CN117427622A - ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel and preparation method and application thereof - Google Patents
ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel and preparation method and application thereof Download PDFInfo
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 140
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 89
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 76
- 239000004964 aerogel Substances 0.000 title claims abstract description 61
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 60
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 35
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 35
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 35
- 239000000661 sodium alginate Substances 0.000 claims abstract description 35
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 35
- 239000011780 sodium chloride Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 16
- 238000007885 magnetic separation Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 metal cations Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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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
- B01J20/22—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]
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
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- 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
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- B01J20/28047—Gels
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel and a preparation method thereof, wherein Fe is generated on the surface of halloysite by an in-situ growth method 3 O 4 The method comprises the steps of forming magnetic halloysite by nano particles, wrapping sodium alginate on the surface of the magnetic halloysite, growing ZIF-8 nano particles on the surface in situ to form ZIF-8 in-situ modified magnetic halloysite, and finally taking polyvinylidene fluoride as a matrix, wherein the ZIF-8 in-situ modified magnetic halloysite is used as a nano filler, and the ZIF is prepared by taking sodium chloride as a sacrificial template-8 in situ modification of magnetic halloysite/polyvinylidene fluoride composite aerogel. The ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is applied to oil-water separation. The invention solves the hydrophilic problem of halloysite and the problem that ZIF-8 material is easy to fall off, and prepares the multi-scale and multi-stage composite adsorption which has the advantages of super-hydrophobic/super-oleophylic property, large oil absorption, low cost and easy recovery.
Description
Technical Field
The invention relates to halloysite/polyvinylidene fluoride composite aerogel and a preparation method and application thereof, and belongs to the technical field of adsorbents.
Background
The marine oil leakage can seriously pollute the marine ecological environment, and the existing methods for treating the oil leakage mainly comprise a physical treatment method, a chemical treatment method, a biological treatment method and the like. Compared with biological treatment and chemical treatment, the physical treatment is simple in operation and can quickly relieve the problem of petroleum leakage and pollution. However, various adsorption materials used at present have lower efficiency in terms of cleaning and recycling spilled oil, are inconvenient to recycle, and in addition, the adsorption materials with better natures are generally high in preparation cost.
The metal organic frameworks (Metal Organic Frameworks, MOFs) are crystalline porous materials with periodic network structures formed by self-assembly interconnection of inorganic metal centers (metal ions or metal clusters) and bridged organic ligands. Compared with other porous materials, MOFs have adjustable high porosity, high specific surface area, excellent thermochemical stability and modifiable wettability, but MOFs are used as independent adsorption materials, whether in powder form or spherical form, the MOFs are easy to fall off in the use process, the falling MOFs can cause environmental pollution, most of the environment cannot be subjected to autonomous absorption treatment, and therefore secondary pollution caused in the application process is even more than the original polluted difficult-to-treat condition, and the application of MOFs in the oil-water separation field is greatly limited as a result of inversion of the original end.
The halloysite monoclinic system water-containing layered silicate clay mineral is a tubular nanotube, and has a hollow channel inside, and has the advantages of unique hollow tubular structure, large specific surface area, abundant reserves, low cost, wide material sources and the like, so that the water-containing layered silicate clay mineral has good application prospects in the field of oil-water separation. However, halloysite has excellent hydrophilicity, and the oil-water selectivity of halloysite is greatly reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel, which solves the problems of low oil-water selectivity caused by halloysite hydrophilicity and easy shedding of the ZIF-8, and ensures that the composite aerogel has super-hydrophobic/super-oleophylic characteristics. The invention provides a preparation method and application of ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
The technical scheme of the invention is as follows: ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel, wherein polyvinylidene fluoride is used as a matrix, ZIF-8 in-situ modified magnetic halloysite is used as a nano filler, and the ZIF-8 in-situ modified magnetic halloysite is used for generating Fe on the surface of the halloysite 3 O 4 And after the nano particles form magnetic halloysite, ZIF-8 nano particles are grown on the surface of the magnetic halloysite in situ.
