CN114591532B - Polyimide composite foam material with photocatalytic performance and preparation method and application thereof - Google Patents
Polyimide composite foam material with photocatalytic performance and preparation method and application thereof Download PDFInfo
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- CN114591532B CN114591532B CN202210274164.8A CN202210274164A CN114591532B CN 114591532 B CN114591532 B CN 114591532B CN 202210274164 A CN202210274164 A CN 202210274164A CN 114591532 B CN114591532 B CN 114591532B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 63
- 239000004642 Polyimide Substances 0.000 title claims abstract description 61
- 229920001721 polyimide Polymers 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000006261 foam material Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910009202 Y—Mn Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 238000004043 dyeing Methods 0.000 claims abstract description 8
- 238000007639 printing Methods 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 24
- 239000006260 foam Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical group S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000003746 yttrium Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011240 wet gel Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005513 bias potential Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the field of wastewater purification, and particularly relates to a polyimide composite foam material with photocatalytic performance, and a preparation method and application thereof. The invention firstly prepares Y-Mn codoped g-C 3 N 4 (ii) a And preparation of Ce-Co codoped Cu 3 P; then co-doping polyamic acid, graphene oxide and Y-Mn with g-C 3 N 4 Co-doping of Cu with Ce-Co 3 Adding the P into water, adding triethylamine, stirring and uniformly dispersing to obtain a water dispersion; vacuum freeze drying and thermal imidization to obtain the composite foam material. The invention utilizes the synergistic effect of the components, improves the treatment capacity of the printing and dyeing wastewater, has higher reuse rate, and is an ideal material for treating the printing and dyeing wastewater.
Description
Technical Field
The invention belongs to the technical field of wastewater purification. More particularly, relates to a polyimide composite foam material with photocatalytic performance, and a preparation method and application thereof.
Background
The organic pollutants can be treated by physical method, chemical method, biological method, photolysis method, etc. The physical method can only enrich pollutants in water, can not realize degradation, and can not fundamentally solve the pollution problem; the chemical method uses chemical reagents, so secondary pollution is easy to generate; the microorganism used in the biological method has strict requirements on degradation conditions and is skillfully long; the pure photolysis method uses an ultraviolet light source, which results in high energy consumption and high cost. The photocatalytic degradation method has the advantages of mild conditions, no secondary pollution, high efficiency, low consumption, capability of thoroughly degrading organic pollutants and the like, and has potential application in the field of water pollution treatment. However, in the process of treating organic pollution by a photocatalytic degradation method, in order to simultaneously realize high efficiency and energy saving, a visible light catalyst with high efficiency and different reusability needs to be used, so that the research and development of a reusable high-efficiency visible light catalyst is a problem which needs to be solved urgently by an expedition person.
The polymer enriches the catalytic material system due to the advantages of rich raw material sources, stable skeleton, diversified synthesis and modification means and the like. Similar to the inorganic semiconductor energy band structure, the polymer respectively forms a valence band and a conduction band by a bonding orbital and an anti-bonding orbital, the band gap between the valence band and the conduction band is determined by the conjugation degree of a pi electron orbit, the band gap width of the polymer is generally between 1.5eV and 3eV, and the polymer has better absorption capacity for visible light and even light in a near infrared region. Depending on the type of carrier transport, polymers can be classified as: n-type polymers (electrons are the predominant carrier), p-type polymers (holes are the predominant carrier), and bipolar polymers (electron or hole transportable). Polyimide (PI) is a polymer with five-membered imide ring, and PI is originally often used as a material carrier in the field of photocatalysis due to the characteristics of good chemical stability, high mechanical strength, convenient processing and the like, lei and the like adopt a deposition method to prepare nano TiO 2 the/PI/Ni foam photo-anode shows strong visible light absorption in the range of 400-700nm, and under the high photoinduction current of 175 mu A/cm < 2 >, the photo-electro-catalytic degradation efficiency of simulated sunlight irradiation for 180min on methylene blue is 98.8 percent, which is mainly attributed to TiO 2 The formation of the PI heterojunction and the applied bias potential results in a higher separation efficiency of the photogenerated carriers.
