CN106669608A - Graphene oxide coated metal organic framework material and preparation method thereof - Google Patents
Graphene oxide coated metal organic framework material and preparation method thereof Download PDFInfo
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- CN106669608A CN106669608A CN201611192050.XA CN201611192050A CN106669608A CN 106669608 A CN106669608 A CN 106669608A CN 201611192050 A CN201611192050 A CN 201611192050A CN 106669608 A CN106669608 A CN 106669608A
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- organic framework
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Abstract
The invention discloses a graphene oxide coated metal organic framework material and a preparation method thereof. The graphene oxide coated metal organic framework material is characterized in that the mass ratio of graphene oxide to a metal organic framework material is 1-100 to 20,000; the number of the coated graphene oxide layers is 1-10. The preparation method of the graphene oxide coated metal organic framework material comprises the following steps: dispersing the metal organic framework material in water and uniformly stirring and dispersing; then adding a polydiene dimethyl ammonium chloride solution, trihydroxymethyl aminomethane and sodium chloride, stirring and then centrifugally drying; re-dispersing the modified metal organic framework material into the water, adding a small amount of a graphene oxide aqueous solution, stirring and centrifuging to obtain the graphene oxide coated metal organic framework material. The preparation method of the graphene oxide coated metal organic framework material is simple in process and operated under normal temperature; the raw materials are rich and controllable; the process is environmentally friendly; the number of the graphene oxide layers coating the prepared composite is 1-10.
Description
Technical field
The present invention relates to a kind of graphene oxide coated metal organic framework material and preparation method thereof.
Background technology
Metal-organic framework materials (metal organic framework, MOF) are with metal ion or ion cluster as section
Point, by organic ligand as connector, the class formed by Coordinate self-assembly has the organic-inorganic of regular pore structure miscellaneous
Change coordination polymer crystal.This material has that specific surface area is big, aperture is adjustable, the features such as various structures, excellent performance, is inhaling
The fields such as attached, separation have a wide range of applications and study.
Graphene oxide (graphene oxide, GO) is the two-dimensional network structure flexibility material that a kind of monoatomic layer is constituted
Material, thickness is about 1 nanometer, and surface distributed the carboxyl isopolarity oxygen-containing functional group at substantial amounts of hydroxyl, epoxy radicals and edge, has
Good hydrophilic.
Metal-organic framework materials due to its distinctive structure, generally with poor water stability and dispersibility, so as to
Limit its application.The graphene oxide of metal-organic framework materials and stability is combined can well solve problem above,
For the more applications of metal-organic framework materials exploitation.For example the poor metal-organic framework materials of dispersibility in water phase are wrapped up
After one layer of graphene oxide, the dispersibility of material can be improved, when the mixed substrate membrane containing nano-grade molecular sieve casting solution of high filler loading capacity is prepared, can
To reduce the sedimentation of metallic organic framework granule and dispersion problem.Simultaneous oxidation Graphene has the unique biography of water and carbon dioxide
Defeated passage, when the metallic organic framework mixed substrate membrane containing nano-grade molecular sieve casting solution with separating property is prepared, can effectively improve organic
Thing is dehydrated the performance with carbon dioxide capture.
The content of the invention
The invention aims to improve the deficiencies in the prior art and to provide a kind of graphene oxide coated metal organic
Framework material, it is a further object of the present invention to provide the preparation method of above-mentioned material.
The technical scheme is that：A kind of graphene oxide coated metal organic framework material, it is characterised in that oxidation
The mass ratio of Graphene and metal-organic framework materials is 1-100：20000；The graphene oxide number of plies of its parcel is 1-10 layers.
Present invention also offers the preparation method of above-mentioned graphene oxide coated metal organic framework material, its concrete step
It is rapid as follows：
1) metal-organic framework materials are added in deionized water, and are sufficiently stirred for dispersion；
2) polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane and Sodium Chloride are added into metallic organic framework material
In the dispersion liquid of material, stirring, centrifugal drying obtains powder；
3) by step 2) in the powder that obtains be dispersed in water and add graphene oxide water solution again, stir, prepare
Into graphene oxide-metal-organic framework materials mixed solution；
4) above-mentioned solution centrifugal is dried, obtains the metallic organic framework composite wood that different graphene oxides wrap up the number of plies
Material.
It is preferred that above-mentioned metal-organic framework materials be ZIFs series, MILs series, UiO-66 series, MOF-801 or
MAF-6 common metal-organic framework materials.
Preferred steps 2) described in polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane, Sodium Chloride, metal
The mass ratio of organic framework material and water is：20-35：3-4：1-2：1-2：1500；Polydiallyldimethyl ammonium chloride solution is 20-
35wt% aqueous solutions.
Preferred steps 3) in graphene oxide water solution mass fraction be 0.01-0.1mg/mL；Graphene oxide and metal
Organic framework material mass ratio is 1-100：20000.
