CN111514867A - Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof - Google Patents
Polyethyleneimine grafted nano Fe3O4-graphene adsorption material and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 106
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 105
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000004964 aerogel Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 38
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 29
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- 239000003463 adsorbent Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 13
- LRTRXDSAJLSRTG-UHFFFAOYSA-N 4-bromobutanoyl chloride Chemical compound ClC(=O)CCCBr LRTRXDSAJLSRTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- -1 bromobutyryl Chemical group 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 125000003277 amino group Chemical group 0.000 abstract description 5
- 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 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 238000010992 reflux Methods 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 239000000975 dye Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 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 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The invention relates to the technical field of adsorption materials, and discloses polyethyleneimine grafted nano Fe3O4-graphene adsorption material comprising the following formulation raw materials and components: bromobutylation nano Fe3O4Epoxy graphene aerogel and polyethyleneimine. By the pair of nano Fe3O4And graphene are subjected to surface modification, so that nano Fe is improved3O4And stoneThe dispersibility of the graphene in water and the bridging effect of the polyethyleneimine enable the nano Fe3O4The graphene aerogel magnetic adsorption material is organically combined with graphene aerogel, the graphene aerogel magnetic adsorption material and the graphene aerogel are tightly combined, phase separation is difficult to occur, the composite adsorption material has excellent magnetic adsorption performance, and rich amino groups of polyethyleneimine in the composite adsorption material can be combined with Cu2+Complex adsorption occurs, and amino groups are protonated to form-NH under acidic conditions3 +Can generate positive and negative charge electrostatic attraction with the sulfonic acid radical negative ions of Congo red to graft the polyethyleneimine with the nano Fe3O4The graphene composite adsorption material shows excellent adsorption performance.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to polyethyleneimine grafted nano Fe3O4-an adsorbent material of graphene and a process for its preparation.
Background
At present, the problem of water pollution in China is increasingly severe, and the water pollution is mainly caused by industrial wastewater, domestic sewage and the likeThe pollution caused by discharge without treatment mainly comprises heavy metal ion pollutants, organic solvents, organic dyes and the like, and the heavy metal pollutants such as Cu2+、Cd2+、Hg2+The heavy metal ions, which are mainly polluted by industrial pollution, can be enriched and migrated after entering the environment or the ecosystem; organic dyes such as methylene blue, Congo red and the like are widely applied in the fields of textiles, cosmetics, foods and the like, when dye wastewater and the like are discharged into natural water without being treated, the ecological environment can be seriously damaged, the health and safety of natural organisms and human beings are harmed, and the dye wastewater has the characteristics of complexity, difficult degradation, high chromaticity and the like; .
At present, the material methods for heavy metal ion pollution and organic dye pollution mainly comprise a chemical oxidation method, a physical adsorption method and the like, the adsorption materials mainly comprise activated carbon, graphene, a carbon molecular sieve, polyacrylamide and the like, the graphene aerogel has an ultrahigh specific surface area and a unique porous structure, and is an ideal adsorbent for treating wastewater, and the magnetic nano Fe is an iron oxide nano-material3O4The adsorbent has the characteristics of simple preparation, good adsorption performance, low toxicity, secondary recycling and the like, is a green and environment-friendly adsorbent, and can be used for adsorbing nano Fe3O4The graphene is combined with graphene to obtain a composite adsorption material, but the graphene has a large specific surface area, strong pi-pi bond interaction exists among particles, and Fe3O4Dipole-dipole forces between the nanoparticles, resulting in graphene and Fe3O4The nano particles are easy to agglomerate and only physically blend the nano Fe3O4And the graphene are combined, and the two materials are easy to fall off and are separated, so that the magnetic property and the adsorption property of the composite material are seriously influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides polyethyleneimine grafted nano Fe3O4The adsorbing material of-graphene and the preparation method thereof solve the problems of graphene and Fe3O4The nano particles are easy to agglomerate, and the problem of easy phase separation between the nano particles and the nano particles is solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: polyethyleneimine grafted nano Fe3O4-adsorption material of graphene: comprises the following raw materials and components, namely bromobutyryl nano Fe3O4The weight ratio of the epoxidized graphene aerogel to the polyethyleneimine is 20-40:30-50: 100.
