CN106925224A - A kind of method of modifying of metal-organic polyhedra and products thereof and application - Google Patents
A kind of method of modifying of metal-organic polyhedra and products thereof and application Download PDFInfo
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- CN106925224A CN106925224A CN201710117679.6A CN201710117679A CN106925224A CN 106925224 A CN106925224 A CN 106925224A CN 201710117679 A CN201710117679 A CN 201710117679A CN 106925224 A CN106925224 A CN 106925224A
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- metal
- organic polyhedra
- organic
- polyhedra
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- 239000013213 metal-organic polyhedra Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 91
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000010953 base metal Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkyltrimethylammonium halides Chemical class 0.000 claims description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- NBDAHKQJXVLAID-UHFFFAOYSA-N 5-nitroisophthalic acid Chemical class OC(=O)C1=CC(C(O)=O)=CC([N+]([O-])=O)=C1 NBDAHKQJXVLAID-UHFFFAOYSA-N 0.000 claims description 3
- 150000003022 phthalic acids Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical class 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 62
- 239000001294 propane Substances 0.000 abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 31
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 31
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 230000004913 activation Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000004847 absorption spectroscopy Methods 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 14
- 230000008859 change Effects 0.000 description 14
- 150000002739 metals Chemical class 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical compound O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000007812 deficiency Effects 0.000 description 3
- BJLUCDZIWWSFIB-UHFFFAOYSA-N 5-tert-butylbenzene-1,3-dicarboxylic acid Chemical group CC(C)(C)C1=CC(C(O)=O)=CC(C(O)=O)=C1 BJLUCDZIWWSFIB-UHFFFAOYSA-N 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical class NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical class [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical class [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
Abstract
The present invention provides a kind of method of modifying of metal-organic polyhedra and products thereof and application, including, by metal-organic polyhedra, quaternary ammonium salt addition solvent, stirring, centrifuge washing obtains final product metal-organic polyhedra material modified after drying；Wherein, the metal-organic polyhedra, it is copper base metal organic polyhedra, is prepared from by cupric salt and 5 substitution base M-phthalic acids；Wherein, the quaternary ammonium salt, it is many alkylpolyoxyethylenes.Metal-organic polyhedra of the invention is material modified to be obtained by the quaternary ammonium salt with different length alkyl chain is modified to copper base metal organic polyhedra, method is simple, the alkyl chain of the different length introduced by quaternary ammonium salt has hydrophobicity, can significantly improve the hydrothermal stability of metal-organic polyhedra material and improve the situation of its activation easily aggregation.Modified metal organic polyhedra obtained by the present invention, its adsorption rate gain for being directed to propane reaches as high as 131%, and it is directed to propylene adsorption rate gain and reaches as high as 67%.
Description
Technical field
The invention belongs to field of material preparation, and in particular to a kind of method of modifying of metal-organic polyhedra and products thereof with
Using.
Background technology
Metal-organic polyhedra material is that one kind passes through self assembly shape under certain condition by metal ion and organic ligand
Into the new material with discrete molecules structure.Metal-organic polyhedra material collection organic macromolecule polymer and inorganic birds of the same feather flock together
Some features of compound, various structures and synthesis condition is relatively mild.Metal-organic polyhedra material has closed
Cavity structure and abundant physicochemical properties, in gas absorption, catalysis and to construct metal as supramolecular structure unit organic
The aspects such as framework material have wide practical use.
However, some shortcomings of metal-organic polyhedra material limit its application：First it is metal-organic polyhedra material
The water stability of material is poor, and it long-time stable can exist in mother liquor, but will become once exposed to structure in air
It is unstable.Further drawback is metal-organic polyhedra material using preceding needing activation, the metal-organic polyhedra material after activation
Material tends to aggregation, and active sites are blocked, so as to cause absorption property and catalytic performance reduction.
Quaternary ammonium salt with different length alkyl chain its alkyl chain has hydrophobicity, if can be had to metal using alkyl chain
Machine polyhedron is modified, and can improve the stability of metal-organic polyhedra material and improve the feelings easily assembled after material activation
Condition, so as to expand the range of application of metal-organic polyhedra material.
The content of the invention
The purpose of this part is to summarize some aspects of embodiments of the invention and briefly introduce some preferable implementations
Example.May be done in this part and the description of the present application summary and denomination of invention a little simplified or omitted to avoid making our department
Point, the purpose of specification digest and denomination of invention obscure, and this simplification or omission cannot be used for limiting the scope of the present invention.
