CN113559927A - g-C3N4CuS quantum dot modified COFs composite material and preparation method thereof - Google Patents
g-C3N4CuS quantum dot modified COFs composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 25
- 239000002096 quantum dot Substances 0.000 title claims description 36
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- XAGMMULTLDDGLX-UHFFFAOYSA-N 4-[1,3-bis(4-aminophenyl)-2,4-dihydrotriazin-5-yl]aniline Chemical compound NC1=CC=C(C=C1)N1NN(CC(=C1)C1=CC=C(C=C1)N)C1=CC=C(C=C1)N XAGMMULTLDDGLX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000012691 Cu precursor Substances 0.000 claims abstract description 13
- 239000002262 Schiff base Substances 0.000 claims abstract description 11
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 18
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 10
- 229940015043 glyoxal Drugs 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229940123317 Sulfonamide antibiotic Drugs 0.000 abstract description 6
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- 239000011734 sodium Substances 0.000 description 6
- 150000004753 Schiff bases Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- IZJAOWYNDLDRKM-UHFFFAOYSA-N sodium;(4-aminophenyl)sulfonyl-(6-methoxypyrimidin-4-yl)azanide Chemical compound [Na+].C1=NC(OC)=CC([N-]S(=O)(=O)C=2C=CC(N)=CC=2)=N1 IZJAOWYNDLDRKM-UHFFFAOYSA-N 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JLDCNMJPBBKAHH-UHFFFAOYSA-N sodium;(4-aminophenyl)sulfonyl-pyrimidin-2-ylazanide Chemical compound [Na+].C1=CC(N)=CC=C1S(=O)(=O)[N-]C1=NC=CC=N1 JLDCNMJPBBKAHH-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 229960001182 sulfadiazine sodium Drugs 0.000 description 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 229960001544 sulfathiazole Drugs 0.000 description 1
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/39—Photocatalytic properties
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- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a g-C3N4The modified COFs composite material is in a core-shell structure and comprises 2,4, 6-trihydroxybenzene-1, 3, 5-Triaminobenzaldehyde, 1, 3, 5-tri (4-aminophenyl) triazine and functionalized g-C3N4g-C obtained by condensation of Schiff base3N4The modified COFs composite material comprises a modified COFs composite material inner core and CuS quantum dots modified on the surface. The preparation method comprises the following steps: s1: preparation of Ammonified g-C3N4(ii) a S2: preparation of g-C3N4Modified COFs composite materials; s3: g to C3N4Adding the modified COFs composite material into 0.1mol/L copper precursor solution, magnetically stirring to prepare suspension, adding thioglycollic acid, stirring for dissolving, and then dropwise adding 0.5mol/L Na2And (5) stirring the S solution at 80-120 ℃ for reaction for 0.5-2 h, centrifuging, washing and drying to obtain the S-containing aqueous solution. The modified COFs composite material has the characteristics of three-dimensional topological structure, high porosity, high catalytic activity and the like, the degradation rate of the modified COFs composite material on sulfonamide antibiotics reaches over 90 percent, and the complete degradation of the antibiotics is realized.
Description
Technical Field
The invention belongs to the field of synthesis of nano-catalysts, and particularly relates to g-C3N4A CuS quantum dot modified COFs composite material and a preparation method thereof.
Background
The COFs are composed of C, H, O, N, B and other light elements according to covalent bonds, are generally constructed by covalent bonds (C-C, C-O, B-O and the like), and are crystalline materials with ordered pore structures formed under the conditions of reversible polymerization and thermodynamic control, and have high specific surface area, very low density, high thermal stability and high orderliness. COFs can be prepared and synthesized through a series of organic reactions (Schiff base reaction or boric acid esterification reaction), and simultaneously have very strong chemical modifiability, in other words, COFs can be designed in an angle-oriented mode through organic chemistry or be synthesized into structural units with different functions. Like the MOFs, COFs are also frameworks formed by the bonding of organic units between atoms and structures with nanopores. Professor in the university of Jilin explores the design and synthesis of porous aromatic skeleton COFs materials with specific surface areas as high as 7100m2The experiment shows that the specific surface area of the COFs material is obviously higher than that of other kinds of pore materials. COFs are considered to be one of the most promising hydrogen storage materials due to their advantages of large surface area, high porosity and extremely low density, while at the same time, they play an irreplaceable role in the fields of photoelectricity, catalysis, selective separations, etc.
