CN116102780A - Preparation method and application of porous nano sponge material - Google Patents
Preparation method and application of porous nano sponge material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 27
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 27
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960004198 guanidine Drugs 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims abstract description 10
- 229960000789 guanidine hydrochloride Drugs 0.000 claims abstract description 10
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940083982 sodium phytate Drugs 0.000 claims abstract description 10
- 239000007853 buffer solution Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 4
- -1 europium ions Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 26
- 239000011651 chromium Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000002949 phytic acid Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002354 radioactive wastewater Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/405—Impregnation with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The invention provides a preparation method of a porous nano sponge material, which comprises the following steps: immersing the cleaned melamine sponge into a dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution at 30 ℃, cleaning and drying to obtain a treated melamine sponge; mixing guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate under nitrogen, stirring for 2 hours at 100 ℃, and introducing one end of a four-neck flask into a hydrochloric acid solution; heating to 160 ℃ and stirring to obtain guanidine polymer, and adding deionized water to obtain guanidine polymer aqueous solution; immersing the treated melamine sponge into guanidine polymer aqueous solution at 30 ℃ for magnetic stirring, and then drying in vacuum at 50 ℃ to obtain the material. The surface morphology structure and the surface functional group of the material are also studied, and the material is applied to the removal of europium ions and hexavalent chromium ions in wastewater. The porous nano sponge material prepared by the invention has the excellent performances of high absorptivity, high mechanical strength, good elasticity, long superhydrophobic stability and the like, and can be used for treating industrial wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method and application of a porous nano sponge material.
Background
The new energy nuclear energy is taken as a measure for economically and effectively relieving the world energy crisis, has a plurality of advantages, and can supply power with the maximum load, low carbon emission, stability, safety, low cost and reliability. However, long-term operation of radiochemicals, nuclear power plants and nuclear fuel circulation facilities results in more and more radionuclides being discharged into the body of water, which will inevitably occur in the rock circles and groundwater due to the strong migration characteristics of radionuclides. In particular, to 241 Am sum of 243 Trivalent actinides represented by Am have a long half-life and strong radioactivity, which not only pose serious environmental problems, but also pose a terrible threat to humans. Furthermore, even the promising modern industrial industry, because it produces heavy metal contaminated wastewater with non-biodegradable properties and bioaccumulation effects, has not been neglected. At present, the main environmental pollution problem of coexistence of various radionuclides and heavy metal ions has attracted widespread attention in countries around the world. Europium is the most active metal in rare earth elements, is widely applied to the manufacture of nuclear fuel control materials and neutron shielding materials, is a chemical homolog of trivalent lanthanide compounds, and has similar adsorptivityBut has great influence on human health. Chromium, one of the most common heavy metal contaminants, is generally present in hexavalent and trivalent forms. Among them, hexavalent chromium is more toxic than trivalent chromium, and needs to be emphasized. Therefore, eu (III) can be used to simulate trivalent lanthanides and Cr (VI) can be used to simulate the macroscopic chemical behavior of heavy metal contaminants. In view of this, in order to preserve the environment and human health, it is necessary for humans to find and apply advanced scientific techniques to efficiently treat radioactive wastewater.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art, and provides a preparation method and application of a porous nano sponge material.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a porous nano sponge material comprises the following steps:
s1, cleaning melamine sponge with deionized water and absolute ethyl alcohol in sequence, and drying at 50 ℃ to obtain cleaned melamine sponge;
s2, adding dopamine hydrochloride into tris (hydroxymethyl) aminomethane to obtain a dopamine hydrochloride-tris (hydroxymethyl) aminomethane buffer solution;
s3, immersing the melamine sponge cleaned in the step S1 into the dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution obtained in the step S2 under the condition of 30 ℃, magnetically stirring, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying under the condition of 50 ℃ to obtain the treated melamine sponge;
s4, under the protection of nitrogen, putting guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate into a four-neck flask, mixing, stirring for 2 hours at the temperature of 100 ℃ and the rotating speed of 400rpm/min, and introducing one end of the four-neck flask into a 0.1mol/L hydrochloric acid solution; then under the protection of nitrogen, the temperature is raised to 160 ℃, and the mixture is stirred for 5 hours under the condition of the rotating speed of 400rpm/min and naturally cooled to room temperature, so as to obtain guanidine polymers;
s5, adding deionized water into the guanidine polymer obtained in the S4 to obtain an aqueous guanidine polymer solution; and (3) immersing the treated melamine sponge obtained in the step (S3) into the guanidine polymer aqueous solution at the temperature of 30 ℃, magnetically stirring for 3 hours at the rotating speed of 300rpm/min, and drying at the temperature of 50 ℃ under vacuum condition to obtain the porous nano sponge material.
