CN107376837A - A kind of preparation method of graphene/metal organic frame aeroge absorption/catalysis material - Google Patents
A kind of preparation method of graphene/metal organic frame aeroge absorption/catalysis material Download PDFInfo
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- CN107376837A CN107376837A CN201710625296.XA CN201710625296A CN107376837A CN 107376837 A CN107376837 A CN 107376837A CN 201710625296 A CN201710625296 A CN 201710625296A CN 107376837 A CN107376837 A CN 107376837A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 31
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000013291 MIL-100 Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 8
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- -1 methylene formamides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 2
- 239000013179 MIL-101(Fe) Substances 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 239000004964 aerogel Substances 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- 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 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28047—Gels
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The present invention relates to a kind of preparation method of graphene/metal organic frame aeroge absorption/catalysis material, comprise the following steps：It is first according to 1:Graphene oxide and metal organic frame crystal are mixed and made into reaction mixture system by 0.2 5 mass ratio, are subsequently added into crosslinking agent and are warming up to 150 200 DEG C of 24h of insulation reaction 2, and product is isolated after cooling, and washing, which is freeze-dried, to be produced.Graphene produced by the present invention/metal organic frame aerogel material is three-dimensional porous network structure aeroge, has the characteristics that porosity is high, specific surface area is big, good mechanical performance；Dual capability with absorption with pollutant in catalytic degradation water body；It is good with removal efficiency height, reusability, simple, convenient the features such as recycling is separated after use.
Description
Technical field
The invention belongs to nano composite material technical field, and in particular to a kind of graphene/metal organic frame aeroge
The preparation method of absorption/catalysis material.
Background technology
Metal-organic framework materials (MOFs) are a kind of coordination polymers of fast development nearly ten years, and it generally has three
The pore structure of dimension, i.e., the atom centered on metal ion, one or more kinds of organic ligands prolong for support Special composition is three-dimensional
Stretch, this causes MOFs to have wide application in adsoption catalysis field.Compared to other nano materials, metal-organic framework materials
Have the characteristics that：1) species is various, can introduce many organic components as part, including phosphoric acid organic component, sulfonic acid,
Imidazoles, amine, pyridine functional groups, phenols etc.；2) porosity and specific surface area is big and crystalline density is small；3) pore passage structure can be by
Orientation regulation and control, by adjusting inorganic part and organic ligand and the caused MOFization by ultramicropore to the various hole sizes such as mesoporous
Compound, available for a variety of separation processes and selective activization catalytic reaction.But in actual use, the metal of pulverulence has
Machine framework material is difficult recovery, and repeat usage is very low.To solve this problem, it is particularly critical to find effective carrier.
Graphene is typically used as adsorbent applied to the weight in water because having higher specific surface area and substantial amounts of functional group
The Adsorption of the pollutant such as metal and organic matter, but due to π-π stackings and model strong between the graphene sheet layer of two dimension
The power effect of moral China, causes graphene easily to be reunited in aqueous, actual specific surface area is far below theoretical value, to a certain extent
Reduce the absorption property of graphene.Three-dimensional grapheme aeroge (GA) is the porous web of the three-dimensional interconnection based on graphene
Network structure, because it has excellent structural controllability, great specific surface area, unique space interconnection architecture, good electronics
Transmittability, turns into the ideal material of water process, and solve thes problems, such as that graphene is easily reunited in aqueous.
In actual water body processing procedure, single absorption is difficult to remove removal organic polluter completely, therefore introducing has catalysis
The hetero atoms such as metallic site and S, N of activity are particularly significant.The composite that graphene and metal organic frame are combined into,
The various active site of existing metal organic frame, there is provided various catalysis is possible, also can be compared with the templating of good utilisation graphene
Function, effectively provide a kind of scheme of absorption/catalyst macroscopic material.
