CN105536745A - Metal-organic framework solid phase microextraction fiber and preparation method thereof - Google Patents
Metal-organic framework solid phase microextraction fiber and preparation method thereof Download PDFInfo
- Publication number
- CN105536745A CN105536745A CN201510937398.6A CN201510937398A CN105536745A CN 105536745 A CN105536745 A CN 105536745A CN 201510937398 A CN201510937398 A CN 201510937398A CN 105536745 A CN105536745 A CN 105536745A
- Authority
- CN
- China
- Prior art keywords
- steel wire
- stainless steel
- preparation
- fmof
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J20/28023—Fibres or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/3231—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
- B01J20/3244—Non-macromolecular compounds
- B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
-
- 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
- B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
-
- 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
- B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
- B01J20/3295—Coatings made of particles, nanoparticles, fibers, nanofibers
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a metal-organic framework solid phase microextraction fiber and a preparation method thereof. The metal-organic framework solid phase microextraction fiber uses a stainless steel wire as a carrier, and surface roughening treatment is carried out by hydrofluoric acid corrosion. Zn(NO3)2.6H2O, 2,2-Bis-(4-carboxyphenyl)-hexafluoropropane and sodium acetate are used as raw materials for preparing fluorinated metal-organic frameworks (Zn-FMOF for short); aromatic diamine and aromatic dianhydride are used as raw materials for preparing a polyamide acid solution by mixing in ice-bath, the Zn-FMOF powder is added with ultrasonic dispersion, the treated stainless steel wire is inserted into the mixed solution with dipping and coating, the treated stainless steel wire is placed in an oven for solidification at a high temperature, the process is repeated for 5-10 times, and the solid phase microextraction fiber is obtained. The fiber has the characteristics of good stability, excellent adsorptivity, good moisture resistance, long service life, etc., and the fiber can be applied to analysis of trace components in foodstuff, environment, cigarette smoke, and other real samples.
Description
Technical field
The present invention relates to solid-phase micro-extraction fibre technology of preparing, specifically a kind of metallic organic framework solid-phase micro-extraction fibre and preparation method thereof, belongs to analytical chemistry field.
Background technology
SPME (SPME) is a kind of emerging Sample Pretreatment Technique, and it utilizes the coating material be coated on fiber by the target affinity in sample, separation and enrichment.Due to SPME technology be that treasury is got, concentrated, desorb and sample introduction in the Sample Pretreatment Technique Used of one, have easy to use, quick, without the need to organic solvent, the advantage such as sensitive, inexpensive, be widely used in sample pretreatment.
The core of SPME technology is the coating material on fiber, and current commercial coating has single, the mixing or copolymer coated of the different-thickness such as dimethyl silicone polymer (PDMS), polyacrylic acid (PA), polyethylene glycol (CW) and carbon molecular sieve (CAR).For specific sample, select suitable coating extremely important.Current commercial coat type is limited, and expensive, and Applicable temperature is lower, so prepare applied widely, cheap coating to seem extremely important.On the other hand, extracting fiber prepared by prior art is difficult to use under the condition more than 300 DEG C, and needs to be improved further for the adsorption capacity of object.
Metal-organic framework (Metal-OrganicFrameworks, MOFs) material is the porous material that a class is constructed by coordinate bond by metal and organic ligand.The Modulatory character of structure is one of its important feature, by the skeleton structure selecting different metal centers and bridging ligand effectively can regulate MOFs, and duct shape, size and inner surfaces of pores chemical environment etc.Various adjustable pore passage structure, good absorption property, good heat endurance becomes the ideal candidates of SPME coating.Quartz is the common carrier of preparation SPME fiber, but bad mechanical property, very easily there is the fracture of quartzy carrier in operating process, has had a strong impact on the service life of extracting head, and wire carrier such as stainless steel wire can address this problem.The SPME fiber utilizing wire carrier to prepare MOFs coating at present adopts the method for growth in situ, physics sedimentation mostly, but fiber prepared by this method easily comes off in extraction repeatedly and desorption under high temperature process, life-span is shorter, is difficult to ensure extraction efficiency and reappearance.In sum, develop a kind of suitable preparation method and high performance MOFs material is combined in metallic carrier securely, prepare that accumulation ability is strong, the novel MOFs coating SPME fiber of good stability, long service life is very important.
summary of the invention:
The object of the invention aims to provide that a kind of bioaccumulation efficiency is high, the New type of S PME fiber of good stability, long service life.
