CN109763333A - A method of metal organic framework is prepared by modified support - Google Patents
A method of metal organic framework is prepared by modified support Download PDFInfo
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Abstract
The present invention provides a kind of methods for preparing metal organic framework by modified support, the method are as follows: polyacrylonitrile, sodium azide, ammonium chloride are added to the in the mixed solvent of n,N-Dimethylformamide and water, 50~70 DEG C is warming up to after mixing and is stirred to react 6~8h, room temperature is down to reaction solution later, aqueous hydrochloric acid solution is added, white precipitate is precipitated in stirring, precipitating is collected by filtration, washing, drying, obtain polyethylene tetrazolium-copolymerized acrylonitrile solid, are made into hollow-fibre membrane；Prepare MOF film precursor liquid, the hollow-fibre membrane of preparation is immersed in the precursor liquid of MOF film and carries out hydro-thermal reaction, after through methanol ultrasonic cleaning, drying, obtain using polyethylene tetrazolium-copolymerized acrylonitrile hollow-fibre membrane as the metal organic framework film of carrier；Modified carrier can possess more binding sites by the method for the invention, so that the surface for being grown in carrier of the MOF film of preparation uniformly, fine and close.
Description
(1) technical field
The present invention relates to the synthetic methods of metal organic framework, and in particular to it is organic that one kind by modified support prepares metal
The method of skeleton.
(2) background technique
Polymeric substrates cost, in terms of have big advantage.And hollow fibre polymeric membranes have
Very high film specific surface area, up to 50cm2/cm3.But for synthetic polymer, the synthesis condition of MOF/ polymer film
Still more harsh.Such as polymeric substrates would generally be immersed in methanol, ethyl alcohol, in DMF strong solvent, and usually also companion
With high-temperature process.Therefore polymeric substrates should have excellent thermal stability and chemical stability.It can certainly pass through
Change the synthesis condition of MOF film to overcome the problems, such as this.Secondly, it is well known that polymer would generally be swollen in a solvent, such as
Fruit is by the laminated polymer surfaces under solvent swelling state of MOF, and when film is dry, polymeric substrates can be shunk, this can make
The MOF layer for obtaining surface generates crack and even falls off.Therefore the swellability of polymer film should be reduced as far as possible.Furthermore by
In complex bound crystal framework structure, the mechanical strength of MOFs is not usually excellent, and especially anti-shear ability is poor.If
MOF layers are synthesized in polymer surfaces, and when film in use, due to hydrostatic pressure, polymer can be shunk, this will lead to
MOF layers fracture and flake off, to limit its use.
In comparison hollow fibre polymeric membranes for synthesize MOF film during and use when have low cost,
The advantages such as height machinability, high specific surface area.Polymer elasticity usually with higher, and the machinery of MOFs is slight especially
It is that anti-shearing force ability is poor.In low pressure, MOF material can be compressed, and when pressure removal, can reply former film rapidly.So
And when pressure increase is excessive, MOF structure can then collapse completely.Especially when MOF crystal by interior growth film forming after, the feature meeting
Further it is amplified.It is elastomeric poly- under hydrostatic pressure due to generally using pressure-driven when MOF film be used to separate
Polymer substrates can be shunk, and MOF layers are then possible to separate to generate crack and fall off with substrate.Substrate surface
Heterogeneous nucleation site be the key that can synthesize continuous MOF film, while the physico-chemical property of substrate surface and substrate with MOF layers
The adhesiveness and compatibility of connection state decision MOF film.Therefore it while noticing mechanical performance, should also utilize as far as possible
Chemical modification method synthesizes MOF/ polymeric hollow fibre composite membrane.