Preferably, the polyethyleneimine is grafted with nano Fe3O4The preparation method of the graphene adsorption material comprises the following steps:
(1) adding distilled water solvent, ethylene glycol and FeCl into a reaction bottle3And FeCl2Adding ammonia water to adjust the pH value of the solution to 10-11, heating to 80-100 ℃, stirring at a constant speed and refluxing for reaction for 1-2h, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Adding 4-bromobutyryl chloride after ultrasonic dispersion is uniform, heating to 55-65 ℃, stirring at constant speed and refluxing for reaction for 12-24h, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylated nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, pouring the solution into a hydrothermal reaction kettle after the ultrasonic dispersion is uniform, heating to 190 ℃, reacting for 5-10h, and performing centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and three-dimensional graphene aerogel into a reaction bottle, uniformly dispersing by ultrasonic, adding potassium iodide and epichlorohydrin, heating to 100-.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine after ultrasonic dispersion is uniform, heating to 80-110 ℃, stirring at constant speed and refluxing for reaction for 20-30h,distilling the solution under reduced pressure, washing and drying to prepare the polyethyleneimine grafted nano Fe3O4-an adsorbent material of graphene.
Preferably, the ethylene glycol and FeCl in the step (1)3And FeCl2The mass ratio of (A) to (B) is 0.5-1.5:2: 1.
Preferably, the glycol in the step (2) modifies the nano Fe3O4And 4-bromobutyryl chloride in a mass ratio of 1: 10-30.
Preferably, the mass ratio of the three-dimensional graphene aerogel, the potassium iodide and the epichlorohydrin in the step (4) is 1:25-35: 200-.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principle and beneficial technical effects:
the polyethyleneimine grafted nano Fe3O4The hydroxyl of ethylene glycol and iron ions in ferroferric oxide can be coordinated, and the ethylene glycol modified nano Fe is prepared by a coprecipitation method3O4Thereby further improving the nano Fe3O4The hydroxyl content of the Fe-B-N-bromobutyryl chloride is that a large number of hydroxyl and chlorine atoms of 4-bromobutyryl chloride carry out substitution reaction to obtain the bromobutylated nano Fe3O4Reacting chlorine atoms of epoxy chloropropane with hydroxyl groups of graphene aerogel by taking potassium iodide as a catalyst to obtain epoxy functionalized graphene, wherein rich amino groups of polyethyleneimine are respectively reacted with bromobutylation nano Fe3O4The bromine atom reacts with the epoxy group of the epoxy functionalized graphene to obtain the polyethyleneimine grafted nano Fe3O4-a composite adsorption material of graphene.
The polyethyleneimine grafted nano Fe3O4Adsorption material of graphene by nano-Fe3O4And graphene are subjected to surface modification, so that nano Fe is improved3O4The dispersion of graphene in water is avoided, and the nano Fe is avoided3O4The problem of agglomeration with graphene respectively occurs, and simultaneously under the bridging action of polyethyleneimine,making nano Fe3O4Organically combined with graphene aerogel and subjected to covalent bond to obtain nano Fe3O4Closely combined with graphene aerogel, difficult to phase separate, nano Fe3O4The graphene aerogel composite adsorption material has excellent magnetic adsorption and magnetic recovery performance, and rich amino groups of polyethyleneimine in the composite adsorption material can be reacted with Cu2+Complex adsorption occurs, and amino groups are protonated to form-NH under acidic conditions3 +Can generate positive and negative charge electrostatic attraction with the sulfonic acid radical negative ions of Congo red to graft the polyethyleneimine with the nano Fe3O4The graphene composite adsorption material shows excellent adsorption performance.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: polyethyleneimine grafted nano Fe3O4-adsorption material of graphene: comprises the following raw materials and components, namely bromobutyryl nano Fe3O4The weight ratio of the epoxidized graphene aerogel to the polyethyleneimine is 20-40:30-50: 100.
Polyethyleneimine grafted nano Fe3O4The preparation method of the graphene adsorption material comprises the following steps:
(1) adding distilled water solvent, ethylene glycol and FeCl with the mass ratio of 0.5-1.5:2:1 into a reaction flask3And FeCl2Adding ammonia water to adjust the pH value of the solution to 10-11, heating to 80-100 ℃, stirring at a constant speed and refluxing for reaction for 1-2h, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Uniformly dispersing by ultrasonic wave, adding 4-bromobutyryl chloride with the mass ratio of 1:10-30, heating to 55-65 ℃, stirring at constant speed for reflux reaction for 12-24h, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylated nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, pouring the solution into a hydrothermal reaction kettle after the ultrasonic dispersion is uniform, heating to 190 ℃, reacting for 5-10h, and performing centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and the three-dimensional graphene aerogel into a reaction bottle, uniformly dispersing by ultrasonic, adding potassium iodide and epichlorohydrin, heating to 100-.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine after ultrasonic dispersion is uniform, heating to 80-110 ℃, stirring at a constant speed for reflux reaction for 20-30h, distilling the solution under reduced pressure, washing and drying to prepare polyethyleneimine grafted nano Fe3O4-an adsorbent material of graphene.