The object of the invention is to be achieved through the following technical solutions:
A kind of metallic organic framework solid-phase micro-extraction fibre, comprise metallic carrier and the coating being attached to its surface, wherein: metallic carrier is the stainless steel wire of length 5-9cm, one end (about 2-3cm) of stainless steel wire is coated with coating material, the composite (being called for short PI/Zn-FMOF) that this coating material is formed for polyimides (be called for short PI) and Zn-FMOF, the namely composite that formed of polyimides and fluorine duct metallic organic framework.Concrete steps are as follows:
1) preparation of Zn-FMOF
Zn (NO
3)
26H
2o, 2, two (4-carboxyl phenyl) HFC-236fa of 2-and sodium acetate join in the mixed solution of water and isopropyl alcohol (9:1) according to the mol ratio of 1:2.6:1, stirred at ambient temperature is even, solution is transferred to the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), 24h is reacted at 180 DEG C, obtain white needle-like crystals, filter and wash 3 times with water, at 80 DEG C, after drying, grind to form fine particle;
2) preparation of polyamic acid solution
Join under getting the aromatic diamines stirring condition of 2mmol in the conical flask filling 10 ~ 20mL anhydrous dimethyl formamide, under condition of ice bath, add the aromatic dianhydride of equimolar ratio until completely dissolved, obtain polyamic acid yellow solution;
3) stainless steel wire process
Use the ultrasonic process stainless steel wire of acetone, methyl alcohol and distilled water successively, after in atmosphere after drying, steel wire one (about 3cm) is placed in hydrofluoric acid solution 5 ~ 10min, rear distilled water flushing, dried for standby under room temperature;
4) solid-phase micro-extraction fibre preparation
Get the Zn-FMOF powder 0.3 ~ 1g of preparation, be placed in ultrasonic disperse 5 ~ 10min after above-mentioned polyamic acid solution; The stainless steel wire that processed is inserted mixed solution immersion coating, is placed on solidification 20 ~ 30min at 180 ~ 230 DEG C, baking oven, repeat this immersion coating and curing oven process obtains solid-phase micro-extraction fibre 5 ~ 10 times.
Described aromatic diamines is p-phenylenediamine (PPD), 3,3'-bis-amido benzophenone, 4,4'-diaminodiphenyl ethers; Described aromatic dianhydride is pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride.
The invention provides a kind of simple, fast and efficient SPME fiber producing processes, have following advantage: the strategy 1) adopting PI and Zn-FMOF compound, a step prepares PI/Zn-FMOF composite, completes composite in Steel Wire Surface film forming simultaneously; 2) architectural features such as the specific area utilizing Zn-FMOF high, regular duct, thus make PI/Zn-FMOF composite coating possess the enrichment performance good to organic molecule; 3) PI, Zn-FMOF bi-material all has good high-temperature stability, water and air stability, therefore possess high stability and service life based on the PI/Zn-FMOF composite SPME fiber prepared by stainless steel wire, can be applied in the detection of high moist sample simultaneously.
Accompanying drawing explanation
Fig. 1: SPME fiber scanning electron microscope (SEM) photograph prepared by example 1 of the present invention (a is exterior view, and b is sectional view);
Fig. 2: SPME fiber scanning electron microscope (SEM) photograph prepared by example 2 of the present invention.
Detailed description of the invention
The present invention is described further below in conjunction with example, but is not restriction the present invention.
Embodiment 1:
The preparation of 1.Zn-FMOF
According to the mol ratio limited in claims, take 0.36gZn (NO
3)
26H
2two (4-carboxyl phenyl) HFC-236fa of O, 0.47g2,2-and 0.1g sodium acetate join in the mixed solvent of 54mL water and 6mL isopropyl alcohol, and stirred at ambient temperature is even.It is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) that solution is transferred to liner, reacts 24h, obtain white needle-like crystals at 180 DEG C, filters and washes 3 times with water, grind to form fine particle at 80 DEG C after drying.
2. the preparation of polyamic acid solution
Get 2mmol4, join under 4'-diaminodiphenyl ether stirring condition in the conical flask filling 10mL anhydrous dimethyl formamide, under condition of ice bath, add 2mmol pyromellitic dianhydride until completely dissolved, obtain polyamic acid yellow solution.
3. stainless steel wire process
Use the ultrasonic process stainless steel wire of acetone, methyl alcohol and distilled water successively, after in atmosphere after drying, steel wire one (about 3cm) is placed in hydrofluoric acid solution 5min, rear distilled water flushing, dried for standby under room temperature.
Prepared by 4.SPME fiber
Get the Zn-FMOF powder 0.5g of preparation, be placed in ultrasonic disperse 5min after polyamic acid solution.The stainless steel wire processed is inserted mixed solution immersion coating, solidifies 30min at being placed on 200 DEG C, baking oven, repeat this process and obtain SPME fiber 6 times.