Metal organic framework (MOFs) material is due to its specific surface area with superelevation, excellent adsorptivity and various structures
Property etc. unique performance and be widely used in gas storage, separation, liquid separation and catalysis etc. fields.According to answering for different field
With requiring, MOFs can be designed to different shapes, such as capsule, core-shell structure, particle, film.ZIFs is an Asia of MOFs
Race is had been a great concern due to its outstanding thermal stability and chemical stability.ZIFs series is saved by metal Zn or Co
What point and imidazoles connector were combined into, metal-about 145 ° of connector-metal bond angle is similar to zeolite T-O-T bond angle, by
The strong combination between its component causes ZIFs to have very high chemical and thermal stability, and easy preparation method
It is also a big advantage of ZIFs series MOFs.And ZIF-8 is then a Typical Representative in ZIFs series, is most widely used,
Including selective absorption, UF membrane, chromatography is catalyzed, and as sensor etc..With the hydrothermal synthesis under high temperature and self-generated pressure
Nano zeolite (such as silicalite-1) is compared, and the preparation of ZIF-8 nano particle can carry out in the solution at room temperature, cost
It is lower, the time is saved, and more convenient.
(3) summary of the invention
The object of the present invention is to provide a kind of methods for preparing metal organic framework by modified support.
Technical scheme is as follows:
A method of metal organic framework being prepared by modified support, described method includes following steps:
(1) modified polyacrylonitrile
Polyacrylonitrile, sodium azide, ammonium chloride (catalyst) are added to N,N-dimethylformamide and water volume ratio 1:2.5
~5 in the mixed solvent is warming up to 50~70 DEG C after mixing and is stirred to react 6~8h, is down to room temperature (20 to reaction solution later
~30 DEG C), (0.5~0.7mol/L) aqueous hydrochloric acid solution is added, white precipitate is precipitated in stirring, and precipitating is collected by filtration, and washing (is used
Deionized water), it is dry, obtain polyethylene tetrazolium-copolymerized acrylonitrile (PVT-co-PAN) solid, altogether by gained polyethylene tetrazolium-
Polyacrylonitrile solid is fabricated to hollow-fibre membrane；
The ratio between amount of substance of itrile group and sodium azide in the polyacrylonitrile is 1:1.3~3；
The ratio between amount of substance of the ammonium chloride and sodium azide is 1:1.1~2；
After the completion of feeding intake, itrile group in the polyacrylonitrile is dense n,N-Dimethylformamide and the in the mixed solvent of water
Degree is 1~2mol/L；
Polyethylene tetrazolium-copolymerized acrylonitrile the solid is fabricated to hollow-fibre membrane can be on existing by known
Method carries out, specifically for example: it uses laboratory spinning equipment (De Xi electrical equipment factory, 400x480x780mm, Dx1000), it will
PVT-co-PAN solid is dissolved in N,N-dimethylformamide by feed liquid mass volume ratio 1:6~8 (g:mL) and hollow fibre is made
Film is tieed up, gained hollow-fibre membrane diameter is about 2cm or so, and in this, as the carrier of MOF；
(2) metal organic framework film is synthesized
Hollow-fibre membrane prepared by step (1) is immersed in the precursor liquid of MOF film and carries out by the precursor liquid for preparing MOF film
Hydro-thermal reaction, after through methanol ultrasonic (50~100Hz) cleaning, drying, obtain with polyethylene tetrazolium-hollow fibre of copolymerized acrylonitrile
Tie up the metal organic framework film that film is carrier；
The MOF film can be one of following:
ZIF-8、UIO-66、MIL-101(Fe)、MIF-53(Fe)、NH2- MIL-101 (Al) or NH2-MIL-101(Cr)；
It is preferred that ZIF-8 or UIO-66；
When the MOF film be ZIF-8 when, the precursor liquid of MOF film using sodium formate, zinc chloride and 2-methylimidazole as raw material,