Example 1
(1) Adding distilled water solvent, ethylene glycol and FeCl with the mass ratio of 0.5:2:1 into a reaction flask3And FeCl2Adding ammonia water to adjust the pH value of the solution to 10, heating to 80 ℃, stirring at a constant speed and refluxing for reaction for 1h, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Adding 4-bromobutyryl chloride after ultrasonic dispersion is uniform, heating the mixture to 55 ℃ with the mass ratio of 1:10, stirring at a constant speed for reflux reaction for 12 hours, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, pouring the solution into a hydrothermal reaction kettle, heating to 170 ℃, reacting for 5 hours, and carrying out centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and the three-dimensional graphene aerogel into a reaction bottle, adding potassium iodide and epoxy chloropropane after ultrasonic dispersion is uniform, heating to 100 ℃, stirring at a constant speed for reflux reaction for 10 hours, carrying out centrifugal separation on the solution, washing and drying to prepare the epoxy functionalized graphene aerogel, wherein the mass ratio of the potassium iodide to the epoxy chloropropane is 1:25: 200.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine into the epoxy functionalized graphene aerogel after uniform ultrasonic dispersion, wherein the mass ratio of the epoxy functionalized graphene aerogel to the polyethyleneimine is 20:30:100, heating the mixture to 80 ℃, stirring at a constant speed, refluxing and reacting for 20 hours, distilling the solution under reduced pressure, washing and drying to obtain polyethyleneimine grafted nano Fe3O4An adsorbent material 1 of graphene.
Example 2
(1) Adding distilled water solvent, ethylene glycol and FeCl with the mass ratio of 0.8:2:1 into a reaction flask3And FeCl2Adding ammonia water to adjust the pH value of the solution to 11, heating to 100 ℃, stirring at a constant speed and refluxing for reaction for 1h, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Adding 4-bromobutyryl chloride after ultrasonic dispersion is uniform, heating the mixture to 65 ℃ with the mass ratio of 1:15, stirring at a constant speed for reflux reaction for 24 hours, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, pouring the solution into a hydrothermal reaction kettle after uniform ultrasonic dispersion, heating to 180 ℃, reacting for 10 hours, and performing centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and the three-dimensional graphene aerogel into a reaction bottle, uniformly dispersing by ultrasonic, adding potassium iodide and epichlorohydrin according to the mass ratio of 1:28:220, heating to 110 ℃, carrying out reflux reaction for 10 hours under uniform stirring, carrying out centrifugal separation on the solution, washing and drying to prepare the epoxy functionalized graphene aerogel.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine into the epoxy functionalized graphene aerogel after uniform ultrasonic dispersion, wherein the mass ratio of the epoxy functionalized graphene aerogel to the polyethyleneimine is 28:35:100, heating the mixture to 110 ℃, stirring at a constant speed, refluxing and reacting for 20 hours, and carrying out reduced pressure distillation, washing and drying on the solution to prepare the polyethyleneimine grafted nano Fe3O4An adsorption material 2 of graphene.
Example 3
(1) Adding distilled water solvent, ethylene glycol and FeCl with the mass ratio of 1.2:2:1 into a reaction bottle3And FeCl2Adding ammonia water to adjust the pH value of the solution to 11, heating to 100 ℃, stirring at a constant speed and refluxing for reaction for 1.5h, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Uniformly dispersing by ultrasonic wave, adding 4-bromobutyryl chloride with the mass ratio of 1:22, heating to 60 ℃, stirring at a constant speed for reflux reaction for 18 hours, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, pouring the solution into a hydrothermal reaction kettle after uniform ultrasonic dispersion, heating to 80 ℃, reacting for 8 hours, and performing centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and the three-dimensional graphene aerogel into a reaction bottle, uniformly dispersing by ultrasonic, adding potassium iodide and epichlorohydrin according to the mass ratio of 1:32:220, heating to 105 ℃, carrying out reflux reaction for 15 hours under uniform stirring, carrying out centrifugal separation on the solution, washing and drying to obtain the epoxy functionalized graphene aerogel.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine into the epoxy functionalized graphene aerogel and the epoxy functionalized graphene aerogel after uniform ultrasonic dispersion, wherein the mass ratio of the epoxy functionalized graphene aerogel to the polyethyleneimine is 32:45:100, heating the mixture to 100 ℃, and carrying out uniform stirring reflux reactionReacting for 2 hours, distilling the solution under reduced pressure, washing and drying to prepare the polyethyleneimine grafted nano Fe3O4An adsorbent material 3 of graphene.
