CN106925224B - 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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- CN106925224B CN106925224B CN201710117679.6A CN201710117679A CN106925224B CN 106925224 B CN106925224 B CN 106925224B CN 201710117679 A CN201710117679 A CN 201710117679A CN 106925224 B CN106925224 B CN 106925224B
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
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- 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
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- 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
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- 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)
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- 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 method of modifying of a kind of metal-organic polyhedra and products thereof and application, including, metal-organic polyhedra, quaternary ammonium salt are added in solvent, stirring, centrifuge washing, up to metal-organic polyhedra modified material after drying；Wherein, the metal-organic polyhedra is copper base metal organic polyhedra, is prepared by cupric salt and 5- substituent group M-phthalic acid；Wherein, the quaternary ammonium salt is more alkylpolyoxyethylenes.Metal-organic polyhedra modified material of the invention is made 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 case where its activation is easily assembled.Modified metal organic polyhedra obtained by the present invention, the adsorption rate gain for propane reach as high as 131%, reach as high as 67% for the gain of propylene adsorption rate.
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 technique
Metal-organic polyhedra material is that one kind by metal ion and organic ligand passes through self assembly shape under certain condition
At the new material with discrete molecules structure.It metal-organic polyhedra material collection organic macromolecule polymer and inorganic birdss of the same feather flock together
Close some features of object, various structures and synthesis condition is relatively mild.Metal-organic polyhedra material has closed
Cavity structure and physicochemical properties abundant, in gas absorption, catalysis and to construct metal as supramolecular structure unit organic
Framework material etc. has wide practical use.
However, some disadvantages of metal-organic polyhedra material limit its application: being metal-organic polyhedra material first
The water stability of material is poor, it long-time stable can exist in mother liquor, but will become once exposed to structure in air
It is unstable.Further drawback is that metal-organic polyhedra material needs to activate before use, the metal-organic polyhedra material after activation
Material tends to assemble, and active sites are blocked, and reduces so as to cause absorption property and catalytic performance.
Its alkyl chain of quaternary ammonium salt with different length alkyl chain has hydrophobicity, if alkyl chain can be used to have metal
Machine polyhedron is modified, and the stability of metal-organic polyhedra material can be improved and improve the feelings easily assembled after material activation
Condition, to expand the application range of metal-organic polyhedra material.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of the technological gap of above-mentioned and/or existing metal-organic polyhedra modified material, the present invention is proposed.
Therefore, the one of purpose of the present invention is to solve deficiency in the prior art, provides a kind of organic multi-panel of metal
Modifies method.
In order to solve the above technical problems, the present invention provides the following technical scheme that including, by metal-organic polyhedra, season
Ammonium salt is added in solvent, stirring, centrifuge washing, up to metal-organic polyhedra modified material after drying；Wherein, the metal has
Machine polyhedron is copper base metal organic polyhedra, is prepared by cupric salt and 5- substituent group M-phthalic acid；Wherein,
The quaternary ammonium salt is more alkylpolyoxyethylenes.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which: more alkyl
Trimethyl-ammonium halide, wherein more alkyl are 10~18 alkyl chains；More alkylpolyoxyethylenes, halogen used be chlorine or
One of bromine is a variety of.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which: more alkyl
Trimethyl-ammonium halide, wherein more alkyl are 16,18 alkyl chains.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which: more alkyl
Trimethyl-ammonium halide, halogen used are one of chlorine or bromine or a variety of.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which: the cupric
Salt is one of copper acetate dihydrate or Gerhardite or a variety of；The 5- substituent group M-phthalic acid, is 5-
Tert-butyl isophthalic acid, 5- sulfonic group M-phthalic acid, 5- Hydroxy M Phthalic Acid, 5- sodium sulfonate M-phthalic acid, 5- ammonia
One of base M-phthalic acid, 5- nitroisophthalic acid or oreinol dioctyl phthalate are a variety of；The cupric salt and
5- substituent group M-phthalic acid, molar ratio are 1:1~2:1.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which: the metal has
Machine polyhedron and quaternary ammonium salt, mass ratio are 3:1~3:10；The stirring, temperature are 0~60 DEG C, and the solvent is nothing
One of water-ethanol, anhydrous methanol or chloroform are a variety of.
