CN105797595A - Preparation method and application of high-water-stability metal organic framework compound material - Google Patents
Preparation method and application of high-water-stability metal organic framework compound material Download PDFInfo
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- CN105797595A CN105797595A CN201610323033.9A CN201610323033A CN105797595A CN 105797595 A CN105797595 A CN 105797595A CN 201610323033 A CN201610323033 A CN 201610323033A CN 105797595 A CN105797595 A CN 105797595A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a preparation method of a high-water-stability metal organic framework compound material.The preparation method specifically includes the following steps that 1, chromic nitrate nonahydrate and terephthalic acid are dissolved in deionized water according to the molar ratio of 1:1, after ultrasonic dispersion, suspension liquid is transferred into a hydrothermal reaction still, a high-temperature reaction is conducted for 18 h at the temperature of 220 DEG C, and then the material is cooled to room temperature; 2, a product is obtained after centrifugal separation, and the product is washed 2-4 times with N,N-dimethyl formamide at the temperature of 55-65 DEG C; 3, a product is obtained after centrifugal separation, and the product is washed 2-4 times with ethyl alcohol at the temperature of 55-65 DEG C; 4, a product is obtained after centrifugal separation, wherein the product is washed 2-4 times with methyl alcohol at the temperature of 55-65 DEG C; 5, the product is dried for 8 hours in an oven at the temperature of 60 DEG C and dried for 24 h under the 80-DEG C vacuum condition, and then the metal organic framework compound is obtained.The average particle size of the compound is 200 nm, the average pore size of the compound is 1.475 nm, and thickness matching between the compound and a reverse osmosis desalination layer is good.
Description
Technical field
The present invention relates to nano material preparation and technical field of separation membrane preparation, be specifically related to the preparation method of a kind of high water stability metal organic framework compound material and the application in reverse osmosis functional layer thereof.
Background technology
Along with increasingly sharpening of global water resources crisis, water technology has been increasingly becoming the strategic selection solving shortage of water resources, and wherein, pressure-driven membrane separation technique is to develop water technology the most ripe.As the one being most widely used in pressure-driven membrane separation technique, reverse osmosis membrane separation technology is since the sixties in last century rise, and in desalinization, Industrial Wastewater Treatment, the aspect such as municipal sewage treatment plays the most important effect.Membrane structure and membrane material are the key points affecting separating effect, most of reverse osmosis membranes of application all have Film laminated Rotating fields at present, obtain by generating selective separating on ultra-filtration membrane supporting layer, film build method includes surface-coated method, monomer catalyst polymerization, surface grafting polymerization method, interfacial polymerization, LBL self-assembly method etc., wherein, the most successful with interfacial polymerization, its filming performance with excellence and cost advantage.The selective separating of this composite construction and supporting layer can also individually be optimized flux and the stability improving film.Nano hybridization reverse osmosis composite membrane is through being modified reverse osmosis composite membrane obtaining, the nano material with pore passage structure is added in interfacial polymerization process, the hydrone passage run through can be obtained in fine and close selective separating, thus play and put forward high-throughout effect.The nano material that existing nano hybridization reverse osmosis composite membrane adds mostly is inorganic nano material (such as zeolite molecular sieve, mesoporous silicon oxide, CNT etc.), it is poor with the affinity of organic selective separating (such as polyamide etc.), in the selective separating ultimately formed, easily produce the relatively macroscopic-void without rejection effect, this can produce harmful effect to the cutoff performance of film, simultaneously, owing to there is higher operation pressure in reverse osmosis running, the existence of this invalid hole brings risk also can to the longtime running of counter-infiltration system.Therefore, a kind of and organic selective separating is found to have the nano material with pore passage structure of good affinity to be necessary to prepare hybridization compounding film.