Using graphene as substrate fabrication, the research of graphene/metal organic frame composite is mostly focused on list at present
In the modification of one absorbing synergic and two-dimensional structure.Calcium alginate is used for removing the heavy metal ion in sewage frequently as adsorbent
And organic matter, Liy, which combines calcium alginate with graphene oxide, prepares composite, to the quality of adsorption ratio of methylene blue
Up to 114.9~181.8mg/g (Carbohyd.Polym, 2013,95:501-507)；Du etc. is prepared for oxygen using wet-spinning techniques
Graphite alkene/chitosan/silica composite fibre, then silicon dioxide etching is fallen to obtain porous oxidation graphene/shell
Glycan complex fiber material, the material to Congo red maximum adsorption mass ratio be 294.15mg/g (Chem.Eng.J, 2014,
245:99-106).Single absorbing synergic is all based on similar to such composite construction, improves composite to a certain extent
For the adsorption effect of pollutant.Maliyekkal etc. compared for graphene oxide and graphene to chlopyrifos, 5a,6,9,9a-hexahydro-6,9-methano-2,4, horse traction sulphur
The absorption property of phosphorus etc., research find that graphene has higher adsorption capacity to this several agricultural chemicals, and its quality of adsorption is than difference
Up to 1200,1100 and 800mg/g (Small, 2013,9:273-283).Absorption mechanism research shows, between graphene and agricultural chemicals
Direct interaction be quite weak, and hydrone serves as medium in adsorption process, promotes graphene to this several agriculture
The absorption of medicine, therefore it is particularly important to introduce the functional group that direct interaction is strong between agricultural chemicals.Wang is made using one-step method
The composite of class graphene carbon material and ferroso-ferric oxide, bisphenol-A adsorb/degrade (J.Mater.Chem.A,
2016,4,15450-15456), there is provided a kind of effective way for handling pollutant, but, the aqueous solution. for material itself
In the separation of graphene-based material be a great problem that current graphene-based material faces.Yao aoxidizes graphene and magnetic four
Three-iron carries out compound and is adsorbed (Chem.Eng.J.2012,184 to methylene blue:326-332), its adsorbance is 45mg/
G, although the program can improve the separating property of graphene, magnetic particle by the coupling with magnetic ion or other materials
Or the absorption property of the addition of other materials, often influence graphene.
In addition, the composite that above method is prepared is powder, it is unfavorable in absorption/catalysis contaminant degradation
Recycle, and removal process time and effort consuming is inefficient.As a kind of good absorption/catalyst handling water pollution
Thing, the block macroscopic body of visualization with tridimensional network is a kind of effective, feasible material.
The content of the invention
It is an object of the invention to provide a kind of preparation of graphene/metal organic frame aeroge absorption/catalysis material
Method, this method comprise the following steps：By graphene oxide, metal organic frame crystal and dispersant (water, dimethyl formyl
One or more in amine, methanol, ethanol) it is well mixed, add after crosslinking agent to obtain reaction mixture system, temperature reaction,
Last cool drying obtains target product.
In such scheme, the mass ratio of reaction mixture system graphene oxide and metal organic frame crystal is 1:0.2-
5。
In such scheme, the concentration of reaction mixture system graphene oxide is 2-8mg/mL.
In such scheme, the metal organic frame crystal is selected from MIL-100 (Fe), MIL-101 (Fe), MIL-100
(Cr), any one in MIL-101 (Cr), ZIF-8.
In such scheme, any one of the crosslinking agent in ammoniacal liquor, ethylenediamine, propane diamine, butanediamine, crosslinking agent
Dosage be reaction mixture system amount 0.5-2vt%.
In such scheme, reaction mixture system is warming up to 120-200 DEG C of insulation reaction 2-24h.
In such scheme, room temperature is cooled to after the completion of reaction, it is scrubbed, be freeze-dried to obtain target product.
The washing is specially using any one in deionized water, methanol, ethanol, N-N methylene formamides or several
Kind washed product 2-6 times；The freeze-drying is specially that product is placed in into -80 DEG C of environment freezing 0.5-5h, is then transferred to -80 DEG C
It is freeze-dried 12-48h.
Compared with prior art, beneficial effects of the present invention are：(1) composite made from is three-dimensional network-like structure
Graphene/metal organic frame aeroge and unconventional powder, pollutant process field is used in without centrifugal filtration, separation
Process is simple, convenient and practical；(2) three-dimensional network shape aeroge effect in terms of pollutant absorption is good, and recycling degree is high, has
Beneficial to the removal of pollutant；(3) introducing of metal organic frame, there is provided abundant functional group and more avtive spots,
Its catalytic degradation effect is good, and the material is absorption/catalysis multifunctional composite；(4) three-dimensional grapheme/metal organic frame
The absorption of aerogel material has cooperative effect with catalysis, can preferably handle pollutant.