A kind of preferred embodiment of method of modifying as metal-organic polyhedra of the present invention, in which:
Another object of the present invention is to solve deficiency in the prior art, provides a kind of modified material of metal-organic polyhedra
Material.
In order to solve the above technical problems, the present invention provides the following technical scheme that including, by metal-organic polyhedra through season
The modified gained of ammonium salt, mass ratio are 3:1~3:10；Wherein, the metal-organic polyhedra, You Qiwei molar ratio be 1:1~
The cupric salt and 5- substituent group M-phthalic acid of 2:1 prepares gained；Wherein, the quaternary ammonium salt is more alkyltrimethylammonium halides
Ammonium.
In order to solve the above technical problems, the present invention provides the following technical scheme that more alkylpolyoxyethylenes,
In more alkyl be 10~18 alkyl chains, halogen be one of bromine or chlorine or a variety of.
In order to solve the above technical problems, the present invention provides the following technical scheme that more alkylpolyoxyethylenes,
In more alkyl be 16,18 alkyl chains, halogen be one of bromine or chlorine or a variety of.
Another object of the present invention is to solve deficiency in the prior art, provides a kind of modified material of metal-organic polyhedra
Expect the application as adsorbent in absorption alkane and alkene.
Beneficial effects of the present invention:
Metal-organic polyhedra modified material of the invention is by the quaternary ammonium salt with different length alkyl chain to copper-based gold
It is modified obtained to belong to organic polyhedra, 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 case where its activation is easily assembled.Modification obtained by the present invention
Metal-organic polyhedra, the adsorption rate gain for propane reach as high as 131%；It can for propylene adsorption rate gain highest
Up to 67%.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, 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 the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Stability test: a certain amount of metal-organic polyhedra modified material is taken to be placed in room 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 will appear an absorption peak, this peak belongs to cupric Paddle-wheel structure.Because different metals is organic more
Face volume property is different, thus the Paddle-wheel structure of different metal-organic polyhedras it is corresponding go out peak position also not phase
Together.The corresponding peak position out of the Paddle-wheel structure of corresponding metal-organic polyhedra modified material is not also identical.If sudden and violent
The peak position out for being exposed at the front and back wet environment 12h sample is constant, illustrates that the stability of sample is good.Conversely, stability is bad.
Adsorbed gas experiment: the sample for taking 0.05g dry is placed in ASAP2020 automatically quick specific surface area 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.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- tert-butyl isophthalic acid as raw material is organic
Polyhedron is denoted as M1.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- sulfonic group M-phthalic acid as raw material is organic
Polyhedron is denoted as M2.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- Hydroxy M Phthalic Acid as raw material is organic more
Face body, is denoted as M3.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- sodium sulfonate M-phthalic acid as raw material is organic
Polyhedron is denoted as M4.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- amino isophthalic acid as raw material is organic more
Face body, is denoted as M5.
The metal prepared using copper acetate dihydrate or Gerhardite and 5- nitroisophthalic acid as raw material is organic more
Face body, is denoted as M6.
The metal prepared using copper acetate dihydrate or Gerhardite and oreinol dioctyl phthalate as raw material is organic more
Face body, is denoted as M7.
Embodiment 1
It weighs 0.7870g cetyl trimethylammonium bromide to be dissolved in 10mL ethanol solution, adds 0.2670g
Said mixture is stirred to react by metal-organic polyhedra M1 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Stop sample after reacting
Product centrifugation, centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 705nm and 705nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
32ml/g, the adsorbance to propylene are 50ml/g.
Embodiment 2
It weighs 0.5652g Cetyltrimethylammonium bromide to be dissolved in 10mL anhydrous methanol, adding 0.2670g metal has
Said mixture is stirred to react by machine polyhedron M1 at normal temperature, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 705nm and 705nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
36ml/g, the adsorbance to propylene are 58ml/g.
Embodiment 3
It weighs 0.4844g tetradecyltrimethylammonium bromide to be dissolved in 10mL anhydrous methanol, adding 0.2670g metal has
Said mixture is stirred to react by machine polyhedron M1 at normal temperature, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 712nm and 712nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
31ml/g, the adsorbance to propylene are 43ml/g.