The functional modification of the COFs material is to modify the COFs material through a conjugated system and an active functional group in the synthesis process of the COFs material or to dope goldBelonging to or non-metal elements, or compounding with other compounds to improve the application performance. For example: the S/COFs composite material obtained by modifying the COFs material by using sulfur is used as the positive electrode of the lithium-sulfur battery, and experiments show that the modification of the sulfur can increase the transfer capacity of lithium ions; COFs material is modified by using metal, and the COFs material is utilized to react with CO2The coordination function of the COFs material is used for improving the adsorption quantity of the COFs material; the patent with the application number of CN201810143237.3 discloses a magnetic sulfonic group functionalized COFs material and a preparation method and application thereof, wherein a covalent organic framework is formed by performing Schiff base condensation reaction on 2,4, 6-triacyl phloroglucinol and 2, 5-diaminobenzene sulfonic acid, and Fe functionalized by amino is utilized3O4/SiO2Modifying the core-shell nano particles; the patent with the application number of CN202010502483.0 discloses a three-dimensional graphene/COFs composite material, and a preparation method and application thereof, and the graphene hydrogel, poly (benzenetricarboxylic acid) and benzidine are mixed and stirred to prepare a compound of graphene and COFs. As a new material, the COFs material is rarely researched in the research and development and functional modification directions of the new COFs material.
g-C3N4The polymer semiconductor is a typical polymer semiconductor, CN atoms in the structure of the polymer semiconductor form a highly delocalized pi conjugated system through sp2 hybridization, the forbidden bandwidth is 2.7eV, and the polymer semiconductor can absorb blue-violet light with the wavelength less than 475nm in a solar spectrum. g-C3N4Has very suitable semiconductor band edge positions and meets the thermodynamic requirements of photolysis of water to produce hydrogen and oxygen. Compared with the traditional TiO2Photocatalyst, g-C3N4And can also effectively activate molecular oxygen to generate superoxide radical for the photocatalytic conversion of organic functional groups and the photocatalytic degradation of organic pollutants.
In order to further develop and explore novel COFs materials and derivatives thereof, the invention adopts 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tri (4-aminophenyl) triazine and functionalized g-C for the first time3N4Preparation of g-C by Schiff base condensation3N4Modifying the COFs composite material, further growing CuS quantum dots in situ in a network frame structure, and applying the CuS quantum dots to the network frame structureAnd (4) degrading the sulfonamide antibiotics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide g-C3N4A CuS quantum dot modified COFs composite material and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
g-C3N4The modified COFs composite material is of a core-shell structure and comprises 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine and functionalized g-C3N4g-C obtained by condensation of Schiff base3N4The modified COFs composite material comprises a modified COFs composite material inner core and CuS quantum dots modified on the surface.
g-C3N4The preparation method of the/CuS quantum dot modified COFs composite material comprises the following steps:
s1: preparation of Ammonified g-C3N4: nano g-C3N4Adding the mixture into deionized water, performing ultrasonic dispersion, adding urea and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, uniformly stirring, performing hydrothermal reaction at 80-100 ℃ for 0.5-2 h, centrifuging, washing and drying to obtain the aminated g-C3N4；
S2: preparation of g-C3N4Modified COFs composite material:
dissolving glyoxal cross-linking agent in deionized water, and then adding ammoniated g-C3N4Stirring and reacting for 0.5-1.5 h to obtain functionalized g-C3N4Suspending the solution;
adding 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 1, 3, 5-tri (4-aminophenyl) triazine into 1, 4-dioxane, ultrasonically dispersing, and adding the obtained functionalized g-C3N4Uniformly stirring the suspension and 3mol/L acetic acid solution, carrying out hydrothermal reaction at 100-120 ℃ for 2-3 d, centrifuging, washing and drying to obtain g-C3N4Modified COFs composite materials;
the ammoniated g-C3N4Crosslinked with glyoxalThe dosage ratio of the agent, deionized water, 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tri (4-aminophenyl) triazine, 1, 4-dioxane and acetic acid solution is 0.2 g: (0.2-0.25) g: (2-3) mL: (1-1.2) g: (2.4-2.8) g: 50mL of: (1-2) mL;
s3: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: g to C3N4Adding the modified COFs composite material into 0.1mol/L copper precursor solution, magnetically stirring to prepare suspension, adding thioglycollic acid, stirring for dissolving, and then dropwise adding 0.5mol/L Na2Stirring the S solution at 80-120 ℃ for reaction for 0.5-2 h, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material.
