CN102059095A - Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants - Google Patents
Method for preparing graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants Download PDFInfo
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- CN102059095A CN102059095A CN 201010579924 CN201010579924A CN102059095A CN 102059095 A CN102059095 A CN 102059095A CN 201010579924 CN201010579924 CN 201010579924 CN 201010579924 A CN201010579924 A CN 201010579924A CN 102059095 A CN102059095 A CN 102059095A
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- graphene
- aromatic hydrocarbon
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- polycyclic aromatic
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 15
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 51
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
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- 239000000178 monomer Substances 0.000 claims description 4
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- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
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- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
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- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
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- 229910052799 carbon Inorganic materials 0.000 description 11
- BIJNHUAPTJVVNQ-UHFFFAOYSA-N 1-Hydroxypyrene Chemical compound C1=C2C(O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 BIJNHUAPTJVVNQ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011165 3D composite Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a graphene composite material adsorbing polycyclic aromatic hydrocarbon pollutants. The graphene composite material is prepared by dispersing the graphene in a precursor solution of a support body material and enabling the precursor of the support body material to generate cure reaction. The specific preparation steps and adsorption process are as follows: (1) preparing a graphene dispersion solution; (2) preparing the precursor solution of the support body material; (3) mixing the graphene dispersion solution and the precursor solution of the support body material; (4) initializing the precursor solution of the support body material for cure reaction, and adding graphene to obtain the graphene composite material; and (5) soaking the prepared graphene composite adsorption material in a polycyclic aromatic hydrocarbon solution, wherein the polycyclic aromatic hydrocarbon is adsorbed on the surface of graphene due to pi-pi mutual action between the graphene and the polycyclic aromatic hydrocarbon. According to the invention, the enrichment and adsorption capacities of the graphene on the polycyclic aromatic hydrocarbon are improved by means of large pi system and super large specific surface area.
Description
Technical field:
The present invention relates to a kind of preparation method and application of adsorbing the graphene composite material of environmental contaminants polycyclic aromatic hydrocarbon.
Background technology:
Polycyclic aromatic hydrocarbon (Polycyclic Aromatic Hydrocarbons) is to contain the above aromatic of two phenyl ring, wherein there be many being proved to be to have carcinogenic toxicity, it is the persistence organic pollutant of a quasi-representative, be prevalent in the material of the daily contacts of people such as food, drinking water, ornament materials and human lives's the natural environment, long-time exposure can be brought out cancers such as lung cancer, cutaneum carcinoma, has been classified as the pollutant of preferential control by various countries.Preparation has optionally adsorbent to polycyclic aromatic hydrocarbon, is applied to remove the polycyclic aromatic hydrocarbon in the environment on the one hand; Be applied to the enrichment polycyclic aromatic hydrocarbon on the other hand and improve mensuration sensitivity.
Aspect the sorbing material of polycyclic aromatic hydrocarbon, State Patent Office discloses the patent No.: 200910201394.6, " adsorbent of a kind of polyaromatic hydrocarbon pollutant and its production and application " patent of invention, this patent adopts biomass porous sorbing material and cationic surfactant to carry out modified-reaction to prepare the multiring aromatic hydrocarbon adsorbent, though this adsorbent lipophilic group increases, lipophile significantly increases, polyaromatic hydrocarbon pollutant in the good adsorbed water of energy, but this type of material lacks specificity to polycyclic aromatic hydrocarbon.Porous carbon materials (document: Yuan, M.J., Tong, S.T., Zhao, S.Q.﹠amp are also arranged in the world; Jia, C.Q.Adsorption of polycyclic aromatic hydrocarbons from water usingpetroleum coke-derived porous carbon.J Hazard Mater 181,1115-1120, (2010) .), mesopore molecular sieve (document: Araujo, R.S., Azevedo, D.C.S., Cavalcante, C.L., Jimenez-Lopez, A.﹠amp; Rodriguez-Castellon, E.Adsorption ofpolycyclic aromatic hydrocarbons (PAHs) from isooctane solutions by mesoporous molecular sieves:Influence of thesurface acidity.Micropor Mesopor Mat 108,213-222, (2008) .) etc. be applied to the absorption of polycyclic aromatic hydrocarbon.But this type of material lacks specificity to polycyclic aromatic hydrocarbon, and the rate of recovery is not high in actual applications.In addition, CNT also is applied to the absorption of polycyclic aromatic hydrocarbon, (document 1:Gotovac, S.et al.Effect, of nanoscale curvature of single-walledcarbon nanotubes on adsorption of polycyclic aromatic hydrocarbons.Nano Lett 7,583-587, (2007). document 2:Debnath, S., Cheng, Q., Hedderman, T.G.﹠amp; Byrne, H.J.A study of the interaction between single-walled carbonnanotubes and polycyclic aromatic hydrocarbons:Toward structure-property relationships.J Phys Chem C 112,10418-10422, (2008). document 3:Debnath, S., Cheng, Q.H., Hedderman, T.G.﹠amp; Byrne, H.J.Comparative Studyof the Interaction of Different Polycyclic Aromatic Hydrocarbons on Different Types of Single-Walled CarbonNanotubes.J Phys Chem C 114,8167-8175, (2010) .).But the CNT cost is higher, and adsorption efficiency is unsatisfactory.