Embodiment 4
It weighs 0.2506g octadecyltrimethylammonium chloride to be dissolved in 10mL dehydrated alcohol, adding 0.2670g metal has
Said mixture is stirred to react by machine polyhedron M1 at 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 709nm and 709nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
37ml/g, the adsorbance to propylene are 60ml/g.
Embodiment 5
It weighs 0.2304g hexadecyltrimethylammonium chloride to be dissolved in 10mL anhydrous methanol, adding 0.2670g metal has
Said mixture is stirred to react by machine polyhedron M1 at 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 708nm and 708nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
33ml/g, the adsorbance to propylene are 52ml/g.
Embodiment 6
It weighs 0.2102g tetradecyl trimethyl ammonium chloride to be dissolved in 10mL dehydrated alcohol, adding 0.2670g metal has
Said mixture is stirred to react by machine polyhedron M1 at 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with nothing
Water-ethanol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 710nm and 710nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
31ml/g, the adsorbance to propylene are 42ml/g.
Embodiment 7
It weighs ten alkyl trimethyl ammonium bromide of 0.3396g to be dissolved in 10mL absolute methanol solution, adds 0.2670g metal
Said mixture is stirred to react by organic polyhedra M1 at a temperature of 60 DEG C, and the reaction time is for 24 hours.Stop reaction after by sample from
The heart repeatedly washs centrifugation, naturally dry with ethanol solution.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 706nm and 706nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
30ml/g, the adsorbance to propylene are 40ml/g.
Embodiment 8
It weighs 0.6660g dodecyl trimethyl ammonium bromide to be dissolved in 10mL chloroform, adding 0.2446g metal has
Said mixture is stirred to react by machine polyhedron M2 at normal temperature, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, with two
Chloromethanes repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 698nm and 698nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
11ml/g, the adsorbance to propylene are 9ml/g.
Embodiment 9
It weighs 0.6660g dodecyl trimethyl ammonium bromide to be dissolved in 10mL dehydrated alcohol, adding 0.2382g metal has
Said mixture is stirred to react by machine polyhedron M3 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction,
Centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 702nm and 702nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
26ml/g, the adsorbance to propylene are 29ml/g.
Embodiment 10
It weighs 0.6660g dodecyl trimethyl ammonium bromide to be dissolved in 10mL dehydrated alcohol, adding 0.2307g metal has
Said mixture is stirred to react by machine polyhedron M6 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction,
Centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 716nm and 716nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
15ml/g, the adsorbance to propylene are 22ml/g.
Embodiment 11
It weighs eight alkyl trimethyl ammonium chloride of 0.2086g to be dissolved in 10mL dehydrated alcohol, it is organic to add 0.2070g metal
Said mixture is stirred to react by polyhedron M1 at 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction, use is anhydrous
Ethyl alcohol repeatedly washs centrifugation, naturally dry.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 719nm and 719nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
19ml/g, the adsorbance to propylene are 32ml/g.
Embodiment 12
It weighs 0.6660g dodecyl trimethyl ammonium bromide to be dissolved in 10mL dehydrated alcohol, adding 0.2325g metal has
Said mixture is stirred to react by machine polyhedron M4 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction,
Centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 718nm and 718nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
18ml/g, the adsorbance to propylene are 24ml/g.
Embodiment 13
It weighs 0.6660g dodecyl trimethyl ammonium bromide to be dissolved in 10mL dehydrated alcohol, adding 0.4182g metal has
Said mixture is stirred to react by machine polyhedron M5 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction,
Centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 704nm and 704nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
19ml/g, the adsorbance to propylene are 20ml/g.
Embodiment 14
It weighs 0.2320g eicosyl trimethylammonium bromide to be dissolved in 5mL dehydrated alcohol, adding 0.2056g metal has
Said mixture is stirred to react by machine polyhedron M7 at a temperature of 45 DEG C, and the reaction time is for 24 hours.Sample is centrifuged after stopping reaction,
Centrifugation, naturally dry are repeatedly washed with dehydrated alcohol.Gained sample is metal-organic polyhedra modified material.