The PI composite aerogel PI/AgBr @ Ag is prepared by utilizing a sol-gel method and combining a supercritical drying technology by Zhao and the like. The method comprises the steps of taking NMP as a solvent, BPDA as an anhydride monomer, 2,2 '-dibromo-4,4' -dimethylbenzidine as an amine monomer, mixing and dissolving the NMP and the BPDA in NMP, adding a mixed solution of pyridine and acetic anhydride to promote imidization, preparing PI gel after 5min, aging and replacing with ethanol to obtain PI wet gel, and using CO to prepare the PI wet gel 2 The supercritical drying obtains PI aerogel, and the formation of the aerogel greatly enlarges the specific surface area (292 m) of PI 2 (g), the specific surface area of PI/AgBr @ Ag reaches 192m 2 The high porosity and a large number of dangling bonds of the structure provide more light absorption and reaction active sites for photocatalysis, the net structure is also favorable for reducing the agglomeration of AgBr @ Ag nanoparticles, and the contact area of AgBr @ Ag and PI is increased, so that high-efficiency photocatalysis performance is obtained.
Although PI has been studied as a photocatalyst carrier or a photocatalyst in the prior art, the above photocatalyst still has a low utilization rate of sunlight, and is not easy to recycle, has a long treatment period, and cannot meet the requirements of actual production.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the prior art, and provide a polyimide composite foam material with photocatalytic performance, and a preparation method and application thereof.
The invention aims to provide a preparation method of a polyimide composite foam material with photocatalytic performance. The invention firstly prepares Y-Mn codoped g-C 3 N 4 (ii) a And preparation of Ce-Co codoped Cu 3 P; then co-doping polyamic acid, graphene oxide and Y-Mng-C 3 N 4 Co-doping of Cu with Ce-Co 3 Adding the P into water, adding triethylamine, stirring and uniformly dispersing to obtain an aqueous dispersion; vacuum freeze drying and thermal imidization to obtain the composite foam material. The invention utilizes the synergistic effect of the components, improves the treatment capacity of the printing and dyeing wastewater, has higher reuse ratio, and is an ideal material for treating the printing and dyeing wastewater.
The invention also aims to provide a polyimide composite foam material with photocatalytic performance and application thereof.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
(II) preparation of Ce-Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) Co-doping polyamic acid, graphene oxide and Y-Mn prepared in step (I) with g-C 3 N 4 And the Ce-Co codoped Cu prepared in the step (II) 3 Adding the P into water, adding triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain the composite foam material.
Preferably, the Y-Mn codoping g-C 3 N 4 The preparation method comprises the following steps:
a) Adding yttrium salt and manganese salt into distilled water, then adding melamine, performing magnetic stirring at 70-90 ℃ for 20-40 min, performing ultrasonic treatment for 20-40 min to obtain a mixed solution, and drying at 100-120 ℃ for 12-14 h to obtain a precursor;
b) Grinding the precursor, and calcining in nitrogen atmosphere to obtain the target product Y-Mn/g-C 3 N 4 A photocatalytic material;
preferably, in step (a), yttrium salt to manganese salt to melamine = (0.005-0.015) to (0.015-0.075) 1; the yttrium salt is yttrium nitrate or yttrium acetate; the manganese salt is one of manganese nitrate, manganese acetate and manganese chloride.
Preferably, in the step (b), the calcination is carried out at 500-600 ℃ for 3-5 h; the temperature rise rate of the calcination is 3-6 ℃/min.