Summary of the invention:
The present invention is directed to the deficiencies in the prior art, the preparation method of the graphene composite material of the selectivity of a kind of raising to polycyclic aromatic hydrocarbon (being specific adsorption) and adsorption capacity is provided.
For realizing above purpose, the technical scheme that patent of the present invention adopts is:
The preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant, it is characterized in that: Graphene is dispersed in the precursor solution of support body material, make the presoma generation curing reaction of support body material then, promptly can be made into graphene composite material, concrete making step and adsorption process are as follows:
(1) prepares the Graphene dispersion soln of mass content between 0.01%-20%;
(2) precursor solution of preparation support body material;
(3) the Graphene dispersion soln is mixed mutually with the precursor solution of support body material, wherein the mass content of Graphene is at 0.01%-15%;
(4) presoma of initiation support body material makes it to take place curing reaction, and in solidify reaction process, Graphene is entrained in the support body material that is generated, and promptly obtains graphene composite material; The mass content of Graphene in the solid composite material that is generated is between 0.05%-25%;
(5) the Graphene composite adsorbing material for preparing is soaked in the solution that contains polycyclic aromatic hydrocarbon, kept 0.2-10 hour, perhaps with the adsorption column of polycyclic aromatic hydrocarbons contaminated liquid by the filling graphene composite material, Graphene contacts the π-π that can take place between Graphene and the polycyclic aromatic hydrocarbon and interacts with polycyclic aromatic hydrocarbon; Because the π between Graphene and the polycyclic aromatic hydrocarbon-π interacts, polycyclic aromatic hydrocarbon is attracted on the Graphene surface; The adsorption capacity of polycyclic aromatic hydrocarbon becomes positive correlation with Graphene at the surperficial content of composite.
Described Graphene comprises Graphene and graphene oxide.
Described support body material is the material that the structural bearing body is provided for Graphene, and this support body material is in order to prevent the self aggregation of Graphene, and this support body material can be a high molecular polymer, also can be inorganic solid.
Described high molecular polymer can select polyethylene, polyaniline, polyvinyl chloride, polypropylene, polyvinyl chloride and polystyrene, polyformaldehyde, Merlon, polyimides, polyarylether, Nomex, Corvic, polyacrylonitrile etc., preferred polyaniline, polystyrene.
Described inorganic solid can be selected calcium carbonate, silica, calcium silicates, calcium phosphate, aluminium oxide, zinc oxide, copper sulfide, preferred calcium carbonate, silica.
Described presoma refers to the monomer of high molecular polymer, or forms the ion gun and the precipitating reagent of inorganic solid.
Described the Graphene dispersion soln being mixed mutually with the precursor solution of support body material, also can be that Graphene directly is dispersed in the precursor solution of support body material.
The presoma of described initiation support body material makes it to take place curing reaction, refers to the polymerisation of monomer, or the precipitation reaction of inorganic compound.
Graphene is a kind of novel two-dimentional carbon nanomaterial, and by the cellular lattice of six sides of a monolayer carbon atomic building, it can infinitely extend on two-dimensional space.The specific area that Graphene has super large (can reach 2630m
2/ g), thereby have big adsorption capacity.Graphene contains a large amount of π systems, can π-π take place with other π system and interact.The present invention utilizes the above characteristics of Graphene, combines by the pi-pi accumulation effect with the π system of polycyclic aromatic hydrocarbon, thereby reaches efficient, the selective absorption effect of polycyclic aromatic hydrocarbon.In addition, the preparation cost of Graphene class material is lower, and this provides good basis for its practical application.
The reunion that causes for fear of the pi-pi accumulation of Graphene own and reduce adsorption efficiency, it is compound that the present invention adopts support body material and Graphene to carry out, and keeps the characterization of adsorption and the stability of Graphene.Described sorbing material of the present invention will be applied to materials such as sewage disposal, micro-example enrichment, chromatographic column filler, SPE and SPME as the adsorbent of polycyclic aromatic hydrocarbon.
