CN105642258A - Production method of sandwich solid phase extraction membrane - Google Patents

Production method of sandwich solid phase extraction membrane Download PDF

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Publication number
CN105642258A
CN105642258A CN201511003066.7A CN201511003066A CN105642258A CN 105642258 A CN105642258 A CN 105642258A CN 201511003066 A CN201511003066 A CN 201511003066A CN 105642258 A CN105642258 A CN 105642258A
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membrane
phase extraction
inorganic
solid phase
film
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贾志谦
郭越新
姜明辰
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Beijing Normal University
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Beijing Normal University
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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
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • 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
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention belongs to the technical field of function materials, and discloses a production method of a sandwich solid phase extraction membrane. The method comprises the following steps: filtering adsorbent particles by a base film to form a nanometer or micrometer thickness adsorbent layer, carrying out knife coating on the surface of the adsorbent layer with a membrane solution, and carrying out immersion deposition or a sol-gel process to obtain a porous surface membrane in order to obtain the sandwich solid phase extraction membrane. The base membrane has a supporting effect, the surface membrane has adsorbent layer fixing and protecting and liquid distributing effects, and the obtained solid phase extraction membrane has high adsorption capacity and large integral strength, can be used in enrichment of a trace quantity of substances in a liquid and adsorption and separation of a trace amount of substances, and can be used to sample analysis pretreatment and adsorption treatment of pollutants in water.