Another aspect of the inventionThe technical scheme is as follows: a preparation method of ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel comprises the following steps: fe is generated on the surface of halloysite by an in-situ growth method 3 O 4 The nano particles form magnetic halloysite, sodium alginate is wrapped on the surface of the magnetic halloysite, ZIF-8 nano particles are grown on the surface of the magnetic halloysite in situ to form ZIF-8 in situ modified magnetic halloysite, finally polyvinylidene fluoride is used as a matrix, the ZIF-8 in situ modified magnetic halloysite is used as a nano filler, and the ZIF-8 in situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is prepared by using sodium chloride as a sacrificial template.
Further, the preparation method comprises the steps of:
s1, adding halloysite into an aqueous solution of ferric salt, stirring, adjusting the pH value of a reaction solution to be alkaline under a protective atmosphere after reaction, continuously stirring for reaction, washing to be neutral through magnetic separation and deionized water, and freeze-drying to obtain magnetic halloysite;
s2, adding the magnetic halloysite into an aqueous solution of sodium alginate, performing magnetic separation after uniformly dispersing and stirring, and sequentially performing centrifugal cleaning by using alcohol and deionized water to obtain the magnetic halloysite with the surface coated with sodium alginate;
s3, dispersing the magnetic halloysite coated with sodium alginate on the surface into a hexahydrate zinc nitrate aqueous solution for stirring, performing magnetic separation after reaction, dispersing a magnetically separated sample into a dimethylimidazole aqueous solution, performing in-situ growth reaction under stirring, performing magnetic separation, washing with deionized water, and performing freeze drying to obtain ZIF-8 in-situ modified magnetic halloysite;
and S4, uniformly grinding the polyvinylidene fluoride and sodium chloride, adding the ZIF-8 in-situ modified magnetic halloysite, uniformly stirring, heating, drying and forming the mixed powder, removing the sodium chloride, and freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
Further, the iron salt is formed by FeCl 3 ·6H 2 O and FeSO 4 ·7H 2 O is composed according to the mol ratio of 3-1:1, the concentration of the aqueous solution of the ferric salt is 0.1-0.8 mg/ml, and the erloting is prepared by the following steps ofThe mass ratio of the stone to the ferric salt is 1:0.5-3.
Further, the concentration of the sodium alginate aqueous solution is 2-15 mg/ml, and the mass ratio of the magnetic halloysite to the sodium alginate is 1:0.5-5.
Further, in the step S3, the mass ratio of the sodium alginate magnetic halloysite to the zinc nitrate hexahydrate coated on the surface is 1-5:1, and the concentration of the zinc nitrate hexahydrate aqueous solution is 0.02-0.2 g/ml.
Further, the concentration of the dimethyl imidazole aqueous solution is 0.05-0.3 g/ml, and the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 1-3:1.
Further, in the step S4, the mass ratio of the polyvinylidene fluoride, the sodium chloride and the ZIF-8 in-situ modified magnetic halloysite is 1:5-10:0.1-0.6.
Further, the heating temperature is 100-300 ℃ during the heating, drying and forming, and the sodium chloride removal is to soak the formed sample in water at 60-150 ℃ for 15-30 h, and change the water every 1-4 hours.
The invention also provides a technical scheme that: the application of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is characterized in that the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is used for oil-water separation.
Compared with the prior art, the technical scheme provided by the invention has the advantages that:
(1) According to the invention, a reaction site is provided for ZIF-8 growth by means of chelation between sodium alginate and metal cations, ZIF-8 nanoparticles are grown on the surface of halloysite in situ, so that the problems that ZIF-8 is unstable and easy to fall off in the use process are solved, the hydrophobic property of halloysite is effectively improved, and meanwhile, the application of ZIF-8 materials and halloysite in the field of oil-water separation is effectively promoted.
(2) The aerogel prepared by the invention takes hydrophobic polyvinylidene fluoride as a matrix and has a micro-nano multi-stage structure of ZIF-8 and halloysite, and the hollow tubular structure of halloysite and the nano pore canal of ZIF-8 are utilized in a coordinated manner, so that the oil absorption and oil absorption rate of the aerogel are effectively improved.