Preferably, the melamine sponge in S1 is 0.5cm x 2cm in size.
Preferably, the concentration of the dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution in S2 is 1.0g/L.
Preferably, the rotation speed of the magnetic stirring in the step S3 is 500rpm/min, and the time of the magnetic stirring is 5h.
Preferably, the ratio of guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate in S4 is 2.0g:2.0g:0.6g.
Preferably, the aqueous solution of guanidine polymer in S5 has a ratio of guanidine polymer to deionized water of 1g to 99mL.
Preferably, the drying time in S5 is 24 hours.
Preferably, the specific surface area of the porous nano-sponge material in S5 is 192.68m 2 And/g, particle size of 18.25nm.
The invention also provides application of the prepared porous nano sponge material, and the porous nano sponge material is used for removing europium ions and hexavalent chromium ions in industrial wastewater. Compared with the prior art, the invention has the following advantages:
in the present invention, melamine Sponge (MS) is selected as the structural support in order to provide sufficient mechanical strength of the adsorbent. The porous nano-sponge material is prepared by taking dopamine hydrochloride (PDA) as an adhesive. In particular, phytic acid is used as a donor of phosphate groups, and can keep inherent super-hydrophilicity, stronger complexing capacity under higher pH condition and environmental friendliness in the modification process. In this example, dopamine was first modified on the sponge skeleton by self-polymerization of dopamine. Then, guanidine hydrochloride, sodium phytate and 1, 6-hexamethylenediamine are polymerized together by a melt polymerization method at high temperature, and the resultant material is dissolved in water and then attached to the treated melamine sponge (PDA-MS). The prepared PGH-HDPA-PDA-MS porous nano sponge material has the excellent performances of high absorptivity, high mechanical strength, good elasticity, long super-hydrophobic stability and the like, and can be used for treating industrial wastewater.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
Fig. 1 is an SEM image of a porous nano-sponge material according to example 1 of the present invention.
FIG. 2 is a Fourier transform infrared spectrum of the porous nano-sponge material of example 1 of the present invention.
FIG. 3 is a graph showing the specific surface area and particle size distribution of the porous nano-sponge material according to example 1 of the present invention.
FIG. 4 is a graph showing the effect of pH on Eu (III) and Cr (VI) adsorption onto porous nanosponges in example 2 of the present invention.
FIG. 5 is a graph showing the effect of contact time on adsorption of Eu (III) and Cr (VI) on porous nano-sponge material in example 3 of the present invention.
FIG. 6 is a graph showing the effect of Eu (III) initial concentration on Eu (III) adsorption onto a porous nano-sponge material in example 4 of the present invention.
FIG. 7 is a graph showing the effect of the initial concentration of Cr (VI) on the adsorption of Cr (VI) onto a porous nanosponge material in example 5 of the invention.