Description

A kind of preparation method of sandwich solid-phase extraction membrane
Technical field
The invention belongs to technical field of function materials.
Background technology
Solid-Phase Extraction (SolidPhaseExtraction, SPE), is utilize solid absorbent to be adsorbed by the target compound in liquid, then attached with elution or heating desorption, thus reaching to separate and be enriched with the purpose of target compound. Needed for SPE, solvent is only about the 1/10 of liquid-liquid extraction, cost is low, environmental friendliness, the problems such as emulsifying can be avoided, method favorable reproducibility, currently mainly it is applied to following two field: the enrichment of trace materials and separation in (1) liquid, such as underwater trace pollutant, animal foodstuff veterinary drug residue thing and other harmful substances, fruit and vegerable Pesticide Residues thing, blood Chinese medicine and metabolite thereof etc., it is possible to as the pre-treatment means of sample analysis. (2) in water, the efficient absorption of trace contaminant (heavy metal ion, polycyclic aromatic hydrocarbon, phenols, dyestuff etc.) is removed, the advantage with enrichment times height (> 500), can make the waste water water yield and handling significantly low. SPE obtains application widely in fields such as Environmental Science and Engineering, Food Science, biomedicine, pharmaceutical engineering, fine chemistry industry, organic synthesiss.
Solid-phase extraction membrane (SolidPhaseExtractionDisk, SPED) generally with PTFE fiber or glass fibre for skeleton (accounting for 10%), SPE absorbent particles (accounting for 90%) it is loaded with between fiber, diaphragm thickness is less than 1mm, specific surface area is at about 500m2/g, diaphragm diameter has 90mm, 47mm, 11mm, 7mm, 0.7mm equal-specification, can be contained on filter, injector syringe, 96 hole filtering tables and use. Solid-phase extraction membrane has the advantage that adsorbent granularity little (as bonded silica gel particle diameter is about 8 ��m, aperture is about 6nm), specific surface area and adsorption capacity are big, and mass transfer rate is fast; Diaphragm watch area is big, and filtration resistance is little, bed is thin and fills uniformly, it is to avoid channel, and filtering rate is up to more than 10 times (��100ml/min) of SPE post, and the used time is shorter, can be used for the Rapid Extraction of water sample with bulk mass; Eluent consumption few (about 10 �� l/mg adsorbent), can save follow-up evaporation-concentration step; Diaphragm regenerating easily. But, there is also following deficiency: (1) diaphragm section is symmetrical structure, surface is easily by less particles holography. (2) adsorbent content high (90%), absorbent particles easily comes off, and causes contaminated aqueous solution, also have impact on the stability of the response rate and diaphragm is reused. (3) diaphragm thickness is bigger than normal, and adsorbent particle diameter needs to be reduced to improve adsorption capacity further.Additionally, absorbent particles is scattered in polymeric membrane liquid, then pass through immersion precipitation and can prepare adsorbent/macromolecule mixed-matrix solid-phase extraction membrane, the gathering but adsorbent easily suspends in polymeric membrane liquid, it is difficult to dispersed, there is also the problems such as absorbent particles comes off, have impact on the repeatability of film preparation and performance.
Summary of the invention
It is an object of the invention to overcome the shortcoming of conventional solid spe membrane, adopt filtration/immersion precipitation or filtration/sol-gel process to prepare sandwich type structural solid-phase extraction membrane.
The principle of technical solution of the present invention is: Filtration Adsorption agent granule on basement membrane, the adsorbent layer of formation nanometer or micron thickness, then scrape coating liquid on its surface, obtained the top layer film of porous by immersion precipitation or sol-gel process, thus obtaining sandwich solid-phase extraction membrane. Each layer of this film has difference in functionality: (1) basement membrane intensity is good, stable chemical nature, and liquid flowing resistance is little after pretreatment, can play better supporting role. (2) adsorbent layer employing nanometer or micron order absorbent particles, improve adsorbent specific surface area, effectively reduce inside diffusional resistance, can improve the rate of adsorption, shortens the Solid-Phase Extraction time. Meanwhile, adsorbent layer thickness nanometer or micron order, make filtration resistance reduce, channeling can be avoided. It addition, fluid passage (i.e. particulate interspaces) size reduces, it is also beneficial to mass transfer. (3) superficial film has fixing protection adsorbent layer and is uniformly distributed the dual function of liquid, and aperture is little, microgranule can be avoided to enter rete and result in blockage. It addition, the basement membrane edge outside adsorbent layer, film liquid penetrates in the micropore of basement membrane, plays the effect of good fixed absorbent layer, improves bulk strength and the stability of solid-phase extraction membrane.
A kind of preparation method of sandwich solid-phase extraction membrane, it is characterized in that: Filtration Adsorption agent granule on basement membrane, the adsorbent layer of formation nanometer or micron thickness, then coating liquid is scraped on its surface, the top layer film of porous is obtained, thus obtaining sandwich solid-phase extraction membrane by immersion precipitation or sol-gel process. Described basement membrane type is micro-filtration membrane, ultrafilter membrane. Described basement membrane is inoranic membrane, polymeric membrane, inorganic/hybrid films, inorganic/polymer compound film, macromolecule/polymer compound film. Described basement membrane pattern is flat, hollow fiber form, tubular type, rolling. Described sorbent material is inorganic, organic and inorganic/organic hybrid, inorganic/organic composite. Described top layer membrane material is inorganic, macromolecule, inorganic/organic hybrid, inorganic/organic composite.
Accompanying drawing explanation
The surface SEM figure of Fig. 1 polyether sulfone-sulfonated polyether sulfone/polystyrene-divinylbenzene microspheres/politef solid-phase extraction membrane
The section SEM figure of Fig. 2 polyether sulfone-sulfonated polyether sulfone/polystyrene-divinylbenzene microspheres/politef spe membrane
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is further described.
Embodiment 1: the preparation of polyether sulfone-sulfonated polyether sulfone/polystyrene-divinylbenzene microspheres/politef basement membrane solid-phase extraction membrane
Weigh 0.1g polystyrene-divinylbenzene microspheres (PS-PDVB), add 4ml dehydrated alcohol, ultrasonic disperse 20min, in the upper filtration of politef (PTFE) micro-filtration membrane (diameter 50.0mm), dry. The polyether sulfone (PES) weighing certain mass is dissolved in DMF, and sonic oscillation makes it dissolve, and adds a certain amount of sulfonated polyether sulfone (SPES) and PVP (hydrophilizing agent), ultrasonic 30min, obtaining mixed solution, magnetic agitation dissolves 4h, stands 12h deaeration.By film liquid blade coating on PS-PDVB/PTFE film, after standing 5s, immerse in the DMF aqueous solution of 10%, soak 12h, changed a water every 6 hours, dry, obtain solid-phase extraction membrane. Fig. 1 is the surface SEM figure of gained solid-phase extraction membrane, it can be seen that the equally distributed nano-scale pore structure in film surface, hole density is bigger. Fig. 2 is the section SEM figure of spe membrane, it can be seen that top layer film has uniform finger-like pore structure, can as the micro-distributor of liquid. The spe membrane of preparation is used for para-nitrotoluene aqueous solution (100ml, Solid-Phase Extraction 5ppm), when the rate of filtration is 8.5ml/min, 10ml methanol-eluted fractions, the response rate reaches more than 99%, relative standard deviation is less than 6%, and the response rate reusing 6 times has no obvious reduction.
Embodiment 2: regenerated cellulose/MIL-53 (Al)-NH2The preparation of/polypropylene basement membrane solid-phase extraction membrane
Weigh 0.1g metal-organic framework compound MIL-53 (Al)-NH2, add 4ml dehydrated alcohol, ultrasonic disperse 20min, polypropylene (PP) micro-filtration membrane filters, dry. Cellulose membrane liquid magnetic agitation is dissolved 4h, stands 12h deaeration. By film liquid blade coating at MIL-53 (Al)-NH2On/PP film, after standing 5s, it is immersed in the water, a water is changed every 6 hours, take out after 24h and dry, obtain solid-phase extraction membrane, for paranitrophenol aqueous solution (100ml, Solid-Phase Extraction 5ppm), when the rate of filtration is 9.0ml/min, 10ml methanol-eluted fractions, the response rate reaches more than 99%, and relative standard deviation is less than 5%, reusing 5 times, the response rate has no reduction.
Embodiment 3: the preparation of alumina/silica/polypropylene basement membrane solid-phase extraction membrane
Weigh 0.1g nano silicon, add 5ml water ultrasonic disperse 20min, filtration drying in polypropylene (PP) micro-filtration membrane. By alumina sol blade coating on silicon dioxide/PP film, standing and drying, obtain solid-phase extraction membrane, for the Solid-Phase Extraction of phenol in aqueous solution (100ml, 5ppm), when the rate of filtration is 10.0ml/min, 10ml methanol-eluted fractions, the response rate reaches more than 98%, relative standard deviation, less than 6%, is reused 5 times, and the response rate has no reduction.