Methanol is that solvent is prepared, and the temperature of hydro-thermal reaction is 80 DEG C, time 12h；The sodium formate, zinc chloride, 2- methyl miaow
The mass ratio of azoles is 1:1.5~3:1.5~2, and the volumetric usage of solvent methanol is calculated as 140~155mL/g with the quality of sodium formate；
Alternatively, the precursor liquid of MOF film is original with zinc nitrate hexahydrate, 2-methylimidazole when the MOF film is ZIF-8
Material, methanol are that solvent is prepared, and the temperature of hydro-thermal reaction is 80 DEG C, time 12h；The zinc nitrate hexahydrate, 2- methyl
The mass ratio of imidazoles is 1:2~2.5, and the volumetric usage of solvent methanol is calculated as 45~55mL/g with the quality of zinc nitrate hexahydrate；
When the MOF film is UIO-66, the precursor liquid of MOF film is using zirconium chloride, terephthalic acid (TPA) as raw material, methanol, vinegar
Acid is that solvent is prepared, and the temperature of hydro-thermal reaction is 120 DEG C, and the time is for 24 hours；The quality of the zirconium chloride, terephthalic acid (TPA)
Than for 1:0.5~0.9, solvent methanol, acetic acid volumetric usage be respectively in terms of the quality of zirconium chloride 240~250mL/g, 7~
8mL/g；
When the MOF film is MIL-101 (Fe), the precursor liquid of MOF film is original with ferric chloride hexahydrate, terephthalic acid (TPA)
Material, methanol are that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15min；The ferric chloride hexahydrate, terephthaldehyde
The mass ratio of acid is 1:0.5~0.7, and the volumetric usage of solvent methanol is calculated as 155~165mL/ with the quality of ferric chloride hexahydrate
g；
When the MOF film is MIF-53 (Fe), the precursor liquid of MOF film is original with ferric chloride hexahydrate, terephthalic acid (TPA)
Material, methanol are that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15h；The ferric chloride hexahydrate, terephthalic acid (TPA)
Mass ratio be 1:0.5~0.7, the volumetric usage of solvent methanol is calculated as 15~20mL/g with the quality of ferric chloride hexahydrate；
When the MOF film is NH2When-MIL-101 (Al), the precursor liquid of MOF film is with Aluminium chloride hexahydrate, 2- amino to benzene
Dioctyl phthalate is raw material, and methanol is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15h；The Aluminium chloride hexahydrate,
The mass ratio of 2- amino terephthalic acid (TPA) is 1:1~1.2, and the volumetric usage of solvent methanol is calculated as with the quality of Aluminium chloride hexahydrate
80~90mL/g；
When the MOF film is NH2When-MIL-101 (Cr), the precursor liquid of MOF film is with Chromium nitrate (Cr(NO3)3),nonahydrate, 2- amino to benzene
Dioctyl phthalate, sodium hydroxide are raw material, and deionized water is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 12h；It is described
Chromium nitrate (Cr(NO3)3),nonahydrate, 2- amino terephthalic acid (TPA), sodium hydroxide mass ratio be 1:0.4~0.5:0.2~0.3, solvent go from
The volumetric usage of sub- water is calculated as 17~20mL/g with the quality of Chromium nitrate (Cr(NO3)3),nonahydrate.
The beneficial effects of the present invention are: it can enable to possess more bound sites by the modified carrier of this method
Point, so that the surface for being grown in carrier of the MOF film of preparation uniformly, fine and close.
(4) Detailed description of the invention
Fig. 1 is to be prepared in embodiment 1 using PVT-co-PAN hollow-fibre membrane as 100 times of scannings of the ZIF-8 of carrier electricity
Mirror figure；
Fig. 2 is to be prepared in embodiment 1 using PVT-co-PAN hollow-fibre membrane as 1000 times of electricity of scanning of the ZIF-8 of carrier
Mirror figure (1)；
Fig. 3 is to be prepared in embodiment 1 using PVT-co-PAN hollow-fibre membrane as 1000 times of electricity of scanning of the ZIF-8 of carrier
Mirror figure (2)；
Fig. 4 is to be prepared in embodiment 1 using PVT-co-PAN hollow-fibre membrane as 2000 times of electricity of scanning of the ZIF-8 of carrier
Mirror figure.