Owing to organic structure is contained in inside, metal organic framework compound material and organic substance have good affinity, may apply in water treatment procedure, build the hydrone passage in reverse osmosis composite membrane.What secondary structure unit that metal organic framework compound is made up of inorganic metal ion and oxygen-containing or nitrogen organic ligand were linked together by strong chemical bond and formed has the cancellated porous coordination polymer material of three-dimensional periodic, since can obtaining stable pore passage structure, performance characteristics due to its excellence, metal organic framework compound material causes the extensive concern of people, its structure can design, controllable, can obtain the duct of multiple nano-scale by the rational design of topological structure and the expansion of organo-functional group；Its specific surface area, porosity, what the parameter such as size of granule also can be artificial is controlled.Metal current organic frame compound-material is at gas (H2, N2, CO2, CH4Deng) separation and the research of adsorbing domain the most deep and extensive, utilize metal organic framework compound material to be developed the most in the process to the technology preparing molecular screen membrane or mixed substrate membrane containing nano-grade molecular sieve.But in the close isolated and purified field of liquid, the application of metal organic framework compound material is the most at the early-stage, film containing metal organic framework compound material is applied in the separation process of infiltration evaporation or organic solvent by a few studies, show good effect, but it is limited by most metals organic frame compound-material (MOF-5, HKUST-1 etc.) water stability, these conclusions can not be copied in water treatment field, also needs to carry out particular study.In addition; when applied metal organic frame compound-material to reverse osmosis membrane builds aquaporin; its size can run through desalination layer with the thickness matching of desalination layer when particle size is the biggest, destroys the stability of desalination layer; affect the rejection of film; when the size of particles is too small, nano-particle can be reunited, and undersized nano-particle can be desalted layer and be coated with completely; the length of hydrone passage is shorter, and flux improves limited.Therefore, research and development are suitable in reverse osmosis membrane functional layer being formed the high water stability metal organic framework compound of the specific dimensions of hydrone passage is necessary.
Summary of the invention
For the problems and shortcomings in existing metal organic framework compound materials application to water treatment procedure, it is an object of the invention to provide the preparation method of a kind of high water stability metal organic framework compound, and high water stability metal organic framework compound is used for the hydrone passage building in reverse osmosis composite membrane functional layer.
The preparation method of a kind of high water stability metal organic framework compound, specifically includes following steps:
(1) nine water chromic nitrates and p-phthalic acid are pressed 1:1 mol ratio dissolve in deionized water, after ultrasonic disperse is complete, suspension is transferred in hydrothermal reaction kettle, at 220 DEG C, is cooled to room temperature after pyroreaction 18h；
(2) centrifugation obtains product, is cleaned 2-4 time with the DMF of 55-65 DEG C by product；
(3) centrifugation obtains product, by product with ethanol purge 2-4 time of 55-65 DEG C；
(4) centrifugation obtains product, is cleaned 2-4 time with the methanol of 55-65 DEG C by product；
(5) being dried 8 hours in 60 DEG C of baking ovens, be dried 24h and i.e. obtain metal organic framework compound under 80 DEG C of vacuum conditions, its grain size is 200nm, and specific surface area is 3264m2/ g, average pore size is 1.475nm.
Above-mentioned high water stability metal organic framework compound is added in the oil phase in interfacial polymerization process, prepares the reverse osmosis composite membrane of high water stability metal organic framework compound doping, concretely comprise the following steps:
The above-mentioned high water stability metal organic framework compound nanoparticle of 0.025 ~ 0.1wt% is distributed in the oil-phase solution containing 0.05 ~ 0.3wt% many units acyl chlorides, porous counterdie is soaked in the aqueous phase solution containing 0.5-3wt% polyamine 0.3 ~ 2
Minute, remove the moisture of counterdie surface excess after taking-up, then be dipped in oil-phase solution 0.5 ~ 2 minute, fully rinse with deionized water afterwards.
Further, described polyamine one in ethylenediamine, hexamethylene diamine, p-phenylenediamine, m-diaminobenzene. and o-phenylenediamine；One or more in pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, 5-isocyanate group m-phthaloyl chloride of described polynary acyl chlorides；Described oil phase is normal hexane.
Compared with prior art, height water stability metal organic framework compound of the present invention is prepared in aqueous, and product has high water stability, can apply in water environment for a long time；Using water heat transfer, technique is simple and convenient, and cost is relatively low, and without adding the additives such as Fluohydric acid. in preparation process, safety is good, and building-up process is reproducible, and product property is reliable；By DMF, ethanol, three cleaning processes of methanol, can the remaining part in eluting metal organic framework compound completely, it is ensured that product has high specific surface area (3000m2/ more than g)；The high water stability metal organic framework compound average particle diameter size of preparation is 200nm, average pore size is 1.475nm, good with the thickness matching of reverse osmosis deaslination layer, structure hydrone passage on a functional can be inlayed, play its good hole basket structure admirably, it is possible to increase the performance of reverse osmosis membrane.
Accompanying drawing explanation
Fig. 1 is the high water stability metal organic framework compound Scanning Electron microscope figure of preparation in embodiment 1；
Fig. 2 is the X ray diffracting spectrum (a) of the high water stability metal organic framework compound of preparation and the X ray diffracting spectrum (b) being in water for a long time in embodiment 1；
Fig. 3 is high water stability metal organic framework compound hole cage and the window structure schematic diagram of preparation in embodiment 1；
Fig. 4 is undoped p (a) and the reverse osmosis membrane profile of doping (b) high water stability metal organic framework compound in embodiment 1；
Fig. 5 is the high water stability metal organic framework compound performance of composite antiosmosis membrane test figure of different dopings in embodiment 1.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details.
Embodiment 1:
The preparation method of the high water stability metal organic framework compound described in this enforcement comprises the steps:
(1) nine water chromic nitrates and p-phthalic acid are dissolved in deionized water according to mol ratio 1:1, after ultrasonic 30min dispersion completely, be transferred to suspension, containing in teflon-lined hydrothermal reaction kettle, after reacting 18 hours at 220 DEG C, be cooled to room temperature；
(2) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 2 times with the DMF of 60 DEG C by the product obtained；
(3) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, by 60 DEG C of ethanol purge of product of obtaining 2 times；
(4) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 2 times with 60 DEG C of methanol by the product obtained；
(5) it is dried 8 hours in 60 DEG C of baking ovens；
(6) under 80 DEG C of vacuum conditions, it is dried 24h and i.e. obtains high water stability metal organic framework compound, the average 200nm of its grain size, specific surface area 3264-3562m2/ g, average pore size is 1.475nm.
Above-mentioned high water stability metal organic framework compound is added in the oil phase in interfacial polymerization process, prepares the reverse osmosis composite membrane of high water stability metal organic framework compound of adulterating, concretely comprise the following steps:
Being soaked in aqueous phase 0.5 minute by porous counterdie, in aqueous phase, m-diaminobenzene. concentration is 2wt%, and high water stability metal organic framework compound nanoparticle concentration is 0.025wt%, takes out and remove with air knife the moisture of surface residual；It is immersed in again in the pyromellitic trimethylsilyl chloride hexane solution of 0.1wt%, interface polymerization reaction 0.5 minute, solidifies 5 minutes at 50 DEG C after taking-up, the reverse osmosis composite membrane of the high water stability metal organic framework compound that obtains adulterating after deionized water fully rinses.
Fig. 1 is the scanning electron microscope diagram obtained under the conditions of high water stability metal organic framework compound 3kV, and as can be seen from the figure this compound has regular octahedron structure, and size is uniform, tactical rule, smooth surface；Fig. 2 is the X ray diffracting spectrum (a) of described high water stability metal organic framework compound and the X ray diffracting spectrum (b) being in water for a long time, the X ray diffracting spectrum peak position that material over time is in water can keep consistent with the material not being placed in water environment, illustrates that it has higher water stability；Fig. 3 is hole cage and the sash profile of prepared high water stability metal organic framework compound inner space, and it can be as in hydrone channel application to reverse osmosis membrane functional layer.Fig. 4 a and b is respectively undoped p and the reverse osmosis membrane scanning electron microscope profile of high water stability metal organic framework compound of adulterating in embodiment 1；Figure 4, it is seen that the film of doping is compared with unadulterated film, not having obvious defect, constructed aquaporin to be tightly combined with desalination layer, size is mated.Can be seen that from the test of Fig. 5, in certain addition, reverse osmosis composite membrane compared to undoped p height water stability metal organic framework compound nano material, the interpolation of high water stability metal organic framework compound nano material can improve flux on the premise of ensureing higher salt-stopping rate, improves the performance of film.
Embodiment 2:
The preparation method of the high water stability metal organic framework compound described in this enforcement comprises the steps:
(1) nine water chromic nitrates and p-phthalic acid are dissolved in deionized water according to mol ratio 1:1, after ultrasonic 30min dispersion completely, be transferred to suspension, containing in teflon-lined hydrothermal reaction kettle, after reacting 18 hours at 220 DEG C, be cooled to room temperature；
(2) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 4 times with the DMF of 55 DEG C by the product obtained；
(3) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, by 55 DEG C of ethanol purge of product of obtaining 4 times；
(4) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 4 times with 55 DEG C of methanol by the product obtained；
(5) it is dried 8 hours in 60 DEG C of baking ovens；
(6) under 80 DEG C of vacuum conditions, it is dried 24h and i.e. obtains high water stability metal organic framework compound, the average 200nm of its grain size, specific surface area 3562m2/ g, average pore size is 1.475nm.