Preferably, in S1, the nano g-C3N4The dosage ratio of the deionized water to the urea to the N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 1 g: 10mL of: (0.2-0.4) g: (0.3-0.6) mL.
Preferably, the copper precursor solution comprises one or more of a copper chloride solution, a copper sulfate solution, a copper nitrate solution and a copper acetate solution.
Preferably, the nano g-C3N4The preparation method comprises the following steps: adding melamine into absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 0.5g/mL, ultrasonically dispersing, evaporating ethyl alcohol at 90-150 ℃, then placing in a muffle furnace, heating to 550-600 ℃, calcining at constant temperature for 4-6 h, and fully grinding to obtain the nano g-C3N4。
Preferably, in S3, g-C3N4Modified COFs composite material, copper precursor solution, thioglycollic acid and Na2The dosage ratio of the S solution is 1 g: (5-10) mL: (0.1-0.5) mL: (1-2) mL.
Preferably, the copper precursor solution and Na2The volume ratio of the S solution is 5: 1.
the invention has the beneficial effects that:
1. the invention adopts 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tri (4-aminophenyl) triazine and functionalized g-C for the first time3N4g-C is condensed by Schiff base3N4Grafted to a COFs structure, and further growing CuS quantum dots in situ in a network framework structure to synthesize g-C with a three-dimensional topological structure, high porosity and high catalytic activity3N4The degradation rate of the/CuS quantum dot modified COFs composite material to sulfanilamide antibiotics reaches over 90 percent, so that the sulfanilamide antibiotics are completely degraded into non-toxic micromolecular inorganic compounds and CO2、H2O。
2. The invention utilizes Schiff base reaction between aldehyde group and amino group to react g-C3N4Grafted to a COFs structure, realizes intramolecular bonding through chemical bonds, and remarkably improves g-C compared with the traditional composite method3N4The structural stability of the modified COFs composite material.
3. The invention realizes CuS quantum dots and g-C by using a chemical precipitation method3N4The combination of the modified COFs composite material forms a heterojunction structure due to different Fermi levels of the three materials, changes the transmission path of electrons, and enables the photo-generated electrons to be spontaneously transferred from the CuS quantum dot crystal face to g-C3N4And a conduction band of COFs (complementary metal-organic frameworks), and efficiently separating photogenerated electrons from holes, so that the holes are accumulated on the CuS quantum dots, and the photogenerated electrons are accumulated on g-C3N4And COFs, the photocatalytic oxidation reduction capability is obviously improved; the COFs have a developed pore channel structure and a high specific area, so that sufficient growth sites are provided for the CuS quantum dots, agglomeration among the CuS quantum dots is avoided, and a good surface effect and a good quantum size are kept; meanwhile, the forbidden bandwidth of the CuS quantum dots is only 1.5eV, the spectral response range of the CuS quantum dots to visible light and near infrared regions is wide, and the g-C quantum dots have the same spectrum as the visible light and near infrared regions3N4The modified COFs composite material can effectively improve the sunlight absorption rate and the effective utilization rate.