Stability test: above-mentioned metal-organic polyhedra modified material is exposed to room temperature, the environment of relative humidity 75%
Its uv-visible absorption spectroscopy appearance at 717nm and 717nm respectively before and after middle 12h, peak position does not occur obviously to become out
Change, illustrates that the water stability of above-mentioned metal-organic polyhedra modified material is good.
Adsorption applications test: 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.Above-mentioned metal-organic polyhedra modified material is to the adsorbance of propane at a temperature of 0 DEG C
22ml/g, the adsorbance to propylene are 34ml/g.
As seen from the above-described embodiment, modified metal organic polyhedra is made in the present invention, on the one hand steady in metal polyhedron water
Qualitative aspect shows good result, this is because the hydrophobicity of alkyl chain plays main function in modifying agent.
On the other hand, modified metal organic polyhedra is made in the present invention, and the adsorption rate gain for propane reaches as high as
131%；It reaches as high as 67% for the gain of propylene adsorption rate.It can be seen that metal-organic polyhedra through the method for the present invention at
After reason, absorption property is obviously improved, and more excellent with the promotion effect of 10~18 alkyl chains, further, wherein 16,18
Alkyl chain stabilization the most excellent in the promotion of absorption property.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (3)
1. a kind of method of modifying of metal-organic polyhedra, it is characterised in that: including,
Metal-organic polyhedra, quaternary ammonium salt are added in solvent, stirring, centrifuge washing, up to metal-organic polyhedra after drying
Modified material；
Wherein, the metal-organic polyhedra is copper base metal organic polyhedra, by cupric salt and 5- substituent group isophthalic two
Formic acid is prepared；Wherein, the cupric salt is one of copper acetate dihydrate or Gerhardite or a variety of；
The 5- substituent group M-phthalic acid is 5- tert-butyl isophthalic acid, 5- sulfonic group M-phthalic acid, 5- hydroxyl isophthalic two
In formic acid, 5- sodium sulfonate M-phthalic acid, 5- amino isophthalic acid, 5- nitroisophthalic acid or oreinol dioctyl phthalate
It is one or more；The cupric salt and 5- substituent group M-phthalic acid, molar ratio are 1:1~2:1；
Wherein, the quaternary ammonium salt is more alkylpolyoxyethylenes, more alkylpolyoxyethylenes, wherein more alkyl
For 16,18 alkyl chains, halogen used is one of chlorine or bromine or a variety of；
Wherein, the metal-organic polyhedra and quaternary ammonium salt, mass ratio are 3:1~3:10；The stirring, temperature be 0~
60 DEG C, the solvent is one of dehydrated alcohol, anhydrous methanol or chloroform or a variety of.
2. a kind of metal-organic polyhedra modified material, it is characterised in that: the metal-organic polyhedra modified material, pass through by
Metal-organic polyhedra, quaternary ammonium salt are added in solvent, stirring, centrifuge washing, are made after dry；
Wherein, the metal-organic polyhedra is copper base metal organic polyhedra, by cupric salt and 5- substituent group isophthalic two
Formic acid is prepared；Wherein, the cupric salt is one of copper acetate dihydrate or Gerhardite or a variety of；
The 5- substituent group M-phthalic acid is 5- tert-butyl isophthalic acid, 5- sulfonic group M-phthalic acid, 5- hydroxyl isophthalic two
In formic acid, 5- sodium sulfonate M-phthalic acid, 5- amino isophthalic acid, 5- nitroisophthalic acid or oreinol dioctyl phthalate
It is one or more；The cupric salt and 5- substituent group M-phthalic acid, molar ratio are 1:1~2:1；
Wherein, the quaternary ammonium salt is more alkylpolyoxyethylenes, more alkylpolyoxyethylenes, wherein more alkyl
For 16,18 alkyl chains, halogen used is one of chlorine or bromine or a variety of；
Wherein, the metal-organic polyhedra and quaternary ammonium salt, mass ratio are 3:1~3:10；The stirring, temperature be 0~
60 DEG C, the solvent is one of dehydrated alcohol, anhydrous methanol or chloroform or a variety of.
3. a kind of metal-organic polyhedra modified material as claimed in claim 2 is as adsorbent in absorption alkane and alkene
Using.
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