Example 4
(1) Adding distilled water solvent, ethylene glycol and FeCl with the mass ratio of 1.5:2:1 into a reaction bottle3And FeCl2Adding ammonia water to adjust the pH value of the solution to 11, heating to 100 ℃, stirring at a constant speed and refluxing for reaction for 2 hours, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Adding 4-bromobutyryl chloride after ultrasonic dispersion is uniform, heating the mixture to 65 ℃ with the mass ratio of 1:30, stirring at a constant speed for reflux reaction for 24 hours, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃, reacting for 10 hours, and carrying out centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and the three-dimensional graphene aerogel into a reaction bottle, adding potassium iodide and epichlorohydrin after ultrasonic dispersion is uniform, heating to 110 ℃, stirring at a constant speed, refluxing for reaction for 20 hours, carrying out centrifugal separation on the solution, washing and drying to prepare the epoxy functionalized graphene aerogel.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine into the epoxy functionalized graphene aerogel after uniform ultrasonic dispersion, wherein the mass ratio of the epoxy functionalized graphene aerogel to the polyethyleneimine is 40:50:100, heating the mixture to 110 ℃, stirring at a constant speed, refluxing and reacting for 30 hours, distilling the solution under reduced pressure, washing and drying to obtain polyethyleneimine grafted nano Fe3O4An adsorbent material 4 of graphene.
Comparative example 1
(1) Adding distilled water solvent into a reaction bottleEthylene glycol and FeCl with the mass ratio of 0.3:2:13And FeCl2Adding ammonia water to adjust the pH value of the solution to 10, heating to 100 ℃, stirring at a constant speed and refluxing for reaction for 2 hours, centrifugally separating the solution by using distilled water and ethanol, washing and drying to prepare the glycol modified nano Fe3O4。
(2) Adding a trichloromethane solvent and glycol modified nano Fe into a reaction bottle3O4Adding 4-bromobutyryl chloride after ultrasonic dispersion is uniform, heating the mixture to 65 ℃ with the mass ratio of 1:8, stirring at a constant speed for reflux reaction for 12 hours, distilling the solution under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4。
(3) Adding a distilled water solvent and graphene oxide into a reaction bottle, uniformly dispersing by ultrasonic, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃, reacting for 5 hours, and carrying out centrifugal separation, washing and drying on the solution to prepare the three-dimensional graphene aerogel.
(4) Adding a distilled water solvent and three-dimensional graphene aerogel into a reaction bottle, uniformly dispersing by ultrasonic, adding potassium iodide and epichlorohydrin according to a mass ratio of 1:20:280, heating to 110 ℃, carrying out reflux reaction for 10 hours under uniform stirring, carrying out centrifugal separation on the solution, washing and drying to obtain the epoxy functionalized graphene aerogel.
(5) Adding 1, 4-dioxane solvent and nanometer Fe with butyrylated bromide into a reaction bottle3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine into the epoxy functionalized graphene aerogel after uniform ultrasonic dispersion, wherein the mass ratio of the epoxy functionalized graphene aerogel to the polyethyleneimine is 15:20:100, heating the mixture to 110 ℃, stirring at a constant speed, refluxing and reacting for 20 hours, distilling the solution under reduced pressure, washing and drying to obtain polyethyleneimine grafted nano Fe3O4Adsorption material of graphene comparative 1.
Congo red is added into hydrochloric acid solution with the pH value of 2, the concentration is 0.1 percent, and the polyethyleneimine grafted nano Fe in the examples and the comparative examples is added3O4And (3) adsorbing material of graphene, wherein the concentration of the adsorbing material is 0.5%, stirring at a constant speed for 6 hours for adsorption, testing the absorbance and residual concentration of Congo red by using an ND5000 ultramicro ultraviolet-visible spectrophotometer, and calculating the adsorption rate.
