CN107198891A - super-hydrophobic metal organic framework array and preparation method and application thereof - Google Patents
super-hydrophobic metal organic framework array and preparation method and application thereof Download PDFInfo
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- CN107198891A CN107198891A CN201710469859.0A CN201710469859A CN107198891A CN 107198891 A CN107198891 A CN 107198891A CN 201710469859 A CN201710469859 A CN 201710469859A CN 107198891 A CN107198891 A CN 107198891A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 49
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 235000019476 oil-water mixture Nutrition 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003491 array Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001369 Brass Inorganic materials 0.000 claims description 9
- 239000010951 brass Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010773 plant oil Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 3
- 239000004280 Sodium formate Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 abstract 1
- 235000019254 sodium formate Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 150000008614 2-methylimidazoles Chemical class 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000001556 benzimidazoles Chemical class 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Lubricants (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a preparation method of a super-hydrophobic metal organic framework array, which comprises the following steps: placing inorganic or organic materials as a substrate in an organic solvent, performing ultrasonic treatment, and drying to obtain a pretreated substrate; dissolving zinc nitrate hexahydrate, 2-methylimidazole and anhydrous sodium formate in ethanol, performing ultrasonic treatment, adding the obtained solution into the pretreated substrate, and reacting at 50-150 ℃ for 5-10 hours to obtain a ZnO array; and dissolving benzimidazole in N, N-dimethylformamide, performing ultrasonic treatment, then adding the ZnO array, and reacting at 80-140 ℃ for 10 hours to obtain the super-hydrophobic metal organic framework array. The super-hydrophobic metal organic framework array can be applied to the field of oil-water separation; the invention can achieve super-hydrophobicity without any low surface energy substance modification, and the array has higher thermal stability and can efficiently separate a plurality of oil-water mixtures.
Description
(1) technical field
The present invention relates to super hydrophobic material preparation and the technical field of oiliness sewage treatment, and in particular to a kind of super-hydrophobic gold
Belong to organic backbone array and preparation method thereof and water-oil separating application.
(2) background technology
In recent years, the preparation and application of super hydrophobic material receive the extensive concern of people.Super hydrophobic material not only has
Excellent water-resistance, and have in fields such as automatically cleaning, anti-corrosion of metal, ice-covering-proof, water-oil separating and pipeline transportation drag reductions huge
Big application value.At present, in order to reach super-hydrophobic effect, a large amount of low-surface energy substances are used to prepare super hydrophobic surface, especially
It is fluorinated material.But fluorine material is expensive and environment is adversely affected with human body, for example, PFOS
Strictly limited by European Union due to poisonous to biological and mammal kind.Moreover, super hydrophobic surface prepared by some polymer exists
Super-hydrophobicity can be lost because of structural failure or low-surface energy substance decomposition under 200-300 DEG C of high temperature, and in preparation technology,
Some method and technologies are cumbersome, need particular device instrument, matrix selection to there is limitation.Based on these, using environmentally friendly
Floride-free and heat-staple material super hydrophobic surface is prepared by simple method is very gratifying.
Metal organic framework (MOFs) material is due to its unique performance, the specific surface area of such as superelevation, excellent adsorptivity
Energy, structure diversity etc. and be widely used in gas storage, separation and catalysis etc. field.Will according to the application of different field
Ask, MOF materials are designed to different shapes, such as capsule, particle, core shell structure, film.MOF materials can in body fluid quilt
Degrade and available for biological medicine, it was demonstrated that it is friendly to organism and environment.And the wetability of MOF materials can by with
Body regulates and controls, and intrinsic hydrophobicity framework can be realized easily by using hydrophobic grouping as part.It is many at present super thin
Water MOF materials are produced, but these super-hydrophobic MOF concentrate on particle or powder grade, and other structures are seldom designed.Point
The array structure of grade can make liquid occupy very limited amount of contact area in the outer surface of coarse structure, make liquid and matrix it
Between be full of air so that surface has prominent hydrophobicity.ZIF-7 has excellent intrinsic hydrophobicity and heat endurance, is
Prepare the ideal chose of super-hydrophobic metal organic framework array.It is super thin that constructed suitable micro-nano graduation coarse structure assigns it
Aqueous energy.Prepared metal organic framework array has excellent hydrophobicity and heat under without the modification of any low-surface energy substance
Stability, can efficiently separate a variety of oil water mixtures.