Drawings
FIG. 1 shows g-C of the present invention3N4Flow chart of a preparation method of the/CuS quantum dot modified COFs composite material.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The invention provides an embodiment g-C3N4The modified COFs composite material is of a core-shell structure and comprises 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine and functionalized g-C3N4g-C obtained by condensation of Schiff base3N4The modified COFs composite material inner core and the CuS quantum dots modified on the surface; the preparation method comprises the following steps:
s1: preparation of nano g-C3N4: adding melamine into absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 0.5g/mL, ultrasonically dispersing, evaporating ethyl alcohol at 90-150 ℃, then placing in a muffle furnace, heating to 550-600 ℃, calcining at constant temperature for 4-6 h, and fully grinding to obtain the nano g-C3N4；
S2: preparation of Ammonified g-C3N4: nano g-C3N4Adding the mixture into deionized water, performing ultrasonic dispersion, adding urea and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, uniformly stirring, performing hydrothermal reaction at 80-100 ℃ for 0.5-2 h, centrifuging, washing and drying to obtain the aminated g-C3N4(ii) a Nano g-C3N4The dosage ratio of the deionized water to the urea to the N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 1 g: 10mL of: (0.2-0.4) g: (0.3-0.6) mL;
s3: preparation of g-C3N4Modified COFs composite material:
dissolving glyoxal cross-linking agent in deionized water, and then adding ammoniated g-C3N4Stirring and reacting for 0.5-1.5 h to obtain functionalized g-C3N4Suspending the solution;
adding 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 1, 3, 5-tri (4-aminophenyl) triazine into 1, 4-dioxane, ultrasonically dispersing, and adding the obtained functionalized g-C3N4Uniformly stirring the suspension and 3mol/L acetic acid solution, carrying out hydrothermal reaction at 100-120 ℃ for 2-3 d, centrifuging, washing and drying to obtain g-C3N4Modified COFs composite materials;
the ammoniated g-C3N4The preparation method comprises the following steps of (1) preparing glyoxal crosslinking agent, deionized water, 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine, 1, 4-dioxane and acetic acid solution, wherein the dosage ratio is 0.2 g: (0.2-0.25) g: (2-3) mL: (1-1.2) g: (2.4-2.8) g: 50mL of: (1-2) mL;
s4: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: g to C3N4Adding the modified COFs composite material into 0.1mol/L copper precursor solution, wherein the copper precursor solution comprises one or more of copper chloride solution, copper sulfate solution, copper nitrate solution and copper acetate solution, magnetically stirring to prepare suspension, adding thioglycollic acid, stirring for dissolving, and then dropwise adding 0.5mol/L Na2Stirring the S solution at 80-120 ℃ for reaction for 0.5-2 h, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material; g-C3N4Modified COFs composite material, copper precursor solution, thioglycollic acid and Na2The dosage ratio of the S solution is 1 g: (5-10) mL: (0.1-0.5) mL: (1-2) mL, and the copper precursor solution and Na2The volume ratio of the S solution is 5: 1.
the invention still further provides g-C of this example3N4The application of the/CuS quantum dot modified COFs composite material in degrading sulfonamide antibiotics, wherein the sulfonamide antibiotics comprise one or more of sulfadiazine, sulfadiazine sodium, sulfamonomethoxine sodium, phthalein sulfathiazole and sulfamethoxazole.
Example 1
g-C3N4The preparation method of the/CuS quantum dot modified COFs composite material comprises the following steps:
s1: preparation of nano g-C3N4: adding 10g of melamine into 20mL of absolute ethyl alcohol, ultrasonically dispersing, evaporating the ethyl alcohol at 90 ℃, then placing the mixture into a muffle furnace, heating to 550 ℃, calcining at constant temperature for 4 hours, and fully grindingGrinding to obtain nanometer g-C3N4；
S2: preparation of Ammonified g-C3N4: 0.5g of nano g-C3N4Adding into 5mL deionized water, ultrasonic dispersing, adding 0.1g urea and 0.15mL N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, stirring, hydrothermal reacting at 80 deg.C for 0.5h, centrifuging, washing, and drying to obtain ammoniated g-C3N4；
S3: preparation of g-C3N4Modified COFs composite material:
0.2g of glyoxal crosslinker was dissolved in 2mL of deionized water, followed by 0.2g of aminated g-C3N4Stirring and reacting for 0.5h to obtain functionalized g-C3N4Suspending the solution;
adding 1g of 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 2.4g of 1, 3, 5-tris (4-aminophenyl) triazine into 50mL of 1, 4-dioxane, ultrasonically dispersing, and adding the functionalized g-C3N4Suspension and 1mL of 3mol/L acetic acid solution are stirred uniformly, and then are subjected to hydrothermal reaction for 2d at 100 ℃, and after centrifugation, washing and drying, g-C is obtained3N4Modified COFs composite materials;
s4: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: 1g of g-C3N4Adding the modified COFs composite material into 5mL of 0.1mol/L copper chloride solution, magnetically stirring to prepare suspension, adding 0.1mL of thioglycollic acid, stirring to dissolve, and then dropwise adding 1mL of 0.5mol/L Na2S solution, stirring and reacting for 0.5h at 80 ℃, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material.