In view of the material modified technological gap of above-mentioned and/or existing metal-organic polyhedra, it is proposed that the present invention.
Therefore, one of purpose of the invention is to solve deficiency of the prior art, there is provided a kind of organic multiaspect of metal
Modifies method.
In order to solve the above technical problems, the invention provides following technical scheme：Including by metal-organic polyhedra, season
Ammonium salt is added in solvent, stirring, centrifuge washing, and it is material modified to obtain final product metal-organic polyhedra after drying；Wherein, the metal has
Machine polyhedron, it is copper base metal organic polyhedra, is prepared from by cupric salt and 5- substitution base M-phthalic acids；Wherein,
The quaternary ammonium salt, it is many alkylpolyoxyethylenes.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：Many alkyl
Trimethyl-ammonium halide, wherein many alkyl are 10~18 alkyl chains；Many alkylpolyoxyethylenes, its halogen used be chlorine or
One or more in bromine.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：Many alkyl
Trimethyl-ammonium halide, wherein many alkyl are 16,18 alkyl chains.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：Many alkyl
Trimethyl-ammonium halide, its halogen used is one or more in chlorine or bromine.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：The cupric
Salt, it is one or more in copper acetate dihydrate or Gerhardite；The 5- replaces base M-phthalic acid, and it is 5-
Tert-butyl isophthalic acid, 5- sulfonic groups M-phthalic acid, 5- Hydroxy M Phthalic Acids, 5- sodium sulfonates M-phthalic acid, 5- ammonia
One or more in base M-phthalic acid, 5- nitroisophthalic acids or oreinol dioctyl phthalate；The cupric salt and
5- replaces base M-phthalic acid, and its mol ratio is 1:1~2:1.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：The metal has
Machine polyhedron and quaternary ammonium salt, its mass ratio are 3:1~3:10；The stirring, its temperature is 0~60 DEG C, the solvent, and it is nothing
One or more in water-ethanol, absolute methanol or chloroform.
As a kind of preferred scheme of the method for modifying of metal-organic polyhedra of the present invention, wherein：
Another object of the present invention is to solve deficiency of the prior art, there is provided a kind of metal-organic polyhedra is modified material
Material.
In order to solve the above technical problems, the invention provides following technical scheme：Including by metal-organic polyhedra through season
The modified gained of ammonium salt, its mass ratio is 3:1~3:10；Wherein, the metal-organic polyhedra, is that mol ratio is 1 by it:1~
2:1 cupric salt and 5- substitution base M-phthalic acid prepares gained；Wherein, the quaternary ammonium salt is many alkyltrimethylammonium halides
Ammonium.
In order to solve the above technical problems, the invention provides following technical scheme：Many alkylpolyoxyethylenes, its
In many alkyl be 10~18 alkyl chains, halogen is one or more in bromine or chlorine.
In order to solve the above technical problems, the invention provides following technical scheme：Many alkylpolyoxyethylenes, its
In many alkyl be 16,18 alkyl chains, halogen is one or more in bromine or chlorine.
Another object of the present invention is to solve deficiency of the prior art, there is provided a kind of metal-organic polyhedra is modified material
Expect the application in absorption alkane and alkene as adsorbent.
Beneficial effects of the present invention：
It is to copper-based gold by the quaternary ammonium salt with different length alkyl chain that metal-organic polyhedra of the invention is material modified
Category organic polyhedra is modified to be obtained, and method is simple, and the alkyl chain of the different length introduced by quaternary ammonium salt has hydrophobicity, can be bright
The aobvious water stability for improving metal-organic polyhedra material simultaneously improves the situation that its activation is easily assembled.It is modified obtained by the present invention
Metal-organic polyhedra, its adsorption rate gain for being directed to propane reaches as high as 131%；It is directed to propylene adsorption rate gain highest can
Up to 67%.
Specific embodiment
To enable the above objects, features and advantages of the present invention more obvious understandable, with reference to specific embodiment pair
Specific embodiment of the invention is described in detail.
Many details are elaborated in the following description in order to fully understand the present invention, but the present invention can be with
Other manner described here is different from using other to implement, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Secondly, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the invention
Special characteristic, structure or characteristic in formula." in one embodiment " that different places occur in this manual not refers both to
Same embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.
