CN107096568A - Metal organic framework film for catalytic degradation organic pollution and preparation method thereof - Google Patents
Metal organic framework film for catalytic degradation organic pollution and preparation method thereof Download PDFInfo
- Publication number
- CN107096568A CN107096568A CN201710312666.4A CN201710312666A CN107096568A CN 107096568 A CN107096568 A CN 107096568A CN 201710312666 A CN201710312666 A CN 201710312666A CN 107096568 A CN107096568 A CN 107096568A
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- Prior art keywords
- zif
- film
- pan
- organic framework
- solution
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000015556 catabolic process Effects 0.000 title claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 31
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 1
- JGIDSJGZGFYYNX-YUAHOQAQSA-N indian yellow Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC1=CC=C(OC=2C(=C(O)C=CC=2)C2=O)C2=C1 JGIDSJGZGFYYNX-YUAHOQAQSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of for metal organic framework film of catalytic degradation organic pollution and preparation method thereof.Its step is：1）By the nano-particle ultrasonic disperses of ZIF 67 in N, N dimethylformamides (DMF) solution, polyacrylonitrile is added（PAN）, stirring to the nano-particles of ZIF 67 and polyacrylonitrile are well mixed；2）Using mixed solution as spinning solution, using electrostatic spinning technique, the PAN of ZIF 67 film is obtained.The PAN films of ZIF 67 prepared by the present invention have good pliability, with very high catalytic activity, and can for a long time recycle, solve metal-organic framework materials and easily reunite in the solution, be difficult the problem of reuse.The application aspect of organic pollution shows superperformance in degrading waste water.
Description
Technical field
The invention belongs to environment field of nanometer material technology, and in particular to a kind of metal for catalytic degradation organic pollution has
Machine skeleton film and preparation method thereof.
Background technology
The today developed rapidly in urbanization and industrialization, environmental pollution has become the focus in the world, caused more next
The strong interest of more people.Wherein, Organic Pollution, especially organic dyestuff pollute, because it can be to water transparency and gas
Solubility causes to have a strong impact on, and possesses high toxicity, carcinogenicity and mutagenicity in addition with some dyestuffs, can pass through biological chain
And accumulate.Therefore, a kind of effective ways that can be used in handling the industrial wastewater containing organic dyestuff are found, for alleviating China
The severe problem of environmental pollution faced is particularly important.
The advanced oxidation processes based on potentiometric titrations, because it possesses higher oxidizing potential, possess good in recent years
Selectivity and the series of advantages such as high efficiency, have become a kind of selection having a bright future.Lin Kun Apparatus seminars
（Chemosphere 130 (2015) 66-72）Report first by cabaltous nitrate hexahydrate and 2-methylimidazole（2-MIM）Instead
ZIF-67 should be prepared, and applied to catalysis potentiometric titrations aspect.But, because MOF materials are easily reunited in itself, it is difficult to return
Receive, have impact on its application among actual production.
The content of the invention
It is an object of the invention to provide a kind of metal organic framework film for catalytic degradation organic pollution and its
Metal-organic framework materials ZIF-67 is prepared into film by preparation method, this method by electrostatic spinning technique, and this method is made
ZIF-67-PAN films there is good pliability, with very high catalytic activity, and can recycle for a long time.
Realize that the object of the invention technical scheme is as follows：
It is a kind of for metal organic framework film of catalytic degradation organic pollution and preparation method thereof, comprise the following steps that：
Step 1, by metal-organic framework materials ZIF-67, ultrasound, to scattering completely, is made into dense in DMF
The dispersion liquid for 0.04 ~ 0.12g/mL is spent, the mass ratio added with ZIF-67 is 4：The polyacrylonitrile of (1 ~ 3), stirring to mixing
Uniformly, electrostatic spinning solution is obtained；
Step 2, the malleation for setting spinning voltage is 10 ~ 12 kilovolts, and negative pressure is 1 ~ 3 kilovolt, injects speed for 0.08 ~ 0.1 mm/
Min, the electrostatic spinning solution that step 1 is obtained carries out electrostatic spinning, obtains ZIF-67-PAN films.
Preferably, in step 1, in being stirred at 60 ~ 70 DEG C to well mixed.