(5) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Embodiment 1:
By the mixed solution of 10mL n,N-Dimethylformamide and 50mL distilled water be added three-necked flask in, then successively according to
Secondary addition 10.5g polyacrylonitrile, 21.5g ammonium chloride, 15.5g sodium azide are heated to 60 DEG C after mixing, stir lower reaction
7h, without Precipitation in reaction process；It will be poured into again in the beaker of 100mL after mixed solution cooling after reaction, then to burning
The aqueous hydrochloric acid solution that 500mL concentration is 0.6mol/L is added in cup, stirring to white precipitate is precipitated complete；The precipitating of precipitation is used
Distillation water washing 3 times is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 19.60gPVT-co-PAN solid.Then molten
Then solution will be fabricated in n,N-Dimethylformamide by laboratory spinning equipment after the dissolution of obtained PVT-co-PAN solid
Hollow-fibre membrane.Then sodium formate 0.4725g, zinc chloride 0.945g and 2-methylimidazole 0.8505g are weighed in 100mL beaker
In, it measures after methanol 70mL is poured into and seals, ultrasound to solution clarification obtains precursor liquid.It is to carry with modified hollow-fibre membrane
Body, carrier is vertically disposed on bracket and (its surface enable uniformly to grow MOF) be then placed in reaction kettle, a reaction
A bracket is placed in kettle, two carriers of a bracket pour into precursor liquid in reaction kettle and are allowed to submerge carrier, then anti-by four groups
It answers kettle to be placed on progress hydro-thermal reaction 12h in 80 DEG C of baking oven, produces ZIF-8, impregnate in methyl alcohol and seal after taking-up, ultrasound is several
Second, with methanol soaking and washing 2-3 time (2-3 hours each), in being put into 60 DEG C of baking ovens drying 12h after take out, obtain with
PVT-co-PAN hollow-fibre membrane be carrier metal organic framework film, later with scanning electron microscope observed made from metal have
The case where machine framework film.(Fig. 2 is the electron microscope containing bulky grain, and Fig. 3 is the electron microscope of single-size)
Embodiment 2:
By the mixed solution of 10mL n,N-Dimethylformamide and 25mL distilled water be added three-necked flask in, then successively according to
Secondary addition 10.6g polyacrylonitrile, 21.4g ammonium chloride, 15.6g sodium azide are heated to 60 DEG C after mixing, stir lower reaction
7h, without Precipitation in reaction process；It will be poured into again in the beaker of 100mL after mixed solution cooling after reaction, then to burning
The aqueous hydrochloric acid solution that 400mL concentration is 0.5mol/L is added in cup, stirring to white precipitate is precipitated complete；The precipitating of precipitation is used
Distillation water washing 3 times is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 21.47gPVT-co-PAN solid.Then molten
Then solution will be fabricated in n,N-Dimethylformamide by laboratory spinning equipment after the dissolution of obtained PVT-co-PAN solid
Hollow-fibre membrane.Then sodium formate 0.108g, zinc chloride 0.216g and 2-methylimidazole 0.1944g are weighed in 50mL beaker,
It measures after methanol 16mL pours into beaker and seals, ultrasound to solution clarification obtains precursor liquid.It is with modified hollow-fibre membrane
Carrier is placed on bracket and is then placed in reaction kettle by carrier, one bracket of placement in a reaction kettle, and one two, bracket
Carrier pours into precursor liquid in reaction kettle and is allowed to submerge carrier, and hydro-thermal reaction 12h is then carried out in 80 DEG C of baking oven, is produced
ZIF-8 is impregnated in methyl alcohol and is sealed after taking-up, and several seconds of ultrasound is cleaned 2-3 times with methanol, dried in being put into 60 DEG C of baking ovens
Take out, obtained using PVT-co-PAN hollow-fibre membrane as the metal organic framework film of carrier after 12h, later with scanning electron microscope into
Row observes the case where metal organic framework film obtained.
