CN114534700B - Durable super-hydrophobic metal-organic framework sponge material and preparation method and application thereof - Google Patents
Durable super-hydrophobic metal-organic framework sponge material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 33
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 39
- 235000019198 oils Nutrition 0.000 claims description 38
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 235000019476 oil-water mixture Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000010705 motor oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940099373 sudan iii Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 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
- 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
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—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
- B01J20/28011—Other properties, e.g. density, crush strength
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of super-hydrophobic materials, in particular to a durable super-hydrophobic metal-organic framework sponge material, a preparation method and application thereof. Solves the problems of high production cost, single function and use of toxic and harmful reagents in the existing method for preparing the super-hydrophobic material, and is applied to oil-water separation. The preparation method comprises the following steps: zrCl is added to 4 And C 8 H 6 O 6 Dissolving in DMF and stirring, cleaning melamine sponge, and immersing in the solution; pouring into a high-pressure reaction kettle, reacting at high temperature, cooling to room temperature, and cleaning UiO-66- (OH) with DMF and acetone 2 Modifying sponge for several times and vacuum drying; uiO-66- (OH) 2 Immersing the modified sponge into a stearic acid ethanol solution containing certain 3-aminopropyl trimethoxy silane for a certain time, taking out and drying to obtain a target product.
Description
Technical Field
The invention relates to the technical field of super-hydrophobic materials, in particular to a durable super-hydrophobic metal-organic framework sponge material, a preparation method and application thereof.
Background
The increasingly serious environmental pollution seriously threatens the sustainable development of human society. Among the various environmental problems, water pollution is a serious problem. Up to now, petroleum hydrocarbon products are the main energy source in the world. In the oil industry, oil leakage and oil spill accidents often occur during offshore oil exploitation and oil transportation. This serious water pollution threatens the health of humans including other living beings in the world. Thus, the treatment of industrial oily wastewater and the separation of spilled oil has become a worldwide challenging task. The world spends more than $100 billion per year on oil leak clearance. Conventional cleaning methods are in situ oil burning or mechanical pumping. Traditional mechanical extraction processes are time consuming and laborious and inefficient. On the other hand, fuel combustion generates a large amount of air pollution. Therefore, development of economic, environment-friendly and efficient oil-water separation materials is urgently required. In order to solve the serious problem, great efforts are made to develop efficient oil-water separation materials.
At present, super-hydrophobic/super-oleophilic materials are a typical type of oil-water separation materials. The contact angle between the surface of the super-hydrophobic/super-oleophilic material and the water drop is larger than 150 degrees, and the contact angle between the super-hydrophobic/super-oleophilic material and the oil drop is close to or equal to 0 degrees. The superhydrophobic-superhydrophilic properties allow the oil to be easily absorbed by the material while the aqueous phase is repelled by the material, so that the oil can be separated from the water-oil mixture. The selected material has high porosity, so that the material has large adsorption capacity, and high-efficiency oil-water separation can be realized. However, in the preparation process of many super-hydrophobic/super-oleophilic materials at present, harmful medicines such as fluoride and the like are generally used for modification, so that the environment is polluted and the materials are harmful to human health.
Disclosure of Invention
The invention aims to provide a preparation method of a super-hydrophobic material, which has the advantages of simple process, convenient use and repeated use. The super-hydrophobic material has the performances of high oil absorption capacity, selective separation of oil-water mixture and material recycling.
In order to achieve the above purpose, the technical scheme of the application is as follows: the durable super-hydrophobic metal organic framework sponge material is characterized by comprising the following steps of:
1) ZrCl is added to 4 And C 8 H 6 O 6 Dissolving in DMF and stirring, and cleaning melamine spongeImmersing in the solution;
2) Pouring the solution obtained in the step 1) into a high-pressure reaction kettle, reacting at high temperature, cooling to room temperature, cleaning the sponge for several times, and vacuum drying to obtain UiO-66- (OH) 2 Modifying the sponge;
3) Preparing ethanol solution of stearic acid and 3-aminopropyl trimethoxy silane, stirring and heating for activation, and using the activated solution as modification solution to obtain UiO-66- (OH) 2 Immersing the modified sponge into the modifying liquid for a certain time, taking out and drying to obtain a target product UiO-66- (OH) 2 @STA@MS。
Preferably, in the step 1), zrCl is added according to the molar ratio of the durable super-hydrophobic metal organic framework sponge material 4 :C 8 H 6 O 6 =1:1.176。
Preferably, in the step 2), the high temperature is 100 ℃ and the reaction time is 24 hours.
Preferably, in the step 3), the concentration of stearic acid is 0.067mol.L -1 The concentration of 3-aminopropyl trimethoxysilane was 0.042 mol.L -1 。
Preferably, in step 3), the above-mentioned durable super-hydrophobic metal organic framework sponge material is activated for 1h at 60 ℃.