Preferably, the Ce-Co codoped Cu 3 The preparation method of P comprises the following steps:
(1) Sequentially dissolving copper salt, cerium salt, cobalt salt, yellow phosphorus and a surfactant in a certain amount of deionized water, and stirring to uniformly mix the materials;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 6-14 h at 160-220 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain the final product Ce and Co Co-doped Cu 3 P。
Preferably, in the step (1), the molar ratio of the copper salt, the cerium salt, the cobalt salt and the yellow phosphorus is 1: 0.1-0.4 g;
preferably, in the step (1), the copper salt is one of copper nitrate, copper acetate or copper chloride; the cobalt source compound is selected from one or more of cobalt chloride, cobalt nitrate and cobalt acetate; the cerium salt is one of cerium nitrate, cerium acetate and cerium chloride; the surfactant is selected from sodium dodecyl benzene sulfonate and/or cetyl trimethyl ammonium bromide.
Preferably, in the step (2), the washing agent is ethanol and/or deionized water, the washing times are 2-3 times, and the drying is carried out at 80-100 ℃ for 8-12 h.
Preferably, in the step (1) in the step (III), the polyamic acid, the graphene oxide and the Y-Mn are codoped with g-C 3 N 4 Co-doping of Cu with Ce-Co 3 The mass ratio of P is 100 (8-16): 3 to 6:4 to 8; the mass ratio of the polyamic acid to water is (2; the mass ratio of the polyamic acid to the triethylamine is 100 (50-70).
Preferably, in the step (2) in the step (III), the freeze-drying temperature is-65 to-45 ℃, and the drying time is 90 to 110 hours; the vacuum degree is 3-9 Pa; the thermal imidization method is to program temperature under the following conditions: 1 to 3h at 80 to 100 ℃,2 to 4h at 170 to 210 ℃,2 to 4h at 270 to 290 ℃.
The polyimide composite foam material with the photocatalytic performance is prepared based on the preparation method of the polyimide composite foam material with the photocatalytic performance.
Based on the application of the polyimide composite foam material with photocatalytic performance, the composite foam material is used for treating printing and dyeing wastewater in organic wastewater.
The invention has the following beneficial effects:
(1) First co-doping g-C by Y and Mn 3 N 4 The g-C is improved by utilizing the synergistic effect of Y and Mn 3 N 4 The utilization rate of sunlight is improved, and the photocatalytic performance is improved;
(2) Co-doping of Cu with Ce and Co 3 P, increasing Cu by synergistic effect of Ce and Co 3 The utilization rate of P to sunlight further improves the photocatalytic performance;
(3) By co-doping Y and Mn with g-C 3 N 4 Co-doping of Cu with Ce and Co 3 The foam material is prepared by compounding P, graphene and polyimide, and through the mutual matching of the components, the effective separation of photoproduction electrons and cavities is improved, the utilization rate of sunlight is greatly improved, the photocatalytic performance is improved, and the photocatalytic degradation capability of printing and dyeing wastewater is improved;
(4) The polyimide is prepared into a foam shape, so that the specific surface area is increased, the adsorption capacity on pollutants is improved, meanwhile, the foam structure is favorable for recovery, and the doped g-C is prepared by an in-situ method 3 N 4 And doped Cu 3 P is limited in the foam, so that the loss of the photocatalyst is reduced, and the stability and the reutilization rate of the photocatalyst are improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.01mol of yttrium nitrate and 0.045mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, then carrying out ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ under the nitrogen atmosphere, wherein the heating rate of the calcination temperature rise is 4 ℃/min, and obtaining the target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and are stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized water, and drying for 10h at 90 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide, and 0.45g of Y-Mn co-doped g-C prepared in step (I) 3 N 4 And 0.6g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Example 2
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.015mol of yttrium acetate and 0.015mol of manganese chloride into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring for 20min at 90 ℃, carrying out ultrasonic treatment for 20min to obtain a mixed solution, and drying for 12h at 120 ℃ to obtain a precursor;
b) Grinding the precursor, calcining for 3h at 600 ℃ in a nitrogen atmosphere, wherein the temperature rise rate of the calcination is 6 ℃/min, and obtaining a target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co-doped Cu 3 P
(1) 1mol of copper acetate, 0.03mol of cerium chloride, 0.02mol of cobalt acetate, 6-yellow phosphorus and 0.4g of hexadecyl trimethyl ammonium bromide are sequentially dissolved in 100mL of deionized water and stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 8h at 220 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by using ethanol, and drying for 8h at 100 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.6g of graphene oxide and 0.3g of Y-Mn co-doped g-C prepared in the step (I) 3 N 4 And 0.8g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 90g of water, adding 7g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 90 hours at the temperature of minus 65 ℃ and the vacuum degree of 9Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 1h at 100 ℃, 2h at 210 ℃ and 2h at 290 ℃.