(3) The aerogel prepared by the method provided by the invention provides a reaction site for ZIF-8 growth by utilizing the chelation of sodium alginate and metal cations, and meanwhile, the aerogel has magnetism, and the quick recovery of the adsorption material can be realized through simple magnetic adsorption.
(4) The halloysite with abundant reserves, low price and wide sources is successfully applied to the oil-water separation aerogel, so that the manufacturing cost of the adsorption material is effectively reduced.
Drawings
FIG. 1 is a process diagram of a preparation method of an oil-water separation aerogel provided by an embodiment of the invention.
Detailed Description
The present invention is further described below with reference to examples, which are to be construed as merely illustrative of the present invention and not limiting of its scope, and various modifications to the equivalent arrangements of the present invention will become apparent to those skilled in the art upon reading the present description, which are within the scope of the appended claims.
Example 1
Referring to fig. 1, the preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel comprises the following steps:
(a) Preparation of ZIF-8 in-situ modified magnetic halloysite
S1 100mg of ferric salt (FeCl) 3 ·6H 2 O and FeSO 4 ·7H 2 O in a molar ratio of 2:1) was dissolved in 200ml of deionized water, then 100mg of halloysite was added thereto, and the reaction was stirred for 3 hours under N 2 Dropwise adding NH into the reaction liquid under atmosphere 3 ·H 2 O, continuously stirring and reacting for 3 hours until the pH value of the solution reaches 13, magnetically separating, washing with deionized water to be neutral, and freeze-drying to obtain magnetic halloysite;
s2, adding the magnetic halloysite prepared in the step S1 into an aqueous sodium alginate solution, wherein the mass ratio of the magnetic halloysite to the sodium alginate is 1:3, the concentration of the aqueous sodium alginate solution is 5mg/ml, the ultrasonic dispersion is uniform, stirring is carried out for 5 hours, magnetic separation is carried out, and alcohol and deionized water are sequentially used for cleaning, so that the magnetic halloysite with the surface coated with the sodium alginate is obtained;
s3, dispersing the magnetic halloysite coated with the sodium alginate on the surface, which is prepared in the step S2, in a zinc nitrate hexahydrate water solution, wherein the mass ratio of the magnetic halloysite coated with the sodium alginate on the surface to the zinc nitrate hexahydrate is 1:1, and the concentration of the zinc nitrate hexahydrate water solution is 0.03 g/ml. After stirring the reaction solution for 3 hours, magnetically separating, and dispersing the product in a dimethyl imidazole aqueous solution, wherein the concentration of the dimethyl imidazole aqueous solution is 0.15g/ml, and the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 2:1. And (3) in-situ growing for 5 hours under stirring, magnetic separation, washing with deionized water, and freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite (ZIF-8@magnetic halloysite).
(b) Preparation of ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel
1g of PVDF (polyvinylidene fluoride, derived from a Michael reagent, having an average molecular weight of 400000, and hereinafter referred to as PVDF using the same reagent) and 6g of sodium chloride were put into a mortar, and after sufficiently grinding uniformly, 0.1g of the prepared ZIF-8@magnetic halloysite was added and stirred uniformly. Putting the mixed powder into a glass beaker, then putting into a 200 ℃ oven, thermoforming for 45min, taking out a block sample, soaking the block sample in 85 ℃ water for 20 h, and replacing the water every 3h to remove a sodium chloride template, thereby forming a porous structure. And finally, freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
Example 2
This embodiment differs from embodiment 1 in that: in step (b) of this example, 0.2g of ZIF-8@magnetic halloysite was added.
Example 3
This embodiment differs from embodiment 1 in that: in step (b) of this example, 0.25g of ZIF-8@magnetic halloysite was added.
Example 4
This embodiment differs from embodiment 1 in that: in step (b) of this example, 0.3g of ZIF-8@magnetic halloysite was added.
The ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel prepared by the embodiment can be used for oil-water separation.
Comparative example 1
The aerogel was prepared in the same manner as in step (b) of example 1, but no ZIF-8@ magnetic halloysite was added during the experiment to prepare pure polyvinylidene fluoride.
