CN110280150A - A kind of preparation method of the porous base composite ultrafiltration membrane material of high anti-pollution Kynoar - Google Patents

A kind of preparation method of the porous base composite ultrafiltration membrane material of high anti-pollution Kynoar Download PDF

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CN110280150A
CN110280150A CN201910611074.1A CN201910611074A CN110280150A CN 110280150 A CN110280150 A CN 110280150A CN 201910611074 A CN201910611074 A CN 201910611074A CN 110280150 A CN110280150 A CN 110280150A
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preparation
membrane material
pvdf
ultrafiltration membrane
pcps
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栾奕
李秀娟
禹杰
赵艳明
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/50—Control of the membrane preparation process
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to field of compound material, are related to a kind of preparation method of porous coordination composite ultrafiltration membrane material of Kynoar.The preparation method is that transition metal ions is fixed on pvdf membrane using the molecule with double amine groups, and the growth in situ of Porous coordination polymer is realized in organic ligand solution.The present invention has the advantages that developing the new method that " one kettle way " prepares PVDF/PCPs composite ultrafiltration membrane material；It is connected between PVDF and PCPs with chemical bond, forms the ultrafiltration membrane material of high stable；By adjusting the type of organic ligand and metal source ion, content in precursor solution, reaction condition etc. can pore structure, increment etc. to PCPs control effectively, the orientations of film properties is regulated and controled to realize；PVDF/PCPs ultrafiltration membrane material prepared by the present invention integrates porosity and hydrophily, improves the stain resistance of ultrafiltration membrane, extends service life.

Description

A kind of preparation method of the porous base composite ultrafiltration membrane material of high anti-pollution Kynoar
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of Kynoar metal organic frame Compound Ultrafiltration The preparation method of membrane material.
Background technique
With the development of economy with the raising of productivity, shortage of water resources and water pollution become increasingly conspicuous, traditional water process Technique be difficult to meet water security and solve the problems, such as reusing sewage this.Ultrafiltration is one kind using static pressure difference as driving force, according to phase The novel membrane for water treatment technology separated to the difference of molecular mass, can effectively filter suspension waste, colloid, sea Algae, germ, virus etc. are widely used in water treatment field to realize isolating and purifying for sewage.The core technology of ultrafiltration is Film, the selection and preparation of membrane material are the key that Membrane Separation for Water Treatment.
As common ultrafiltration membrane material, Kynoar (PVDF) has high mechanical strength, and chemical stability is good, is not easy Corroded by acid, alkali, strong oxidizer and halogen, the advantages that high temperature resistant radiation hardness, is widely used in oil field, chemical industry, municipal wastewater The fields such as processing.However, the high hydrophobicity of pvdf membrane and low pollution resistance (due to the absorption of protein on the surface thereof) limit Their uses in water treatment procedure.Many researchs are dedicated to using physical blending at present, and chemical graft and surface are modified etc. Multiple technologies improve or change the property of pvdf membrane.But that there are still antifouling properties is poor, membrane structure is unstable, synthesis technology The problems such as complicated.
Porous coordination polymer (Porous Coordination Polymers, PCPs) also known as metal organic framework (Metal-Organic Frameworks, MOFs) material, as a kind of novel organic-inorganic hybrid material, because it is abundant Hole, uniform duct and the advantages that high-specific surface area, become the research hotspot of field of porous materials.Its is abundant to receive Metre hole structure is conducive to the introducing of hydrophilic functional group and the absorption of contaminant molecule, to improve the resistance tocrocking of ultrafiltration membrane Energy and service life.
The invention reside in providing a kind of novel preparation method of Kynoar metal organic frame composite ultrafiltration membrane material, if Meter preparation integrates the novel pollution-resistant membrane material of porosity and resistance tocrocking, and to solving, current membrane material is easy to pollute, flux The problems such as low, is significant.
Summary of the invention
The present invention proposes a kind of new side for preparing Kynoar metal organic frame composite ultrafiltration membrane material PVDF/PCPs The preparation method of method, the invention patent technology is simply controllable, low in cost, and raw material are simple and easy to get, can be prepared on a large scale, made Standby composite hyperfiltration membrane can be used for the field of waste water treatment such as the removal of heavy metal ion, the separation of protein.