Detailed Description
Example 1
The preparation method of the porous nano sponge material of the embodiment comprises the following steps:
s1, cleaning commercial Melamine Sponge (MS) with the size of 0.5cm multiplied by 2cm with deionized water and absolute ethyl alcohol in sequence, and drying at the temperature of 50 ℃ to obtain cleaned melamine sponge;
s2, adding dopamine hydrochloride into tris (hydroxymethyl) aminomethane to obtain a dopamine hydrochloride-tris (hydroxymethyl) aminomethane buffer solution with the concentration of 1.0 g/L;
s3, immersing the melamine sponge cleaned in the S1 into the dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution obtained in the S2 at the temperature of 30 ℃, magnetically stirring for 5 hours at the rotating speed of 500rpm/min, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying at the temperature of 50 ℃ to obtain the treated melamine sponge, which is named as PDA-MS;
s4, under the protection of nitrogen, guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate are put into a four-neck flask to be mixed, and then stirred for 2 hours at the temperature of 100 ℃ and the rotating speed of 400rpm/min, and one end of the four-neck flask is introduced into 0.1mol/L hydrochloric acid solution for absorbing generated ammonia; then under the protection of nitrogen, the temperature is raised to 160 ℃, the stirring is carried out for 5 hours under the condition of the rotating speed of 400rpm/min, and the guanidine polymer is obtained after natural cooling to the room temperature, and is named as PGH-HDPA;
the dosage ratio of guanidine hydrochloride to 1, 6-hexamethylenediamine to sodium phytate is 2.0g:2.0g:0.6g;
s5, adding deionized water into the guanidine polymer obtained in the S4 to obtain an aqueous guanidine polymer solution; the dosage ratio of the guanidine polymer to deionized water in the guanidine polymer aqueous solution is 1g:99mL; immersing the treated melamine sponge obtained in the step S3 into the guanidine polymer aqueous solution at the temperature of 30 ℃, magnetically stirring for 3 hours at the rotating speed of 300rpm/min, and then drying for 24 hours at the temperature of 50 ℃ under vacuum condition to obtain a porous nano sponge material, which is named as PGH-HDPA-PDA-MS porous nano sponge material; the specific surface area of the porous nano sponge material is 192.68m 2 /g。
The result of morphology characterization of the obtained PGH-HDPA-PDA-MS porous nano sponge material by using SEM is shown in figure 1, the left graph is a morphology graph, and the right graph is a partial enlarged graph. With reference to fig. 1, it is observed that the PGH-HDPA-PDA-MS porous nano sponge material has an irregular porous structure and the surface of the material is smoother (left graph of fig. 1); PGH-HDPA-PDA-MS shows the three-dimensional integrated network skeleton morphology of porous nanomesh material (right panel of FIG. 1);
FIG. 2 shows the Melamine Sponge (MS) in step S1, the treated melamine sponge (PDA-MS) in step S3 and the stepsAnd (3) performing Fourier transform infrared spectrogram on the PGH-HDPA-PDA-MS porous nano sponge material in the step S5. FTIR spectra of the sponges were further explored and are shown in fig. 2. The spectra of PGH-HDPA-PDA-MS and PDA-MS retained the MS spectrum 811cm compared to the original MS -1 The triazine ring at which is curved. At the same time at 1290cm -1 Stretching of the C-O groups in the phenols and 1621cm -1 The aromatic ring at which some of the typical absorption characteristics of PDA's are seen. The peaks of the N-H groups and catechol-OH groups are at 3400cm -1 Overlapping the two parts;
PGH-HDPA-PDA-MS sponge at 3400cm due to imide group formation after PGH-HDPA modification -1 The peak values of the N-H groups and-OH groups in catechol were changed, and the peak values were shifted to 3169cm due to the enrichment of primary/secondary amine and phosphate-OH groups -1 . It was also found that a new strong peak in the PGH-HDPA-PDA-MS spectrum was clearly observed at 960cm -1 A phosphate peak at;
FIG. 3 is a graph showing the specific surface area and particle size distribution of the synthesized PGH-HDPA-PDA-MS porous nano-sponge material. As can be seen from the analysis of FIG. 3, the specific surface area of the PGH-HDPA-PDA-MS porous nano-sponge material is 192.68m 2 The specific particle size/g was 18.25nm.