Example 3
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.005mol of yttrium nitrate and 0.075mol of manganese acetate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 70 ℃ for 40min, performing ultrasonic treatment for 40min to obtain a mixed solution, and drying at 100 ℃ for 14h to obtain a precursor;
b) Grinding the precursor, calcining for 5h at 500 ℃ in a nitrogen atmosphere, wherein the heating rate of the calcination is 3 ℃/min, and obtaining a target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper chloride, 0.01mol of cerium chloride, 0.04 mol of cobalt nitrate, 3mol of yellow phosphorus and 0.1g of sodium dodecyl benzene sulfonate are sequentially dissolved in a certain amount of 100mL of deionized water and stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 14h at 160 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying at 80 ℃ for 12h to obtain a final product, namely Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 0.8g of graphene oxide and 0.6g of Y-Mn co-doped g-C prepared in the step (I) 3 N 4 And 0.4g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 490g of water, adding 5g of triethylamine, stirring, and uniformly dispersing to obtain a water dispersion liquid;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 110h at the temperature of minus 65 ℃ and the vacuum degree of 3Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 80 ℃ for 3h,170 ℃ for 4h,270 ℃ for 4h.
Comparative example 1
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-doped g-C 3 N 4 ；
a) Adding 0.055mol of yttrium nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, carrying out ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ under the nitrogen atmosphere, wherein the heating rate of the calcination temperature rise is 4 ℃/min, and obtaining a target product Y/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and are stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized water, and drying for 10h at 90 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide, 0.45g of Y-doped g-C prepared in step (I) 3 N 4 And 0.6g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 2
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Mn-doped g-C 3 N 4 ；
a) Adding 0.055mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, carrying out ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ under the nitrogen atmosphere, wherein the heating rate of the calcining temperature rise is 4 ℃/min, and obtaining the target product Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and are stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized water, and drying for 10h at 90 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide, 0.45g of Mn-doped g-C prepared in step (I) 3 N 4 And 0.6g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 3
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.01mol of yttrium nitrate and 0.045mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, performing ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ in a nitrogen atmosphere, wherein the temperature rise rate of the calcination temperature rise isAt 4 ℃/min to obtain a target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-doped Cu 3 P
(1) 1mol of copper nitrate, 0.05mol of cerium nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and the mixture is stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 10h at 90 ℃ to obtain the final product Ce-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide, and 0.45g of Y-Mn co-doped g-C prepared in step (I) 3 N 4 And 0.6g of Ce-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 4
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.01mol of yttrium nitrate and 0.045mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, performing ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ in a nitrogen atmosphere, wherein the temperature rise rate of the calcination temperature rise is 4 ℃/min, and obtaining a target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Co-doped Cu 3 P
(1) 1mol of copper nitrate, 0.05mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and are stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 10 hours at 90 ℃ to obtain the final product Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide and 0.45g of Y-Mn co-doped g-C prepared in step (I) 3 N 4 And 0.6g of Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 5