The technical scheme is that
1) a kind of preparation of Kynoar metal organic frame composite ultrafiltration membrane material
Transition metal ions is fixed on pvdf membrane substrate using double amino molecule groups, organic ligand is added, realizes PCPs Growth in situ of the precursor solution on pvdf membrane prepares the PVDF/PCPs composite ultrafiltration membrane material of efficient stable.Molecule one The amino group at end can form class covalent bond with the fluorine on PVDF, and the amino of the other end can be formed with metal ion to be coordinated, thus So that PCPs stablizes growth on PVDF.Specific step is as follows:
Pvdf membrane is immersed in the aqueous solution of certain density double amino molecule solutes, a certain amount of transition metal ions is added Source, ultrasonic disperse；Then the organic solution containing organic ligand is added, controls reaction temperature and reaction time；Finally by membrane material Material takes out, washing, dry to get arriving PVDF/PCPs composite ultrafiltration membrane material.
2) antifouling property is tested
It is compound to the PVDF/PCPs prepared super using laboratory filter device using bovine serum albumin(BSA) as research object (BSA) Filter membrane is tested.Film is placed on sample stage, in 0.10 MPa, filters 30 min of pure water under room temperature, record pure water is logical Measure J0；500 mg/L BSA phosphate buffers are poured into filter tank and are filtered, original liquid concentration c is measured and recorded1And filtrate is dense Spend c2；With pure water to ultrafiltration membrane repeated flushing, then water flux test is carried out, record restores water flux Jr。
Membrane flux recovery rate (FRR) is calculated by following formula:
FRR=Jr/ J0×100%
BSA rejection (Ru) is calculated by following formula:
Ru=(c1-c2)/ c1×100%
3) tensile strength is tested: the PVDF/PCPs composite hyperfiltration membrane of 0.5cm wide being placed on tensile testing machine, in room temperature condition Under with the loading velocity stretched film of 100 mm/min, until film is broken, records breaking strength at this time, be repeated 5 times and be averaged.
Double amino molecules include ethylenediamine, p-phenylenediamine, 2,5- diamino-pyridines, 2- nitro-Isosorbide-5-Nitrae-phenylenediamine etc..
The transition metal source includes: copper nitrate, copper chloride, copper sulphate, copper acetate, cobalt nitrate, cobalt chloride, nitric acid Zirconium, zirconium chloride, zirconium sulfate, acetic acid zirconium, cobaltous sulfate, cobalt acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, nickel nitrate, chlorination Nickel, nickel sulfate, nickel acetate etc. are one such.
Double amino molecules are ethylenediamine, p-phenylenediamine, 2,5- diamino-pyridines or 2- nitro-Isosorbide-5-Nitrae-phenylenediamine etc.；Institute The double amino molecule solution concentrations stated are 10% ~ 40%, preferably 20% ~ 30%, most preferably 25% ~ 30%
The organic ligand includes: terephthalic acid (TPA), Trimesic acid, 2- amino terephthalic acid (TPA), 2- hydroxyl terephthaldehyde Acid, 2- bromo terephthalic acid, 2,5-Dihydroxyterephthalic acid, 2,3- dihydric para-phthalic acids, 2,5- dihydroxybiphenyls two Formic acid, 2,5- sulfydryl terephthalic acid (TPA)s, 4,6- dihydroxy M-phthalic acids etc. are one such.
The organic solvent includes: dehydrated alcohol, anhydrous methanol, n-butanol, isopropanol, benzyl alcohol,
Methylene chloride, chloroform, chloroethanes, tetrahydrofuran, acetonitrile, toluene, n,N dimethylformamide, N, N diethyl formyl Amine, dimethyl sulfoxide etc. are one such or several.
The present invention has the advantages that 1) develop the method that " one kettle way " prepares PVDF/PCPs composite ultrafiltration membrane material, grasp Make easy, lower production costs, suitable large-scale production；2) it is connected between PVDF and PCPs material by chemical bond, formation PVDF/PCPs ultrafiltration membrane material stability is high；3) by adjust precursor solution in the type of organic ligand and metal source ion, Content, the time of reaction, reaction temperature etc. can pore structure, increment etc. to PCPs control effectively, thus realize to film The orientation of performance regulates and controls；4) the PVDF/PCPs ultrafiltration membrane material prepared by the present invention integrates porosity and hydrophily, improves The strainability and antifouling property of ultrafiltration membrane material, extends service life.