Brief description of the drawings
Fig. 1 is the photo in kind of three-dimensional grapheme/metal organic frame aeroge prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of three-dimensional grapheme/metal organic frame aeroge prepared by the embodiment of the present invention 1；
Fig. 3 is the photograph in kind of different shape three-dimensional grapheme/metal organic frame aeroge prepared by the embodiment of the present invention 2
Piece；
Fig. 4 is three-dimensional grapheme/suction of the metal organic frame aeroge to methylene blue prepared by the embodiment of the present invention 3
Attached/degraded contrast photo；
Fig. 5 is three-dimensional grapheme/suction of the metal organic frame aeroge to methylene blue prepared by the embodiment of the present invention 3
Attached/degradation rate figure.
Embodiment
To make those of ordinary skill in the art fully understand the technical scheme and beneficial effect of the present invention, below in conjunction with tool
Body embodiment and accompanying drawing are further described.It should be understood that following examples are only better embodiment, do not form pair
Any restriction of the present invention.
Embodiment 1
According to graphene oxide：MIL-100 (Fe)=1：2 mass ratio, concentration is molten for 3mg/ml graphene oxide
Liquid mixes with MIL-100 (Fe) crystal, stirs.1vt% ethylenediamine solution is subsequently added into, then mixed solution is filled
Enter in high pressure water heating kettle, be warming up to 160 DEG C of insulation reactions 14 hours.Stood after the completion of reaction and be cooled to room temperature, after product takes out
Respectively washed 2 times with deionized water, ethanol respectively, then by products therefrom be put into ultra low temperature freezer in -80 DEG C freeze 2 hours, so
After be transferred in freeze drier -80 DEG C dry 24 hours, produce three-dimensional grapheme/MIL-100 (Fe) aerogel material.
MIL-100 used in the present embodiment (Fe) crystal is synthetic product, and its building-up process is：By 4mmol
FeCI3.6H2O is mixed in 80ml deionized waters with the Trimesic acids of 4mmol 1,3,5-, and it is equal that mechanical agitation 30min is allowed to mixing
It is even, then mixed liquor is transferred in hydro-thermal autoclave, is warming up to 120 DEG C of insulation reaction 12h.Reaction stands after terminating and is cooled to room
Temperature, mixed liquor is centrifuged, gained solid deionized water and ethanol respectively washing 3 times, be dried in vacuo 12h at 60 DEG C, obtain MIL-
100 (Fe) crystal.
Three-dimensional grapheme/MIL-100 (Fe) aerogel material material object photo and SEM photograph prepared by embodiment 1 is respectively such as
Shown in Fig. 1 and Fig. 2.Fig. 1 can be seen that product is three-dimensional network shape aeroge really (its height is about 1.7cm, diameter 1.0cm)；
As can be seen from Figure 2, the porosity of product is high, and graphene is well combined with MIL-100 (Fe), and MIL-100 (Fe) uniformly divides
It is dispersed on the lamella of graphene.
Embodiment 2
According to graphene oxide：ZIF-8=1：1 mass ratio, by concentration be 2mg/ml graphene oxide solution with
ZIF-8 crystal mixes, and stirs.1vt% ethylenediamine is subsequently added into, then mixed liquor is fitted into high pressure water heating kettle,
It is warming up to 160 DEG C of insulation reactions 14 hours.Stood after the completion of reaction and be cooled to room temperature, respectively with deionized water, ethanol after taking-up
Each washing 2 times, then products therefrom is put into ultra low temperature freezer -80 DEG C and freezed 2 hours, be then transferred in freeze drier -
80 DEG C of dryings 24 hours, produce three-dimensional grapheme/ZIF-8 aerogel materials.
ZIF-8 crystal used in the present embodiment is synthetic product, and its building-up process is：By 6mmol Zn (NO3)2.4H2O
It is mixed in 4mmol methylimidazoles in 80ml deionized waters, mechanical agitation 30min is allowed to well mixed, then by mixed liquor
It is transferred in hydro-thermal autoclave, is warming up to 120 DEG C of insulation reaction 12h.After reaction terminates, standing is cooled to room temperature, by mixed liquor
Respectively washing 3 times of centrifugation, gained solid deionized water and N-N methylene formamide, are dried in vacuo 12h at 60 DEG C, produce ZIF-8
Crystal.
