CN109603572A - A kind of preparation method of ZIF-8 composite membrane - Google Patents
A kind of preparation method of ZIF-8 composite membrane Download PDFInfo
- Publication number
- CN109603572A CN109603572A CN201811520527.1A CN201811520527A CN109603572A CN 109603572 A CN109603572 A CN 109603572A CN 201811520527 A CN201811520527 A CN 201811520527A CN 109603572 A CN109603572 A CN 109603572A
- Authority
- CN
- China
- Prior art keywords
- zif
- composite membrane
- film
- preparation
- zno
- 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.)
- Pending
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
-
- 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
- B01D69/04—Tubular membranes
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of preparation methods of ZIF-8 composite membrane, this method is using ZnO nano piece as source metal, ZIF-8/PES composite membrane is obtained by hydro-thermal growth in situ, the film has preferable separating property to gas separation, it is thicker to solve existing metal organic framework composite membrane separating layer using the method for the present invention, the problems such as distributional pattern is uneven and separating property, prepared composite membrane has preferable separation property and stability, expands the scope of application of film.
Description
(1) technical field
The present invention relates to a kind of preparation methods of metal-organic framework materials composite membrane, and in particular to a kind of ZIF-8 is compound
The preparation method of film.
(2) background technique
Environmental energy issue concerns to the living environment and following global evolution of the mankind, have become current one it is important
Project.Membrane separation technique obtains rapidly in recent years because its is environmental-friendly, separated volume is small, low energy consumption, the advantages such as easy to operate
Development, and more and more paid attention to.Currently, being used widely in the industry is polymer film, but with point
The variation of development and separation system from technology, many polymer films are difficult to reach the requirement efficiently separated；Meanwhile for more
The separation process of kind mixed system hinders further there are the relationship that permselective property and permeation flux restrict each other
Development.Therefore, the membrane material with excellent properties is selected and found, is always the hot spot of membrane separation technique exploitation and research.
Metal-organic framework materials (Metal-organic frameworks, abbreviation MOFs) are a kind of novel porous
Framework material is made of organic and inorganic two parts, while possessing organic and inorganic porous material property.With zeolite molecular sieve
It is compared with porous organic material, MOFs material has wider bore hole size range, and hole configurations is easier with size
It is designed and accurately adjusts.In addition, the well table face of MOFs material has more various chemical property and is easier to be modified.
These characteristics be MOF film to the very similar gas molecule of molecular dynamics diameter such as
WithThe equal efficient selective membrane separation of carry out provides guarantee.Therefore, MOF film gas applied by porous material
Body separation field has more extensive application prospect.At the same time, the MOF film porosity and specific surface area big using MOFs,
The interaction between guest molecule and multi-function metal central ion or organic ligand is greatly strengthened, to improve the gas of film
Detection performance.The characteristic for designing and modifying adjusting of MOFs bore hole size simultaneously also further imparts MOF film to gas point
The selective detection performance of son.
(3) summary of the invention
The object of the present invention is to provide a kind of preparation methods of metal organic framework composite membrane for gas separation, use
It is thicker that this method solves existing metal organic framework composite membrane separating layer, and distributional pattern is uneven and separating property etc. is asked
Topic, prepared composite membrane have preferable separation property and stability, expand the scope of application of film.
The present invention obtains ZIF-8/PES composite membrane using ZnO nano piece as source metal, by hydro-thermal growth in situ, the film pair
Gas separation has preferable separating property.