Claims (6)

1. the preparation method of a sandwich solid-phase extraction membrane, it is characterized in that: Filtration Adsorption agent granule on basement membrane, the adsorbent layer of formation nanometer or micron thickness, then coating liquid is scraped on its surface, the top layer film of porous is obtained, thus obtaining sandwich solid-phase extraction membrane by immersion precipitation or sol-gel process.
2. method according to claim 1, it is characterised in that: described basement membrane type is micro-filtration membrane, ultrafilter membrane.
3. method according to claim 1, it is characterised in that: described basement membrane is inoranic membrane, polymeric membrane, inorganic/polymer hybridisation film, inorganic/polymer compound film, macromolecule/polymer compound film.
4. method according to claim 1, it is characterised in that: described basement membrane pattern is flat, hollow fiber form, tubular type, rolling.
5. method according to claim 1, it is characterised in that: described sorbent material is inorganic, organic and inorganic/organic hybrid, inorganic/organic composite.
6. method according to claim 1, it is characterised in that: described top layer membrane material is inorganic, macromolecule, inorganic/organic hybrid, inorganic/organic composite.
CN201511003066.7A 2015-12-30 2015-12-30 Production method of sandwich solid phase extraction membrane Pending CN105642258A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586048A (en) * 2018-06-12 2019-12-20 北京师范大学 Preparation method of sandwich type adsorption functional membrane
CN114259887A (en) * 2021-12-29 2022-04-01 西南大学 Preparation method of efficient durable solid phase extraction membrane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102824856A (en) * 2012-08-31 2012-12-19 北京工业大学 Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology
CN103481624A (en) * 2013-08-09 2014-01-01 天津工业大学 Preparation method of multilayer sandwich type electrostatic-spinning polymer nanofiber composite membrane
CN104028111A (en) * 2013-03-08 2014-09-10 北京师范大学 Method for preparing sandwich graphene oxide separation membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102824856A (en) * 2012-08-31 2012-12-19 北京工业大学 Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology
CN104028111A (en) * 2013-03-08 2014-09-10 北京师范大学 Method for preparing sandwich graphene oxide separation membrane
CN103481624A (en) * 2013-08-09 2014-01-01 天津工业大学 Preparation method of multilayer sandwich type electrostatic-spinning polymer nanofiber composite membrane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586048A (en) * 2018-06-12 2019-12-20 北京师范大学 Preparation method of sandwich type adsorption functional membrane
CN114259887A (en) * 2021-12-29 2022-04-01 西南大学 Preparation method of efficient durable solid phase extraction membrane
CN114259887B (en) * 2021-12-29 2022-12-27 西南大学 Preparation method of efficient durable solid-phase extraction membrane

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