Preferred steps 2) in mixing speed be 400-600r/min, mixing time be 2-3 hours；Step 3) in stirring
Speed is 400-600r/min, and mixing time is 6-7 hours.
Material prepared by this method can fully combine the characteristic of metal-organic framework materials and graphene oxide, not destroy
The nature of metal-organic framework materials improves dispersibility in its water stability and aqueous solution simultaneously, is preparing high filler loading capacity
During mixed substrate membrane containing nano-grade molecular sieve casting solution, the sedimentation of metallic organic framework granule and dispersion problem are reduced, while improving separating property.
Beneficial effect：
The present invention is the method that room temperature prepares graphene oxide coated metal organic framework material, its graphene oxide parcel
The number of plies is 1-10 layers.Graphene oxide prepared by the present invention and metallic organic framework composite, normal-temperature operation, process green ring
Protect, it is gentle controllable, simple to operate, the graphene oxide parcel number of plies is adjustable, the graphene oxide coated metal organic backbone of preparation
Composite, the nature for not destroying metal-organic framework materials improves dispersibility in stability and water simultaneously, high preparing
During the mixed substrate membrane containing nano-grade molecular sieve casting solution of loading, the sedimentation of metallic organic framework granule and dispersion problem are reduced, while improve separating
Performance.
Description of the drawings
Fig. 1 for institute's prepared material in embodiment 1 transmission electron microscope picture；
Fig. 2 for institute's prepared material in embodiment 2 transmission electron microscope picture；
Fig. 3 for institute's prepared material in embodiment 3 transmission electron microscope picture；
Fig. 4 is the transmission electron microscope picture of the MOF-801 materials before wrapping up in embodiment 1 and 2；
Fig. 5 is the MIL-53-NH before wrapping up in embodiment 32The transmission electron microscope picture of material.
Specific embodiment
Embodiment 1
By the metal-organic framework materials MOF-801 dispersed with stirring after vacuum drying in deionized water.By polydiene two
Methyl chloride ammonium salt solution, trishydroxymethylaminomethane and Sodium Chloride are added in above-mentioned mixed liquor, are stirred at room temperature 2 hours, rotating speed
500r/min, wherein polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane, Sodium Chloride, metal-organic framework materials
It is 20 with the mass ratio of water：3：1：1：1500.Wherein polydiallyldimethyl ammonium chloride solution is 35wt% aqueous solutions.Will be above-mentioned molten
The metal-organic framework materials powder obtained in liquid is distributed in deionized water, and adds 1mL graphene oxide water solutions, wherein
Graphene oxide water solution mass fraction is 0.1mg/mL.Graphene oxide is 1 with metal-organic framework materials mass ratio：200,
Reaction 6 hours is stirred at room temperature, rotating speed 500r/min, centrifugal filtration, vacuum drying obtains the organic bone of graphene oxide coated metal
Frame material.Fig. 1 is the composite electron microscope for preparing, and Fig. 4 is the metal-organic framework materials electron microscope before parcel, from Fig. 1 and
Contrast in Fig. 4 can show that the graphene oxide parcel number of plies is 10 layers, and the material is preparing the mixing with dehydration of organic solvent
During matrix membrane casting solution, the dispersibility in casting solution can be effectively improved.
Embodiment 2
By the metal-organic framework materials MOF-801 dispersed with stirring after vacuum drying in deionized water.By polydiene two
Methyl chloride ammonium salt solution, trishydroxymethylaminomethane and Sodium Chloride are added in above-mentioned mixed liquor, are stirred at room temperature 3 hours, rotating speed
400r/min, wherein polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane, Sodium Chloride, metal-organic framework materials
It is 35 with the mass ratio of water：3：2：1：1500.Polydiallyldimethyl ammonium chloride solution concentration 20wt%.To obtain in above-mentioned solution
Metal-organic framework materials powder be distributed in deionized water, and 0.1mL graphene oxide water solutions are added, wherein aoxidizing stone
Black aqueous solution mass fraction is 0.1mg/mL.Graphene oxide and metal-organic framework materials mass ratio 1：2000, room temperature is stirred
Reaction 6 hours is mixed, rotating speed 600r/min, centrifugal filtration, vacuum drying obtains graphene oxide coated metal organic framework material.
The contrast from Fig. 2 and Fig. 4 can be seen that the graphene oxide parcel number of plies is 3-4 layers, and the material is being prepared with separating property
During metallic organic framework mixed substrate membrane containing nano-grade molecular sieve casting solution, the performance of carbon dioxide capture can be effectively improved.