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.01mol of yttrium nitrate and 0.045mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, performing ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ under the nitrogen atmosphere, wherein the heating rate of the calcination temperature rise is 4 ℃/min, and obtaining the target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphene oxide and 1.05g of Y-Mn co-doped g-C prepared in step (I) 3 N 4 Adding 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain waterA dispersion liquid;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 6
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and the mixture is stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized water, and drying for 10h at 90 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(II) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.2g of graphite oxide, and 1.05g of Ce-Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 7
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
a) Adding 0.01mol of yttrium nitrate and 0.045mol of manganese nitrate into 50mL of distilled water, then adding 1mol of melamine, magnetically stirring at 80 ℃ for 30min, performing ultrasonic treatment for 30min to obtain a mixed solution, and drying at 110 ℃ for 13h to obtain a precursor;
b) Grinding the precursor, calcining for 4h at 550 ℃ in a nitrogen atmosphere, wherein the temperature rise rate of the calcination temperature rise is 4 ℃/min, and obtaining a target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and the mixture is stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10h at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized water, and drying for 10h at 90 ℃ to obtain a final product, namely the Ce and Co Co-doped Cu 3 P；
(III) preparation of polyimide syntactic foam
(1) 10g of Polyamic acid, 1.65g of Y-Mn codoped g-C prepared in step (I) 3 N 4 And 0.6g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, carrying out vacuum freeze drying for 100h at-55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
Comparative example 8
A preparation method of a polyimide composite foam material with photocatalytic performance comprises the following steps:
(I) Preparation of Ce-Co codoped Cu 3 P
(1) 1mol of copper nitrate, 0.02mol of cerium nitrate, 0.03mol of cobalt nitrate, 4mol of yellow phosphorus and 0.3g of sodium dodecyl benzene sulfonate are sequentially dissolved in 100mL of deionized water, and are stirred to be uniformly mixed;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at 200 ℃, naturally cooling to room temperature, washing the obtained product for 3 times by deionized waterDrying at 90 ℃ for 10h to obtain the final product Ce and Co Co-doped Cu 3 P；
(II) preparation of polyimide syntactic foam
(1) 10g of polyamic acid, 1.65g of graphene oxide, and 0.6g of Ce-Co Co-doped Cu prepared in step (II) 3 Adding P into 240g of water, adding 6g of triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, carrying out vacuum freeze drying for 100 hours at the temperature of minus 55 ℃ and under the vacuum degree of 6Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 3h at 190 ℃ and 3h at 280 ℃.
The polyimide composite foams of examples 1 to 3 and comparative examples 1 to 8 were used in photocatalytic degradation experiments, and the specific test results are shown in table 1. The specific method comprises the following steps:
5mg of photocatalyst is added into the aqueous solution of rhodamine B (the concentration is 1 multiplied by 10) -4 M), stirring for 10min under the dark condition, then stirring under the irradiation of a xenon lamp (350W), and measuring the degradation rate at 5min and 10 min; and a degradation rate of 10min after 5 repeated uses.
5mg of photocatalyst was added to an aqueous solution of methyl orange (concentration: 1X 10) -4 M), stirring for 10min under dark condition, then stirring under the irradiation of a xenon lamp (350W), and measuring the degradation rate at 5min and 10min and the degradation rate at 10min after 5 times of repeated use.