Taken together, the preparation of PGH-HDPA-PDA-MS porous nano-sponge material was successful.
In the embodiment, melamine Sponge (MS) is used as a substrate, and when the MS is used as a structural carrier, the MS has the remarkable characteristic of repeated utilization, can reduce resource consumption and material cost, and pursues the maximum adsorption effect; dopamine hydrochloride (PDA) has good surface activity and unique wrapping performance, can be chelated with the surface of a material, and promotes the adsorption effect; sodium Phytate (PA) is used as a chelating agent, a preservative and an antioxidant, and has a certain adsorption capacity to metal ions due to the existence of good active groups; guanidine hydrochloride is rich in a large amount of amino, and compared with common amino, the derivative has stronger binding capacity between guanidine groups and negative ions, and can play a role in inhibiting bacteria while modifying the adsorbent. These excellent properties make it possible to use it as a base material for composite materials.
In the preparation method of this example, commercial Melamine Sponge (MS) was used as the structural support in order to provide sufficient mechanical strength of the adsorbent. The porous nano-sponge material is prepared by taking dopamine hydrochloride (PDA) as an adhesive. In particular, phytic acid is used as a donor of phosphate groups, and can keep inherent super-hydrophilicity, stronger complexing capacity under higher pH condition and environmental friendliness in the modification process. In this example, dopamine was first modified on the sponge skeleton by self-polymerization of dopamine. Then, guanidine hydrochloride, sodium phytate and 1, 6-hexamethylenediamine are polymerized together by a melt polymerization method at high temperature, and the resultant material is dissolved in water and then attached to the treated melamine sponge (PDA-MS). The prepared PGH-HDPA-PDA-MS porous nano sponge material has the excellent performances of high absorptivity, high mechanical strength, good elasticity, long super-hydrophobic stability and the like, and can be used for treating industrial wastewater.
Example 2
This example is where t=303 k, m/v=0.67 g/L, C Eu(Ⅲ) ＝9.87×10 -5 mol/L，I＝0.01mol/L NaNO 3 And t=303 k, m/v=0.67 g/L, C Cr(Ⅵ) ＝2.88×10 -4 mol/L，I＝0.01mol/L NaNO 3 Under the condition, the adsorption rate of Eu (III) and Cr (VI) on the PGH-HDPA-PDA-MS porous nano-sponge material prepared in example 1 is studied as a function of the pH value of the solution.
Experimental results As shown in FIG. 4, the adsorption rate of PGH-HDPA-PDA-MS to Eu (III) increases sharply with pH from 2 to 9, and becomes stable gradually after reaching the maximum value at pH of about 10. This is because the surface charge of the protonated PGH-HDPA-PDA-MS porous sponge material is positive at pH 2 to 4, when the adsorbent is in contact with the cation Eu 3+ Electrostatic repulsion exists between the two, so that the PGH-HDPA-PDA-MS with positive charges cannot fully adsorb Eu (III), and the adsorption rate is relatively low. With the increase of pH, the surface charge of the PGH-HDPA-PDA-MS composite material is negative charge due to the deprotonation reaction, so that the attraction between the PGH-HDPA-PDA-MS and Eu (III) is enhanced, and the adsorption rate of the PGH-HDPA-PDA-MS and Eu (III) is higher and higher;
after the pH value is more than 10, the adsorption rate of PGH-HDPA-PDA-MS to Eu (III) tends to be stable, because the Eu (III) in the solution is saturated under the environment;
the initial pH of the solution plays an important role in the adsorption of Cr (VI) by affecting the surface charge and ionization degree of PGH-HDPA-PDA-MS and changing the morphology of Cr (VI) in the solution. At a pH of less than 2, cr (VI) is mainly HCrO 4 - And Cr (V) 2 O 7 2- In the form of (2);
at pH values of 2 to 7, cr (VI) is still mainly HCrO 4 - And Cr (V) 2 O 7 2- In the form of (2); with further increase of pH value, the main form is CrO 4 2- And (5) transferring. With the increase of the pH value, the adsorption amount of the PGH-HDPA-PDA-MS to Cr (VI) tends to increase and then decrease, and the adsorption amount is maximum at the pH value of 2.