The present invention compared with prior art, its remarkable advantage:
(1) makes full use of super large specific area with the Graphene of monolithic layer stable existence and improve enrichment adsorption capacity polycyclic aromatic hydrocarbon;
(2) contain a large amount of π systems on the Graphene lamella, compare, have more selectivity with traditional polycyclic aromatic hydrocarbon sorbing material;
(3) the Graphene preparation cost is low, and raw material is easy to get;
(4) can be according to the support body material of different needs replacing with Graphene, applied range.
Description of drawings:
Accompanying drawing 1 is: the differential pulse voltammetry curve map behind graphene oxide among the embodiment 5-eight (γ-aminopropyl) silsesquioxane three-dimensional composite material modified glassy carbon electrode and naked glass-carbon electrode absorption 1-hydroxyl pyrene 0,10,20,30,40, the 50min.Illustration is the relation curve between adsorption time and the differential pulse voltammetry peak point current.
The specific embodiment:
The preparation method of embodiment 1-4 explanation sorbing material:
Embodiment 1
Take by weighing a certain amount of graphite oxide and place ultra-pure water, ultrasonic 30min obtains the graphene oxide suspension of 0.05wt%.Draw the wherein ultra-pure water of 5mL adding 5mL, add 3.5 μ L hydrazine hydrates (50wt%) and 35 μ L ammoniacal liquor (28wt%) then respectively.Fully behind the mixing, add last layer silicone oil water evaporates and cause gathering when preventing to heat on liquid level, 95 ℃ of water-bath 1h promptly obtain mass content and are 0.025% Graphene dispersion soln.Under vigorous stirring, add 0.1moL/L lauryl sodium sulfate 10mL, 0.2mol/L calcium chloride solution 10mL, lasting stirring makes solution even.Add 0.2mol/L sodium carbonate liquor 30mL fast, generate precipitation.Centrifugal collecting precipitation, it is inferior to give a baby a bath on the third day after its birth respectively with deionized water and absolute ethyl alcohol, obtains the graphene composite material that calcium carbonate supports after the drying.
Embodiment 2
The 0.05g Graphene is added the neopelex solution of 5mL 5%, ultrasonic 10 minutes, promptly obtain mass content and be 1% Graphene dispersion liquid, standby.The mixed solution of ethyl orthosilicate, absolute ethyl alcohol and deionized water stirs 1h, slowly splash into ready Graphene dispersion soln, continue to stir 2～3h, Graphene is fully mixed with sol solution, solution does not have precipitation, then uniform complex sol is contained in the culture dish of 100mL, uses rubber belt sealing, aging dry, obtain composite xerogel.In the plural gel dry run, matrix SiO
2Form loose structure, Graphene evenly disperses wherein.Carry out sintering processes at 200～1000 ℃ subsequently, it is residual to remove polymer, obtains the graphene composite material that mesoporous silicon oxide supports after the cooling.
Embodiment 3
A certain amount of styrene is inserted in the separatory funnel, and NaOH solution and the deionized water with 0.1mol/L washs four times successively, removes polymerization inhibitor wherein.Add the good styrene of 250mL water and washing in five mouthfuls of flasks, feed nitrogen, stirring and refluxing is heated to 70 ℃.Add the 0.2-1g Graphene, dispersed with stirring 30min.With initator K
2S
2O
8Be dissolved in the distilled water of 50mL, be heated to 70 ℃, be added drop-wise in five mouthfuls of bottles, 30min drips off, and reacts 15h, obtains the polystyrene emulsion of the Graphene dispersion of brownish black.This emulsion can be coated on the carrier such as glass, and oven dry promptly obtains the composite of the polycyclic aromatic hydrocarbon that polystyrene supports.
Embodiment 4
Prepare the electronegative graphene oxide solution of 1.0mg/mL.Glass-carbon electrode successively with 1,0.5, the aluminum oxide polishing powder of 0.05um polishes on polishing cloth, all clean 5min after each polishing at acetone and deionized water for ultrasonic, after the drying at room temperature, electrode is soaked 20min in containing 1wt% PDDA (PDDA) solution of 0.5mol/L NaCl, carefully clean with deionized water, dry 10-15min, in the electronegative graphene oxide solution of 1.0mg/mL, soak 30min then, carefully clean dry 10～15min again with deionized water; Positively charged eight (γ-aminopropyl) silsesquioxane solution at 1.0mg/mL soaks 30min then, carefully cleans with deionized water again, dry 10～15min; Repeat above step 20 time, promptly obtain being modified at the three-dimensional compound framework material of graphene oxide and eight (γ-aminopropyl) silsesquioxane on the glass-carbon electrode.
Present embodiment 5 is intended to illustrate the adsorption applications of prepared composite to polycyclic aromatic hydrocarbon for the representative that is adsorbed as with a kind of polycyclic aromatic hydrocarbon.