Compared with prior art, the inventive method is simple, and obtained ZIF-67-PAN films solve metal organic framework
Material is easily reunited in the solution, the problem being not easily recycled, and has good catalytic activity simultaneously.Therefore, in degrading waste water
The application aspect of middle organic pollution has very big application potential.
Brief description of the drawings
Fig. 1 is ZIF-67-PAN film preparation schematic diagrames.
Fig. 2 is the X-ray powder diffraction figure of the ZIF-67 and ZIF-67-PAN films of embodiment 1.
Fig. 3 is the ZIF-67-PAN films of embodiment 1, the PAN films of blank, the contrast of ZIF-67 degraded Indian yellows 17
Figure.
Fig. 4 is the ZIF-67-PAN film catalysts degraded circulation experiment of embodiment 1.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
Step 1,0.6 g ZIF-67 powder is dissolved in 5 mL DMF, ultrasound is completely dispersed it, added
0.8 g polyacrylonitrile, at 60 DEG C, magnetic agitation makes ZIF-67 nano-particles and PAN well mixed.
Step 2, the mixed solution that step 1 is obtained is poured into 5 mL syringe, using electrostatic spinning technique, malleation is
10 kilovolts, negative pressure is 2 kilovolts, injects speed for 0.09 mm/min, obtains ZIF-67-PAN films.
It is as shown in Figure 1 that it prepares schematic diagram.Obtain the X-ray powder diffraction figure of ZIF-67-APN films as shown in Fig. 2
There it can be seen that containing ZIF-67 on film.
Embodiment 2
Step 1,0.2 g ZIF-67 powder is dissolved in 5 mL DMF, ultrasound is completely dispersed it, added
0.8 g polyacrylonitrile, at 60 DEG C, magnetic agitation makes ZIF-67 nano-particles and PAN well mixed.
Step 2, the mixed solution that step 1 is obtained is poured into 5 mL syringe, using electrostatic spinning technique, malleation is
11 kilovolts, negative pressure is 1 kilovolt, injects speed for 0.09 mm/min, obtains ZIF-67-PAN films.
Embodiment 3
Step 1,0.4 g ZIF-67 powder is dissolved in 5 mL DMF, ultrasound is completely dispersed it, added
0.8 g polyacrylonitrile, at 60 DEG C, magnetic agitation makes ZIF-67 nano-particles and PAN well mixed.
Step 2, the mixed solution that step 1 is obtained is poured into 5 mL syringe, using electrostatic spinning technique, malleation is
12 kilovolts, negative pressure is 3 kilovolts, injects speed for 0.09 mm/min, obtains ZIF-67-PAN films.
Catalytic degradation application example
ZIF-67-PAN films in example 1 are used to be catalyzed potassium hydrogen persulfate degradable organic pollutant Indian yellow 17.
Compound concentration is 500 mg L first-1The mL of 17 solution of Indian yellow 100, add 50 mg potassium hydrogen persulfate claim,
The above-mentioned mg of ZIF-67-PAN 23 are taken to be added to as catalyst in the solution of Indian yellow 17, the MB solution for being not added with any catalyst is done
Blank control test, at interval of 30 seconds, takes 3mL solution to be analyzed, does the ultra-violet absorption spectrum of solution, concentration ratio is then done again
ValueC/C 0 To time t curve (C 0 For the initial concentration of Indian yellow 17,CBe the time be t when Indian yellow 17 concentration), such as Fig. 3 institutes
Show.Fig. 4 is circulation experiment, there it can be seen that its catalytic activity can still keep more than 98% after 5 circulations, illustrates this hair
The ZIF-67-PAN films of bright preparation can be very good recycling.ZIF-67-PAN films are applied to actual filtering dress
Put, 100 mg L-1The solution of Indian yellow 17 in its natural state pass through ZIF-67-PAN films, substantially can be with degradable.
Can significantly it find out from practical application effect, ZIF-67-PAN films prepared by the present invention have good catalysis
Activity, and the problem of nano-particle is not easily recycled utilization in actual applications is solved, the organic pollution in degrading waste water
Aspect has good application prospect.