Preferably, in step 3), uiO-66- (OH) is a durable super-hydrophobic metal organic framework sponge material as described above 2 The time for soaking the modified sponge in the stearic acid ethanol solution is 4 hours.
The application of the durable super-hydrophobic metal-organic framework sponge material in separating oil from oil-water mixture.
Preferably, the above application, the method is as follows: in mixtures of oils and water, uiO-66- (OH) 2 At STA@MS, the oil-imbibed UiO-66- (OH) was removed 2 And (5) performing @ STA @ MS to complete oil-water separation.
Preferably, for the above applications, the oils include n-hexane, methylene chloride, toluene, chloroform, engine oil, soybean oil.
The beneficial effects of the invention are as follows:
1. the invention adopts melamine sponge as a substrate material, and constructs a micro-nano structure UiO-66- (OH) on the surface of the substrate material 2 Thereby improving the roughness of the whole three-dimensional structure of the substrate material. Further modifying stearic acid (STA) to reduce the surface energy of the material, and taking 3-aminopropyl trimethoxy silane (KH-540) as a stable adhesive, so that the material is finally changed into a super-hydrophobic material with high strength, mechanical stability and extremely strong oil-water separation performance.
2. The preparation method for preparing the super-hydrophobic material does not need to use expensive reagents, equipment and harsh experimental conditions, has low production cost, and the synthesized material has super-hydrophobic characteristics, and has high adsorption efficiency on oil in an oil-water separation experiment, good stability, large adsorption capacity, high separation efficiency and strong cycle performance. Solves the problem of high production cost existing in the existing method for preparing the super-hydrophobic material.
3. The super-hydrophobic material prepared by the invention has large selective adsorption capacity, adopts low-cost and environment-friendly melamine sponge as a substrate material, and still maintains the original adsorption capacity after modification.
4. The super-hydrophobic material prepared by the invention does not use traditional fluoride and other harmful medicines for super-hydrophobic modification, and the synthesis method is environment-friendly and economic.
Drawings
FIG. 1 is MS, uiO-66- (OH) 2 @MS and UIO-66- (OH) 2 Scanning electron microscope pictures of @ STA @ MS; wherein, (a 1-a 2) are original MS sponge SEM images; (b 1-b 2) is UiO-66- (OH) 2 SEM image of MS material; (c 1-c 2) is UiO-66- (OH) 2 SEM image of sta@ms material.
FIG. 2 is a hydrophobic property diagram of a superhydrophobic sponge; wherein (a) is UiO-66- (OH) 2 @ STA @ MS (embedded as specific contact angle values); (b) is MS; (c) Is UIO-66- (OH) 2 Photographs of submerged @ sta @ ms material.
FIG. 3A is UiO-66- (OH) 2 Saturated adsorption capacity histogram of @ sta @ ms for different oils and organic solvents.
FIG. 3B is UiO-66- (OH) 2 Graph of adsorption-desorption cycles for different oils and organic solvents for sta@ms.
FIG. 4 is a diagram of UiO-66- (OH) 2 Photographs of static oil-water separation of oil products with different densities by an @ STA @ MS; wherein (a 1-a 3) is a selective adsorption process of the material to the light oil; (b 1-b 3) is a selective adsorption process of heavy oil by the material.
FIG. 5A is UiO-66- (OH) 2 Photographs of dynamic oil-water separation (gravity separation) of oil products with different densities by an STA@MS; wherein (a 1-a 2) is UiO-66- (OH) 2 The @ STA @ MS material was used for gravity separation (light oil/water) of oil-water mixtures; (b 1-b 2) is UiO-66- (OH) 2 The @ sta @ ms material was used for gravity separation (heavy oil/water) of oil-water mixtures.
FIG. 5B is UiO-66- (OH) 2 Photographs of dynamic oil-water separation (pump separation) of oil products with different densities at STA@MS; wherein (a 1-a 3) is UiO-66- (OH) 2 The @ sta @ ms material is used for pump separation (heavy oil/water) of oil-water mixtures; (b 1-b 3) is UiO-66- (OH) 2 The @ sta @ ms material was used for pump separation (light oil/water) of oil-water mixtures.
FIG. 6 is a diagram of UiO-66- (OH) 2 Experimental diagrams of mechanical stability of @ STA @ MS; wherein, (a) a stretching experiment; (b) torsion testing; (c) a compression experiment; (d) mechanical abrasion test.
FIG. 7 is a schematic illustration of the preparation of UiO-66- (OH) by in situ synthesis 2 @ STA @ MS material and its multifunctional applications.