Embodiment 3:
The mixed solution of 10mL n,N-Dimethylformamide and 25mL distilled water is added in three-necked flask, then successively successively
10.5g polyacrylonitrile, 21.5g ammonium chloride, 15.5g sodium azide is added, is heated to 60 DEG C after mixing, stirs lower reaction
7h, without Precipitation in reaction process；It will be poured into again in the beaker of 100mL after mixed solution cooling after reaction, then to burning
The aqueous hydrochloric acid solution that 400mL concentration is 0.7mol/L is added in cup, stirring to white precipitate is precipitated complete；The precipitating of precipitation is used
Distillation water washing 3 times is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 20.15gPVT-co-PAN solid.Then molten
Then solution will be fabricated in n,N-Dimethylformamide by laboratory spinning equipment after the dissolution of obtained PVT-co-PAN solid
Hollow-fibre membrane.Then weigh zirconium chloride 61mg, terephthalic acid (TPA) 43mg in 50mL beaker, measure 15mL methanol and
0.447mL acetic acid seals after pouring into beaker, and ultrasound to solution clarification obtains precursor liquid.It is to carry with modified hollow-fibre membrane
Carrier is placed on bracket and is then placed in reaction kettle by body, and a bracket, two, a bracket loads are placed in a reaction kettle
Body pours into precursor liquid in reaction kettle and is allowed to submerge carrier, is then placed in 120 DEG C of baking ovens and heats for 24 hours, produce UIO-66, takes out
After impregnate in methyl alcohol and seal, several seconds of ultrasound clean 2-3 times with methanol, taken out after drying 12h in being put into 60 DEG C of baking ovens,
It obtains using PVT-co-PAN hollow-fibre membrane as the metal organic framework film of carrier, carries out observation with scanning electron microscope later and be made
Metal organic framework film the case where.
Embodiment 4:
By the mixed solution of 10mL n,N-Dimethylformamide and 50mL distilled water be added three-necked flask in, then successively according to
Secondary addition 10.6g polyacrylonitrile, 21.4g ammonium chloride, 15.6g sodium azide are heated to 60 DEG C after mixing, stir lower reaction
7h, without Precipitation in reaction process；It will be poured into again in the beaker of 100mL after mixed solution cooling after reaction, then to burning
The aqueous hydrochloric acid solution that 400mL concentration is 0.5mol/L is added in cup, stirring to white precipitate is precipitated complete；The precipitating of precipitation is used
Distillation water washing 3 times is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 19.87gPVT-co-PAN solid.Then molten
Then solution will be fabricated in n,N-Dimethylformamide by laboratory spinning equipment after the dissolution of obtained PVT-co-PAN solid
Hollow-fibre membrane.Then zinc nitrate hexahydrate 0.2232g and 2-methylimidazole 0.9236g are weighed in 100mL beaker, measures first
Alcohol 80mL is sealed after pouring into, and ultrasound to solution clarification obtains precursor liquid.Using modified hollow-fibre membrane as carrier, by carrier
It is placed on bracket and is then placed in reaction kettle, a bracket, two carriers of a bracket, reaction kettle are placed in a reaction kettle
In pour into precursor liquid and be allowed to submerge carrier, four groups of reaction kettles are then placed on progress hydro-thermal reaction 12h in 80 DEG C of baking oven, are produced
ZIF-8 is impregnated in methyl alcohol and is sealed after taking-up, and several seconds of ultrasound is cleaned 2-3 times with methanol, dried in being put into 60 DEG C of baking ovens
Take out, obtained using PVT-co-PAN hollow-fibre membrane as the metal organic framework film of carrier after 12h, later with scanning electron microscope into
Row observes the case where metal organic framework film obtained.