Example 3
This example is by measuring at T=303K, m/V=0.67 g/L, C Eu(Ⅲ) ＝9.87×10 -5 mol/L，I＝0.01mol/L NaNO 3 And t=303 k, m/v=0.67 g/L, C Cr(Ⅵ) ＝2.88×10 -4 mol/L，I＝0.01mol/L NaNO 3 Under the condition, the adsorption rate of Eu (III) and Cr (VI) on the PGH-HDPA-PDA-MS porous nano sponge material prepared in example 1 is studied as a function of different contact times.
As shown in FIG. 5, the adsorption rate of PGH-HDPA-PDA-MS to Eu (III) and Cr (VI) increases with time, the adsorption efficiency of Eu (III) increases greatly before 150 minutes, and increases slowly during 150 minutes to 300 minutes, approaches equilibrium, and reaches equilibrium after reacting to 300 minutes;
the adsorption rate of Cr (VI) increases rapidly before 120 minutes, increases slowly from 150 to 180 minutes, reaches equilibrium at 180 minutes; and it can be derived that PGH-HDPA-PDA-MS has much better Eu (III) adsorption efficiency than Cr (VI) in the same time.
Example 4
This example is by measuring at m/V=0.67 g/L, I=0.01 mol/L NaNO 3 Under the conditions of t=303 k and ph=5.5±0.1, the initial concentration of Eu (iii) was studied to determine the initial concentration of Eu (iii) based on PGH-HDPA-PDA-M prepared in example 1S adsorption influence on the porous nano sponge material;
as shown in FIG. 6, the initial Eu (III) concentration was 1.5X10 -5 The adsorption effect before the mol/L was not obvious, but as a whole, it was found that the trend was gradually increasing at 9.0X10 -4 mol/L to 1.2X10 -3 Between mol/L, the adsorption amount gradually becomes the highest gradually, and the Eu (III) and the amino group on the surface of the PGH-HDPA-PDA-MS undergo a complexing reaction to form a stable complex.
Example 5
This example is by measuring at m/V=0.67 g/L, I=0.01 mol/L NaNO 3 The adsorption effect of different Cr (vi) initial concentrations on Cr (vi) on PGH-HDPA-PDA-MS porous nanomichonds prepared in example 1 was studied at t=303 k, ph=4.0±0.1.
As shown in FIG. 7, when the initial concentration of Cr (VI) is low, the adsorption equilibrium capacity is low and the adsorption effect is poor, but the overall tendency is to gradually increase, and the concentration of Cr (VI) reaches 3.6X10 -3 The mol/L has not had a tendency to equilibrate, and the PGH-HDPA-PDA-MS surface has not been completely complexed, indicating that the concentration of Cr (VI) can still be increased and eventually equilibrated.