Claims (5)
1. Polyethyleneimine grafted nano Fe3O4-an adsorbent material of graphene, characterized in that: comprises the following raw materials and components, namely bromobutyryl nano Fe3O4The weight ratio of the epoxidized graphene aerogel to the polyethyleneimine is 20-40:30-50: 100.
2. The polyethyleneimine grafted nano Fe as claimed in claim 13O4-an adsorbent material of graphene, characterized in that: the polyethyleneimine is grafted with nano Fe3O4The preparation method of the graphene adsorption material comprises the following steps:
(1) adding ethylene glycol and FeCl into distilled water solvent3And FeCl2Adding ammonia water to adjust the pH value of the solution to 10-11, heating to 80-100 ℃, reacting for 1-2h, centrifugally separating, washing and drying to prepare the glycol modified nano Fe3O4；
(2) Adding glycol modified nano Fe into trichloromethane solvent3O4Uniformly dispersing by ultrasonic wave, adding 4-bromobutyryl chloride, heating to 55-65 ℃, reacting for 12-24h, distilling under reduced pressure, washing and drying to prepare the bromobutylation nano Fe3O4；
(3) Adding graphene oxide into a distilled aqueous solvent, uniformly dispersing by ultrasonic, pouring the solution into a hydrothermal reaction kettle, heating to 190 ℃ for reaction for 5-10h, carrying out centrifugal separation, washing and drying to prepare the three-dimensional graphene aerogel;
(4) adding three-dimensional graphene aerogel into a distilled aqueous solvent, uniformly dispersing by using ultrasonic waves, adding potassium iodide and epoxy chloropropane, heating to 100-110 ℃, reacting for 10-20h, centrifugally separating, washing and drying to prepare epoxy functionalized graphene aerogel;
(5) adding bromobutyryl nano Fe into 1, 4-dioxane solvent3O4And epoxy functionalized graphene aerogel, adding polyethyleneimine after ultrasonic dispersion is uniform, heating to 80-110 ℃, reacting for 20-30h, carrying out reduced pressure distillation, washing and drying to prepare polyethyleneimine grafted nano Fe3O4-an adsorbent material of graphene.
3. The polyethyleneimine grafted nano Fe as claimed in claim 23O4-an adsorbent material of graphene, characterized in that: ethylene glycol and FeCl in the step (1)3And FeCl2The mass ratio of (A) to (B) is 0.5-1.5:2: 1.
4. The polyethyleneimine grafted nano Fe as claimed in claim 23O4-an adsorbent material of graphene, characterized in that: the glycol modified nano Fe in the step (2)3O4And 4-bromobutyryl chloride in a mass ratio of 1: 10-30.
5. The polyethyleneimine grafted nano Fe as claimed in claim 23O4-an adsorbent material of graphene, characterized in that: the mass ratio of the three-dimensional graphene aerogel, the potassium iodide and the epichlorohydrin in the step (4) is 1:25-35: 200-.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705174A (en) * | 2020-12-16 | 2021-04-27 | 周翠红 | Fe3O4Grafted polyethyleneimine-graphene composite adsorption material and preparation method thereof |
| CN112938956A (en) * | 2021-02-07 | 2021-06-11 | 中南大学湘雅医院 | Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof |
| CN116813018A (en) * | 2023-08-30 | 2023-09-29 | 上海朗蔚环保科技有限公司 | Semiconductor industrial production wastewater treatment process |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803898A (en) * | 2006-01-12 | 2006-07-19 | 贵州大学 | Nanometer antibacterial plastic |
| US20120036962A1 (en) * | 2009-04-14 | 2012-02-16 | Yeoung Sang Yun | Surface-modified biomass, preparation method thereof, and method for recovering valuable metals using the same |
| CN102671625A (en) * | 2012-05-02 | 2012-09-19 | 湖北富邦科技股份有限公司 | Method for preparing graphene magnetic nanometer composite materials |
| CN106512956A (en) * | 2016-11-23 | 2017-03-22 | 辽宁石油化工大学 | Magnetic graphene collagen composite adsorbing material and preparation method thereof |
| CN106582562A (en) * | 2015-10-20 | 2017-04-26 | 中国科学院大连化学物理研究所 | Magnetic graphene oxide composite nanomaterial and preparation method thereof |
| CN107096511A (en) * | 2017-04-26 | 2017-08-29 | 中国原子能科学研究院 | A kind of sorbing material and the method that reactor coolant Radionuclide silver is removed using it |