Detailed Description
Example 1A durable super hydrophobic Metal organic framework Material UiO-66- (OH) 2 Preparation of @ STA @ MS
Preparation of UiO-66- (OH) 2 @STA@MS
Synthesis of UiO-66- (OH) by simple hydrothermal method 2 And (3) a sponge. 90mg ZrCl 4 And 90mg C 8 H 6 O 6 Dissolve in 50mL DMF and sonicate for 30 min. Then, the melamine sponge was washed with ethanol and water, dried, cut into 2cm×2cm×1cm pieces, and fully immersed in the above uniform solution. Subsequently, the above mixture was poured into a100 mL Teflon-lined autoclave at 100 ℃The reaction was sealed in an oven for 24 hours. After the reaction vessel had cooled naturally to room temperature, the resulting pale yellow UiO-66- (OH) was washed with DMF and acetone 2 The sponge is modified for several times and dried for 12 hours in a vacuum oven at 80 ℃ to obtain UIO-66- (OH) 2 @MS。
Dissolving 0.568g STA and 225 μLKH-540 in 30mL ethanol, activating the solution at 60deg.C for 1h, and adding a block of UiO-66- (OH) 2 The @ MS was immersed in the above solution for 4 hours at 60 ℃. After the reaction is finished, the sponge is taken out and dried overnight at 80 ℃ to prepare UiO-66- (OH) with super-hydrophobic-super-oleophilic surface wettability 2 @STA@MS。
(II) detection
1、MS,UiO-66-(OH) 2 @MS and UIO-66- (OH) 2 Microscopic morphology of @ sta @ ms it was observed using a scanning electron microscope.
As shown in FIG. 1, (a 1), (b 1) and (c 1) are MS, uiO-66- (OH), respectively 2 @MS and UIO-66- (OH) 2 The overall morphology of the @ STA @ MS material structure (the test voltage is 10.0kV, the scale is 100 μm) has the same pore size and microstructure, which indicates that the original pore structure of MS is not destroyed by mild chemical reaction. (a2) (b 2) and (c 2) are MS, uiO-66- (OH), respectively 2 @MS and UIO-66- (OH) 2 Local morphology of the @ STA @ MS material structure (test voltage 10.0kV, scale 10 μm). As shown in the diagram (b 2), the skeleton of the MS sponge is uniformly covered with a layer of UiO-66- (OH) 2 A nanosphere. As can be clearly seen from the graph (c 2), uiO-66- (OH) was performed using STA and KH-540 2 After the modified sponge is subjected to super-hydrophobization, the protrusions on the surface of the framework can be found to be obvious, and the modified sponge is uniformly distributed.
2. The hydrophobicity of the sponge material was characterized by contact angle, and its surface wettability was measured with deionized water on a KRUSS optical contact angle meter DSA100, germany, to measure its contact angle.
UiO-66-(OH) 2 Wetting ability of the @ sta @ ms material as shown in fig. 2 (a), the water droplet can remain intact sphere-like on its surface for a long period of time with a contact angle of 156.9 °. As shown in fig. 2 (b), the water droplets are not any hydrophobic on a common sponge. As shown in FIG. 2 (c), it can be observed thatThe material immersed under water is wrapped with a layer of air film, which is not soaked by water.
3. The adsorption amount is a standard for evaluating the performance of the oil absorbing material. The adsorption amount can be measured by the following procedure. UiO-66- (OH) 2 The @ STA @ MS sample was weighed, then placed in different types of oils and organic solvents for adsorption testing, then the sample was removed, the surface oils and organic solvents were wiped off with filter paper, and then the oil absorbing sample was weighed again. The adsorption capacity (Q) is calculated by the following equation:
Q=(m t -m 0 )/m 0 wherein m is 0 And m t The weights of the samples before and after adsorption, respectively.
Example 2 superhydrophobic metal-organic framework material UiO-66- (OH) 2 Application of @ STA @ MS in separation of oil-water mixture
1. Examine uiO-66- (OH) 2 Saturated adsorption capacity of sta@ms material for two oils (soybean oil, engine oil) and organic solvents (dichloromethane, chloroform, toluene, n-hexane). The results are shown in FIG. 3A. As can be seen in FIG. 3A, uiO-66- (OH) 2 The saturated adsorption capacity of the @ STA @ MS material on different oils and organic solvents is up to 20.583-57.922 times of the self-mass, and the material has higher adsorption capacity.
2. Examine uiO-66- (OH) 2 Number of recycling of @ sta @ ms material. After saturated adsorption of different kinds of oils or organic solvents by the material, lightly extruding the material, discharging a large amount of adsorbed oils or organic solvents, then washing and drying the material by absolute ethyl alcohol to realize controllable desorption, and then carrying out an adsorption experiment again to carry out a recycling test. As a result, as shown in fig. 3B, the saturated adsorption amount was maintained substantially stable as the number of cycles was increased, and the recovered material was reused for 18 cycles in adsorption-desorption, and the separation efficiency was still greater than 97%.