Technical scheme is as follows:
A kind of preparation method of ZIF-8 composite membrane, the preparation method include the following steps:
(1) ZnO nano piece is synthesized
Two water zinc acetates are dissolved in deionized water, aqueous zinc acetate solution is obtained, are added in gained aqueous zinc acetate solution
Sodium hydrate aqueous solution stirs 10~40min, stands 20~90min, is centrifuged, washs later, dry (40~80 DEG C), obtaining
ZnO nano piece；
The two water zinc acetate, sodium hydroxide mass ratio be 1:1.6~8；
The aqueous zinc acetate solution concentration is 0.055mol/L；
The sodium hydrate aqueous solution concentration is 0.4~2mol/L；
The revolving speed of the centrifugation is 3000~8000r/min, and the time is 3~10min, deionized water and ethyl alcohol when centrifugation
Washing；
(2) ZnO nano piece obtained by step (1) is taken, the ZnO aqueous solution of 0.01~2mg/L is configured to, polymer film is impregnated
Polymer film, is put into the methanol of the 2-methylimidazole of 0.1~1mol/L by 10~120min in the ZnO aqueous solution again later
In solution, 0.5~4h is reacted at 30~80 DEG C, carries out the activation in the nucleating growth site of ZnO nano piece；
The material of the polymer film is, for example, polyether sulfone (PES), polyacrylonitrile (PAN), and shape is hollow-fibre membrane；
(3) by 0.5~10 parts by weight ZnCl2, 0.5~10 parts by weight 2-methylimidazole, 0.5~5 parts by weight sodium formate, 10
The mixing of~100 parts by weight Methanol, is configured to ZIF-8 precursor liquid, described by being immersed in by the polymer film of step (2) processing
In ZIF-8 precursor liquid, 5~48h is reacted at 40~150 DEG C, takes out film later, and cleaning (uses methanol), it is multiple to obtain the ZIF-8
Close film.
ZIF-8 composite membrane prepared by the present invention can be applied to gas separation, such as separating hydrogen/carbon dioxide,
The intake pressure difference of middle hydrogen/carbon dioxide is 0.01~5MPa, preferably 0.01~2MPa.
Compared with prior art, advantages of the present invention: successfully synthesizing ultra-thin ZIF-8 composite membrane using ZnO nano piece, tool
There is good screening function, and there is universality to the preparation of tubular membrane, gas separating property is obviously improved.
(4) Detailed description of the invention
Fig. 1 is the TEM electromicroscopic photograph of the ZnO nano piece ZIF-8/PES composite membrane in the embodiment of the present invention 1；
Fig. 2 is the ZnO nano piece TEM electromicroscopic photograph in the embodiment of the present invention 1；
Fig. 3 is the TEM electromicroscopic photograph of ZnO nano piece ZIF-8/PES composite membrane section in the embodiment of the present invention 1；
Fig. 4 is the TEM electromicroscopic photograph of ZIF-8/PAN composite membrane section in the embodiment of the present invention 2；
Fig. 5 is the TEM electromicroscopic photograph of ZIF-8/PAN composite membrane in the embodiment of the present invention 3.
(5) specific embodiment
Combined with specific embodiments below, the present invention is described in detail, but the present invention is not limited to the following embodiments,
It does not depart from the content of present invention and range, change all should be comprising within the technical scope of the present invention.
Embodiment 1:
(1) preparation of ZnO nano piece: firstly, by 1.6000g Zn (CH3COO)2·2H2O is completely dissolved in 100mL deionization
In water, the NaOH solution 100ml of 0.4mol/l is configured, under stiring, NaOH solution is slowly added to, stirs 20min, stand
30min is centrifuged 3000r/min, 3min.Then it is washed 3 times with dehydrated alcohol and deionization, it is dry, obtain ZnO nano piece.Fig. 2
For ZnO nano piece TEM electromicroscopic photograph
(2) preparation of ZnO/PES film: by ZnO nano piece prepared among the above, the ZnO/ aqueous solution with 1mg/l will
PES film impregnates 120min in the above solution.
(3) by the PES film in step 2, it is molten the activation in the growth site of ZnO/PES film: to be put into 1M 2-methylimidazole methanol
In liquid, 1h is reacted at 40 DEG C, carries out the activation in the nucleating growth site of ZnO nano piece.
(4) above-mentioned film the synthesis of ZnO/PES film: is synthesized into ZIF-8, quality in such a way that hydro-thermal is generated in-situ on film
Compare ZnCl2: 2-methylimidazole: sodium formate: methanol=1:2:1:20, the interior reaction of reaction kettle, temperature is 80 DEG C, for 24 hours, i.e., the time is
Obtain ZIF-8/PES composite membrane.
Gas separation test is carried out to ZIF-8/PES composite membrane, test condition: 25 DEG C of temperature, admission pressure 0.1Mpa,
Measure the separating property of gas are as follows: the flux of the hydrogen of obtained film is 3.74 × 10-5mol s-1m-2Pa-1, H2/CO2And H2/N2
Selectivity be respectively 3.70 and 2.53.