Stability is tested：Take that a certain amount of metal-organic polyhedra is material modified to be placed in normal temperature, relative humidity 75%
Environment in, test its uv-visible absorption spectroscopy respectively at 0h and 12h.Metal-organic polyhedra material is in 670-750nm
Between an absworption peak occurs, this peak belongs to cupric Paddle-wheel structures.Because different metals is organic more
Face volume property is different, thus the Paddle-wheel structures of different metal-organic polyhedras it is corresponding go out peak position also not phase
Together.The corresponding material modified Paddle-wheel structures of metal-organic polyhedra it is corresponding go out peak position also differ.If sudden and violent
Be exposed at sample before and after wet environment 12h goes out that peak position is constant, illustrates the good stability of sample.Conversely, stability is bad.
Adsorbed gas is tested：Take the dry samples of 0.05g and be placed in the full-automatic quick specific surface areas of ASAP2020 and porosity
Analyzer is analyzed.The pretreatment temperature of metal-organic polyhedra material is 50 DEG C, and pretreatment time is 6h.Metal is organic more
The pretreatment temperature of the modifies material in face is 120 DEG C, and pretreatment time is 3h.
It is organic with the metal that copper acetate dihydrate or Gerhardite and 5- tert-butyl isophthalic acids are prepared as raw material
Polyhedron, is denoted as M1.
It is organic with the metal that copper acetate dihydrate or Gerhardite and 5- sulfonic groups M-phthalic acid are prepared as raw material
Polyhedron, is denoted as M2.
It is organic many with the metal that copper acetate dihydrate or Gerhardite and 5- Hydroxy M Phthalic Acids are prepared as raw material
Face body, is denoted as M3.
It is organic with the metal that copper acetate dihydrate or Gerhardite and 5- sodium sulfonates M-phthalic acid are prepared as raw material
Polyhedron, is denoted as M4.
It is organic many with the metal that copper acetate dihydrate or Gerhardite and 5- amino isophthalic acids are prepared as raw material
Face body, is denoted as M5.
It is organic many with the metal that copper acetate dihydrate or Gerhardite and 5- nitroisophthalic acids are prepared as raw material
Face body, is denoted as M6.
It is organic many with the metal that copper acetate dihydrate or Gerhardite and oreinol dioctyl phthalate are prepared as raw material
Face body, is denoted as M7.
Embodiment 1
Weigh 0.7870g cetyl trimethylammonium bromides to be dissolved in 10mL ethanol solutions, add 0.2670g
Metal-organic polyhedra M1, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.By sample after stopping reacting
Product are centrifuged, and centrifugation is repeatedly washed with absolute ethyl alcohol, are dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 705nm and 705nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
32ml/g, the adsorbance to propylene is 50ml/g.
Embodiment 2
Weigh 0.5652g Cetyltrimethylammonium bromides to be dissolved in 10mL absolute methanols, adding 0.2670g metals has
Machine polyhedron M1, by said mixture stirring reaction, reaction time 24h at normal temperatures.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 705nm and 705nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
36ml/g, the adsorbance to propylene is 58ml/g.
Embodiment 3
Weigh 0.4844g TTABs to be dissolved in 10mL absolute methanols, adding 0.2670g metals has
Machine polyhedron M1, by said mixture stirring reaction, reaction time 24h at normal temperatures.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 712nm and 712nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
31ml/g, the adsorbance to propylene is 43ml/g.
Embodiment 4
Weigh 0.2506g OTACs to be dissolved in 10mL absolute ethyl alcohols, adding 0.2670g metals has
Machine polyhedron M1, by said mixture at 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 709nm and 709nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
37ml/g, the adsorbance to propylene is 60ml/g.
Embodiment 5
Weigh 0.2304g hexadecyltrimethylammonium chlorides to be dissolved in 10mL absolute methanols, adding 0.2670g metals has
Machine polyhedron M1, by said mixture at 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 708nm and 708nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
33ml/g, the adsorbance to propylene is 52ml/g.
Embodiment 6
Weigh 0.2102g tetradecyl trimethyl ammonium chlorides to be dissolved in 10mL absolute ethyl alcohols, adding 0.2670g metals has
Machine polyhedron M1, by said mixture at 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 710nm and 710nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
31ml/g, the adsorbance to propylene is 42ml/g.