Comparative example 2
The aerogel was prepared in the same manner as in step (b) of example 1, but 0.25g of unmodified halloysite was added during the experiment to prepare a halloysite/polyvinylidene fluoride composite aerogel.
Comparative example 3
Preparing 80ml of zinc nitrate hexahydrate water solution with the concentration of 0.03 and g/ml, then adding 32 and ml of dimethyl imidazole water solution with the concentration of 0.15g/ml under rapid stirring, stirring for in-situ growth for 5 hours, magnetic separation, washing with deionized water, and freeze-drying to obtain the pure ZIF-8 nano particles. An aerogel was then prepared following step (b) of example 1, but 0.25g of the pure ZIF-8 nanoparticles prepared as described above was added during the experiment to produce a ZIF-8/polyvinylidene fluoride composite aerogel.
The composite aerogels prepared in the above examples and comparative examples were evaluated for water contact angle and adsorption capacity for petroleum, which is defined as the mass ratio of adsorbed oil to the foam composite aerogel itself when the composite aerogel is saturated with oil. The results are shown in Table 1. The specific test method comprises the following steps:
water contact angle test: a contact angle tester (model SDC-350H) was used to test the contact angle between the test specimen and water, and the sample was sanded with sandpaper prior to testing to ensure the sample plane level. Samples were placed on a laboratory bench, water was added dropwise to the surface of the samples using a syringe in an amount of 5 μl, and at least six different positions on each sample were tested, and the results were averaged.
Adsorption capacity test: first, 100 ml of petroleum was poured into a beaker, and an initial sample was weighed, and the initial weight was recorded as M0. Then, the sample was immersed in petroleum for about 10 minutes, and the residual liquid on the surface was drained off after removal, and the sample was wiped with filter paper to remove the excess oil. The adsorbed sample was then weighed and the weight was recorded as M1. The measurement was repeated three times, and the average value was calculated as the adsorption result of the sample. The adsorption capacity for petroleum was (M1-M0)/M0.
TABLE 1 Water contact Angle and Petroleum adsorption Capacity of aerogels prepared in examples 1-4 and comparative examples
The above results show that when the mass ratio of the fixed PVDF to the sodium chloride is 1:6 and the mass ratio of the PVDF to the ZIF-8@magnetic halloysite is 1:0.25, the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel has optimal hydrophobicity and adsorption capacity to petroleum.
Comparative example 1 the introduction of ZIF-8@ magnetic halloysite can significantly increase the hydrophobicity and adsorption capacity of the aerogel to petroleum compared to the examples. The composite aerogel of the comparative example 2 has poor hydrophobic property and small adsorption amount to petroleum because the unmodified halloysite has certain hydrophilicity and lacks the nano pore canal of ZIF-8 for cooperative adsorption. When ZIF-8 was added alone to the composite aerogel of comparative example 3, there was no Fe 3 O 4 The nanoparticle and halloysite cooperatively construct a micro-nano multi-stage structure, and meanwhile, the hollow tubular cooperative adsorption effect of the halloysite is lacked, and the hydrophobic property and the adsorption capacity to petroleum are obviously lower than those of the ZIF-8 in-situ modified magnetic halloysite/PVDF composite aerogel.