Embodiment 2:
The preparation of 1.Zn-FMOF
According to the mol ratio limited in claims, take 0.36gZn (NO
3)
26H
2two (4-carboxyl phenyl) HFC-236fa of O, 0.47g2,2-and 0.1g sodium acetate join in the mixed solvent of 54mL water and 6mL isopropyl alcohol, and stirred at ambient temperature is even.Solution is transferred in the stainless steel cauldron of tetrafluoroethene, reacts 24h, obtain white needle-like crystals at 180 DEG C, filters and washes 3 times with water, grind to form fine particle at 80 DEG C after drying.
2. the preparation of polyamic acid solution
Join under getting 2mmol p-phenylenediamine (PPD) stirring condition in the conical flask filling 15mL anhydrous dimethyl formamide, under condition of ice bath, add 2mmol3 until completely dissolved, 3', 4,4'-benzophenone tetracarboxylic dianhydride, obtain polyamic acid yellow solution.
3. stainless steel wire process
Use the ultrasonic process stainless steel wire of acetone, methyl alcohol and distilled water successively, after in atmosphere after drying, steel wire one (about 3cm) is placed in hydrofluoric acid solution 8min, rear distilled water flushing, dried for standby under room temperature.
Prepared by 4.SPME fiber
Get the Zn-FMOF powder 0.8g of preparation, be placed in ultrasonic disperse 10min after polyamic acid solution.The stainless steel wire processed is inserted mixed solution immersion coating, solidifies 25min at being placed on 220 DEG C, baking oven, repeat this process and obtain SPME fiber 5 times.
Claims (3)
1. a metallic organic framework solid-phase micro-extraction fibre, comprise metallic carrier and the coating being attached to its surface, it is characterized in that: metallic carrier is the stainless steel wire of length 5-9cm, one end of stainless steel wire is coated with coating material, the composite that this coating material is formed for polyimides PI and Zn-FMOF, is called for short PI/Zn-FMOF.
2. a preparation method for metallic organic framework solid-phase micro-extraction fibre as claimed in claim 1, is characterized in that: the method step is as follows:
1) preparation of Zn-FMOF
Zn (NO
3)
26H
2o, 2, two (4-carboxyl phenyl) HFC-236fa of 2-and sodium acetate join in the mixed solution of water and isopropyl alcohol (9:1) according to the mol ratio of 1:2.6:1, stirred at ambient temperature is even, solution is transferred to the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), 24h is reacted at 180 DEG C, obtain white needle-like crystals, filter and wash 3 times with water, at 80 DEG C, after drying, grind to form fine particle;
2) preparation of polyamic acid solution
Join under getting the aromatic diamines stirring condition of 2mmol in the conical flask filling 10 ~ 20mL anhydrous dimethyl formamide, under condition of ice bath, add the aromatic dianhydride of equimolar ratio until completely dissolved, obtain polyamic acid yellow solution;
3) stainless steel wire process
Use the ultrasonic process stainless steel wire of acetone, methyl alcohol and distilled water successively, after in atmosphere after drying, one, steel wire is placed in hydrofluoric acid solution 5 ~ 10min, rear distilled water flushing, dried for standby under room temperature;
4) solid-phase micro-extraction fibre preparation
Get the Zn-FMOF powder 0.3 ~ 1g of preparation, be placed in ultrasonic disperse 5 ~ 10min after above-mentioned polyamic acid solution; The stainless steel wire that processed is inserted mixed solution immersion coating, is placed on solidification 20 ~ 30min at 180 ~ 230 DEG C, baking oven, repeat this immersion coating and curing oven process obtains solid-phase micro-extraction fibre 5 ~ 10 times.