Embodiment 7
Weigh the alkyl trimethyl ammonium bromides of 0.3396g ten to be dissolved in 10mL absolute methanol solutions, add 0.2670g metals
Organic polyhedra M1, by said mixture at a temperature of 60 DEG C stirring reaction, reaction time 24h.Stop reaction after by sample from
The heart, centrifugation is repeatedly washed with ethanol solution, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 706nm and 706nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M1 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 36ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
30ml/g, the adsorbance to propylene is 40ml/g.
Embodiment 8
Weigh 0.6660g DTABs to be dissolved in 10mL chloroforms, adding 0.2446g metals has
Machine polyhedron M2, by said mixture stirring reaction, reaction time 24h at normal temperatures.Sample is centrifuged after stopping reaction, with two
Chloromethanes repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 698nm and 698nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M2 is 8ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 6ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
11ml/g, the adsorbance to propylene is 9ml/g.
Embodiment 9
Weigh 0.6660g DTABs to be dissolved in 10mL absolute ethyl alcohols, adding 0.2382g metals has
Machine polyhedron M3, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction,
Centrifugation is repeatedly washed with absolute ethyl alcohol, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 702nm and 702nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M3 is 15ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 18ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
26ml/g, the adsorbance to propylene is 29ml/g.
Embodiment 10
Weigh 0.6660g DTABs to be dissolved in 10mL absolute ethyl alcohols, adding 0.2307g metals has
Machine polyhedron M6, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction,
Centrifugation is repeatedly washed with absolute ethyl alcohol, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 716nm and 716nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M6 is 11ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 19ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
15ml/g, the adsorbance to propylene is 22ml/g.
Embodiment 11
Weigh the alkyl trimethyl ammonium chlorides of 0.2086g eight to be dissolved in 10mL absolute ethyl alcohols, add 0.2070g metals organic
Polyhedron M1, by said mixture at 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction, with anhydrous
Ethanol repeatedly washs centrifugation, dries naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 719nm and 719nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M7 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 23ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
19ml/g, the adsorbance to propylene is 32ml/g.
Embodiment 12
Weigh 0.6660g DTABs to be dissolved in 10mL absolute ethyl alcohols, adding 0.2325g metals has
Machine polyhedron M4, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction,
Centrifugation is repeatedly washed with absolute ethyl alcohol, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 718nm and 718nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M4 is 14ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 16ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
18ml/g, the adsorbance to propylene is 24ml/g.
Embodiment 13
Weigh 0.6660g DTABs to be dissolved in 10mL absolute ethyl alcohols, adding 0.4182g metals has
Machine polyhedron M5, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction,
Centrifugation is repeatedly washed with absolute ethyl alcohol, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 704nm and 704nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M5 is 12ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 15ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
19ml/g, the adsorbance to propylene is 20ml/g.
Embodiment 14
Weigh 0.2320g eicosyl trimethylammonium bromides to be dissolved in 5mL absolute ethyl alcohols, adding 0.2056g metals has
Machine polyhedron M7, by said mixture at a temperature of 45 DEG C stirring reaction, reaction time 24h.Sample is centrifuged after stopping reaction,
Centrifugation is repeatedly washed with absolute ethyl alcohol, is dried naturally.It is material modified that gained sample is metal-organic polyhedra.
Stability is tested：Above-mentioned metal-organic polyhedra is material modified exposed to normal temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance 717nm and 717nm at respectively, goes out peak position and does not occur substantially to become before and after middle 12h
Change, illustrate that the material modified water stability of above-mentioned metal-organic polyhedra is good.
Adsorption applications are tested：Above-mentioned metal-organic polyhedra M7 is 16ml/g to the adsorbance of propane at a temperature of 0 DEG C, right
The adsorbance of propylene is 22ml/g.The material modified adsorbance at a temperature of 0 DEG C to propane of above-mentioned metal-organic polyhedra is
22ml/g, the adsorbance to propylene is 34ml/g.
As seen from the above-described embodiment, the prepared modified metal organic polyhedra of the present invention, on the one hand steady in metal polyhedron water
Qualitative aspect shows good result, because the hydrophobicity of alkyl chain serves Main Function in modifying agent.