Detailed description of the invention
Fig. 1 is pvdf membrane surface SEM figure.
Fig. 2 is that the truncation surface SEM of pvdf membrane schemes.
Fig. 3 is that the surface SEM of PVDF/CuBTC composite hyperfiltration membrane schemes.
Fig. 4 is that the truncation surface SEM of PVDF/CuBTC composite hyperfiltration membrane schemes.
Specific embodiment
Below with reference to specific embodiment, technical scheme is described further.
The embodiment of the present disclosure discloses a kind of preparation method of porous base composite ultrafiltration membrane material of Kynoar, the preparation Method specifically includes the following steps:
S1) pvdf membrane is immersed in the aqueous solution containing double amino molecule solutes, it is spare；
S2 transition metal) is added to S1) preparation immersed in aqueous solution of the pvdf membrane containing double amino molecule solutes, surpass Sound dispersion, then adds the organic solution containing organic ligand；
S3 reaction temperature and reaction time) are controlled；Finally membrane material is taken out, washs, dry, obtains the porous base of Kynoar Composite ultrafiltration membrane material.
According to the embodiment of the present disclosure, the concentration of the aqueous solution of double amino molecule solutes is 10% ~ 40% in the S1；It is described double Amino molecule is ethylenediamine, p-phenylenediamine, 2,5- diamino-pyridine or 2- nitro -1,4- phenylenediamine.
According to the embodiment of the present disclosure, the concentration of the aqueous solution of double amino molecule solutes in the S1 is 25% ~ 30%.
According to the embodiment of the present disclosure, the molar ratio in the S2 between transition metal source and organic ligand is 1 ~ 3:1.
According to the embodiment of the present disclosure, the organic ligand is terephthalic acid (TPA), Trimesic acid, 2- amino terephthaldehyde Acid, 2- hydroxyterephthalic acid, 2- bromo terephthalic acid, 2,5- dihydric para-phthalic acid, 2,3- dihydric para-phthalic acid, 2,5- dihydroxybiphenyl dioctyl phthalate, 2,5- sulfydryl terephthalic acid (TPA) or 4,6- dihydroxy M-phthalic acid.
According to the embodiment of the present disclosure, the transition metal source is copper nitrate, copper chloride, copper sulphate, copper acetate, nitric acid Cobalt, cobalt chloride, zirconium nitrate, zirconium chloride, zirconium sulfate, acetic acid zirconium, cobaltous sulfate, cobalt acetate, zinc nitrate, zinc chloride, zinc sulfate, acetic acid Zinc, nickel nitrate, nickel chloride, nickel sulfate or nickel acetate.
According to the embodiment of the present disclosure, the organic solvent is dehydrated alcohol, anhydrous methanol, n-butanol, isopropanol, benzene first Alcohol, methylene chloride, chloroform, chloroethanes, tetrahydrofuran, acetonitrile, toluene, N,N-dimethylformamide, N, N- diethyl first One or more of amide or dimethyl sulfoxide.
According to the embodiment of the present disclosure, the S2) in ultrasonic disperse be technique are as follows: under conditions of 40 ~ 60 kHz of frequency 20 ~ 60 min of ultrasonic disperse.
According to the embodiment of the present disclosure, the S3) in reaction temperature be 60 ~ 140 DEG C, the reaction time is 10 ~ 24 h.
According to the embodiment of the present disclosure, the technique of washing and drying in the S3 are as follows: by membrane material deionized water, N, N- The mixing of one or more of dimethylformamide, dehydrated alcohol, anhydrous methanol, acetonitrile is washed, and washing times 3 ~ 5 times, Then dry 3 ~ 6 h in the baking oven that temperature is 40 ~ 60 DEG C.
Case study on implementation 1:
1) pvdf membrane is impregnated into the ethylenediamine solution that 5 mL volumetric concentrations are 10% 2 h, 2.3 mmol tetra- is added and are hydrated nitre The 2- amino terephthalic acid (TPA) of 0.8 mmol is dissolved in the anhydrous N of 10 mL, N dimethyl by sour zinc, 60 kHz ultrasonic disperse, 20 min It in formamide (DMF) and pours into pvdf membrane reaction solution, 30 min of ultrasonic disperse reacts 20 h in 100 DEG C of baking ovens, to film It takes out after natural cooling, is washed respectively three times with DMF and methanol, be then placed in 50 DEG C of baking ovens dry 5 h to get PVDF/ is arrived IRMOF-3 composite ultrafiltration membrane material.