Above-mentioned high water stability metal organic framework compound is added in the oil phase in interfacial polymerization process, prepares the reverse osmosis composite membrane of high water stability metal organic framework compound of adulterating, concretely comprise the following steps:
Being soaked in aqueous phase 0.5 minute by porous counterdie, in aqueous phase, m-diaminobenzene. concentration is 0.5wt%, and high water stability metal organic framework compound nanoparticle concentration is 0.1wt%, takes out and remove with air knife the moisture of surface residual；It is immersed in again in the pyromellitic trimethylsilyl chloride hexane solution of 0.05wt%, interface polymerization reaction 0.5 minute, solidifies 5 minutes at 50 DEG C after taking-up, the reverse osmosis composite membrane of the high water stability metal organic framework compound that obtains adulterating after deionized water fully rinses.
Embodiment 3:
The preparation method of the high water stability metal organic framework compound described in this enforcement comprises the steps:
(1) nine water chromic nitrates and p-phthalic acid are dissolved in deionized water according to mol ratio 1:1, after ultrasonic 30min dispersion completely, be transferred to suspension, containing in teflon-lined hydrothermal reaction kettle, after reacting 18 hours at 220 DEG C, be cooled to room temperature；
(2) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 3 times with the DMF of 65 DEG C by the product obtained；
(3) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, by 65 DEG C of ethanol purge of product of obtaining 3 times；
(4) centrifugation obtains product, and centrifugal rotational speed is 8000r/min, is cleaned 3 times with 65 DEG C of methanol by the product obtained；
(5) it is dried 8 hours in 60 DEG C of baking ovens；
(6) under 80 DEG C of vacuum conditions, it is dried 24h and i.e. obtains high water stability metal organic framework compound, the average 200nm of its grain size, specific surface area 3428m2/ g, average pore size is 1.475nm.
Above-mentioned high water stability metal organic framework compound is added in the oil phase in interfacial polymerization process, prepares the reverse osmosis composite membrane of high water stability metal organic framework compound of adulterating, concretely comprise the following steps:
Being soaked in aqueous phase 0.5 minute by porous counterdie, in aqueous phase, m-diaminobenzene. concentration is 3wt%, and high water stability metal organic framework compound nanoparticle concentration is 0.05wt%, takes out and remove with air knife the moisture of surface residual；It is immersed in again in the pyromellitic trimethylsilyl chloride hexane solution of 0.3wt%, interface polymerization reaction 0.5 minute, solidifies 5 minutes at 50 DEG C after taking-up, the reverse osmosis composite membrane of the high water stability metal organic framework compound that obtains adulterating after deionized water fully rinses.
Claims (4)
1. the preparation method of one kind high water stability metal organic framework compound, it is characterised in that specifically include following steps:
(1) nine water chromic nitrates and p-phthalic acid are pressed 1:1 mol ratio dissolve in deionized water, after ultrasonic disperse is complete, suspension is transferred in hydrothermal reaction kettle, at 220 DEG C, is cooled to room temperature after pyroreaction 18h；
(2) centrifugation obtains product, is cleaned 2-4 time with the DMF of 55-65 DEG C by product；
(3) centrifugation obtains product, by product with ethanol purge 2-4 time of 55-65 DEG C；
(4) centrifugation obtains product, is cleaned 2-4 time with the methanol of 55-65 DEG C by product；
(5) it is dried 8 hours in 60 DEG C of baking ovens, under 80 DEG C of vacuum conditions, is dried 24h i.e. obtains metal organic framework compound, the average 200nm of its grain size, specific surface area 3264-3562m2/ g, average pore size is 1.475nm.
2. the reverse osmosis composite membrane of the high water stability metal organic framework compound doping described in a claim 1, it is characterised in that described high water stability metal organic framework compound is added in the oil phase in interfacial polymerization process.
The reverse osmosis composite membrane of high water stability metal organic framework compound the most according to claim 2 doping, it is characterized in that, concrete preparation method is: be distributed to by the high water stability metal organic framework compound nanoparticle of 0.025 ~ 0.1wt% in the oil-phase solution containing 0.05 ~ 0.3wt% many units acyl chlorides, porous counterdie is soaked 0.3 ~ 2 minute in the aqueous phase solution containing 0.5-3wt% polyamine, the moisture of counterdie surface excess is removed after taking-up, it is dipped into again in oil-phase solution 0.5 ~ 2 minute, fully rinses with deionized water afterwards.
The reverse osmosis composite membrane of high water stability metal organic framework compound the most according to claim 3 doping, it is characterised in that described polyamine one in ethylenediamine, hexamethylene diamine, p-phenylenediamine, m-diaminobenzene. and o-phenylenediamine；One or more in pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, 5-isocyanate group m-phthaloyl chloride of described polynary acyl chlorides；Described oil phase is normal hexane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349807A (en) * | 2017-07-20 | 2017-11-17 | 浙江工业大学 | A kind of Fe（BTC）Big flux polyamide nano composite membrane inlayed and its production and use |
| CN108452684A (en) * | 2018-03-20 | 2018-08-28 | 时代沃顿科技有限公司 | A kind of metal organic frame reverse osmosis membrane and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013122334A1 (en) * | 2012-02-15 | 2013-08-22 | 한국과학기술연구원 | Membrane for water treatment comprising metal-organic framework and method for manufacturing same |
| CN103877871A (en) * | 2014-03-31 | 2014-06-25 | 大连欧科膜技术工程有限公司 | Composite separating membrane and preparation method and application thereof |
| CN104022301A (en) * | 2014-06-23 | 2014-09-03 | 天津大学 | Macromolecular phytic acid supported metal organic framework composite membrane as well as preparation method and application thereof |
| CN104037432A (en) * | 2014-04-17 | 2014-09-10 | 天津大学 | High polymer-modified metal organic framework material composite membrane, and preparation and application thereof |
| CN104117390A (en) * | 2014-06-20 | 2014-10-29 | 南开大学 | Preparation method of silver nano particle loaded metal organic framework complex catalyst |
| CN104211580A (en) * | 2014-08-04 | 2014-12-17 | 湘潭大学 | Method for catalytically synthesizing bisphenol F with phosphotungstic acid modified metal organic frame |
| US20150251139A1 (en) * | 2014-03-04 | 2015-09-10 | The Texas A&M University System | Methods to Enhance Separation Performance of Metal-Organic Framework Membranes |
| CN105457508A (en) * | 2008-04-15 | 2016-04-06 | 纳米水公司 | Hybrid nano particle TFC film |
-
2016
- 2016-05-13 CN CN201610323033.9A patent/CN105797595A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457508A (en) * | 2008-04-15 | 2016-04-06 | 纳米水公司 | Hybrid nano particle TFC film |
| WO2013122334A1 (en) * | 2012-02-15 | 2013-08-22 | 한국과학기술연구원 | Membrane for water treatment comprising metal-organic framework and method for manufacturing same |
| US20150251139A1 (en) * | 2014-03-04 | 2015-09-10 | The Texas A&M University System | Methods to Enhance Separation Performance of Metal-Organic Framework Membranes |
| CN103877871A (en) * | 2014-03-31 | 2014-06-25 | 大连欧科膜技术工程有限公司 | Composite separating membrane and preparation method and application thereof |
| CN104037432A (en) * | 2014-04-17 | 2014-09-10 | 天津大学 | High polymer-modified metal organic framework material composite membrane, and preparation and application thereof |
| CN104117390A (en) * | 2014-06-20 | 2014-10-29 | 南开大学 | Preparation method of silver nano particle loaded metal organic framework complex catalyst |
| CN104022301A (en) * | 2014-06-23 | 2014-09-03 | 天津大学 | Macromolecular phytic acid supported metal organic framework composite membrane as well as preparation method and application thereof |
| CN104211580A (en) * | 2014-08-04 | 2014-12-17 | 湘潭大学 | Method for catalytically synthesizing bisphenol F with phosphotungstic acid modified metal organic frame |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349807A (en) * | 2017-07-20 | 2017-11-17 | 浙江工业大学 | A kind of Fe（BTC）Big flux polyamide nano composite membrane inlayed and its production and use |
| CN107349807B (en) * | 2017-07-20 | 2020-05-22 | 浙江工业大学 | Fe (BTC) -inlaid large-flux polyamide nano composite film and preparation method and application thereof |
| CN108452684A (en) * | 2018-03-20 | 2018-08-28 | 时代沃顿科技有限公司 | A kind of metal organic frame reverse osmosis membrane and preparation method thereof |
| WO2019179082A1 (en) * | 2018-03-20 | 2019-09-26 | 时代沃顿科技有限公司 | Metal organic frame reverse osmosis membrane and preparation method therefor |
| CN108452684B (en) * | 2018-03-20 | 2020-04-24 | 时代沃顿科技有限公司 | Metal organic framework reverse osmosis membrane and preparation method thereof |
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