Embodiment 2:
(1) preparation of ZnO nano piece: firstly, by 1.6000g Zn (CH3COO)2·2H2O is completely dissolved in 100mL deionization
In water, the NaOH solution 100ml of 0.4mol/l is configured, under stiring, NaOH solution is slowly added to, stirs 20min, stand
30min is centrifuged 3000r/min, 3min.Then it is washed 3 times with dehydrated alcohol and deionization.It is dry, obtain ZnO nano piece.
(2) PAN membrane part hydrolyzes: PAN film being put into the NaOH solution of 2M and impregnates 2h.
(3) preparation of ZnO/PAN film: by ZnO nano piece prepared among the above, the ZnO/ methanol solution with 1mg/l will
PAN film impregnates 120min in the above solution.
(4) by the PAN film in step 2, it is molten the activation in the growth site of ZnO/PAN film: to be put into 1M 2-methylimidazole methanol
In liquid, 1h is reacted at 40 DEG C, carries out the activation in the nucleating growth site of ZnO nano piece.
(5) synthesis of ZnO/PAN film: synthesizing ZIF-8 in such a way that hydro-thermal is generated in-situ for above-mentioned film on film,
ZnCl2: 2-methylimidazole: sodium formate:Reaction in reaction kettle, temperature are 80 DEG C, time 10h, i.e.,
Obtain ZIF-8/PAN composite membrane.
Gas separation test is carried out to ZIF-8/PAN composite membrane, test condition: 25 DEG C of temperature, admission pressure 0.1Mpa,
Measure the separating property of gas are as follows: the flux of the hydrogen of obtained film is 8.88 × 10-8mol s-1m-2Pa-1, H2/CO2And H2/N2
Selectivity be respectively 3.70 and 14.72.
Embodiment 3:
(1) preparation of ZnO nano piece: firstly, by 1.6000g Zn (CH3COO)2·2H2O is completely dissolved in 100mL deionization
In water, the NaOH solution 100ml of 0.4mol/l is configured, under stiring, NaOH solution is slowly added to, stirs 20min, stand
30min is centrifuged 3000r/min, 3min.Then it is washed 3 times with dehydrated alcohol and deionization.It is dry, obtain ZnO nano piece.
(2) preparation of ZnO/PAN film: by ZnO nano piece prepared among the above, the ZnO/ methanol solution with 0.5mg/l,
PAN film is impregnated into 30min in the above solution.
(3) by the PAN film in step 2, it is molten the activation in the growth site of ZnO/PAN film: to be put into 1M 2-methylimidazole methanol
In liquid, 1h is reacted at 40 DEG C, carries out the activation in the nucleating growth site of ZnO nano piece.
(4) synthesis of ZnO/PAN film: synthesizing ZIF-8 in such a way that hydro-thermal is generated in-situ for above-mentioned film on film,
ZnCl2: 2-methylimidazole: sodium formate: reaction in methanol=1:2:1:20 reaction kettle, temperature are 80 DEG C, the time be 12h to get
To ZIF-8/PAN composite membrane.
Gas separation test is carried out to ZIF-8/PAN composite membrane, test condition: 25 DEG C of temperature, admission pressure 0.1Mpa,
Measure the separating property of gas are as follows: the flux of the hydrogen of obtained film is 4.20 × 10-8mol s-1m-2Pa-1, H2/CO2And H2/N2
Selectivity be respectively 8.56 and 9.30.
Claims (7)
1. a kind of preparation method of ZIF-8 composite membrane, which is characterized in that the preparation method includes the following steps:
(1) ZnO nano piece is synthesized
Two water zinc acetates are dissolved in deionized water, aqueous zinc acetate solution is obtained, hydrogen-oxygen is added in gained aqueous zinc acetate solution
Change sodium water solution, stir 10~40min, stand 20~90min, is centrifuged, washs later, is dry, obtaining ZnO nano piece；
The two water zinc acetate, sodium hydroxide mass ratio be 1:1.6~8；
(2) ZnO nano piece obtained by step (1) is taken, the ZnO aqueous solution of 0.01~2mg/L is configured to, polymer film is immersed in institute
10~120min in ZnO aqueous solution is stated, polymer film is put into the methanol solution of the 2-methylimidazole of 0.1~1mol/L again later
In, 0.5~4h is reacted at 30~80 DEG C, carries out the activation in the nucleating growth site of ZnO nano piece；
(3) by 0.5~10 parts by weight ZnCl2, 0.5~10 parts by weight 2-methylimidazole, 0.5~5 parts by weight sodium formate, 10~100
Parts by weight Methanol mixing, is configured to ZIF-8 precursor liquid, before being immersed in the ZIF-8 by the polymer film of step (2) processing
It drives in liquid, 5~48h is reacted at 40~150 DEG C, takes out film later, clean, obtain the ZIF-8 composite membrane.