TABLE 1 test results of examples 1-3 and comparative examples 1-8
As can be seen from Table 1, by comparing examples 1-3 with comparative examples 1-8, the polyimide syntactic foam prepared by the present application effectively promotes the utilization rate of appreciable light by utilizing the mutual coordination among the components, has excellent photocatalytic performance, has excellent degradation capability on printing and dyeing wastewater, and has excellent stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a polyimide composite foam material with photocatalytic performance is characterized by comprising the following steps: which comprises the following steps:
(I) Preparation of Y-Mn codoped g-C 3 N 4 ；
The Y-Mn codoped g-C 3 N 4 The preparation method comprises the following steps:
a) Adding yttrium salt and manganese salt into distilled water, then adding melamine, magnetically stirring for 20-40min at 70-90 ℃, carrying out ultrasonic treatment for 20-40min to obtain a mixed solution, and drying for 12-14h at 100-120 ℃ to obtain a precursor;
b) Grinding the precursor, and calcining in nitrogen atmosphere to obtain the target product Y-Mn/g-C 3 N 4 A photocatalytic material;
(II) preparation of Ce-Co-doped Cu 3 P；
The Ce-Co codoped Cu 3 The preparation method of P comprises the following steps:
(1) Sequentially dissolving copper salt, cerium salt, cobalt salt, yellow phosphorus and a surfactant in a certain amount of deionized water, and stirring to uniformly mix the materials;
(2) Transferring the solution obtained in the step (1) into a polytetrafluoroethylene reaction kettle, reacting for 6-14h at 160-220 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain a final product, namely the Cu Co-doped with Ce and Co 3 P；
(III) preparation of polyimide syntactic foam:
(1) co-doping polyamic acid, graphene oxide and Y-Mn prepared in step (I) with g-C 3 N 4 And the Ce-Co codoped Cu prepared in the step (II) 3 Adding the P into water, adding triethylamine, stirring and uniformly dispersing to obtain a water dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain the composite foam material.
2. The method of claim 1, wherein the method comprises the steps of: in the step a) of the step (I), yttrium salt to manganese salt to melamine = (0.005-0.015) to (0.015-0.075) is 1; the yttrium salt is yttrium nitrate or yttrium acetate; the manganese salt is one of manganese nitrate, manganese acetate and manganese chloride.
3. The preparation method of the polyimide composite foam material with photocatalytic performance as claimed in claim 1 or 2, characterized by comprising the steps of: in the step b) of the step (I), the calcination is carried out for 3 to 5h at 500 to 600 ℃; the heating rate of the calcination was 3~6 ℃/min.
4. The method of claim 1, wherein the method comprises the steps of: in the step (1) of the step (II), the molar ratio of the copper salt, the cerium salt, the cobalt salt and the yellow phosphorus is 1: 0.1 to 0.4g.
5. The method for preparing polyimide syntactic foam having photocatalytic properties according to claim 1 or 4, wherein: in the step (1) of the step (II), the copper salt is one of copper nitrate, copper acetate or copper chloride; the cobalt source compound is selected from one of cobalt chloride, cobalt nitrate and cobalt acetate; the cerium salt is one of cerium nitrate, cerium acetate and cerium chloride; the surfactant is selected from sodium dodecyl benzene sulfonate and/or cetyl trimethyl ammonium bromide.
6. The method of claim 1, wherein the method comprises the steps of: in the step (2) of the step (II), in the step (2), the detergent is ethanol and/or deionized water, the washing times are 2~3 times, and the drying is carried out at 80 to 100 ℃ for 8 to 12h.
7. The method of claim 1, wherein the method comprises the steps of: in the step (1) of the step (III), the polyamic acid, the graphene oxide and the Y-Mn are co-doped with g-C 3 N 4 Co-doping of Cu with Ce-Co 3 The mass ratio of P is 100 (8-16): 3 to 6; the mass ratio of the polyamic acid to water is (2; the mass ratio of the polyamic acid to the triethylamine is 100 (50-70).
8. The method for preparing polyimide syntactic foam having photocatalytic properties according to claim 1 or 7, wherein: in the step (2) in the step (III), the freeze drying temperature is-65 to-45 ℃, and the drying time is 90 to 110h; the vacuum degree is 3 to 9Pa; the thermal imidization method is to program temperature under the following conditions: 1 to 3h at 80 to 100 ℃,2 to 4h at 170 to 210 ℃,2 to 4h at 270 to 290 ℃.
9. The polyimide syntactic foam having photocatalytic properties prepared by the method for preparing a polyimide syntactic foam having photocatalytic properties according to any one of claims 1 to 8.
10. Use of a polyimide syntactic foam having photocatalytic properties according to claim 9, characterized in that: the composite foam material is used for treating printing and dyeing wastewater in organic wastewater.
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