3. Examine uiO-66- (OH) 2 The practical application of spill clean-up of sta@ms materials simulates the separation of the mixed oil from the mixture under natural conditions. Selective adsorption experiments were performed by mixing Sudan III-stained n-hexane (light oil) and dichloromethane (heavy oil), respectively, with water, and obtaining the results asFig. 4. As can be seen from FIG. 4, uiO-66- (OH) 2 The @ STA @ MS material was able to selectively adsorb n-hexane and methylene chloride. As shown in fig. 4 (a 1) to (a 3), when the material is contacted with n-hexane on the water upper layer, n-hexane can be rapidly absorbed into the material within a few seconds, static separation of n-hexane from water can be achieved, and no red contaminant is observed in the water; as shown in fig. 4 (b 1) to (b 3), when the material is contacted with dichloromethane in the underwater layer, dichloromethane can be rapidly absorbed into the material within a few seconds, static separation of water from dichloromethane can be achieved, and no red contaminant is observed in the water. In conclusion, the material separation efficiency is high, and no pollution is caused.
4. Examine uiO-66- (OH) 2 Continuous oil-water separation capability of the @ STA @ MS material. The separation process is shown in FIG. 5, where UiO-66- (OH) is shown in FIG. 5A 2 The @ STA @ MS material was plugged into the funnel and the light oil/water (heavy oil/water) mixture was poured into the funnel due to UiO-66- (OH) 2 Super-hydrophobic-super-lipophilic of the @ sta @ ms material, the organic phase flowing down, while the aqueous phase is trapped in the funnel; in FIG. 5B peristaltic pump tubing is inserted into the UiO-66- (OH) 2 @ sta @ ms material and placing this end in a light oil/water (heavy oil/water) mixture, the organic phase is gradually transferred all the way into the beaker at the other end of the catheter, driven by a peristaltic pump. After the separation, the aqueous phase and the organic phase have no residue on each other.
Example 3 superhydrophobic metal-organic framework Material UiO-66- (OH) 2 Investigation of mechanical stability of @ STA @ MS
1. Examination of UiO-66- (OH) 2 Mechanical stability of @ sta @ ms material. As shown in FIG. 6 a, for UiO-66- (OH) 2 Carrying out a stretching experiment on the @ STA @ MS material; as shown in FIG. 6 b, for UiO-66- (OH) 2 Performing a torsion experiment on the @ STA @ MS material; as shown in FIG. 6 c, for UiO-66- (OH) 2 Performing a pressing experiment on the @ STA @ MS material; as shown in FIG. 6d, for UiO-66- (OH) 2 Wear experiments were performed on sta@ms materials. Each experiment was repeated a number of times, uiO-66- (OH) 2 The contact angle of the @ STA @ MS material can still be kept above 150 degrees, and the oil-water separation efficiency can still be kept above 90 percent.
Claims (6)
1. The durable super-hydrophobic metal organic framework sponge material is characterized by comprising the following steps of:
1) ZrCl in molar ratio 4 :C 8 H 6 O 6 =1:1.176, zrCl 4 And C 8 H 6 O 6 Dissolving in DMF and stirring, cleaning melamine sponge, and immersing in the solution;
2) Pouring the solution obtained in the step 1) into a high-pressure reaction kettle, reacting for 24 hours at 100 ℃, cooling to room temperature, cleaning the sponge for several times, and vacuum drying to obtain UiO-66- (OH) 2 Modifying the sponge;
3) Preparing ethanol solution of stearic acid and 3-aminopropyl trimethoxy silane, activating at 60deg.C for 1 hr under stirring, and collecting UiO-66- (OH) as modification solution 2 Immersing the modified sponge into the modifying liquid for a certain time, taking out and drying to obtain a target product UiO-66- (OH) 2 @STA@MS。
2. The durable super-hydrophobic metal organic framework sponge material as claimed in claim 1 wherein in step 3) the concentration of stearic acid is 0.067 mol-L -1 The concentration of 3-aminopropyl trimethoxysilane was 0.042 mol.L -1 。
3. A durable superhydrophobic metal-organic framework sponge according to claim 1, wherein in step 3), uiO-66- (OH) 2 The soaking time of the modified sponge in the modifying liquid is 4 hours.
4. Use of a durable super hydrophobic metal organic framework sponge material according to claim 1 for separating oils from oil-water mixtures.
5. The use according to claim 4, characterized in that the method is as follows: in mixtures of oils and water, uiO-66- (OH) 2 At STA@MS, the oil-imbibed UiO-66- (OH) was removed 2 @STA@MS, oil-water separation is completed。
6. The method of claim 5, wherein the oil comprises engine oil or soybean oil.
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