2. the preparation method of ZIF-8 composite membrane as described in claim 1, which is characterized in that in step (1), the zinc acetate
Concentration of aqueous solution is 0.055mol/L.
3. the preparation method of ZIF-8 composite membrane as described in claim 1, which is characterized in that in step (1), the hydroxide
Sodium water solution concentration is 0.4~2mol/L.
4. the preparation method of ZIF-8 composite membrane as described in claim 1, which is characterized in that in step (2), the polymer
The material of film is polyether sulfone or polyacrylonitrile.
5. the preparation method of ZIF-8 composite membrane as described in claim 1, which is characterized in that in step (2), the polymer
The shape of film is hollow-fibre membrane.
6. ZIF-8 composite membrane made from preparation method as described in claim 1.
7. application of the ZIF-8 composite membrane as claimed in claim 6 in gas separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811520527.1A CN109603572A (en) | 2018-12-12 | 2018-12-12 | A kind of preparation method of ZIF-8 composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811520527.1A CN109603572A (en) | 2018-12-12 | 2018-12-12 | A kind of preparation method of ZIF-8 composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109603572A true CN109603572A (en) | 2019-04-12 |
Family
ID=66009013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811520527.1A Pending CN109603572A (en) | 2018-12-12 | 2018-12-12 | A kind of preparation method of ZIF-8 composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109603572A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111729518A (en) * | 2020-06-30 | 2020-10-02 | 南京工业大学 | Preparation method and application of ligand-doped metal organic framework hybrid ZIF-8membrane |
| KR20210008963A (en) * | 2019-07-15 | 2021-01-26 | 한국세라믹기술원 | Gas Separation Membrane and Method for Perparation thereof |
| CN113083042A (en) * | 2021-04-12 | 2021-07-09 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-composite material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794115A (en) * | 2012-08-01 | 2012-11-28 | 大连理工大学 | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film |
| CN104437116A (en) * | 2014-12-08 | 2015-03-25 | 大连理工大学 | Method for performing induced synthesis on MOFs (metal-organic frameworks) membrane by implanting homologous metal oxide particles into surface of macroporous carrier by virtue of swabbing process |
| CN105293563A (en) * | 2014-06-23 | 2016-02-03 | 清华大学 | Zinc oxide nano-sheet cluster and preparation method thereof |
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| CN107413204A (en) * | 2017-07-17 | 2017-12-01 | 大连理工大学 | The method for preparing highly oriented two-dimensional metallic organic backbone nanometer chip film using the inducing zinc growth of graphene oxide confinement |
| WO2017207424A1 (en) * | 2016-05-31 | 2017-12-07 | Eth Zurich | Self-supporting mof membranes |
| US20180326398A1 (en) * | 2017-05-10 | 2018-11-15 | Georgia Tech Research Corporation | Apparatus, Methods and Systems For Fabricating Thin Nanoporous Membranes |
-
2018
- 2018-12-12 CN CN201811520527.1A patent/CN109603572A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794115A (en) * | 2012-08-01 | 2012-11-28 | 大连理工大学 | Preparation method of metal organic framework ZIF-8 (zero insert force-9) film |
| CN105293563A (en) * | 2014-06-23 | 2016-02-03 | 清华大学 | Zinc oxide nano-sheet cluster and preparation method thereof |
| CN104437116A (en) * | 2014-12-08 | 2015-03-25 | 大连理工大学 | Method for performing induced synthesis on MOFs (metal-organic frameworks) membrane by implanting homologous metal oxide particles into surface of macroporous carrier by virtue of swabbing process |
| US20160243525A1 (en) * | 2016-05-02 | 2016-08-25 | LiSo Plastics, L.L.C. | Multilayer Polymeric Membrane and Process |
| WO2017207424A1 (en) * | 2016-05-31 | 2017-12-07 | Eth Zurich | Self-supporting mof membranes |
| US20180326398A1 (en) * | 2017-05-10 | 2018-11-15 | Georgia Tech Research Corporation | Apparatus, Methods and Systems For Fabricating Thin Nanoporous Membranes |