2) antifouling property test is carried out to the PVDF/IRMOF-3 composite hyperfiltration membrane prepared and tensile strength is tested.
Case study on implementation 2:
1) pvdf membrane is impregnated into the p-phenylenediamine aqueous solution that 5 mL volumetric concentrations are 25% 2 h, 4.0 mmol tri- hydration is added Copper nitrate, 40 kHz ultrasonic disperse, 60 min, by the Trimesic acid of 2.0 mmol be dissolved in 12 mL deionized waters/ethyl alcohol (v:v= It 1:1) in mixed solution, and pours into pvdf membrane reaction solution, 30 min of ultrasonic disperse reacts 15 h in 60 DEG C of baking ovens, to film It takes out after natural cooling, is washed respectively five times with deionized water and methanol, be then placed in 40 DEG C of baking ovens dry 6 h to get arriving PVDF/CuBTC composite ultrafiltration membrane material.
2) antifouling property test is carried out to the PVDF/CuBTC composite hyperfiltration membrane prepared and tensile strength is tested.
Case study on implementation 3:
1) pvdf membrane is impregnated into 2, the 5- diamino-pyridine solution that 5 mL volumetric concentrations are 40% 2 h, 0.5 mmol chlorine is added Change zirconium, the 2- amino terephthalic acid (TPA) of 0.5 mmol is dissolved in 8 mL DMF, pours into PVDF by 50 kHz ultrasonic disperse, 40 min In film reaction liquid, 0.9 mL acetic acid is added, 30 min of ultrasonic disperse reacts 24 h in 120 DEG C of baking ovens, to film natural cooling After take out, washed respectively three times with DMF and methanol, be then placed in 60 DEG C of baking ovens dry 3 h to get to PVDF/UiO-66- NH2Composite ultrafiltration membrane material.
2) to the PVDF/UiO-66-NH prepared2Composite hyperfiltration membrane carries out antifouling property test and tensile strength test.
Case study on implementation 4:
1) pvdf membrane is impregnated into the 2- nitro-Isosorbide-5-Nitrae-phenylenediamine aqueous solution that 5 mL volumetric concentrations are 30% 2 h, is added 2.0 The 2-methylimidazole of 3.0 mmol is dissolved in 12 mL methanol and is poured by mmol zinc chloride, 40 kHz ultrasonic disperse, 30 min In pvdf membrane reaction solution, 2 mmol sodium formates are added, 25 min of ultrasonic disperse reacts 10 h in 140 DEG C of baking ovens, certainly to film It so takes out after cooling, is washed respectively four times with deionized water and methanol, be then placed in 45 DEG C of baking ovens dry 4 h to get arriving PVDF/ZIF-8 composite ultrafiltration membrane material.
2) antifouling property test is carried out to the PVDF/ZIF-8 composite hyperfiltration membrane prepared and tensile strength is tested.
The performance test results of each embodiment arrange as shown in table 1:
The performance test results of each embodiment of table 1
Embodiment number Pure water flux (L/m2H) Restore water flux (L/m2H) Membrane flux recovery rate (%) BSA rejection (%) Tensile strength (MPa)
Pvdf membrane 41 24 58.5 98 33.5
One 285 268 94.0 99 32.2
Two 302 278 92.0 98 30.6
Three 313 298 95.2 99 31.4
Four 328 305 93.0 99 33.1
Test result shows pure water flux and the recovery of the PVDF/PCPs composite ultrafiltration membrane material of various embodiments of the present invention preparation Pure water flux greatly promotes, and hydrophily is obviously improved, and membrane flux recovery rate is above 92%, and antifouling property is significant, uses the longevity Life extends；98% or more, tensile strength is not lost BSA rejection substantially.
In specification of the invention, numerous specific details are set forth.It is to be appreciated, however, that the embodiment of the present invention can be with It practices without these specific details.In some instances, well known method, system and skill is not been shown in detail Art, so as not to obscure the understanding of this specification.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme should all cover within the scope of the claims and the description of the invention.