Embodiment 5:
The mixed solution of 10mL DMF and 50mL distilled water is added in three-necked flask, then successively sequentially adds 10.6g and gathers
Acrylonitrile, 12.84g ammonium chloride, 14.30g sodium azide are heated to 60 DEG C after mixing, stir lower reaction 7h, reaction process
Middle no Precipitation；It will pour into again in the beaker of 100mL after mixed solution cooling after reaction, be then added into beaker
400mL concentration is the aqueous hydrochloric acid solution of 0.7mol/L, and stirring to white precipitate is precipitated complete；By the distillation washing of the precipitating of precipitation
It washs 3 times, is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 19.75g PVT-co-PAN solid.It is then dissolved in N, N-
Then dimethylformamide will be fabricated to doughnut after the dissolution of obtained PVT-co-PAN solid by laboratory spinning equipment
Film.Then sodium formate 0.108g, zinc chloride 0.216g and 2-methylimidazole 0.1944g are weighed in 50mL beaker, measures methanol
16mL is sealed after pouring into beaker, and ultrasound to solution clarification obtains precursor liquid.Using modified hollow-fibre membrane as carrier, will carry
Body is placed on bracket and is then placed in reaction kettle, and a bracket, two carriers of a bracket, reaction are placed in a reaction kettle
Precursor liquid is poured into kettle to be allowed to submerge carrier, and hydro-thermal reaction 12h is then carried out in 80 DEG C of baking oven, ZIF-8 is produced, after taking-up
It impregnates in methyl alcohol and seals, several seconds of ultrasound is cleaned 2-3 times with methanol, is taken out after drying 12h in being put into 60 DEG C of baking ovens, i.e.,
Be made using PVT-co-PAN hollow-fibre membrane as the metal organic framework film of carrier, observed later with scanning electron microscope made from
The case where metal organic framework film.
Embodiment 6:
The mixed solution of 10mL DMF and 50mL distilled water is added in three-necked flask, then successively sequentially adds 5.3g poly- third
Alkene nitrile, 10.7g ammonium chloride, 7.8g sodium azide are heated to 60 DEG C after mixing, stir lower reaction 7h, nothing in reaction process
Precipitation；It will be poured into again in the beaker of 100mL after mixed solution cooling after reaction, it is dense that 500mL be then added into beaker
Degree is the aqueous hydrochloric acid solution of 0.5mol/L, and stirring to white precipitate is precipitated complete；The precipitating of precipitation is washed with distilled water 3 times,
It is then placed in drying in 120 DEG C of drying box and for 24 hours, obtains 11.25g PVT-co-PAN solid.Then zirconium chloride 61mg is weighed,
In 50mL beaker, the methanol and 0.447mL acetic acid for measuring 15mL seal terephthalic acid (TPA) 43mg after pouring into beaker, ultrasonic to molten
Liquid clarification obtains precursor liquid.Using modified hollow-fibre membrane as carrier, carrier is placed on bracket and is then placed in reaction
In kettle, a bracket is placed in a reaction kettle, two carriers of a bracket pour into precursor liquid in reaction kettle and are allowed to submergence and carry
Body is then placed in 120 DEG C of baking ovens and heats for 24 hours, produces UIO-66, impregnates in methyl alcohol and seal after taking-up, and several seconds of ultrasound is used
Methanol cleans 2-3 times, takes out after drying 12h in being put into 60 DEG C of baking ovens, obtains with PVT-co-PAN hollow-fibre membrane as load
The metal organic framework film of body, later with scanning electron microscope observed made from metal organic framework film the case where.