Example 5
The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel comprises the following steps:
(a) Preparation of ZIF-8 in-situ modified magnetic halloysite
S1 50mg of iron salt (FeCl) 3 ·6H 2 O and FeSO 4 ·7H 2 O in a molar ratio of 3:1) was dissolved in 500ml of deionized water, then 100mg of halloysite was added thereto, and the reaction was stirred for 3 hours under N 2 Dropwise adding NH into the reaction liquid under atmosphere 3 ·H 2 O, continuously stirring and reacting for 3 hours until the pH value of the solution reaches 13, magnetically separating, washing with deionized water to be neutral, and freeze-drying to obtain the magnetic materialHalloysite;
s2, adding the magnetic halloysite prepared in the step S1 into an aqueous sodium alginate solution, wherein the mass ratio of the magnetic halloysite to the sodium alginate is 1:0.5, the concentration of the aqueous sodium alginate solution is 2mg/ml, the ultrasonic dispersion is uniform, stirring is carried out for 5 hours, magnetic separation is carried out, and alcohol and deionized water are sequentially used for cleaning, so that the magnetic halloysite with the surface coated with the sodium alginate is obtained;
s3, dispersing the magnetic halloysite coated with the sodium alginate on the surface, which is prepared in the step S2, in a zinc nitrate hexahydrate water solution, wherein the mass ratio of the magnetic halloysite coated with the sodium alginate on the surface to the zinc nitrate hexahydrate is 3:1, and the concentration of the zinc nitrate hexahydrate water solution is 0.02g/ml. After stirring the reaction solution for 3 hours, magnetically separating, and dispersing the product in a dimethyl imidazole aqueous solution, wherein the concentration of the dimethyl imidazole aqueous solution is 0.05 g/ml, and the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 1:1. And (3) in-situ growing for 5 hours under stirring, magnetic separation, washing with deionized water, and freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite (ZIF-8@magnetic halloysite).
(b) Preparation of ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel
1g of PVDF (polyvinylidene fluoride) and 5g of sodium chloride are put into a mortar, fully and uniformly ground, and then 0.5g of prepared ZIF-8@magnetic halloysite is added and uniformly stirred. Putting the mixed powder into a glass beaker, then putting into a 100 ℃ oven, thermoforming for 55min, taking out a block sample, soaking the block sample in water of 60 ℃ for 30 h, and replacing the water every 4h to remove a sodium chloride template, thereby forming a porous structure. And finally, freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
Example 6
The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel comprises the following steps:
(a) Preparation of ZIF-8 in-situ modified magnetic halloysite
S1 300mg of iron salt (FeCl) 3 ·6H 2 O and FeSO 4 ·7H 2 O in a molar ratio of 1:1) was dissolved in 375ml deionized water, then 100mg halloysite was added and stirredMixing and reacting for 3h, and adding the mixture into N 2 Dropwise adding NH into the reaction liquid under atmosphere 3 ·H 2 O, continuously stirring and reacting for 3 hours until the pH value of the solution reaches 13, magnetically separating, washing with deionized water to be neutral, and freeze-drying to obtain magnetic halloysite;
s2, adding the magnetic halloysite prepared in the step S1 into an aqueous sodium alginate solution, wherein the mass ratio of the magnetic halloysite to the sodium alginate is 1:5, the concentration of the aqueous sodium alginate solution is 15mg/ml, the ultrasonic dispersion is uniform, stirring is carried out for 5 hours, magnetic separation is carried out, and alcohol and deionized water are sequentially used for cleaning, so that the magnetic halloysite with the surface coated with the sodium alginate is obtained;
s3, dispersing the magnetic halloysite coated with the sodium alginate on the surface, which is prepared in the step S2, in a zinc nitrate hexahydrate water solution, wherein the mass ratio of the magnetic halloysite coated with the sodium alginate on the surface to the zinc nitrate hexahydrate is 5:1, and the concentration of the zinc nitrate hexahydrate water solution is 0.2g/ml. After stirring the reaction solution for 3 hours, magnetically separating, and dispersing the product in a dimethyl imidazole aqueous solution, wherein the concentration of the dimethyl imidazole aqueous solution is 0.3g/ml, and the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 5:1. And (3) in-situ growing for 5 hours under stirring, magnetic separation, washing with deionized water, and freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite (ZIF-8@magnetic halloysite).
(b) Preparation of ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel
1g of PVDF (polyvinylidene fluoride) and 10g of sodium chloride are put into a mortar, fully and uniformly ground, and then 0.6g of prepared ZIF-8@magnetic halloysite is added and uniformly stirred. Putting the mixed powder into a glass beaker, then putting into a baking oven at 300 ℃ for thermoforming for 45min, taking out a block sample, soaking the block sample in water at 150 ℃ for 10 h, and replacing the water every 1h to remove a sodium chloride template, thereby forming a porous structure. And finally, freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
The water contact angle and the adsorption capacity for petroleum of the composite aerogel prepared in the above example are shown in table 2.