| CN107413204A (en) * | 2017-07-17 | 2017-12-01 | 大连理工大学 | The method for preparing highly oriented two-dimensional metallic organic backbone nanometer chip film using the inducing zinc growth of graphene oxide confinement |
Non-Patent Citations (2)
| Title |
|---|
| SAMUEL C. HESS等: "MOF Channels within Porous Polymer Film: Flexible, Self-Supporting ZIF-8 Poly(ether sulfone) Composite Membrane", 《CHEMISTRY OF MATERIALS》 * |
| 罗杨合: "《化学分离分析方法与技术研究》", 31 January 2014, 中国商务出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210008963A (en) * | 2019-07-15 | 2021-01-26 | 한국세라믹기술원 | Gas Separation Membrane and Method for Perparation thereof |
| KR102233697B1 (en) | 2019-07-15 | 2021-03-30 | 한국세라믹기술원 | Gas Separation Membrane and Method for Perparation thereof |
| CN111729518A (en) * | 2020-06-30 | 2020-10-02 | 南京工业大学 | Preparation method and application of ligand-doped metal organic framework hybrid ZIF-8membrane |
| CN111729518B (en) * | 2020-06-30 | 2022-05-17 | 南京工业大学 | Preparation method and application of ligand-doped metal organic framework hybrid ZIF-8membrane |
| CN113083042A (en) * | 2021-04-12 | 2021-07-09 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-composite material and preparation method thereof |
| CN113083042B (en) * | 2021-04-12 | 2021-12-21 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Hydrophobic-ZIF-71 filled PEBA mixed matrix membranes for recovery of biobutanol via pervaporation | |
| CN106390768B (en) | A kind of zeolite imidazole ester skeleton/polyamide composite film and preparation method thereof | |
| CN109603572A (en) | A kind of preparation method of ZIF-8 composite membrane | |
| CN105126642B (en) | A kind of preparation of metal organic framework film with separate gas application | |
| Abdelhamid | Removal of carbon dioxide using zeolitic imidazolate frameworks: adsorption and conversion via catalysis | |
| CN109195700A (en) | self-supporting MOF film | |
| CN107158964B (en) | Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation | |
| CN110026097B (en) | Preparation method of PIM-1@ MOFs/polymer composite pervaporation membrane | |
| CN107469648B (en) | Preparation method of polytetrafluoroethylene hollow fiber composite membrane | |
| Si et al. | Carbonized ZIF-8 incorporated mixed matrix membrane for stable ABE recovery from fermentation broth | |
| CN108097070B (en) | Zeolite imidazole ester doped polyether block amide gas separation membrane and preparation method and application thereof | |
| CN110105580B (en) | Hierarchical pore zeolite imidazole ester framework material and preparation method thereof | |
| CN107312181B (en) | Method for rapidly preparing Cu-BTC | |
| CN105879708B (en) | A kind of method for preparing the metal organic framework films of Co ZIF 67 using not homologous zinc oxide film induction | |
| Kang et al. | In situ confinement of free linkers within a stable MOF membrane for highly improved gas separation properties | |
| CN106310984A (en) | Dopamine-modified metal organic compound/polyether co-polyamide mixed substrate membrane and preparation and application thereof | |
| Guo et al. | Post-synthetic modification of highly stable UiO-66-NH2 membranes on porous ceramic tubes with enhanced H2 separation | |
| CN112934007B (en) | Method for preparing ZIF-8/GO composite gas separation membrane by converting ZIF-8 precursor | |
| CN111617645A (en) | Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material | |
| CN108479434B (en) | Preparation method and application of Li-doped HKUST-1 membrane material | |
| CN112156659A (en) | M-gate metal organic framework membrane and preparation method and application thereof | |
| Wang et al. | A polyvinyl alcohol‐based mixed matrix membrane with uniformly distributed Schiff base network‐1 for ethanol dehydration | |
| CN110917822A (en) | High-flux high-selectivity thin-layer composite membrane for hydrogen separation and preparation method thereof | |
| CN113385055B (en) | Preparation method of composite material UiO-66@ HNT-based mixed matrix film | |
| CN110227359A (en) | A kind of N2The preparation method and application of preferential infiltration ZIF-8 composite membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190412 |