Claims (3)
1. a kind of method for preparing metal organic framework by modified support, which is characterized in that described method includes following steps:
(1) modified polyacrylonitrile
The mixing that polyacrylonitrile, sodium azide, ammonium chloride are added to N,N-dimethylformamide and water volume ratio 1:2.5~5 is molten
In agent, it is warming up to 50~70 DEG C after mixing and is stirred to react 6~8h, is down to room temperature to reaction solution later, it is added 0.5~
White precipitate is precipitated in 0.7mol/L aqueous hydrochloric acid solution, stirring, and precipitating is collected by filtration, and washing, drying obtain polyethylene tetrazolium-altogether
Gained polyethylene tetrazolium-copolymerized acrylonitrile solid is fabricated to hollow-fibre membrane by polyacrylonitrile solid；
The ratio between amount of substance of itrile group and sodium azide in the polyacrylonitrile is 1:1.3~3；
The ratio between amount of substance of the ammonium chloride and sodium azide is 1:1.1~2；
(2) metal organic framework film is synthesized
Hollow-fibre membrane prepared by step (1) is immersed in the precursor liquid of MOF film and carries out hydro-thermal by the precursor liquid for preparing MOF film
Reaction, after through methanol ultrasonic cleaning, drying, obtain using polyethylene tetrazolium-copolymerized acrylonitrile hollow-fibre membrane as the gold of carrier
Belong to organic framework film；
The MOF film can be one of following:
ZIF-8、UIO-66、MIL-101(Fe)、MIF-53(Fe)、NH2- MIL-101 (Al) or NH2-MIL-101(Cr)。
2. the method as described in claim 1, which is characterized in that in step (1), after the completion of feeding intake, in the polyacrylonitrile
Itrile group is 1~2mol/L in the concentration of the in the mixed solvent of N,N-dimethylformamide and water.
3. the method as described in claim 1, which is characterized in that in step (2), when the MOF film is ZIF-8, MOF film
Precursor liquid is using sodium formate, zinc chloride and 2-methylimidazole as raw material, and methanol is that solvent is prepared, and the temperature of hydro-thermal reaction is 80
DEG C, time 12h；The sodium formate, zinc chloride, 2-methylimidazole mass ratio be 1:1.5~3:1.5~2, solvent methanol
Volumetric usage is calculated as 140~155mL/g with the quality of sodium formate；
Alternatively, the precursor liquid of MOF film is using zinc nitrate hexahydrate, 2-methylimidazole as raw material, first when the MOF film is ZIF-8
Alcohol is that solvent is prepared, and the temperature of hydro-thermal reaction is 80 DEG C, time 12h；The zinc nitrate hexahydrate, 2-methylimidazole
Mass ratio is 1:2~2.5, and the volumetric usage of solvent methanol is calculated as 45~55mL/g with the quality of zinc nitrate hexahydrate；
When the MOF film is UIO-66, using zirconium chloride, terephthalic acid (TPA) as raw material, methanol, acetic acid are the precursor liquid of MOF film
Solvent is prepared, and the temperature of hydro-thermal reaction is 120 DEG C, and the time is for 24 hours；The zirconium chloride, terephthalic acid (TPA) mass ratio be
1:0.5~0.9, solvent methanol, acetic acid volumetric usage in terms of the quality of zirconium chloride be respectively 240~250mL/g, 7~8mL/
g；
When the MOF film be MIL-101 (Fe) when, the precursor liquid of MOF film using ferric chloride hexahydrate, terephthalic acid (TPA) as raw material,
Methanol is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15min；The ferric chloride hexahydrate, terephthalic acid (TPA)
Mass ratio be 1:0.5~0.7, the volumetric usage of solvent methanol is calculated as 155~165mL/g with the quality of ferric chloride hexahydrate；
When the MOF film is MIF-53 (Fe), the precursor liquid of MOF film is using ferric chloride hexahydrate, terephthalic acid (TPA) as raw material, first
Alcohol is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15h；The matter of the ferric chloride hexahydrate, terephthalic acid (TPA)
Amount ratio is 1:0.5~0.7, and the volumetric usage of solvent methanol is calculated as 15~20mL/g with the quality of ferric chloride hexahydrate；