Example 2
g-C3N4The preparation method of the/CuS quantum dot modified COFs composite material comprises the following steps:
s1: preparation of nano g-C3N4: adding 10g of melamine into 20mL of absolute ethyl alcohol, ultrasonically dispersing, evaporating the ethyl alcohol at 120 ℃, then placing the mixture into a muffle furnace, heating to 600 ℃, calcining at constant temperature for 5 hours, and fully grinding to obtain the nano g-C3N4；
S2: preparation of Ammonified g-C3N4: 0.5g of nano g-C3N4Adding into 5mL deionized water, ultrasonic dispersing, adding 0.15g urea and 0.2mL N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, stirring, hydrothermal reacting at 90 deg.C for 1h, centrifuging, washing, and drying to obtain ammoniated g-C3N4；
S3: preparation of g-C3N4Modified COFs composite material:
0.25g of glyoxal crosslinker was dissolved in 2.5mL of deionized water, followed by 0.2g of aminated g-C3N4Stirring and reacting for 1h to obtain functionalized g-C3N4Suspending the solution;
adding 1.1g of 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 2.6g of 1, 3, 5-tris (4-aminophenyl) triazine into 50mL of 1, 4-dioxane, ultrasonically dispersing, and adding the functionalized g-C3N4Suspension and 1.5mL of 3mol/L acetic acid solution are stirred uniformly, hydrothermal reaction is carried out for 2.5 days at 110 ℃, and g-C is obtained after centrifugation, washing and drying3N4Modified COFs composite materials;
s4: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: 1g of g-C3N4Adding the modified COFs composite material into 7.5mL of 0.1mol/L copper sulfate solution, magnetically stirring to prepare a suspension, adding 0.3mL of thioglycollic acid, stirring to dissolve, and then dropwise adding 1.5mL of 0.5mol/L Na2S solution, stirring and reacting for 1h at 100 ℃, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material.
Example 3
g-C3N4The preparation method of the/CuS quantum dot modified COFs composite material comprises the following steps:
s1: preparation of nano g-C3N4: adding 10g of melamine into 20mL of absolute ethyl alcohol, ultrasonically dispersing, evaporating the ethyl alcohol at 150 ℃, then placing the mixture into a muffle furnace, heating to 600 ℃, calcining at constant temperature for 6 hours, and fully grinding to obtain the nano g-C3N4；
S2: preparation of Ammonified g-C3N4: 0.5g of nano g-C3N4Adding into 5mL deionized water, ultrasonic dispersing, adding 0.2g urea and 0.3mL N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, stirring, hydrothermal reacting at 100 deg.C for 2h, centrifuging, washing, and drying to obtain ammoniated g-C3N4；
S3: preparation of g-C3N4Modified COFs composite material:
0.25g of glyoxal crosslinker was dissolved in 3mL of deionized water, followed by 0.2g of aminated g-C3N4Stirring and reacting for 1.5h to obtain functionalized g-C3N4Suspending the solution;
adding 1.2g of 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 2.8g of 1, 3, 5-tris (4-aminophenyl) triazine into 50mL of 1, 4-dioxane, ultrasonically dispersing, and adding the functionalized g-C3N4Suspension and 2mL of 3mol/L acetic acid solution are stirred uniformly, hydrothermal reaction is carried out for 3d at 120 ℃, and g-C is obtained after centrifugation, washing and drying3N4Modified COFs composite materials;
s4: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: 1g of g-C3N4Adding the modified COFs composite material into 10mL of 0.1mol/L copper nitrate solution, magnetically stirring to prepare suspension, adding 0.5mL of thioglycollic acid, stirring to dissolve, and then dropwise adding 2mL of 0.5mol/L Na2S solution, stirring and reacting for 2h at 120 ℃, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material.