(3) content of the invention
An object of the present invention is to provide a kind of super-hydrophobic metal organic framework array and preparation method thereof.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of super-hydrophobic metal organic framework array, the super-hydrophobic metal organic framework array is specifically made as follows
It is standby to obtain：
(1) organic or inorganic substrate is immersed in organic solvent for ultrasonic cleaning 30s~5min, be dried to obtain at 80 DEG C
The substrate of pretreatment；The organic or inorganic substrate be amination polyvinylidene fluoride film, polyacrylonitrile film, ceramic membrane, stainless (steel) wire,
Brass screen or carbon cloth；The organic solvent is ethanol, glycerine, acetone or N,N-dimethylformamide；
(2) zinc nitrate hexahydrate, 2-methylimidazole and anhydrous formic acid sodium are dissolved in ethanol, 5~10min of ultrasound is reacted
Mixed liquor, by the substrate vertical immersion of pretreatment obtained by step (1) in gained mixed liquor A, reacts under the conditions of 50~150 DEG C
5~10 hours, after reaction terminates, the post-treated processes of products therefrom A are obtained into ZnO arrays；Described zinc nitrate hexahydrate, 2- first
The mass ratio of base imidazoles and anhydrous formic acid sodium is 1~5：1~2：1；
(3) benzimidazole is taken to be dissolved in DMF, 2~5min of ultrasound is clarified completely to mixed liquid B, will be walked
Suddenly ZnO array vertical immersions obtained by (2) are reacted 10 hours in mixed liquid B under the conditions of 80~140 DEG C, after reaction terminates, institute
Obtain the post-treated processes of reaction product B and obtain super-hydrophobic metal organic framework array.
Further, in step (1), the volume of the organic or inorganic substrate is calculated as 24 with the volume of organic solvent~
60cm3/L；
Further, in step (1), preferably described organic solvent is ethanol or acetone.
Further, in step (2), the amount of alcohol added is calculated as 28~56mL/g with the quality of zinc nitrate hexahydrate.
Further, in step (2), the last handling process of the product A is：After reaction terminates, products therefrom A is placed in second
Ultrasound 15s~60s in alcohol, removes the ZnO of excess surface, dries produce ZnO arrays at room temperature.
Further, in step (3), the addition of described DMF is calculated as 60 with the quality of benzimidazole
~75mL/g.
Further, in step (3), the last handling process of the product B is：After reaction terminates, by products therefrom B through N, N-
After dimethylformamide cleaning, dry at room temperature, that is, obtain super-hydrophobic metal organic framework array.
Further, in step (1), preferably described organic or inorganic substrate is amination polyvinylidene fluoride film, ceramic membrane, no
Become rusty steel mesh or brass screen.
Further, in step (2), preferably described reaction temperature is 90~120 DEG C, and the reaction time is 8~10h.
Further, in step (3), preferably described reaction temperature is 120~140 DEG C.
The second object of the present invention is the provision of the super-hydrophobic metal organic framework array and separated in oil water mixture
Application in field.
Further, the oil water mixture is n-hexane/water, toluene/water, petroleum ether/water, methylene chloride/water, plant
One or more in oil/water, vapour oil/water, chloroform/water；Described separation process operating pressure is oil water mixture
Self gravitation.
Compared with modern technologies, the advantage of the invention is that：
Material of the present invention is all harmless to environment and human body, and the metal organic framework array has excellent dredge
It is aqueous, remain to keep ultra-hydrophobicity under 300 DEG C of high temperature, can be used in the separation of oil water mixture, and with very high point
From efficiency and reusing.
(4) illustrate
Fig. 1 is the scanning electron microscope (SEM) photograph and Static water contact angles figure that the embodiment of the present invention 1 prepares array.
Fig. 2 is the scanning electron microscope (SEM) photograph and Static water contact angles figure for the array that the embodiment of the present invention 2 is obtained.
Fig. 3 is the scanning electron microscope (SEM) photograph and Static water contact angles figure of array prepared by the embodiment of the present invention 3.
(5) embodiment
With reference to specific embodiment, the present invention is described in detail in, but the present invention is not limited to following embodiments,
Do not depart from present invention and scope, change should be all included in the technical scope of the present invention.
Embodiment 1：
(1) stainless (steel) wire of clip 2cm × 3cm × 0.05cm sizes, which is placed in 12mL acetone, is cleaned by ultrasonic 30s, at 80 DEG C
Dry for standby；
(2) 0.89g zinc nitrate hexahydrates, 0.45g 2-methylimidazoles, 0.235g anhydrous formic acid sodium are weighed and is dissolved in 25mL ethanol
In, ultrasonic 10min；The clean stainless (steel) wire obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the solution
In kettle；Reacted 10 hours under the conditions of 90 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.40g benzimidazoles to be dissolved in 30mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 130 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After described ZIF-7 arrays are cleaned with DMF, in room temperature
Under dry, that is, obtain super-hydrophobic metal organic framework array.
Obtained metal organic framework array is as shown in Figure 1.It can clearly be seen that being completely covered on stainless (steel) wire surface
The ZIF-7 arrays of one layer of micro-nano graduation coarse structure.Test and find through contact angle, water static contact angle reaches 151.3 °, i.e.,
Reach super-hydrophobic.
Embodiment 2：
(1) ceramic membrane of clip 2cm × 3cm × 0.1cm sizes, which is placed in 20mL acetone, is cleaned by ultrasonic 30s, is dried at 80 DEG C
It is dry standby；
(2) 0.89g zinc nitrate hexahydrates, 0.45g 2-methylimidazoles, 0.235g anhydrous formic acid sodium are weighed and is dissolved in 25mL ethanol
In, ultrasonic 10min；The clean ceramic membrane obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the clarified solution
In kettle；Reacted 10 hours under the conditions of 90 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.40g benzimidazoles to be dissolved in 30mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 130 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After described ZIF-7 arrays are cleaned with DMF, in room temperature
Under dry, that is, obtain super-hydrophobic metal organic framework array.
To investigate the heat endurance of the super-hydrophobic metal organic framework array of gained, Temperature Programmed Processes, the rate of heat addition 5 are taken
℃min-1, 2h is calcined under the conditions of 300 DEG C.The ZIF-7 arrays obtained after calcining are as shown in Figure 2.It can be seen that through high-temperature calcination
Afterwards, the pattern of ZIF-7 arrays does not have significant change, still keeps graduate array status, and hydrophobicity is not degenerated, and water is quiet
State contact angle reaches 154.7 °, it was demonstrated that prepared metal organic framework array has good heat endurance.
Embodiment 3：
(1) stainless (steel) wire of clip 2cm × 3cm × 0.05cm sizes, which is placed in 12mL acetone, is cleaned by ultrasonic 30s, at 80 DEG C
Dry for standby；
(2) 0.625g zinc nitrate hexahydrates, 0.25g 2-methylimidazoles, 0.125g anhydrous formic acid sodium are weighed and is dissolved in 35mL ethanol
In, ultrasonic 10min；The clean stainless (steel) wire obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the solution
In kettle；Reacted 10 hours under the conditions of 150 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.60g benzimidazoles to be dissolved in 36mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 140 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After described ZIF-7 arrays are cleaned with DMF, in room temperature
Under dry, that is, obtain super-hydrophobic metal organic framework array.
Obtained metal organic framework array is as shown in Figure 3.The ZIF-7 arrays prepared under this condition are by spherical
Grain close-packed arrays are formed.Test and find through contact angle, water static contact angle reaches 140.2 °, shows excellent hydrophobicity.
Embodiment 4：
(1) brass screen of clip 2cm × 3cm × 0.05cm sizes, which is placed in 12mL ethanol, is cleaned by ultrasonic 30s, is dried at 80 DEG C
It is dry standby；
(2) 0.89g zinc nitrate hexahydrates, 0.45g 2-methylimidazoles, 0.235g anhydrous formic acid sodium are weighed and is dissolved in 25mL ethanol
In, ultrasonic 10min；The clean brass screen obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the clarified solution
In kettle；Reacted 10 hours under the conditions of 90 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.40g benzimidazoles to be dissolved in 30mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 130 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After described ZIF-7 arrays are cleaned with DMF, in room temperature
Under dry, that is, obtain super-hydrophobic metal organic framework array.
Obtained super-hydrophobic metal organic framework array is used for oil-water separation mixture, described separator is by two
Separate pipeline is fixedly connected, and described lower pipeline upper surface is engraved structure, and laboratory is by super-hydrophobic metal organic framework array
Lower pipe surface is placed in, is then fixedly connected with upper pipeline.Oil water mixture is directly poured into upper pipeline, due to array surface tool
Have an excellent water repellency and super-oleophilic, oil can rapid osmotic and water is intercepted, so as to realize the quick separating of oil water mixture.
The aqueous solution of 20mg/L dyestuff methylene blue is configured during experiment, takes the aqueous solution 5mL of described methylene blue to add
Enter into 5mL n-hexane and be configured to oil water mixture, then filtered in above-mentioned separator, gained filtrate is carried out
Absorbance is tested.
The absorbance of the aqueous solution of dyestuff methylene blue of the present invention is 1.803, and the absorbance of gained filtrate is
0.003, it is 99.83% that calculating, which obtains separative efficiency,.
Similarly, separative efficiency of the described super-hydrophobic metal organic framework array to toluene, petroleum ether and soybean oil is measured
99% is above, to the separative efficiency of dichloromethane also above 96%.
Embodiment 5：
(1) brass screen of clip 2cm × 3cm × 0.05cm sizes, which is placed in 12mL acetone, is cleaned by ultrasonic 30s, is dried at 80 DEG C
It is dry standby；
(2) 0.89g zinc nitrate hexahydrates, 0.45g 2-methylimidazoles, 0.235g anhydrous formic acid sodium are weighed and is dissolved in 25mL ethanol
In, ultrasonic 10min；The clean brass screen obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the clarified solution
In kettle；Reacted 10 hours under the conditions of 90 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.40g benzimidazoles to be dissolved in 30mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 130 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After described ZIF-7 arrays are cleaned with DMF, in room temperature
Under dry, that is, obtain super-hydrophobic metal organic framework array.
Described super-hydrophobic metal organic framework array is carried out after 10 multi-cycle separations to different oil water mixtures, first
Benzene, n-hexane, the separative efficiency of petroleum ether and soybean oil are still greater than 99%, to the separative efficiency of dichloromethane also greater than 96%.
Illustrate that prepared metal organic framework array has good stability and reusing.
Embodiment 6：
(1) brass screen of clip 2cm × 3cm × 0.05cm sizes, which is placed in 12mL acetone, is cleaned by ultrasonic 30s, is dried at 80 DEG C
It is dry standby；
(2) 0.89g zinc nitrate hexahydrates, 0.45g 2-methylimidazoles, 0.235g anhydrous formic acid sodium are weighed and is dissolved in 25mL ethanol
In, ultrasonic 10min；The clean brass screen obtained in step (1) is vertically arranged in the polytetrafluoroethyl-ne alkene reaction equipped with the clarified solution
In kettle；Reacted 10 hours under the conditions of 90 DEG C, obtain ZnO arrays；ZnO arrays are placed in ultrasound 15s removings surface in ethanol many
Remaining ZnO, dries at room temperature, standby；
(3) weigh 0.40g benzimidazoles to be dissolved in 30mL DMFs, ultrasonic 2min to solution is completely clear
Clearly；The ZnO arrays obtained in step (2) are vertically arranged in the ptfe autoclave equipped with the clarified solution；In 130 DEG C of bars
Reacted 10 hours under part, obtain ZIF-7 arrays；After being cleaned with DMF, dry at room temperature, that is, obtain super thin
Water metal organic framework array.
To investigate the oil water mixture separating property of super-hydrophobic metal organic framework array after calcining, temperature programming is taken
Journey, 5 DEG C of min of the rate of heat addition-1, 2h is calcined under the conditions of 300 DEG C.By calcined product to toluene, n-hexane, petroleum ether and soybean oil
Separative efficiency be both greater than 99%, to the separative efficiency of dichloromethane also greater than 97%.It is also demonstrated that the obtained metal of experiment has
Machine skeleton array has good heat endurance.
Claims (10)
1. a kind of super-hydrophobic metal organic framework array, it is characterised in that the super-hydrophobic metal organic framework array is by as follows
Method is prepared：
(1) organic or inorganic substrate is immersed in organic solvent for ultrasonic cleaning 30s~5min, pre- place is dried to obtain at 80 DEG C
The substrate of reason is standby；The organic or inorganic substrate be amination polyvinylidene fluoride film, polyacrylonitrile film, ceramic membrane, stainless (steel) wire,
Brass screen or carbon cloth；The organic solvent is ethanol, glycerine, acetone or N,N-dimethylformamide；
(2) zinc nitrate hexahydrate, 2-methylimidazole and anhydrous formic acid sodium are dissolved in ethanol, 5~10min of ultrasound obtains reaction mixing
Liquid A, by the substrate vertical immersion of pretreatment obtained by step (1) in the mixed liquor A, react 5 under the conditions of 50~150 DEG C~
10 hours, after reaction terminates, the post-treated processes of products therefrom A are obtained into ZnO arrays；Described zinc nitrate hexahydrate, 2- methyl
The mass ratio of imidazoles and anhydrous formic acid sodium is 1~5：1~2：1；
(3) benzimidazole is dissolved in DMF, 2~5min of ultrasound obtains mixed liquid B, by obtained by step (2)
ZnO array vertical immersions are reacted 10 hours in mixed liquid B under the conditions of 80~140 DEG C, after reaction terminates, gained reaction production
The post-treated processes of thing B obtain super-hydrophobic metal organic framework array.
2. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (1), it is described organic or
The addition of inorganic substrates is calculated as 24~60cm with the volume of organic solvent3/L。
3. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (2), the ethanol adds
Enter amount with the quality of zinc nitrate hexahydrate to be calculated as 28~56mL/g.
4. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (2), the product A
Last handling process be：After reaction terminates, products therefrom A is placed in 15~60s of ultrasound in ethanol, the ZnO of excess surface is removed,
Dry at room temperature and produce ZnO arrays.
5. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (3), described N, N-
The addition of dimethylformamide is calculated as 60~75mL/g with the quality of benzimidazole.
6. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (3), the product B
Last handling process be：After reaction terminates, after products therefrom B is cleaned through DMF, dry at room temperature, i.e.,
Obtain super-hydrophobic metal organic framework array.
7. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (2), the reaction temperature
Spend for 90~120 DEG C, the reaction time is 8~10h.
8. super-hydrophobic metal organic framework array as claimed in claim 1, it is characterised in that in step (3), the reaction temperature
Spend for 120~140 DEG C, the reaction time is 10h.
9. a kind of super-hydrophobic metal organic framework array as claimed in claim 1 answering in oil water mixture separation field
With.
10. application as claimed in claim 9, it is characterised in that the oil water mixture is n-hexane/water, toluene/water, stone
One or more in oily ether/water, methylene chloride/water, plant oil/water, vapour oil/water or chloroform/water.
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