Embodiment 5
To place the methanol-water (V that contains 1-hydroxyl pyrene by resulting graphene oxide of embodiment 4 steps and the three-dimensional composite adsorbing material modified glassy carbon of eight (γ-aminopropyl) silsesquioxane
Methyl alcohol: V
Water=1: 1) in the solution, 1-hydroxyl pyrene is adsorbed by the pi-pi accumulation effect.Then, in the phosphate buffer that contains 0.2mol/L NaOH of 50mmol/L pH=2.0, (the three-dimensional composite adsorbing material modified glassy carbon of graphene oxide and eight (γ-aminopropyl) silsesquioxane is a working electrode with three-electrode system with the CHI660c electrochemical workstation, platinum electrode is to electrode, the Ag/AgCl electrode is a reference electrode), in-0.3～0.8V scope, carry out differential pulse voltammetry (DPV) and measure 1-hydroxyl pyrene.Compare with naked glass-carbon electrode, behind absorption 1-hydroxyl pyrene 40min, the 1-hydroxyl pyrene peak current response (47.78 μ A) of the three-dimensional composite adsorbing material modified glassy carbon of graphene oxide and eight (γ-aminopropyl) silsesquioxane is 125 times of (see figure 1)s of naked glass-carbon electrode peak (0.38 μ A); The surface coverage amount (1.59 * 10 of modified glassy carbon electrode
-9Mol.cm
-2) be naked glass-carbon electrode surface coverage amount (3.15 * 10
-11Mol.cm
-2) 50 times; After sweeping the CV10 circle continuously, the 1-hydroxyl pyrene redox peak point current of the three-dimensional composite material of graphene oxide and eight (γ-aminopropyl) silsesquioxane absorption still keeps original more than 99%, and the redox peak point current of naked glass-carbon electrode has only kept original 81.2% and 69.6%.These results show: graphene oxide and eight (γ-aminopropyl) silsesquioxane three-dimensional composite material modified glassy carbon has very strong adsorption capacity to 1-hydroxyl pyrene.
Claims (8)
1. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant, it is characterized in that: Graphene is dispersed in the precursor solution of support body material, make the presoma generation curing reaction of support body material then, promptly can be made into graphene composite material, concrete making step and adsorption process are as follows:
(1) prepares the Graphene dispersion soln of mass content between 0.01%-20%;
(2) precursor solution of preparation support body material;
(3) the Graphene dispersion soln is mixed mutually with the precursor solution of support body material, wherein the mass content of Graphene is at 0.01%-15%;
(4) presoma of initiation support body material makes it to take place curing reaction, and in solidify reaction process, Graphene is entrained in the support body material that is generated, and promptly obtains graphene composite material; The mass content of Graphene in the solid composite material that is generated is between 0.05%-25%;
(5) the Graphene composite adsorbing material for preparing is soaked in the solution that contains polycyclic aromatic hydrocarbon, kept 0.2-10 hour, perhaps with the adsorption column of polycyclic aromatic hydrocarbons contaminated liquid by the filling graphene composite material, Graphene contacts the π-π that can take place between Graphene and the polycyclic aromatic hydrocarbon and interacts with polycyclic aromatic hydrocarbon; Because the π between Graphene and the polycyclic aromatic hydrocarbon-π interacts, polycyclic aromatic hydrocarbon is attracted on the Graphene surface; The adsorption capacity of polycyclic aromatic hydrocarbon becomes positive correlation with Graphene at the surperficial content of composite.
2. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 1 is characterized in that: described Graphene comprises Graphene and graphene oxide.
3. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 1 is characterized in that: described this support body material can be a high molecular polymer, also can be inorganic solid.
4. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 3, it is characterized in that: described high molecular polymer can select polyethylene, polyaniline, polyvinyl chloride, polypropylene, polyvinyl chloride and polystyrene, polyformaldehyde, Merlon, polyimides, polyarylether, Nomex, Corvic, polyacrylonitrile, preferred polyaniline, polystyrene.
5. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 3, it is characterized in that: described inorganic solid can be selected calcium carbonate, silica, calcium silicates, calcium phosphate, aluminium oxide, zinc oxide, copper sulfide, preferred calcium carbonate, silica.
6. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 1 is characterized in that: described presoma refers to the monomer of high molecular polymer, or forms the ion gun and the precipitating reagent of inorganic solid.
7. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 1, it is characterized in that: described the Graphene dispersion soln being mixed mutually with the precursor solution of support body material, also can be that Graphene directly is dispersed in the precursor solution of support body material.
8. the preparation method of the graphene composite material of absorbing multiring aromatic hydrocarbon pollutant according to claim 1, it is characterized in that: the presoma of described initiation support body material makes it to take place curing reaction, refer to the polymerisation of monomer, or the precipitation reaction of inorganic compound.
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