Comparative example 1 is g-C3N4The preparation method of the modified COFs composite material comprises the following steps:
s1: preparation of nano g-C3N4: adding 10g of melamine into 20mL of absolute ethyl alcohol, ultrasonically dispersing, evaporating the ethyl alcohol at 90 ℃, then placing the mixture into a muffle furnace, heating to 550 ℃, calcining at constant temperature for 4 hours, and fully grinding to obtain the nano g-C3N4；
S2: preparation of Ammonified g-C3N4: 0.5g of nano g-C3N4Adding into 5mL deionized water, ultrasonic dispersing, adding 0.1g urea and 0.15mL N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, stirring, hydrothermal reacting at 80 deg.C for 0.5h, centrifuging, washing, and drying to obtain ammoniated g-C3N4；
S3: preparation of g-C3N4Modified COFs composite material:
0.2g of glyoxal crosslinker was dissolved in 2mL of deionized water, followed by 0.2g of aminated g-C3N4Stirring and reacting for 0.5h to obtain functionalized g-C3N4Suspending the solution;
adding 1g of 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 2.4g of 1, 3, 5-tris (4-aminophenyl) triazine into 50mL of 1, 4-dioxane, ultrasonically dispersing, and adding the functionalized g-C3N4Suspension and 1mL of 3mol/L acetic acid solution are stirred uniformly, and then are subjected to hydrothermal reaction for 2d at 100 ℃, and after centrifugation, washing and drying, g-C is obtained3N4Modified COFs composite materials.
Comparative example 2 is a COFs material, and the preparation method is as follows: adding 1g of 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 2.4g of 1, 3, 5-tris (4-aminophenyl) triazine into 50mL of 1, 4-dioxane, performing ultrasonic dispersion, adding 1mL of 3mol/L acetic acid solution, uniformly stirring, performing hydrothermal reaction at 100 ℃ for 2d, centrifuging, washing, and drying to obtain the COFs material.
The photocatalytic degradation performance of the catalytic materials of examples 1-3 and comparative examples 1-2 on sulfonamide antibiotics is determined:
adding 10mg of catalytic material into 100mL of 50mg/L sulfamonomethoxine sodium aqueous solution, carrying out ultrasonic dispersion, reacting for 60min under the irradiation of sunlight, measuring the light absorption value by using an ultraviolet-visible spectrophotometer, and calculating the degradation rate of the sulfamonomethoxine sodium.
g-C of examples 1 to 3 was measured3N4The degradation rates of the/CuS quantum dot modified COFs composite material on the sulfamonomethoxine sodium are 93.8%, 95.6% and 95.1% respectively, and the degradation rates of the catalytic material on the sulfamonomethoxine sodium are 57.7% and 32.4% respectively in comparative examples 1-2, which shows thatThe modified COFs composite material prepared in the embodiments 1-3 has excellent catalytic degradation capability on sulfonamide antibiotics.
Examples 1-3 functionalized g-C with 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine3N4g-C is condensed by Schiff base3N4Grafted to a COFs structure, and further growing CuS quantum dots in situ in a network framework structure to synthesize g-C with a three-dimensional topological structure, high porosity and high catalytic activity3N4The degradation rate of the/CuS quantum dot modified COFs composite material to sulfanilamide antibiotics reaches over 90 percent, so that the sulfanilamide antibiotics are completely degraded into non-toxic micromolecular inorganic compounds and CO2、H2O。
Examples 1-3 Schiff base reaction of g-C between aldehyde group and amino group3N4Grafted to a COFs structure, realizes intramolecular bonding through chemical bonds, and remarkably improves g-C compared with the traditional composite method3N4The structural stability of the modified COFs composite material.
Examples 1 to 3 implementation of CuS Quantum dots and g-C by chemical precipitation3N4The combination of the modified COFs composite material forms a heterojunction structure due to different Fermi levels of the three materials, changes the transmission path of electrons, and enables the photo-generated electrons to be spontaneously transferred from the CuS quantum dot crystal face to g-C3N4And a conduction band of COFs (complementary metal-organic frameworks), and efficiently separating photogenerated electrons from holes, so that the holes are accumulated on the CuS quantum dots, and the photogenerated electrons are accumulated on g-C3N4And COFs, the photocatalytic oxidation reduction capability is obviously improved; the COFs have a developed pore channel structure and a high specific area, so that sufficient growth sites are provided for the CuS quantum dots, agglomeration among the CuS quantum dots is avoided, and a good surface effect and a good quantum size are kept; meanwhile, the forbidden bandwidth of the CuS quantum dots is only 1.5eV, the spectral response range of the CuS quantum dots to visible light and near infrared regions is wide, and the g-C quantum dots have the same spectrum as the visible light and near infrared regions3N4The modified COFs composite material can effectively improve the sunlight absorption rate and the effective utilization rate.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. g-C3N4the/CuS quantum dot modified COFs composite material is characterized in that the modified COFs composite material is of a core-shell structure and comprises 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine and functionalized g-C3N4g-C obtained by condensation of Schiff base3N4The modified COFs composite material comprises a modified COFs composite material inner core and CuS quantum dots modified on the surface.
2. g-C3N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized by comprising the following steps:
s1: preparation of Ammonified g-C3N4: nano g-C3N4Adding the mixture into deionized water, performing ultrasonic dispersion, adding urea and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, uniformly stirring, performing hydrothermal reaction at 80-100 ℃ for 0.5-2 h, centrifuging, washing and drying to obtain the aminated g-C3N4；
S2: preparation of g-C3N4Modified COFs composite material:
dissolving glyoxal cross-linking agent in deionized water, and then adding ammoniated g-C3N4Stirring and reacting for 0.5-1.5 h to obtain functionalized g-C3N4Suspending the solution;
adding 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde and 1, 3, 5-tri (4-aminophenyl) triazine into 1, 4-dioxane, ultrasonically dispersing, and adding the obtained functionalized g-C3N4Uniformly stirring the suspension and 3mol/L acetic acid solution, carrying out hydrothermal reaction at 100-120 ℃ for 2-3 d, centrifuging, washing and drying to obtain g-C3N4Modified COFs composite materials;
the ammoniated g-C3N4The preparation method comprises the following steps of (1) preparing glyoxal crosslinking agent, deionized water, 2,4, 6-trihydroxybenzene-1, 3, 5-triaminobenzaldehyde, 1, 3, 5-tris (4-aminophenyl) triazine, 1, 4-dioxane and acetic acid solution, wherein the dosage ratio is 0.2 g: (0.2-0.25) g: (2-3) mL: (1-1.2) g: (2.4-2.8) g: 50mL of: (1-2) mL;
s3: preparation of g-C3N4the/CuS quantum dot modified COFs composite material comprises the following components: g to C3N4Adding the modified COFs composite material into 0.1mol/L copper precursor solution, magnetically stirring to prepare suspension, adding thioglycollic acid, stirring for dissolving, and then dropwise adding 0.5mol/L Na2Stirring the S solution at 80-120 ℃ for reaction for 0.5-2 h, centrifuging, washing and drying to obtain g-C3N4the/CuS quantum dot modified COFs composite material.
3. A g-C according to claim 23N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized in that in S1, nano g-C3N4The dosage ratio of the deionized water to the urea to the N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is 1 g: 10mL of: (0.2-0.4) g: (0.3-0.6) mL.
4. A g-C according to claim 23N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized in that the copper precursor solution comprises one or more of a copper chloride solution, a copper sulfate solution, a copper nitrate solution and a copper acetate solution.
5. A g-C according to any one of claims 2 or 33N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized in that the nano g-C3N4The preparation method comprises the following steps: adding melamine into absolute ethyl alcohol, controlling the solid-to-liquid ratio to be 0.5g/mL, ultrasonically dispersing, evaporating the ethyl alcohol at 90-150 ℃, then placing the mixture into a muffle furnace, heating to 550-600 ℃, calcining at constant temperature for 4-6 hours, and fully grinding to obtain the melamine-formaldehyde resin compositionNano g-C3N4。
6. A g-C according to claim 23N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized in that in S3, g-C3N4Modified COFs composite material, copper precursor solution, thioglycollic acid and Na2The dosage ratio of the S solution is 1 g: (5-10) mL: (0.1-0.5) mL: (1-2) mL.
7. A g-C according to claim 63N4The preparation method of the/CuS quantum dot modified COFs composite material is characterized in that the copper precursor solution and Na2The volume ratio of the S solution is 5: 1.
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| CN116273115A (en) * | 2023-02-17 | 2023-06-23 | 上海电力大学 | CuS supported graphite-like carbon nitride photocatalyst and preparation method thereof |
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| CN114453001A (en) * | 2022-03-10 | 2022-05-10 | 江苏理工学院 | Aromatic ring and cyano co-doped carbon nitride nanosheet and preparation method and application thereof |
| CN114453001B (en) * | 2022-03-10 | 2023-06-06 | 江苏理工学院 | Aromatic ring and cyano co-doped carbon nitride nanosheet as well as preparation method and application thereof |
| CN116273115A (en) * | 2023-02-17 | 2023-06-23 | 上海电力大学 | CuS supported graphite-like carbon nitride photocatalyst and preparation method thereof |
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