Three-dimensional grapheme/ZIF-8 aerogel material material object photos prepared by embodiment 2 are as shown in figure 3, Fig. 3 can be seen that：Production
Thing has good machinability, and different shape can be made as requested.
Embodiment 3
According to graphene oxide：MIL-100 (Fe)=1：0.5 mass ratio, by the graphene oxide that concentration is 3mg/ml
Solution mixes with MIL-100 (Fe) crystal, stirs.2vt% ammoniacal liquor is subsequently added into, then mixed liquor is loaded into high pressure
In water heating kettle, 140 DEG C of insulation reactions are warming up to 10 hours.After the completion of reaction stand be cooled to room temperature, spent respectively after taking-up from
Sub- water, methanol are respectively washed 3 times, then products therefrom is put into ultra low temperature freezer into -80 DEG C and freezed 2 hours, and it is dry to be then transferred to freezing
Dried 24 hours at -80 DEG C in dry machine, produce three-dimensional grapheme/MIL-100 (Fe) aerogel material.
To be fully understood by the performance of three-dimensional grapheme/metal organic frame aerogel material prepared by the present invention, it is entered
Methylene blue adsorption number/catalytic degradation performance study is gone, detailed process is as follows：10mg graphenes/MIL-100 (Fe) is put into
In 50ml centrifuge tubes, the methylene blue solution that 30ml concentration is 200mg/L is added, centrifuge tube is placed in constant-temperature table and shaken
(140rpm, 35 DEG C), separated in time sampling detects its absorbance, and converses concentration by methylene blue standard curve；
After solution concentration no longer changes and reaches balance, 0.5ml 30wt% hydrogen peroxide, separated in time sampling are added into solution
Its absorbance is detected, concentration is conversed again by methylene blue standard curve, until concentration no longer changes.
Absorption/degraded material object photo of the gained three-dimensional grapheme of embodiment 3/MIL-100 (Fe) aeroges to methylene blue
With result difference as shown in Figure 4 and Figure 5.As can be seen from Figure 4, this product has good removal effect to methylene blue (left figure is
Solution after absorption/degraded, right figure are the solution before absorption/degraded)；As can be seen from Figure 5, three-dimensional grapheme/MIL-100 (Fe)
Aeroge is for methylene adsorption process, and reach balance in 120min before this, after adding catalysis substrate hydrogen peroxide, methylene blue
Further degraded, its clearance is 98%, has reached the effect of good removal pollutant.
Claims (10)
- A kind of 1. preparation method of graphene/metal organic frame aeroge absorption/catalysis material, it is characterised in that including with Lower step：Graphene oxide, metal organic frame crystal and dispersant is uniform, it must react mixed after adding crosslinking agent Liquid system, temperature reaction are closed, cool drying obtains target product.
- A kind of 2. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：The mass ratio of graphene oxide and metal organic frame crystal is 1 in reaction mixture system:0.2-5.
- A kind of 3. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：The concentration of graphene oxide is 2-8mg/mL in reaction mixture system.
- A kind of 4. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：The metal organic frame crystal be selected from MIL-100 (Fe), MIL-101 (Fe), MIL-100 (Cr), Any one in MIL-101 (Cr), ZIF-8.
- A kind of 5. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：Any one or a few composition of the dispersant in water, dimethylformamide, methanol, ethanol Mixture.
- A kind of 6. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：Any one of the crosslinking agent in ammoniacal liquor, ethylenediamine, propane diamine, butanediamine, the use of crosslinking agent Measure as the 0.5-2vt% of reaction mixture system.
- A kind of 7. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：Reaction mixture system is warming up to 140-200 DEG C of insulation reaction 2-24h.
- A kind of 8. preparation side of graphene according to claim 1/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：It is cooled to room temperature after the completion of reaction, it is scrubbed, be freeze-dried to obtain target product.
- A kind of 9. preparation side of graphene according to claim 8/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：The washing is specially using any one in deionized water, methanol, ethanol, N-N methylene formamides Kind or two kinds of washed products 2-6 times.
- A kind of 10. preparation side of graphene according to claim 8/metal organic frame aeroge absorption/catalysis material Method, it is characterised in that：The freeze-drying is specially that product is placed in -80 DEG C of low temperature environments to freeze 0.5-5h, be then transferred to - 80 DEG C of environment are freeze-dried 12-48h.
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