreaction, synthesizes the firm MOFs rete of growth, but preferentially do not select person's metallic precursor A solution in pipe, the mode of organic ligand B solution outside pipe.
3. the preparation method of a kind of metal organic framework film according to claim 1 is characterized in that the metallic framework compound (A that the mol ratio of metal ion/organic ligand is greater than or equals to form
xB
y) value of X/Y.
4. 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.
5. the preparation method of a kind of metal organic framework film according to claim 1, it levies the carrier that is synthetic film is the earthenware or the plate of porous, porous stainless steel or plate, porous charcoal pipe or plate and porous silicon plate a kind of.
6. 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 H3BTC 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.
7. 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 is 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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