Claims (4)
1. a kind of metal organic framework film for catalytic degradation organic pollution, it is characterised in that prepared by following steps：
Step 1, by metal-organic framework materials ZIF-67 in DMF ultrasound to scattering completely, add with
ZIF-67 mass ratio is 4：The polyacrylonitrile of (1 ~ 3), stirring obtains electrostatic spinning solution to well mixed；
Step 2, the malleation for setting spinning voltage is 10 ~ 12 kilovolts, and negative pressure is 1 ~ 3 kilovolt, injects speed for 0.08 ~ 0.1 mm/
Min, the electrostatic spinning solution that step 1 is obtained carries out electrostatic spinning, obtains ZIF-67-PAN films.
2. film as claimed in claim 1, it is characterised in that in step 1, in being stirred at 60 ~ 70 DEG C to well mixed.
3. film as claimed in claim 1, it is characterised in that in step 1, by metal-organic framework materials ZIF-67 in N,
Ultrasound is made into the dispersion liquid that concentration is 0.04 ~ 0.12g/mL to scattering completely in dinethylformamide.
4. the preparation method of the film as described in claim 1-3 is any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710312666.4A CN107096568A (en) | 2017-05-05 | 2017-05-05 | Metal organic framework film for catalytic degradation organic pollution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710312666.4A CN107096568A (en) | 2017-05-05 | 2017-05-05 | Metal organic framework film for catalytic degradation organic pollution and preparation method thereof |
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| CN201710312666.4A Pending CN107096568A (en) | 2017-05-05 | 2017-05-05 | Metal organic framework film for catalytic degradation organic pollution and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854877A (en) * | 2018-06-13 | 2018-11-23 | 苏州大学 | The quickly method of preparation green MOFs porous microsphere |
| CN109576903A (en) * | 2018-10-29 | 2019-04-05 | 南京理工大学 | FeCo is Prussian blue/preparation method of polyacrylonitrile film |
| CN109763333A (en) * | 2018-12-12 | 2019-05-17 | 浙江工业大学 | Method for preparing metal organic framework through modified carrier |
| CN111733486A (en) * | 2020-06-11 | 2020-10-02 | 南京理工大学 | Carbon fiber film for high-efficiency persulfate catalysis and preparation method thereof |
| CN112501791A (en) * | 2020-12-02 | 2021-03-16 | 新乡学院 | Cobalt-loaded hollow carbon fiber film for efficiently removing 4-nitrophenol and preparation method thereof |
| CN113044952A (en) * | 2021-03-22 | 2021-06-29 | 东莞理工学院 | Preparation method of metal organic framework nanofiber membrane and method for activating monoperoxybisulfate to treat organic wastewater by using same |
| CN114733497A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | Light-reproducible metal-organic framework composite film and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108854877A (en) * | 2018-06-13 | 2018-11-23 | 苏州大学 | The quickly method of preparation green MOFs porous microsphere |
| CN109576903A (en) * | 2018-10-29 | 2019-04-05 | 南京理工大学 | FeCo is Prussian blue/preparation method of polyacrylonitrile film |
| CN109763333A (en) * | 2018-12-12 | 2019-05-17 | 浙江工业大学 | Method for preparing metal organic framework through modified carrier |
| CN109763333B (en) * | 2018-12-12 | 2021-05-07 | 浙江工业大学 | Method for preparing metal organic framework through modified carrier |
| CN111733486A (en) * | 2020-06-11 | 2020-10-02 | 南京理工大学 | Carbon fiber film for high-efficiency persulfate catalysis and preparation method thereof |
| CN111733486B (en) * | 2020-06-11 | 2022-07-22 | 南京理工大学 | Carbon fiber film for high-efficiency persulfate catalysis and preparation method thereof |
| CN112501791A (en) * | 2020-12-02 | 2021-03-16 | 新乡学院 | Cobalt-loaded hollow carbon fiber film for efficiently removing 4-nitrophenol and preparation method thereof |
| CN113044952A (en) * | 2021-03-22 | 2021-06-29 | 东莞理工学院 | Preparation method of metal organic framework nanofiber membrane and method for activating monoperoxybisulfate to treat organic wastewater by using same |
| CN114733497A (en) * | 2022-05-06 | 2022-07-12 | 福州大学 | Light-reproducible metal-organic framework composite film and preparation method and application thereof |
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Application publication date: 20170829 |