Embodiment 3
By the metal-organic framework materials MIL-53-NH after vacuum drying2Dispersed with stirring is in deionized water.By polydiene
Dimethylammonium chloride ammonium salt solution, trishydroxymethylaminomethane and Sodium Chloride are added in above-mentioned mixed liquor, are stirred at room temperature 2 hours, are turned
Fast 600r/min, wherein polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane, Sodium Chloride, metallic organic framework material
The mass ratio of material and water is 30：4：1：2：1500.Polydiallyldimethyl ammonium chloride solution concentration 20wt%.To obtain in above-mentioned solution
To metal-organic framework materials powder be distributed in deionized water, and 0.1mL graphene oxide water solutions are added, wherein aoxidizing
Graphene aqueous solution mass fraction is 0.01mg/mL.Graphene oxide and metal-organic framework materials mass ratio 1：20000, room
Warm stirring reaction 7 hours, rotating speed 400r/min, centrifugal filtration, vacuum drying obtains graphene oxide coated metal organic backbone
Material.The contrast from Fig. 3 and Fig. 5 can be seen that the graphene oxide parcel number of plies is 1-2 layers, and it is high that the composite is applied to preparation
Loading to 50wt% mixed substrate membrane containing nano-grade molecular sieve casting solution when, compared with non-lapping before, can effectively reduce metal organic
The sedimentation of skeleton particle.
Claims (6)
1. a kind of graphene oxide coated metal organic framework material, it is characterised in that graphene oxide and metallic organic framework material
The mass ratio of material is 1-100：20000；The graphene oxide number of plies of its parcel is 1-10 layers.
2. a kind of method for preparing graphene oxide coated metal organic framework material as claimed in claim 1, its concrete step
It is rapid as follows：
1) metal-organic framework materials are added in deionized water, and are sufficiently stirred for dispersion；
2) polydiallyldimethyl ammonium chloride solution, trishydroxymethylaminomethane and Sodium Chloride are added into metal-organic framework materials
In dispersion liquid, stirring, centrifugal drying obtains powder；
3) by step 2) in the powder that obtains be dispersed in water and add graphene oxide water solution again, stir, be configured to oxygen
Graphite alkene-metal-organic framework materials mixed solution；
4) above-mentioned solution centrifugal is dried, obtains the metallic organic framework composite that different graphene oxides wrap up the number of plies.
3. method according to claim 2, it is characterised in that described metal-organic framework materials are ZIFs series, MILs
Series, UiO-66 series, MOF-801 or MAF-6 metal-organic framework materials.
4. method according to claim 2, it is characterised in that step 2) described in polydiallyldimethyl ammonium chloride solution,
The mass ratio of trishydroxymethylaminomethane, Sodium Chloride, metal-organic framework materials and water is：20-35：3-4：1-2：1-2：
1500；
Polydiallyldimethyl ammonium chloride solution is 20-35wt% aqueous solutions.
5. method according to claim 2, it is characterised in that step 3) in graphene oxide water solution mass fraction be
0.01-0.1mg/mL；Graphene oxide is 1-100 with metal-organic framework materials mass ratio：20000.
6. method according to claim 2, it is characterised in that step 2) in mixing speed be 400-600r/min, stirring
Time is 2-3 hours；Step 3) in mixing speed be 400-600r/min, mixing time be 6-7 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN110025592A (en) * | 2018-12-21 | 2019-07-19 | 中山大学 | Cyclodextrin-metal-organic framework materials complex microsphere and preparation method thereof |
| CN110031520A (en) * | 2019-04-30 | 2019-07-19 | 福建师范大学 | The sensor of the preparation method of graphene oxide modified glassy carbon electrode and recognizable phosphite |
| CN111330520A (en) * | 2020-03-09 | 2020-06-26 | 南京大学深圳研究院 | Preparation method and application of graphene and UIO-66 composite aerogel |
| CN113813797A (en) * | 2021-10-20 | 2021-12-21 | 西南石油大学 | Preparation method of emulsion separation membrane with high flux and self-cleaning function |
| CN114870657A (en) * | 2022-03-28 | 2022-08-09 | 南京工业大学 | Graphene oxide film for in-situ growth of porous MOF intercalation, preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN110025592A (en) * | 2018-12-21 | 2019-07-19 | 中山大学 | Cyclodextrin-metal-organic framework materials complex microsphere and preparation method thereof |
| CN110031520A (en) * | 2019-04-30 | 2019-07-19 | 福建师范大学 | The sensor of the preparation method of graphene oxide modified glassy carbon electrode and recognizable phosphite |
| CN111330520A (en) * | 2020-03-09 | 2020-06-26 | 南京大学深圳研究院 | Preparation method and application of graphene and UIO-66 composite aerogel |
| CN113813797A (en) * | 2021-10-20 | 2021-12-21 | 西南石油大学 | Preparation method of emulsion separation membrane with high flux and self-cleaning function |
| CN114870657A (en) * | 2022-03-28 | 2022-08-09 | 南京工业大学 | Graphene oxide film for in-situ growth of porous MOF intercalation, preparation method and application |
| CN114870657B (en) * | 2022-03-28 | 2023-08-22 | 南京工业大学 | Graphene oxide film for in-situ growth of porous MOF intercalation, preparation method and application |
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