When the MOF film is NH2When-MIL-101 (Al), the precursor liquid of MOF film is with Aluminium chloride hexahydrate, 2- amino terephthaldehyde
Acid is raw material, and methanol is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 15h；The Aluminium chloride hexahydrate, 2- ammonia
The mass ratio of base terephthalic acid (TPA) is 1:1~1.2, the volumetric usage of solvent methanol is calculated as 80 with the quality of Aluminium chloride hexahydrate~
90mL/g；
When the MOF film is NH2When-MIL-101 (Cr), the precursor liquid of MOF film is with Chromium nitrate (Cr(NO3)3),nonahydrate, 2- amino terephthaldehyde
Acid, sodium hydroxide are raw material, and deionized water is that solvent is prepared, and the temperature of reaction is 150 DEG C, time 12h；Nine water
Close chromic nitrate, 2- amino terephthalic acid (TPA), sodium hydroxide mass ratio be 1:0.4~0.5:0.2~0.3, solvent deionized water
Volumetric usage 17~20mL/g is calculated as with the quality of Chromium nitrate (Cr(NO3)3),nonahydrate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
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| CN112547018A (en) * | 2020-11-19 | 2021-03-26 | 福建师范大学福清分校 | Magnetic nano composite material and preparation method thereof |
| CN112574429A (en) * | 2020-12-23 | 2021-03-30 | 常州大学 | Organically modified MIL-101(Cr, Cu) material and preparation method and application thereof |
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| CN114316319A (en) * | 2022-01-11 | 2022-04-12 | 天津大学 | Method for preparing oriented MOF film by steam assistance and separation application |
| CN114425243A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN114618308A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of hybrid MOF (Metal organic framework) membrane for polyhydric alcohol dehydration |
| CN115725103A (en) * | 2022-08-30 | 2023-03-03 | 中山大学 | ZIF-8 membrane and preparation method and application thereof |
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| CN110237728A (en) * | 2019-05-28 | 2019-09-17 | 浙江工业大学 | A kind of mixed substrate membrane containing nano-grade molecular sieve and the preparation method and application thereof that metal organic framework is compound with tool microporous polymer certainly |
| CN110237728B (en) * | 2019-05-28 | 2021-12-21 | 浙江工业大学 | Mixed matrix membrane compounded by metal organic framework and polymer with micropores as well as preparation method and application of mixed matrix membrane |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN114425243A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN114425243B (en) * | 2020-10-15 | 2023-05-12 | 中国石油化工股份有限公司 | Metal-organic framework material separation membrane and preparation method and application thereof |
| CN112547018A (en) * | 2020-11-19 | 2021-03-26 | 福建师范大学福清分校 | Magnetic nano composite material and preparation method thereof |
| CN114618308B (en) * | 2020-12-14 | 2023-03-31 | 中国科学院大连化学物理研究所 | Preparation method of hybrid MOF (Metal organic framework) membrane for polyhydric alcohol dehydration |
| CN114618308A (en) * | 2020-12-14 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of hybrid MOF (Metal organic framework) membrane for polyhydric alcohol dehydration |
| CN112574429A (en) * | 2020-12-23 | 2021-03-30 | 常州大学 | Organically modified MIL-101(Cr, Cu) material and preparation method and application thereof |
| CN112755788A (en) * | 2020-12-31 | 2021-05-07 | 太原科技大学 | Modified polyacrylonitrile ultrafiltration membrane, preparation method and application |
| CN113877436A (en) * | 2021-08-31 | 2022-01-04 | 北京理工大学 | Preparation method of silicone rubber modified honeycomb MOF nanosheet membrane |
| CN113877436B (en) * | 2021-08-31 | 2023-07-04 | 北京理工大学 | Preparation method of silicon rubber modified honeycomb MOF nanosheet film |
| CN114316319A (en) * | 2022-01-11 | 2022-04-12 | 天津大学 | Method for preparing oriented MOF film by steam assistance and separation application |
| CN115725103A (en) * | 2022-08-30 | 2023-03-03 | 中山大学 | ZIF-8 membrane and preparation method and application thereof |
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