In summary, the porous nano-sponge material prepared in example 1 can be used for removing europium ions and hexavalent chromium ions in industrial wastewater. The high-strength high-absorption high-elasticity super-hydrophobic water-absorbing agent has the excellent performances of high absorption rate, high mechanical strength, good elasticity, long super-hydrophobic stability and the like, and can be used for treating industrial wastewater.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (9)
1. The preparation method of the porous nano sponge material is characterized by comprising the following steps:
s1, cleaning melamine sponge with deionized water and absolute ethyl alcohol in sequence, and drying at 50 ℃ to obtain cleaned melamine sponge;
s2, adding dopamine hydrochloride into tris (hydroxymethyl) aminomethane to obtain a dopamine hydrochloride-tris (hydroxymethyl) aminomethane buffer solution;
s3, immersing the melamine sponge cleaned in the step S1 into the dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution obtained in the step S2 under the condition of 30 ℃, magnetically stirring, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying under the condition of 50 ℃ to obtain the treated melamine sponge;
s4, under the protection of nitrogen, putting guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate into a four-neck flask, mixing, stirring for 2 hours at the temperature of 100 ℃ and the rotating speed of 400rpm/min, and introducing one end of the four-neck flask into a 0.1mol/L hydrochloric acid solution; then under the protection of nitrogen, the temperature is raised to 160 ℃, and the mixture is stirred for 5 hours under the condition of the rotating speed of 400rpm/min and naturally cooled to room temperature, so as to obtain guanidine polymers;
s5, adding deionized water into the guanidine polymer obtained in the S4 to obtain an aqueous guanidine polymer solution; and (3) immersing the treated melamine sponge obtained in the step (S3) into the guanidine polymer aqueous solution at the temperature of 30 ℃, magnetically stirring for 3 hours at the rotating speed of 300rpm/min, and drying at the temperature of 50 ℃ under vacuum condition to obtain the porous nano sponge material.
2. The method for preparing a porous nano-sponge material according to claim 1, wherein the melamine sponge in S1 has a size of 0.5cm x 2cm.
3. The method for preparing a porous nano-sponge material according to claim 1, wherein the concentration of the dopamine-tris (hydroxymethyl) aminomethane hydrochloride buffer solution in S2 is 1g/L.
4. The method for preparing a porous nano-sponge material according to claim 1, wherein the rotation speed of the magnetic stirring in S3 is 500rpm/min, and the time of the magnetic stirring is 5 hours.
5. The method for preparing the porous nano-sponge material according to claim 1, wherein the dosage ratio of guanidine hydrochloride, 1, 6-hexamethylenediamine and sodium phytate in S4 is 2.0g:2.0g:0.6g.
6. The method for preparing a porous nano-sponge material according to claim 1, wherein the amount ratio of guanidine polymer to deionized water in the aqueous guanidine polymer solution in S5 is 1g:99ml.
7. The method for preparing a porous nano-sponge material according to claim 1, wherein the drying time in S5 is 24 hours.
8. The method for preparing a porous nano-sponge material according to claim 1, wherein the specific surface area of the porous nano-sponge material in S5 is 192.68m 2 And/g, particle size of 18.25nm.
9. Use of a porous nano-sponge material prepared according to any of claims 1-8 for the removal of europium ions and hexavalent chromium ions from industrial waste water.
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| CN110964277A (en) * | 2019-11-30 | 2020-04-07 | 华东理工大学 | Guanidine salt antibacterial agent grafted modified polyvinylidene fluoride and preparation method thereof |
| CN114570339A (en) * | 2022-01-28 | 2022-06-03 | 江苏大学 | Method for preparing salicylaldoxime/polydopamine hollow nano-adsorbent by one-step method and uranium removal application thereof |
| CN115612403A (en) * | 2021-07-14 | 2023-01-17 | 中国科学院天津工业生物技术研究所 | Self-assembly strong-adhesion copolymer film, film coating method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110964277A (en) * | 2019-11-30 | 2020-04-07 | 华东理工大学 | Guanidine salt antibacterial agent grafted modified polyvinylidene fluoride and preparation method thereof |
| CN115612403A (en) * | 2021-07-14 | 2023-01-17 | 中国科学院天津工业生物技术研究所 | Self-assembly strong-adhesion copolymer film, film coating method and application |
| CN114570339A (en) * | 2022-01-28 | 2022-06-03 | 江苏大学 | Method for preparing salicylaldoxime/polydopamine hollow nano-adsorbent by one-step method and uranium removal application thereof |
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