Claims (10)

1. a kind of preparation method of the porous base composite ultrafiltration membrane material of Kynoar, which is characterized in that the preparation method is specific The following steps are included:
S1) pvdf membrane is immersed in the aqueous solution containing double amino molecule solutes, it is spare；
S2 transition metal) is added to S1) preparation immersed in aqueous solution of the pvdf membrane containing double amino molecule solutes, surpass Sound dispersion, then adds the organic solution containing organic ligand；
S3 reaction temperature and reaction time) are controlled；Finally membrane material is taken out, washs, dry, obtains the porous base of Kynoar Composite ultrafiltration membrane material.
2. preparation method according to claim 1, which is characterized in that the aqueous solution of double amino molecule solutes in the S1 Concentration is 10%~40%；Double amino molecule solutes are ethylenediamine, p-phenylenediamine, 2,5- diamino-pyridine or 2- nitro- 1,4- phenylenediamine.
3. preparation method according to claim 1, which is characterized in that the aqueous solution of double amino molecule solutes in the S1 Concentration be 25%~30%.
4. preparation method according to claim 1, which is characterized in that it of transition metal source and organic ligand in the S2 Between molar ratio be 1~3:1.
5. preparation method according to claim 1, which is characterized in that the organic ligand is terephthalic acid (TPA), equal three Benzoic acid, 2- amino terephthalic acid (TPA), 2- hydroxyterephthalic acid, 2- bromo terephthalic acid, 2,5- dihydric para-phthalic acid, 2,3- dihydric para-phthalic acid, 2,5- dihydroxybiphenyl dioctyl phthalate, 2,5- sulfydryl terephthalic acid (TPA) or 4,6- dihydroxy isophthalic Dioctyl phthalate.
6. preparation method according to claim 1, which is characterized in that the transition metal source be copper nitrate, copper chloride, Copper sulphate, copper acetate, cobalt nitrate, cobalt chloride, zirconium nitrate, zirconium chloride, zirconium sulfate, acetic acid zirconium, cobaltous sulfate, cobalt acetate, zinc nitrate, Zinc chloride, zinc sulfate, zinc acetate, nickel nitrate, nickel chloride, nickel sulfate or nickel acetate.
7. preparation method according to claim 1, which is characterized in that the organic solvent be dehydrated alcohol, anhydrous methanol, N-butanol, isopropanol, benzyl alcohol, methylene chloride, chloroform, chloroethanes, tetrahydrofuran, acetonitrile, toluene, N, N- dimethyl methyl Amide, N, one or more of N- diethylformamide or dimethyl sulfoxide.
8. preparation method according to claim 1, which is characterized in that the S2) in ultrasonic disperse be technique are as follows: frequency 20~60min of ultrasonic disperse under conditions of 40~60kHz of rate.
9. preparation method according to claim 1, which is characterized in that the S3) in reaction temperature be 60~140 DEG C, Reaction time be 10~for 24 hours.
10. preparation method according to claim 1, which is characterized in that the technique of washing and drying in the S3 are as follows: will One or more of membrane material deionized water, N,N-dimethylformamide, dehydrated alcohol, anhydrous methanol, acetonitrile are mixed into Row washing, washing times 3~5 times, be then 3~6h dry in 40~60 DEG C of baking oven in temperature.
CN201910611074.1A 2019-07-08 2019-07-08 A kind of preparation method of the porous base composite ultrafiltration membrane material of high anti-pollution Kynoar Pending CN110280150A (en)

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CN112604515A (en) * 2020-11-30 2021-04-06 常州工程职业技术学院 Zn-Co-MOF/PVDF nanofiltration membrane, preparation method and application
CN112604515B (en) * 2020-11-30 2022-09-16 常州工程职业技术学院 Zn-Co-MOF/PVDF nanofiltration membrane, preparation method and application
CN112619440A (en) * 2020-12-28 2021-04-09 中建一局集团安装工程有限公司 Ethylenediamine modified lanthanum oxide-PVDF hybrid membrane material and sewage dephosphorization method
CN114591512A (en) * 2022-03-29 2022-06-07 广州大学 Functionalized zirconium-based metal organic cage and preparation method and application thereof

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Application publication date: 20190927