On the other hand, the prepared modified metal organic polyhedra of the present invention, its adsorption rate gain for being directed to propane is reached as high as
131%；It is directed to propylene adsorption rate gain and reaches as high as 67%.As can be seen here, metal-organic polyhedra through the inventive method at
After reason, absorption property is obviously improved, and more excellent with the lifting effect of 10~18 alkyl chains, further, wherein 16,18
Alkyl chain stabilization the most excellent in the lifting of absorption property.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferably
Embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to technology of the invention
Scheme is modified or equivalent, and without deviating from the spirit and scope of technical solution of the present invention, it all should cover in this hair
In the middle of bright right.
Claims (10)
1. a kind of method of modifying of metal-organic polyhedra, it is characterised in that：Including,
By in metal-organic polyhedra, quaternary ammonium salt addition solvent, stirring, centrifuge washing obtains final product metal-organic polyhedra after drying
It is material modified；
Wherein, the metal-organic polyhedra, it is copper base metal organic polyhedra, by cupric salt and 5- substitution bases isophthalic two
Formic acid is prepared from；
Wherein, the quaternary ammonium salt, it is many alkylpolyoxyethylenes.
2. metal-organic polyhedra method of modifying as claimed in claim 1, it is characterised in that：Many alkyltrimethylammonium halides
Ammonium, wherein many alkyl are 10~18 alkyl chains；Many alkylpolyoxyethylenes, its halogen used is the one kind in chlorine or bromine
Or it is various.
3. metal-organic polyhedra method of modifying as claimed in claim 1, it is characterised in that：Many alkyltrimethylammonium halides
Ammonium, wherein many alkyl are 16,18 alkyl chains.
4. the metal-organic polyhedra method of modifying as any one of claims 1 to 3, it is characterised in that：Many alkyl
Trimethyl-ammonium halide, its halogen used is one or more in chlorine or bromine.
5. metal-organic polyhedra method of modifying as claimed in claim 4, it is characterised in that：The cupric salt, it is a water
One or more in conjunction copper acetate or Gerhardite；The 5- replaces base M-phthalic acid, and it is 5- tert-butyl group isophthalic
Dioctyl phthalate, 5- sulfonic groups M-phthalic acid, 5- Hydroxy M Phthalic Acids, 5- sodium sulfonates M-phthalic acid, 5- amino isophthalic diformazans
One or more in acid, 5- nitroisophthalic acids or oreinol dioctyl phthalate；Between the cupric salt and 5- substitution bases
Phthalic acid, its mol ratio is 1:1~2:1.
6. metal-organic polyhedra method of modifying as claimed in claim 5, it is characterised in that：The metal-organic polyhedra and
Quaternary ammonium salt, its mass ratio is 3:1~3:10；The stirring, its temperature is 0~60 DEG C, the solvent, and it is absolute ethyl alcohol, nothing
One or more in water methanol or chloroform.
7. a kind of metal-organic polyhedra is material modified, it is characterised in that：Including by metal-organic polyhedra through quaternary ammonium salt-modified
Gained, its mass ratio is 3:1~3:10；Wherein, the metal-organic polyhedra, is that mol ratio is 1 by it:1~2:1 divalence
Mantoquita and 5- substitution base M-phthalic acids prepare gained；Wherein, the quaternary ammonium salt is many alkylpolyoxyethylenes.
8. metal-organic polyhedra as claimed in claim 7 is material modified, it is characterised in that：Many alkyltrimethylammonium halides
Ammonium, wherein many alkyl are 10~18 alkyl chains, halogen is one or more in bromine or chlorine.
9. metal-organic polyhedra as claimed in claim 7 is material modified, it is characterised in that：Many alkyltrimethylammonium halides
Ammonium, wherein many alkyl are 16,18 alkyl chains, halogen is one or more in bromine or chlorine.
10. a kind of metal-organic polyhedra as claimed in claim 7 is material modified is adsorbing alkane and alkene as adsorbent
Application.
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| CN107754860A (en) * | 2017-10-26 | 2018-03-06 | 上海应用技术大学 | A kind of catalyst, preparation method and applications for preparing the ethylene glycol of 1 phenyl 1,2 from styrene for one kettle way |
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| CN113583251A (en) * | 2021-08-10 | 2021-11-02 | 中国船舶重工集团公司第七一九研究所 | For NH3Copper-based MOF adsorbent for gas removal and preparation method thereof |
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