TABLE 2 Water contact Angle and Petroleum adsorption Capacity of aerogels prepared in examples 5 and 6
。
Claims (10)
1. A ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is characterized in that polyvinylidene fluoride is used as a matrix, ZIF-8 in-situ modified magnetic halloysite is used as a nano filler, and the ZIF-8 in-situ modified magnetic halloysite is used for generating Fe on the surface of the halloysite 3 O 4 And after the nano particles form magnetic halloysite, ZIF-8 nano particles are grown on the surface of the magnetic halloysite in situ.
2. The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is characterized by comprising the following steps: fe is generated on the surface of halloysite by an in-situ growth method 3 O 4 The nano particles form magnetic halloysite, sodium alginate is wrapped on the surface of the magnetic halloysite, ZIF-8 nano particles are grown on the surface of the magnetic halloysite in situ to form ZIF-8 in situ modified magnetic halloysite, finally polyvinylidene fluoride is used as a matrix, the ZIF-8 in situ modified magnetic halloysite is used as a nano filler, and the ZIF-8 in situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is prepared by using sodium chloride as a sacrificial template.
3. The method for preparing the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 2, comprising the steps of:
s1, adding halloysite into an aqueous solution of ferric salt, stirring, adjusting the pH value of a reaction solution to be alkaline under a protective atmosphere after reaction, continuously stirring for reaction, washing to be neutral through magnetic separation and deionized water, and freeze-drying to obtain magnetic halloysite;
s2, adding the magnetic halloysite into an aqueous solution of sodium alginate, performing magnetic separation after uniformly dispersing and stirring, and sequentially performing centrifugal cleaning by using alcohol and deionized water to obtain the magnetic halloysite with the surface coated with sodium alginate;
s3, dispersing the magnetic halloysite coated with sodium alginate on the surface into a hexahydrate zinc nitrate aqueous solution for stirring, performing magnetic separation after reaction, dispersing a magnetically separated sample into a dimethylimidazole aqueous solution, performing in-situ growth reaction under stirring, performing magnetic separation, washing with deionized water, and performing freeze drying to obtain ZIF-8 in-situ modified magnetic halloysite;
and S4, uniformly grinding the polyvinylidene fluoride and sodium chloride, adding the ZIF-8 in-situ modified magnetic halloysite, uniformly stirring, heating, drying and forming the mixed powder, removing the sodium chloride, and freeze-drying to obtain the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel.
4. The method for preparing the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein the ferric salt is FeCl 3 ·6H 2 O and FeSO 4 ·7H 2 O is composed according to a molar ratio of 3-1:1, the concentration of the aqueous solution of the ferric salt is 0.1-0.8 mg/ml, and the mass ratio of the halloysite to the ferric salt is 1:0.5-3.
5. The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein the concentration of the sodium alginate aqueous solution is 2-15 mg/ml, and the mass ratio of the magnetic halloysite to the sodium alginate is 1:0.5-5.
6. The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein in the step S3, the mass ratio of the magnetic halloysite coated with sodium alginate to the zinc nitrate hexahydrate is 1-5:1, and the concentration of the zinc nitrate hexahydrate water solution is 0.02-0.2 g/ml.
7. The preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein the concentration of the dimethyl imidazole aqueous solution is 0.05-0.3 g/ml, and the mass ratio of the dimethyl imidazole to the zinc nitrate hexahydrate is 1-5:1.
8. The method for preparing the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein in the step S4, the mass ratio of the polyvinylidene fluoride, sodium chloride and the ZIF-8 in-situ modified magnetic halloysite is 1:5-10:0.1-0.6.
9. The method for preparing a ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel according to claim 3, wherein the heating temperature is 100-300 ℃ during heating, drying and molding, and the sodium chloride removal is to soak the molded sample in water at 60-150 ℃ for 15-30 h, and change the water every 1-4 hours.
10. The application of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel is characterized in that the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel prepared by the preparation method of the ZIF-8 in-situ modified magnetic halloysite/polyvinylidene fluoride composite aerogel disclosed in any one of claims 2 to 8 is used for oil-water separation.
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