| CN108636357A (en) * | 2018-06-07 | 2018-10-12 | 石梦成 | A kind of use in waste water treatment cross-linking type graphite oxide aerogel and preparation method thereof |
| CN108786734A (en) * | 2018-06-26 | 2018-11-13 | 信阳学院 | Magnetic oxygenated graphene/polyethyleneimine amine absorber and the preparation method and application thereof |
| CN109593210A (en) * | 2018-12-13 | 2019-04-09 | 青岛理工大学 | Antifouling antibacterial sand of one kind and preparation method thereof |
| CN110152600A (en) * | 2018-03-01 | 2019-08-23 | 济南开发区星火科学技术研究院 | The preparation method of the graphite oxide aerogel with high reusing for water process |
| CN110368901A (en) * | 2019-08-21 | 2019-10-25 | 哈尔滨工业大学 | A kind of preparation method and application of the magnetic oxygenated graphene of amino functional |
| CN110404517A (en) * | 2019-08-15 | 2019-11-05 | 中国科学院长春应用化学研究所 | A kind of polyvinyl alcohol based porous adsorbing material and preparation method thereof |
| CN110684159A (en) * | 2019-09-02 | 2020-01-14 | 浙江海洋大学 | Preparation method of dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer |
-
2020
- 2020-06-03 CN CN202010496597.9A patent/CN111514867A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803898A (en) * | 2006-01-12 | 2006-07-19 | 贵州大学 | Nanometer antibacterial plastic |
| US20120036962A1 (en) * | 2009-04-14 | 2012-02-16 | Yeoung Sang Yun | Surface-modified biomass, preparation method thereof, and method for recovering valuable metals using the same |
| CN102671625A (en) * | 2012-05-02 | 2012-09-19 | 湖北富邦科技股份有限公司 | Method for preparing graphene magnetic nanometer composite materials |
| CN106582562A (en) * | 2015-10-20 | 2017-04-26 | 中国科学院大连化学物理研究所 | Magnetic graphene oxide composite nanomaterial and preparation method thereof |
| CN106512956A (en) * | 2016-11-23 | 2017-03-22 | 辽宁石油化工大学 | Magnetic graphene collagen composite adsorbing material and preparation method thereof |
| CN107096511A (en) * | 2017-04-26 | 2017-08-29 | 中国原子能科学研究院 | A kind of sorbing material and the method that reactor coolant Radionuclide silver is removed using it |
| CN110152600A (en) * | 2018-03-01 | 2019-08-23 | 济南开发区星火科学技术研究院 | The preparation method of the graphite oxide aerogel with high reusing for water process |
| CN108636357A (en) * | 2018-06-07 | 2018-10-12 | 石梦成 | A kind of use in waste water treatment cross-linking type graphite oxide aerogel and preparation method thereof |
| CN108786734A (en) * | 2018-06-26 | 2018-11-13 | 信阳学院 | Magnetic oxygenated graphene/polyethyleneimine amine absorber and the preparation method and application thereof |
| CN109593210A (en) * | 2018-12-13 | 2019-04-09 | 青岛理工大学 | Antifouling antibacterial sand of one kind and preparation method thereof |
| CN110404517A (en) * | 2019-08-15 | 2019-11-05 | 中国科学院长春应用化学研究所 | A kind of polyvinyl alcohol based porous adsorbing material and preparation method thereof |
| CN110368901A (en) * | 2019-08-21 | 2019-10-25 | 哈尔滨工业大学 | A kind of preparation method and application of the magnetic oxygenated graphene of amino functional |
| CN110684159A (en) * | 2019-09-02 | 2020-01-14 | 浙江海洋大学 | Preparation method of dendrimer-modified magnetic nanocrystalline cellulose surface imprinted polymer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112705174A (en) * | 2020-12-16 | 2021-04-27 | 周翠红 | Fe3O4Grafted polyethyleneimine-graphene composite adsorption material and preparation method thereof |
| CN112938956A (en) * | 2021-02-07 | 2021-06-11 | 中南大学湘雅医院 | Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof |
| CN112938956B (en) * | 2021-02-07 | 2022-07-12 | 中南大学湘雅医院 | Magnetic graphene oxide capable of adsorbing beta amyloid protein and preparation method thereof |
| CN116813018A (en) * | 2023-08-30 | 2023-09-29 | 上海朗蔚环保科技有限公司 | Semiconductor industrial production wastewater treatment process |
| CN116813018B (en) * | 2023-08-30 | 2023-11-03 | 上海朗蔚环保科技有限公司 | Semiconductor industrial production wastewater treatment process |
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