3. preparation method as claimed in claim 2, is characterized in that: described aromatic diamines is p-phenylenediamine (PPD), 3,3'-bis-amido benzophenone, 4,4'-diaminodiphenyl ethers; Described aromatic dianhydride is pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510937398.6A CN105536745B (en) | 2015-12-16 | 2015-12-16 | A kind of metal organic framework solid-phase micro-extraction fibre and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510937398.6A CN105536745B (en) | 2015-12-16 | 2015-12-16 | A kind of metal organic framework solid-phase micro-extraction fibre and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105536745A true CN105536745A (en) | 2016-05-04 |
CN105536745B CN105536745B (en) | 2017-09-12 |
Family
ID=55816583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510937398.6A Active CN105536745B (en) | 2015-12-16 | 2015-12-16 | A kind of metal organic framework solid-phase micro-extraction fibre and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105536745B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108034055A (en) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | A kind of covalent organic framework solid-phase micro-extraction fibre and preparation method thereof |
CN111266094A (en) * | 2020-02-21 | 2020-06-12 | 山东省分析测试中心 | Method for analyzing genotoxic impurities of synthetic drugs based on solid-phase microextraction |
WO2020249834A1 (en) | 2019-06-14 | 2020-12-17 | Universidad De La Laguna, Otri | Stationary phase for solid-phase microextraction device |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070248500A1 (en) * | 2006-04-20 | 2007-10-25 | Janusz Pawliszyn | Internally cooled coated fiber device |
CN102989432A (en) * | 2012-12-28 | 2013-03-27 | 南开大学 | Preparation of solid-phase microextraction (SPME) fiber and extraction device assembled by same |
-
2015
- 2015-12-16 CN CN201510937398.6A patent/CN105536745B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070248500A1 (en) * | 2006-04-20 | 2007-10-25 | Janusz Pawliszyn | Internally cooled coated fiber device |
CN102989432A (en) * | 2012-12-28 | 2013-03-27 | 南开大学 | Preparation of solid-phase microextraction (SPME) fiber and extraction device assembled by same |
Non-Patent Citations (1)
Title |
---|
HUIQING REN ET AL.: "Affinity between metal-organic frameworks and polyimides in asymmetric mixed membranes for gas separations", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108034055A (en) * | 2017-12-29 | 2018-05-15 | 中国烟草总公司郑州烟草研究院 | A kind of covalent organic framework solid-phase micro-extraction fibre and preparation method thereof |
WO2020249834A1 (en) | 2019-06-14 | 2020-12-17 | Universidad De La Laguna, Otri | Stationary phase for solid-phase microextraction device |
US11433372B1 (en) | 2019-06-14 | 2022-09-06 | Universidad De La Laguna, Otri | Stationary phase for solid-phase microextraction device |
CN111266094A (en) * | 2020-02-21 | 2020-06-12 | 山东省分析测试中心 | Method for analyzing genotoxic impurities of synthetic drugs based on solid-phase microextraction |
Also Published As
Publication number | Publication date |
---|---|
CN105536745B (en) | 2017-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108034055B (en) | Covalent organic framework solid phase micro-extraction fiber and preparation method thereof | |
Pan et al. | Highly efficient macroporous adsorbents for toxic metal ions in water systems based on polyvinyl alcohol–formaldehyde sponges | |
Zhu et al. | Preparation and characterization of porous carbon material-coated solid-phase microextraction metal fibers | |
CN103394336B (en) | Metal organic framework compound sol-gel coating stirring rod and preparation method and application thereof | |
US20180118974A1 (en) | Dispersion, method for coating objects with this dispersion, and use of the dispersion | |
CN105498553A (en) | Polyvinylidene fluoride and metal-organic framework composite ultra-filtration membrane and preparation and application | |
CN105536745A (en) | Metal-organic framework solid phase microextraction fiber and preparation method thereof | |
Zhou et al. | Cellulose acetate ultrafiltration membranes reinforced by cellulose nanocrystals: Preparation and characterization | |
CN102784562A (en) | Method for preparing metal organic framework film | |
CN105478018B (en) | A kind of preparation method of function multi-walled carbon nano-tube blended ultrafiltration membrane | |
CN107149881A (en) | A kind of dopamine modifying polymer film and preparation method thereof | |
CN102430349A (en) | Reverse osmosis composite membrane and preparation method thereof | |
CN110227358B (en) | Mixed matrix membrane based on two-dimensional layered material and preparation method and application thereof | |
CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
CN105107392A (en) | Multiwalled carbon nanotube surface-embedded modified polyvinylidene fluoride (PVDF) membrane and preparation method thereof | |
CN103464006A (en) | Preparation of PDMS/PVDF (polydimethylsiloxane/polyvinylidene fluoride) blended microporous film | |
CN103230747B (en) | Preparation method of composite film for water treatment | |
CN103991864A (en) | Preparation method of graphene aerogel | |
Koo et al. | Robust multifunctional superhydrophobic organic–inorganic hybrid macroporous coatings and films | |
CN109331798A (en) | A kind of preparation method of solid phase microextraction material | |
CN104248915B (en) | A kind of preparation method improving hydrophilic enhancement mode plate compounding microporous barrier | |
Wang et al. | Investigation of the attapulgite hybrid carbon molecular sieving membranes for permanent gas separation | |
CN113578078A (en) | Preparation method and application of mixed matrix membrane based on nitrogen-doped porous carbon spheres | |
CN106633170A (en) | Nano-diamond filled polyimide based compound aerogel material and preparation method thereof | |
CN103691325A (en) | Preparation method of ethanol permselective inorganic particles/PVDF (Polyvinylidene Fluoride) composite membrane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |