CN105126783A - Sponge coated by metal organic skeleton material coated graphene and preparation method thereof - Google Patents
Sponge coated by metal organic skeleton material coated graphene and preparation method thereof Download PDFInfo
- Publication number
- CN105126783A CN105126783A CN201510467999.5A CN201510467999A CN105126783A CN 105126783 A CN105126783 A CN 105126783A CN 201510467999 A CN201510467999 A CN 201510467999A CN 105126783 A CN105126783 A CN 105126783A
- Authority
- CN
- China
- Prior art keywords
- sponge
- metal
- preparation
- graphene
- parcel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a sponge coated by metal organic skeleton material coated graphene and a preparation method thereof. The preparation method is characterized by comprising the following steps: soaking sponge in an oxidized graphene solution, carrying out centrifugation, drying, then soaking sponge in a synthesis mother liquid of a metal organic skeleton material, allowing sponge to grow in the mother liquid for a while, then taking out the sponge, and drying to obtain the sponge coated by metal organic skeleton material coated graphene. Through the acting force between a metal organic skeleton material and oxidized graphene, the material can massively grow and be wrapped in graphene coated sponge, and due to the hydrophobic and oleophylic properties of the metal organic skeleton material, the obtained sponge can be used to separate oil and water and simulate crude oil recovery on the sea.
Description
Technical field
The invention belongs to technical field of nano material, particularly relate to the preparation method of a kind of metal-organic framework materials parcel Graphene parcel sponge.
Background technology
How to solve organic solvent pollution in water environment, particularly ocean Crude Oil pollutes, and is more and more paid close attention to.The hydrophobic oleophilic oil material of high efficiency, recyclability has huge application prospect at materials chemistry and Environmental Chemistry field.The adsorbent of the hydrophobic oleophilic oil of porous has the ability of well selective absorption greasy dirt in aqueous phase, by the method for distilling or squeeze, is reclaimed by the oil of absorption, thus reaches the object that water oil is separated recycling.But this method is relatively loaded down with trivial details, consuming time longer, there is the intrinsic disadvantages of the recovery of unsustainable property.
Prior art discloses the multiple method for the preparation of hydrophobic oleophilic oil adsorbent, such as: polydimethylsiloxane parcel Graphene parcel sponge adsorbent, but the hydrophobic oleophilic oil adsorbent utilizing metal-organic framework materials to be made into not yet is invented.Metal-organic framework materials is mainly used in gas storage at present and is separated, catalysis, sensing, medicament transport, construct the aspects such as new material as template, most metal-organic framework materials is unstable in water, even expose and will decompose in atmosphere, limit their development and application, thus stable, easily synthesis, acid and alkali-resistance the metal-organic framework materials of invention has huge application potential and value.
Summary of the invention
The present invention, for avoiding the weak point existing for above-mentioned prior art, provides a kind of water oil to be separated, particularly simulates the method that Crude Oil at Sea reclaims, and not only can improve oil absorption, and but also can simplify preparation technology, improves organic efficiency.
In one aspect of the invention, provide a kind of sponge product, described sponge product comprises:
Sponge matrix;
Graphene oxide; With
Parcel and the metallo organic material of growth on graphene oxide sponge.
In one embodiment of the invention, described metallo organic material is by metal ion as tie point, the framework material that organic ligand and metal self assembly are formed.
In one embodiment of the invention, described metal is selected from copper, zinc and chromium; And/or wherein organic ligand is selected from terephthalic acid (TPA), all benzene tricarbonic acid and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid.
Another aspect of the present invention provides a kind of preparation method of sponge product, and described method comprises:
A, sponge is immersed in graphene oxide solution,
B, by soak after sponge centrifugal drying;
C, the mother liquor that the dried sponge with graphene oxide puts into metallo organic material to be grown.
In one embodiment of the invention, before step a, also comprise the step of cleaning sponge.
In one embodiment of the invention, the concentration of graphene oxide described in step a is 0.5-10mg/mL, preferred 2-5mg/mL, more preferred 2-3mg/mL, most preferably 2.5mg/mL.
In one embodiment of the invention, centrifugal drying described in step b carries out under going to the centrifugal rotational speed of 8000 turns per minute per minute 1000, and preferred 2000-6000 turns, more preferably 2500-4000 turns, most preferably 3000 turns.
In one embodiment of the invention, metal-organic framework materials described in step c is by metal ion as tie point, and organic ligand and metal self assembly are formed.
In one embodiment of the invention, described metal is selected from copper, zinc and chromium; And/or wherein organic ligand is selected from terephthalic acid (TPA), all benzene tricarbonic acid and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid.
In one embodiment of the invention, the mother liquor of metal-organic framework materials described in step c is configured by the following and forms:
Mass ratio 2: 1 to 2: 5, preferably 2: 1 to 2: 4, more preferably 2: 2 to 2: 4, most preferably 2: 3 copper chloride and organic ligand;
Volume ratio is 3: 1 to 1: 3, preferably 3: 1 to 1: 1, more preferably 3: 1 to 2: 1, most preferably 3: 1 DMF and water.
In one embodiment of the invention, grow at 60 DEG C to 100 DEG C described in step c, preferably 70 DEG C to 90 DEG C, more preferably 80 DEG C to 85 DEG C, most preferably 85 DEG C, carry out growth 12-48 hour, preferred 18-42 hour, more preferred 24-36 hour, most preferably 24 hours.
Compared with the prior art, beneficial effect of the present invention includes, but are not limited to:
1, the present invention utilizes the active force between metal-organic framework materials and graphene oxide, parcel and growth in the sponge that hydrophobic metals organic framework material is wrapped up at graphene oxide, and synthetic method is simple, and preparation is quick; The metal-organic framework materials parcel Graphene parcel sponge hydrophobicity obtained is strong, and oil absorption is large, can be used for water oil and is separated, also can simulate Crude Oil at Sea and be separated.
2, metal-organic framework materials used in the present invention is in neutrality, slant acidity and the meta-alkalescence aqueous solution, all can stable existence.
Accompanying drawing explanation
The powder x-ray diffraction characterization data of the metal-organic framework materials that Fig. 1 obtains for the embodiment of the present invention 1;
The scanning electron microscope diagram sheet of the metal-organic framework materials parcel Graphene parcel sponge that Fig. 2 obtains for the embodiment of the present invention 1;
Fig. 3 is that the optical camera of sponge cosmetic variation in the embodiment of the present invention 1 building-up process is taken pictures picture;
The contact angle picture of itself and water surveyed respectively by the metal-organic framework materials powder that Fig. 4 obtains for the embodiment of the present invention 1 and metal-organic framework materials parcel Graphene parcel sponge material;
The metal-organic framework materials parcel Graphene parcel sponge that Fig. 5 obtains for the embodiment of the present invention 1 carries out water waterborne oil separation experiment picture;
The metal-organic framework materials parcel Graphene parcel sponge that Fig. 6 obtains for the embodiment of the present invention 1 carries out the picture of water oil separation experiment under water;
The Graphene parcel sponge that Fig. 7 obtains for the embodiment of the present invention 2 and metal-organic framework materials parcel Graphene parcel sponge are placed on filler neck part respectively, carry out water oil and are separated experiment picture;
The metal-organic framework materials parcel Graphene parcel sponge that Fig. 8 obtains for the embodiment of the present invention 3 carries out taking out 70% crude oil 30% diesel oil recovery experiment picture with pump;
The metal-organic framework materials parcel Graphene parcel sponge that Fig. 9 obtains for the embodiment of the present invention 3 carries out simulation offshore oil-absorbing recovery experiment picture;
Detailed description of the invention
In a specific embodiments of the present invention, the preparation method of metal-organic framework materials parcel Graphene parcel sponge carries out as follows:
A, by after sponge cleaning-drying, be immersed in graphene oxide solution, absorb to saturated,
B, will the sponge centrifugal drying of graphene oxide be soaked, obtain graphene oxide/sponge;
C, mother liquor graphene oxide/sponge being put into metal-organic framework materials grow,
D, the sponge after growth is taken out dry, obtain metal-organic framework materials/Graphene/sponge.
In a specific embodiments of the present invention, sponge described in step a is that business buys sponge.
In a specific embodiments of the present invention, cleaning condition described in step a is: use deionized water, ethanol purge 3-5 time.
In a specific embodiments of the present invention, condition dry described in step a is: 100 DEG C of dry 12-24 hour.
In a specific embodiments of the present invention, the concentration of graphene oxide described in step a is 1-4mg/mL.
In a specific embodiments of the present invention, centrifugal rotational speed described in step b is 3000 rpms.
In a specific embodiments of the present invention, drying condition described in step b is 100 DEG C of dry 12-24 hour.
In a specific embodiments of the present invention, the mother liquor of metal-organic framework materials described in step c is copper chloride dihydrate 450mg, part 300mg, deionized water 10ml, DMF 30ml, ultrasonic abundant mixing.
In a specific embodiments of the present invention, described in step c, growth conditions is for put into 100mL reactor by above-mentioned mother liquor and graphene oxide/sponge, then puts into the standing 12-24 hour of 85 DEG C of baking ovens.
In a specific embodiments of the present invention, drying condition described in steps d is vacuumize dry 12-24 hour at 25 DEG C.
Embodiment
Embodiment 1
The preparation method of the present embodiment metal-organic framework materials parcel Graphene parcel sponge carries out as follows:
A, by after sponge cleaning-drying, be immersed in graphene oxide solution, absorb to saturated,
B, by soak after sponge centrifugal drying, obtain graphene oxide/sponge;
C, mother liquor graphene oxide/sponge being put into metal-organic framework materials grow,
D, the sponge after growth is taken out dry, obtain metal-organic framework materials/Graphene/sponge.
Be immersed in different solutions to the metal-organic framework materials that the present embodiment obtains, powder x-ray diffraction sign is carried out after a period of time, result is see Fig. 1, as shown in Figure 1, the metal-organic framework materials that the present embodiment obtains is stablized in aqueous, at pH be in the acid solution of 2 and pH be stable equally in the alkaline solution of 10.
Use sem observation to the metal-organic framework materials parcel Graphene parcel sponge that the present embodiment obtains, result is see Fig. 2.As shown in Figure 2, in metal-organic framework materials that the present embodiment obtains parcel Graphene parcel sponge, metal-organic framework materials raised growth, be wrapped in spongin surface.
To the change optical camera Taking Pictures recording of sponge outward appearance in the present embodiment building-up process, result is see Fig. 3.As shown in Figure 3, sponge white originally becomes the khaki of graphene oxide after step a, b, becomes the blueness of metal-organic framework materials after step c, d.
Use metal-organic framework materials powder and metal-organic framework materials parcel Graphene parcel sponge material to the present embodiment, survey the contact angle of itself and water respectively, result is see Fig. 4.As shown in Figure 4, the water droplet contact angle of metal-organic framework materials powder is 132 °, and the water droplet contact angle of metal-organic framework materials parcel Graphene parcel sponge material is 121 °.
Carry out water waterborne oil discrete testing to metal-organic framework materials that the present embodiment obtains parcel Graphene parcel sponge, result is see Fig. 5.As shown in Figure 5, be placed in the aqueous solution of oil slick by this material, oil can be siphoned away by material, and water can't be siphoned away by material; By squeezing, the oil absorbed can be recycled.
Carry out water oil discrete testing under water to metal-organic framework materials that the present embodiment obtains parcel Graphene parcel sponge, result is see Fig. 6.As shown in Figure 6, when the density of oil is greater than water, is pressed onto by this material and contacts with oil under water, oil can be siphoned away by material equally, and water can't be siphoned away by material.
From above-mentioned experiment, metal-organic framework materials provided by the invention parcel Graphene parcel sponge, has the features such as stable, hydrophobic, oleophylic.
Embodiment 2
The preparation method of the present embodiment metal-organic framework materials parcel Graphene parcel sponge carries out as follows:
A, by after sponge (2cm*2cm*2cm) cleaning-drying, be immersed in graphene oxide solution, absorb to saturated,
B, by soak after sponge centrifugal drying, obtain graphene oxide/sponge;
C, mother liquor graphene oxide/sponge being put into metal-organic framework materials grow,
D, the sponge after growth is taken out dry, obtain metal-organic framework materials/Graphene/sponge.
Graphene that the present embodiment obtains parcel sponge and metal-organic framework materials parcel Graphene parcel sponge are respectively charged into separatory funnel neck, and above funnel, pour the oil that density is greater than water subsequently into, result is see Fig. 7.As shown in Figure 7, the sponge hydrophilic and oleophilic of ordinary oxygen functionalized graphene parcel, can not carry out water-oil separating; And metal-organic framework materials parcel Graphene parcel sponge hydrophobic oleophilic oil, oil infiltration is gone down, and water is retained in funnel.
From above-mentioned experiment, metal-organic framework materials provided by the invention parcel Graphene parcel sponge, has the features such as stable, hydrophobic, oleophylic.
Embodiment 3
The preparation method of the present embodiment metal-organic framework materials parcel Graphene parcel sponge carries out as follows:
A, by after sponge (2cm*2cm*2cm) cleaning-drying, be immersed in graphene oxide solution, absorb to saturated,
B, by soak after sponge centrifugal drying, obtain graphene oxide/sponge;
C, mother liquor graphene oxide/sponge being put into metal-organic framework materials grow,
D, the sponge after growth is taken out dry, obtain metal-organic framework materials/Graphene/sponge.
Carry out taking out crude oil recovery experiment with pump to metal-organic framework materials that the present embodiment obtains parcel Graphene parcel sponge, result is see Fig. 8.As shown in Figure 8, by continuously taking out with pump, the crude oil floated on the surface in the container of the left side is transferred in the recovery beaker on the right, and water can't be pumped; Treat that crude oil recovery is complete, the beaker on the right can successively be emerged bubble, the complete beginning suck of the material oil suction on the left side is described, not water suction.
Carry out simulation offshore oil-absorbing recovery experiment to metal-organic framework materials that the present embodiment obtains parcel Graphene parcel sponge, result is see Fig. 9.As shown in Figure 9, when analog sea constantly teetertotters, take out oil to be transferred to equally with pump and reclaim in beaker, and water can't be sucked away; Treat that oil reclaims complete, reclaim in beaker bubble of successively emerging equally, prove the complete beginning suck of left side material oil suction, not water suction.
From above-mentioned experiment, metal-organic framework materials parcel Graphene parcel sponge material provided by the invention, show good hydrophobic oleophilic oil characteristic, and by improving oil suction technique, can successively, quickly and easily by water-oil separating to reclaim, even if illustrate and having on stormy waves, the sea of rocking, reclaim oil suction experiment and can carry out equally.
Experiment shows, metal-organic framework materials prepared by the present invention parcel Graphene parcel sponge, and have the advantages such as stable, hydrophobic, oleophylic, synthetic method is safe and simple, and being greater than water with the organic solvent being less than water for density can be separated well; And by improving oil suction technique further, the mode adopting pump to take out can realize profit and successively, quickly and easily reclaim separation, practical, simple to operate, can simulate offshore oil-absorbing, still there is good effect on the sea of rocking.
Claims (10)
1. a sponge product, described sponge product comprises:
Sponge matrix;
Graphene oxide in described sponge matrix; With
Parcel and the metallo organic material of growth on graphene oxide sponge.
2. sponge product according to claim 1, wherein said metallo organic material is by metal ion as tie point, the framework material that organic ligand and metal self assembly are formed.
3. sponge product according to claim 2, wherein said metal is selected from copper, zinc and chromium; And/or wherein organic ligand is selected from terephthalic acid (TPA), all benzene tricarbonic acid and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid.
4. a preparation method for sponge product, described method comprises:
A, sponge is immersed in graphene oxide solution,
B, by dry for the sponge after soaking;
C, the mother liquor that the dried sponge with graphene oxide puts into metallo organic material to be grown.
5. preparation method according to claim 4, wherein:
The step of cleaning sponge was also comprised before step a; And/or
The concentration of graphene oxide described in step a is 0.5-10mg/mL.
6. preparation method according to claim 4, wherein drying described in step b is the centrifugal drying carried out under going to the centrifugal rotational speed of 8000 turns per minute per minute 1000.
7. preparation method according to claim 4, wherein metal-organic framework materials described in step c is by metal ion as tie point, and organic ligand and metal self assembly are formed.
8. sponge product according to claim 7, wherein said metal is selected from copper, zinc and chromium; And/or wherein organic ligand is selected from terephthalic acid (TPA), equal benzene tricarbonic acid, 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acid.
9. preparation method according to claim 4, wherein the mother liquor of metal-organic framework materials described in step c is configured by the following and forms:
The copper chloride of mass ratio 2: 1 to 2: 5 and organic ligand;
Volume ratio is DMF and the water of 3: 1 to 1: 3.
10. preparation method according to claim 4, wherein grows described in step c and carries out 12-48 hour at 60 DEG C to 100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467999.5A CN105126783B (en) | 2015-07-30 | 2015-07-30 | Metal-organic framework materials parcel graphene parcel sponge and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467999.5A CN105126783B (en) | 2015-07-30 | 2015-07-30 | Metal-organic framework materials parcel graphene parcel sponge and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105126783A true CN105126783A (en) | 2015-12-09 |
| CN105126783B CN105126783B (en) | 2018-01-30 |
Family
ID=54712556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510467999.5A Active CN105126783B (en) | 2015-07-30 | 2015-07-30 | Metal-organic framework materials parcel graphene parcel sponge and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105126783B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430166A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of MOFs (Metal-Organic Frameworks)-graphene composite material |
| CN107866154A (en) * | 2017-11-23 | 2018-04-03 | 天津工业大学 | A kind of polyimides zinc organic backbone load graphene oxide hybridized film and preparation and application |
| CN109174011A (en) * | 2018-10-12 | 2019-01-11 | 辽宁大学 | A kind of super-hydrophobic metal organic framework composite material and preparation method and application |
| CN109926031A (en) * | 2019-04-04 | 2019-06-25 | 北京工业大学 | A kind of MOFs/ sponge composite material and preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
-
2015
- 2015-07-30 CN CN201510467999.5A patent/CN105126783B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626171A (en) * | 2013-11-28 | 2014-03-12 | 中国科学技术大学 | Preparation method of oil-water separation material |
Non-Patent Citations (1)
| Title |
|---|
| CHI YANG, ET AL.: "Fluorous metal-organic framework with superior adsorption and hydrophobic properties toward oil spill cleanup and hydrocarbon storage", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430166A (en) * | 2016-10-28 | 2017-02-22 | 武汉理工大学 | Preparation method of MOFs (Metal-Organic Frameworks)-graphene composite material |
| CN106430166B (en) * | 2016-10-28 | 2018-11-23 | 武汉理工大学 | A kind of preparation method of MOFs- graphene composite material |
| CN107866154A (en) * | 2017-11-23 | 2018-04-03 | 天津工业大学 | A kind of polyimides zinc organic backbone load graphene oxide hybridized film and preparation and application |
| CN107866154B (en) * | 2017-11-23 | 2019-11-26 | 天津工业大学 | A kind of polyimides-zinc organic backbone load graphene oxide hybridized film and preparation and application |
| CN109174011A (en) * | 2018-10-12 | 2019-01-11 | 辽宁大学 | A kind of super-hydrophobic metal organic framework composite material and preparation method and application |
| CN109926031A (en) * | 2019-04-04 | 2019-06-25 | 北京工业大学 | A kind of MOFs/ sponge composite material and preparation method and application |
| CN109926031B (en) * | 2019-04-04 | 2021-08-17 | 北京工业大学 | MOFs (metal-organic frameworks)/sponge composite material as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105126783B (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105126783A (en) | Sponge coated by metal organic skeleton material coated graphene and preparation method thereof | |
| CN106807338B (en) | A kind of preparation method of the modified graphene enhancing polyurethane sponge for water-oil separating | |
| CN107344095A (en) | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage | |
| CN101733074B (en) | Method for preparing film type biological adsorbing medium | |
| CN106853296A (en) | A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof | |
| CN105575679B (en) | A kind of preparation method of graphene film electrode | |
| CN105056901B (en) | Superhydrophobic and super-oleophilic adsorbent with straw as raw material and preparation method thereof | |
| CN106178986A (en) | A kind of preparation method of super hydrophilic Kynoar@dopamine@silicon dioxide composite material | |
| CN104056607B (en) | A kind of Enteromorpha gel oil absorption material and preparation method thereof | |
| CN104629079B (en) | Flexible super-hydrophobic chitosan oil suction sponge and its preparation method and application | |
| CN105251373A (en) | Reduced graphene oxide emulsion separating film, and preparation method and application thereof | |
| CN110327895A (en) | A kind of graphene oxide/calcium alginate Supported Melamine sponge composite adsorbing material and its preparation method and application | |
| CN107245160B (en) | Hydrophobic modification method of melamine foam, product and application thereof | |
| CN108273476A (en) | A kind of preparation method of the compound porous hydrophobic oil suction sponge material of zein-sodium alginate | |
| CN107312197A (en) | Super-hydrophobic cavernosa material and preparation method thereof | |
| CN107081134A (en) | A kind of modified hair keratin adsorbent and preparation method and application | |
| CN103537120A (en) | Preparation method of sponge used for oil-water separation | |
| CN104941544A (en) | Sporopollen microcapsule, and preparation method and application thereof | |
| CN108704610A (en) | The Mg-Fe ball composite material and preparation method of magnetic carbon modification and application | |
| CN108822333B (en) | Hydrophobic-super-oleophylic sponge and preparation method and application thereof | |
| CN108465460A (en) | A kind of preparation method of super-hydrophobic sponge sorbing material | |
| CN104151600A (en) | Preparation method of super-hydrophobic magnetic sponge | |
| CN105833741B (en) | A kind of preparation method of polyvinylidene fluoride porous membrane | |
| CN110482637A (en) | A kind of Processes and apparatus for clearing up oil pollution of waters | |
| CN106943882B (en) | A kind of modified composite membrane of Prussian blue analogue/carboxy methylcellulose gel and preparation method and purposes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |