CN117443455A - Catechol-formaldehyde resin microsphere photocatalysis hybrid material and preparation method and application thereof - Google Patents
Catechol-formaldehyde resin microsphere photocatalysis hybrid material and preparation method and application thereof Download PDFInfo
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- CN117443455A CN117443455A CN202311799513.9A CN202311799513A CN117443455A CN 117443455 A CN117443455 A CN 117443455A CN 202311799513 A CN202311799513 A CN 202311799513A CN 117443455 A CN117443455 A CN 117443455A
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- catechol
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- formaldehyde resin
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 239000004005 microsphere Substances 0.000 title claims abstract description 58
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 51
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 29
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009396 hybridization Methods 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 34
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 13
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002159 nanocrystal Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000013207 UiO-66 Substances 0.000 abstract description 9
- 241000588724 Escherichia coli Species 0.000 abstract description 8
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 4
- 241000894006 Bacteria Species 0.000 abstract description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 241000192125 Firmicutes Species 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 15
- 230000001580 bacterial effect Effects 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000031700 light absorption Effects 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000003642 reactive oxygen metabolite Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- -1 quaternary ammonium salt compounds Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 241000237536 Mytilus edulis Species 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 235000020638 mussel Nutrition 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052946 acanthite Inorganic materials 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000941 anti-staphylcoccal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- 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
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention provides a catechol-formaldehyde resin microsphere photocatalysis hybrid material, a preparation method and application thereof, belonging to the technical field of photocatalysis antibacterial materials. The material is prepared by a hydrothermal method firstlyFat (CFR) microspheres, and then growing metal organic frameworks (UIO-66 (NH) 2 ) CFR microsphere @ UiO-66 (NH) with core-shell structure 2 ) Composite material and then Ag is prepared by chemical coprecipitation method 2 S nano particles are grown on MOF in situ to prepare catechol-formaldehyde resin microsphere photocatalysis hybridization material. The invention has mild reaction condition, easy operation and controllable material structure. The ROS generated by the prepared nano hybrid material under the irradiation of white light has high sterilization activity on escherichia coli, staphylococcus aureus, pseudomonas aeruginosa and the like, and has good application prospect in the photocatalysis inactivation of gram-negative bacteria and gram-positive bacteria in a water system.
Description
Technical Field
The invention belongs to the technical field of photocatalytic antibacterial materials, and particularly relates to a catechol-formaldehyde resin microsphere photocatalytic hybrid material, a preparation method and application thereof.
Background
Compared with traditional antibacterial agents such as traditional metal ions, quaternary ammonium salt compounds, antibacterial peptides and the like, the photocatalysis antibacterial technology is an efficient, environment-friendly and safe emerging antibacterial technology, mainly utilizes light energy to enable a photocatalyst to generate electron and hole separation, further reacts with oxygen or water to generate Reactive Oxygen Species (ROS) and holes to destroy a bacterial structure, achieves the aim of sterilization, and has important application potential in industry and daily life. The stability, the synergistic catalytic performance and the light absorption capacity and range of different components of the photocatalytic material can have important influence on the photocatalytic antibacterial performance. Therefore, development of a high-efficiency photocatalytic antibacterial technology using visible light is a leading-edge subject of current development in this field, and has important practical application significance.
The main photocatalytic antibacterial materials at present comprise TiO 2 、ZnO、AgPO 3 、CuS、Bi 2 S 3 、MoS 2 、g-C 3 N 4 Etc. And Metal Organic Frameworks (MOFs) are coordination compounds having different dimensional structures formed by coordination of metal ions or metal clusters with organic ligands. Because of the large surface area, high porosity, adjustable structure, rich active sites and other characteristics, the preparation method is reported to be used for photocatalysis antibacterial materials, such as zirconium-based porphyrin MOFs (MOF-545, MOF-525 and the like). In view of the single MOFs material under photoexcitationThe electron-hole pair is easy to compound, the light absorption capacity is poor, and the like, various MOFs compound hybrid photocatalysts (such as AuNR@ZIF-8@AuNC, znAgInSQDs@ZIF-8, au/PCN-224/Cu (II), prussian Blue (PB) @UIO-66-TCPP, agCl/Ag@MOFs and the like) are developed in recent years for constructing binary heterojunction synergistic catalysis to improve the photocatalytic antibacterial performance of MOFs materials, however, porphyrin ligands and zirconium-based MOFs related to the materials are high in cost. Common MOFs materials, such as UiO-66 and UiO-66 (NH 2 ) Although the cost is low, the water stability and the visible light absorption capability are poor, and the carrier separation efficiency is low, so that the photocatalysis antibacterial performance is poor. Therefore, how to develop stable and efficient photocatalytic antibacterial materials by using common low-cost MOFs to the maximum rationalize is a technical problem that needs to be solved in the field at present.
Inspired by marine mussel chemistry, catechol and its derivatives dopamine are widely used in a variety of artificial adhesives or coatings, where polydopamine can be modified on a variety of organic or inorganic surfaces by simple physical interactions or chemical reactions. By utilizing the characteristic, in view of the excellent performance, low cost and visible light absorption capability of the phenolic resin, the development of the phenolic resin nano material with mussel function characteristic can open up unprecedented potential for the diversified design and multifunctional application of the material. In particular, the strong interaction between the material and metal ions provides a precondition for constructing a stable MOFs coating structure on the surface of the material so as to improve the environmental stability of MOFs, which is very important for solving the most common problems in the existing MOF coating, namely the aggregation of the material and the formation of MOF single crystals, and improving the photophysical and photochemical properties of the MOF composite nano material. Based on the method, the efficient heterogeneous photocatalyst with ordered morphology and monodisperse size distribution is skillfully constructed by using mussel chemistry, and is a feasible method. As an inexpensive phenolic resin, catechol-formaldehyde resin (CFR) has many attractive advantages: first, catechol is highly compatible with industrial production due to its low price and can be easily prepared by a simple procedure. Second, metal ions can be effectively sequestered by-OH groups located ortho to CFR. Therefore, the research of constructing the multi-component nano hybrid material by taking the CFR sphere as the template has wide prospect.
Disclosure of Invention
The invention aims to solve the problems of poor stability, poor light absorption capability and easiness in compounding of carriers of the conventional MOFs material, and provides a catechol-formaldehyde resin microsphere photocatalysis hybrid material, a preparation method and application thereof, and the CFR@UiO-66 (NH) constructed by ternary hybridization composite structure 2 )@Ag 2 The S nano hybrid heterojunction photocatalytic material has excellent photocatalytic performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the catechol-formaldehyde resin microsphere photocatalysis hybridization material specifically comprises the following steps:
step one: adding catechol, formaldehyde and ammonia water into water, uniformly mixing, and performing hydrothermal treatment to obtain CFR nano microspheres;
step two: dissolving zirconium tetrachloride and 2-amino terephthalic acid in a solvent, adding the CFR nano microsphere obtained in the first step into the solution, performing ultrasonic dispersion, and stirring for reaction to obtain CFR@UiO-66 (NH) 2 ) Particles;
step three: CFR@UiO-66 (NH) 2 ) Dispersing particles in ethanol by ultrasonic, adding mercaptoethylamine hydrochloride, regulating the pH value of the solution, carrying out reflux reaction, adding silver nitrate, continuing the reflux reaction, and adding an ethanol solution of thioacetamide, and continuing the reflux reaction to obtain the catechol-formaldehyde resin microsphere photocatalysis hybrid material.
Preferably, the mass ratio of the catechol, formaldehyde and ammonia water in the step one is 1 (1.5-2.5) (0.6-1.6), and the concentration of the catechol in the aqueous solution is 2-4 mg/mL.
Preferably, the temperature of the hydrothermal treatment in the step one is 120-160 ℃, and the time of the hydrothermal treatment is 4-8 hours.
Preferably, the mass ratio of the 2-amino terephthalic acid, zirconium tetrachloride and the CFR nano microsphere in the step two is 1 (1.2-1.4) to 0.4-2.
Preferably, the temperature of the stirring reaction in the second step is 120 ℃, and the stirring reaction time is 2-4 hours.
Preferably, the silver nitrate, thioacetamide, mercaptoethylamine hydrochloride and CFR@UiO-66 (NH) 2 ) The mass ratio of the particles is 1 (0.2-0.8): 2: (2-10).
Preferably, the temperature of reflux reaction by adding the mercaptoethylamine hydrochloride in the step three is 80-120 ℃, and the reaction time is 2-4h.
The invention also provides the catechol-formaldehyde resin microsphere photocatalysis hybridization material obtained by the preparation method.
Preferably, the diameter of the catechol-formaldehyde resin microsphere photocatalysis hybridization material is 100-600 nm, uiO-66 (NH) 2 ) Coating the surface of the CFR nano microsphere with the thickness of 10-60 nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
The invention also provides application of the catechol-formaldehyde resin microsphere photocatalysis hybrid material as an antibacterial material.
Principles of the invention
The invention relates to a catechol-formaldehyde resin microsphere photocatalysis hybridization material, a preparation method and application thereof, wherein CFR nano microspheres provide stable supporting environment for MOFs material, ag 2 S nanocrystals and UiO-66 (NH 2 ) Forming a binary heterojunction structure, promoting effective separation of electron-hole pairs in the catalyst, CFR nano-microspheres and Ag 2 The good light absorption of S provides conditions for the photocatalyst to utilize visible light. Meanwhile, ag is oxidized into sulfur by holes in view of the fact that sulfur ions in the chalcogenide semiconductor nanoparticles are easily oxidized into sulfur 2 The hybridized material formed by S encapsulation in MOFs pore canal can not only effectively transfer holes and stabilize sulfur anions in the material and solve the problem that chalcogen semiconductor is easy to be photoetched and unstable, but also promote the close contact of interfaces, and the sulfur anions in the sulfur group semiconductor are stable by energy band matching (Ag 2 Conduction band CB position ratio of S UiO-66 (NH 2 ) More negative) of heterojunction formation providing a strong driving force for the separation of photogenerated carriers, uiO-66 in the heterojunction (NH 2 ) Can be used as an effective electron acceptor to promote the separation of charge carriers generated by photoexcitation. Furthermore, uiO-66 (NH) as Lewis base 2 ) Has a lone pair of electrons that easily form a coordinate bond with a metal ion. Therefore, the metal Ag is effectively inhibited + Is a leak of (2).
The beneficial effects of the invention are that
1. The carrier CFR nano microsphere and Ag provided by the invention 2 S has better visible light absorption, solves the problems of UiO-66 (NH) 2 ) As a single-component photocatalyst, the problem of insufficient visible light capturing capability is solved, and the CFR nano-microsphere can stabilize UiO-66 (NH) 2 ) Improving the environmental stability.
2. The invention utilizes CFR@UiO-66 (NH) 2 ) Porous MOFs in-situ loaded Ag on particle surface 2 S nano-crystal can obtain uniformly dispersed small-size Ag by pore canal domain-limiting effect 2 S nano-crystal, which can prevent aggregation and inhibit metal Ag + Leakage and Ag of (C) 2 And S, photo-etching.
3. The invention is realized by UiO-66 (NH) 2 ) And Ag 2 S nanocrystals are compounded to form a heterojunction, so that the separation of photo-generated electron-hole pairs is promoted, the defect of poor photocatalysis efficiency of single zirconium-based MOFs is greatly overcome, more Reactive Oxygen Species (ROS) are provided by the hybrid catalyst under the irradiation of light, and the synergistic photocatalysis antibacterial effect is enhanced.
4. The CFR@UiO-66 (NH) 2 )@Ag 2 The S photocatalytic hybrid material has the advantages of simple preparation process, mild condition, low cost, wide adjustable range of material structure and performance, stable quality and economy and feasibility.
5. The CFR@UiO-66 (NH) 2 )@Ag 2 Under the irradiation of visible light, the generated ROS of the S photocatalytic hybrid material has high sterilization activity on escherichia coli, staphylococcus aureus, pseudomonas aeruginosa and the like, and has good application prospect in the photocatalytic inactivation of gram-negative bacteria and gram-positive bacteria in a water system.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to these drawings for a person having ordinary skill in the art.
FIG. 1 is a sample of CFR@UiO-66 (NH) prepared in example 1 of the present invention 2 )@Ag 2 S material and X-ray powder diffraction (XRD) pattern of the control sample.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the hybrid material prepared in example 1 of the present invention.
FIG. 3 is a sample of CFR@UiO-66 (NH) prepared in example 1 of the present invention 2 )@Ag 2 Ultraviolet-visible-near infrared diffuse reflection spectrogram of S material.
FIG. 4 is a graph of the prepared CFR@UiO-66 (NH) prepared in example 1 of the present invention 2 )@Ag 2 And a photocatalysis antibacterial performance diagram of the S material after 60 minutes of visible light irradiation.
Detailed Description
The preparation method of the catechol-formaldehyde resin microsphere photocatalysis hybridization material specifically comprises the following steps:
step one: adding catechol, formaldehyde and ammonia water into water, carrying out ultrasonic treatment at room temperature to uniformly mix, carrying out hydrothermal treatment, wherein the temperature of the hydrothermal treatment is preferably 120-160 ℃, the hydrothermal treatment time is preferably 4-8 hours, and after the reaction is finished, obtaining CFR nano microspheres after centrifugal separation, washing by distilled water and absolute ethyl alcohol and vacuum drying of reaction liquid; the mass ratio of the catechol to the formaldehyde to the ammonia water is preferably 1:1.5-2.5:0.6-1.6, and the concentration of the catechol in the aqueous solution is preferably 2-4 mg/mL;
step two: zirconium tetrachloride (ZrCl) 4 ) And 2-amino terephthalic acid (BDC (NH) 2 ) Dissolving in a solvent, preferably N, N-Dimethylformamide (DMF), adding the CFR nano-microspheres prepared in the first step into the solution, and stirring for reaction for 2-4 hours at 120 ℃ after ultrasonic dispersion, wherein the ultrasonic time is preferably 10-20 min; after the reaction, the supernatant was removed by centrifugation, and the solids were treated with DMF and methanol, respectivelyWashing and vacuum drying to obtain CFR@UiO-66 (NH) 2 ) And (3) particles. The mass ratio of the 2-amino terephthalic acid, the zirconium tetrachloride and the CFR nano microsphere is preferably 1 (1.2-1.4): (0.4-2), zrCl 4 The concentration in DMF solvent is preferably 2-3 mg/mL,
step three: CFR@UiO-66 (NH) obtained in the second step 2 ) Dispersing in ethanol by ultrasonic wave, adding mercaptoethylamine hydrochloride, regulating pH value of the solution, reflux reacting at 80-120deg.C, more preferably 100deg.C for 2-4 hr, adding silver nitrate (AgNO) 3 ) Continuously carrying out reflux reaction, wherein the reaction time is preferably 3 hours, dropwise adding an ethanol solution of Thioacetamide (TAA) into the solution, and continuously carrying out reflux reaction, and the reaction time is preferably 3 hours; centrifuging to remove supernatant, washing the solid with ethanol, and vacuum drying to obtain final product CFR@UiO-66 (NH) 2 )@Ag 2 S hybrid material. Said silver nitrate, mercaptoethylamine hydrochloride, thioacetamide and CFR@UiO-66 (NH) 2 ) The mass ratio of the particles is preferably 1 (0.2-0.8): 2 (2-10), more preferably 1:0.6:2: 4, CFR@UiO-66 (NH) 2 ) The concentration of the particles in ethanol is preferably 0.5-1.5 mg/mL, solution ph=8-9.
The invention also provides the catechol-formaldehyde resin microsphere photocatalysis hybridization material CFR@UiO-66 (NH) obtained by the preparation method 2 )@Ag 2 S, S. The diameter of the catechol-formaldehyde resin microsphere photocatalysis hybridization material is 100-600 nm, uiO-66 (NH) 2 ) Coating the surface of the CFR nano microsphere with the thickness of 10-60 nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
The invention also provides application of the catechol-formaldehyde resin microsphere photocatalysis hybrid material as an antibacterial material. The prepared hybrid material is used for catalyzing and inactivating escherichia coli, staphylococcus aureus and pseudomonas aeruginosa by visible light.
According to the invention, the conditions for sterilizing the photocatalytic antibacterial material are preferably: CFR@UiO-66 (NH) 2 )@Ag 2 S dosage is 100 mug/mLThe volume of the bacterial liquid) and the concentration of the bacterial liquid is 2 multiplied by 10 6 CFU/mL, simulated visible light irradiation time was 30 minutes.
For a better understanding of the present invention, the present invention will be described in further detail below with reference to the drawings and examples. The following examples are carried out on the basis of the technology of the present invention and are only used for clearly and thoroughly describing the embodiments and operation steps of the present invention, but the scope of protection of the present invention is not limited to the following examples.
Example 1
S1, preparing CFR nano microspheres:
adding 0.2 g catechol, 0.28 mL formaldehyde solution (37 wt%) and 0.22 mL ammonia (25 wt%) into 60 mL distilled water, and ultrasonic treating at room temperature for 5-10 min to obtain a uniform mixture; transferring the mixed solution into a high-pressure hydrothermal kettle, and reacting for 6 hours at 160 ℃; after the reaction is finished, the reaction solution is centrifugally separated at 8000 rpm, washed by distilled water and absolute ethyl alcohol and dried in vacuum to obtain brown CFR nano-microspheres.
S2、CFR@ UiO-66(NH 2 ) Preparing particles:
0.32. 0.32 g zirconium tetrachloride (ZrCl) was weighed out 4 ) And 0.24 g of 2-amino terephthalic acid (BDC (NH) 2 ) Dissolving in 120 mL of N, N-Dimethylformamide (DMF); adding 0.2 g of newly prepared CFR nano-microspheres into the solution, performing ultrasonic dispersion for 10 minutes, and stirring at 120 ℃ for reaction for 2 hours; after the reaction is finished, centrifuging at 5000 rpm for 10 min, separating and removing supernatant, washing the solid with DMF and methanol respectively, and vacuum drying to obtain CFR@UiO-66 (NH) 2 ) And (3) particles.
S3、CFR@UiO-66(NH 2 )@Ag 2 S hybridized material preparation:
10 mg CFR@UiO-66 (NH 2 ) Ultrasonically dispersing in 30 mL ethanol, then adding 5 mg mercaptoethylamine hydrochloride and adjusting the pH of the solution to be 8-9, and refluxing at 80 ℃ for 3 hours; adding 2.5. 2.5 mg silver nitrate (AgNO) into the solution 3 ) And continuing reflux reaction for 1 hour at 80 ℃; 1.5. 1.5 mg Thioacetamide (TAA) was dissolved in 1.0. 1.0 mL ethanol and added dropwise to the above solution to continue reflux reaction at 80℃for 1 hour; after the reaction, the mixture was centrifuged at 8000 rpm for 10 min to separateRemoving supernatant, washing the obtained solid with ethanol, and vacuum drying to obtain final product CFR@UiO-66 (NH) 2 )@Ag 2 S hybrid material.
CFR@UiO-66 (NH) prepared in example 1 2 )@Ag 2 The diameter of the S hybrid material is 200-400 nm, uiO-66 (NH) 2 ) Coating the surface of CFR nano microsphere with a thickness of about 30 and nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
FIG. 1 is a CFR@UiO-66 (NH) prepared in example 1 2 )@Ag 2 S hybrid material and X-ray powder diffraction (XRD) pattern of control. As can be seen from the figure, uiO-66 (NH 2 ) Successfully coated on CFR nano-microspheres and Ag 2 S nanocrystalline in situ formation in CFR@UiO-66 (NH) 2 ) And (3) upper part.
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the nanomaterial prepared in example 1, wherein FIG. (a) represents CFR nanospheres and FIG. (b) represents CFR@UiO-66 (NH) 2 ) Graph (c) represents CFR@UiO-66 (NH) 2 )@Ag 2 S hybrid material. As can be seen from the figure, uiO-66 (NH 2 ) The shell layer thickness coated on CFR is about 30nm (white arrow in the figure represents the thickness of coating), while Ag 2 S nanocrystalline was successfully introduced into CFR@UiO-66 (NH) 2 ) The upper MOF is arranged in the pore canal.
FIG. 3 is a CFR@UiO-66 (NH) prepared in example 1 2 )@Ag 2 Ultraviolet-visible-near infrared diffuse reflection spectrogram of the S hybridized material. As can be seen from the figure, with UiO-66 (NH 2 ) In contrast, CFR nanomicrospheres and Ag 2 S nanocrystals all had broader visible light absorption, while CFR@UiO-66 (NH 2 )@Ag 2 The S hybrid material generates stronger visible light absorption due to the synergistic effect of different components, which is beneficial to photocatalysis.
Example 2
S1, preparing CFR nano microspheres:
adding 0.2 g catechol, 0.45 mL formaldehyde solution (37 wt%) and 0.15 mL ammonia (25 wt%) into 60 mL distilled water, and ultrasonic treating at room temperature for 10 min to obtain a uniform mixture; transferring the mixed solution into a high-pressure hydrothermal kettle, and reacting for 8 hours at 140 ℃; after the reaction is finished, the reaction solution is centrifugally separated at 8000 rpm, washed by distilled water and absolute ethyl alcohol and dried in vacuum to obtain brown CFR nano-microspheres.
S2、CFR@ UiO-66(NH 2 ) Preparing particles:
0.32. 0.32 g zirconium tetrachloride (ZrCl) was weighed out 4 ) And 0.24 g of 2-amino terephthalic acid (BDC (NH) 2 ) Dissolving in 120 mL of N, N-Dimethylformamide (DMF); adding 0.2 g of newly prepared CFR nano-microspheres into the solution, performing ultrasonic dispersion for 10 minutes, and stirring at 120 ℃ for reaction for 3 hours; after the reaction is finished, centrifuging at 5000 rpm for 10 min, separating and removing supernatant, washing the solid with DMF and methanol respectively, and vacuum drying to obtain CFR@UiO-66 (NH) 2 ) And (3) particles.
S3、CFR@UiO-66(NH 2 )@Ag 2 S hybridized material preparation:
20 mg of CFR@UiO-66 (NH 2 ) Ultrasonically dispersing in 20 mL ethanol, then adding 10 mg mercaptoethylamine hydrochloride and adjusting the pH of the solution to be 8-9, and refluxing at 80 ℃ for 3 hours; adding 5 mg silver nitrate (AgNO) into the solution 3 ) And continuing reflux reaction for 1 hour at 80 ℃; 2.0. 2.0 mg Thioacetamide (TAA) was dissolved in 1.0 mL ethanol and added dropwise to the above solution to continue reflux reaction at 80℃for 1 hour; after the reaction is finished, centrifuging at 8000 rpm for 10 min, separating and removing supernatant, washing the obtained solid by ethanol, and vacuum drying to obtain a final product CFR@UiO-66 (NH) 2 )@Ag 2 S hybrid material.
CFR@UiO-66-NH prepared in example 2 2 @Ag 2 The diameter of the S hybrid material is about 200 nm, uiO-66 (NH 2 ) Coating the surface of the CFR nano microsphere with the thickness of about 15 and nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
Example 3
S1, preparing CFR nano microspheres:
adding 0.2 g catechol, 0.40 mL formaldehyde solution (37 wt%) and 0.35 mL ammonia (25 wt%) into 60 mL distilled water, and ultrasonic treating at room temperature for 10 min to obtain a uniform mixture; transferring the mixed solution into a high-pressure hydrothermal kettle, and reacting for 4 hours at 160 ℃; after the reaction is finished, the reaction solution is centrifugally separated at 8000 rpm, washed by distilled water and absolute ethyl alcohol and dried in vacuum to obtain brown CFR nano-microspheres.
S2、CFR@ UiO-66(NH 2 ) Preparing particles:
0.32. 0.32 g zirconium tetrachloride (ZrCl) was weighed out 4 ) And 0.24 g of 2-amino terephthalic acid (BDC (NH) 2 ) Dissolving in 120 mL of N, N-Dimethylformamide (DMF); adding 0.2 g of newly prepared CFR nano-microspheres into the solution, performing ultrasonic dispersion for 10 minutes, and stirring at 120 ℃ for reaction for 2 hours; after the reaction is finished, centrifuging at 5000 rpm for 10 min, separating and removing supernatant, washing the solid with DMF and methanol respectively, and vacuum drying to obtain CFR@UiO-66 (NH) 2 ) And (3) particles.
S3、CFR@UiO-66(NH 2 )@Ag 2 S hybridized material preparation:
20 mg of CFR@UiO-66 (NH 2 ) Ultrasonically dispersing in 20 mL ethanol, then adding 10 mg mercaptoethylamine hydrochloride and adjusting the pH of the solution to be 8-9, and refluxing at 80 ℃ for 3 hours; adding 5 mg silver nitrate (AgNO) into the solution 3 ) And at 80 o C, continuing reflux reaction for 1 hour; 2.0. 2.0 mg Thioacetamide (TAA) was dissolved in 1.0 mL ethanol and added dropwise to the above solution to continue reflux reaction at 80℃for 1 hour; after the reaction is finished, centrifuging at 8000 rpm for 10 min, separating and removing supernatant, washing the obtained solid by ethanol, and vacuum drying to obtain a final product CFR@UiO-66 (NH) 2 )@Ag 2 S hybrid material.
CFR@UiO-66 (NH) prepared in example 3 2 )@Ag 2 The diameter of the S hybrid material is 400-600 nm, uiO-66 (NH) 2 ) Coating the surface of CFR nano microsphere with a thickness of about 50 and nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
Example 4
CFR@UiO-66 (NH) prepared in example 1 was used 2 )@Ag 2 The S hybrid material inactivated gram negative E.coli (E.coli, source of Haibo organism, model ATCC 25922) and gram positive Staphylococcus aureus (S.aureus,the source is a biological technology, and the model is ATCC 25923). The specific application process is as follows:
the growth of E.coli or Staphylococcus aureus was studied using plate counting. The dishes and media were autoclaved and sterilized prior to the antimicrobial test. Adding a certain amount of bacteria into the newly prepared LB medium, culturing at 37deg.C under shaking at 200rpm overnight, and measuring bacterial concentration by colony counting method to about 2×10 7 CFU/mL. Then centrifuged, washed with sterile Phosphate Buffer (PBS) (ph=7.4) and diluted to 2×10 6 CFU/mL。
The experimental process is divided into an experimental group light group and a Dark control group Dark group;
experimental group light group: bacterial suspension (180. Mu.L, 2X 10 6 CFU/mL) and antibacterial material CFR@UiO-66 (NH) 2 )@Ag 2 S (20. Mu.L, 1 mg/mL) was added to a 96-well plate and a blank Control (Control) without antimicrobial material was replaced with sterilized PBS. Finally, the concentration of the antibacterial material in the system is 100 mu g/mL. Mixing antibacterial material and bacterial suspension to obtain bacterial solution, and using white light LED lamp (400-830 nm,100 mW/cm 2 ) After the bacterial solution is irradiated for 60min and the reaction is finished, the bacterial solution is diluted by 100 times and is coated on an AGAR plate of 50 mu L, and after 24 h culture in a constant temperature incubator at 37 ℃, the antibacterial activity of the nano hybrid material is measured by adopting a plate colony counting method. To be matched with the prepared antibacterial material CFR@UiO-66 (NH) 2 )@Ag 2 S is compared with three control materials CFR, uiO-66 (NH 3 ) And Ag 2 S an antibacterial test was also performed according to the same procedure as above.
Dark control Dark group: bacterial suspension (180. Mu.L, 2X 10 6 CFU/mL) and antibacterial material CFR@UiO-66 (NH) 2 )@Ag 2 S (20. Mu.L, 1 mg/mL) was added to a 96-well plate and a blank Control (Control) without antimicrobial material was replaced with sterilized PBS. Finally, the concentration of the antibacterial material in the system is 100 mu g/mL. Uniformly mixing antibacterial material with bacterial suspension to obtain bacterial solution, culturing bacterial solution under dark condition for 60min, and finishing reactionAfter that, the bacterial solution was diluted 100 times, smeared onto 50. Mu.L of AGAR plates, and after 24-h culture in a constant temperature incubator at 37 ℃, the antibacterial activity of the nano hybrid material was determined by a plate colony counting method. To be matched with the prepared antibacterial material CFR@UiO-66 (NH) 2 )@Ag 2 S is compared with three control materials CFR, uiO-66 (NH 3 ) And Ag 2 S an antibacterial test was also performed according to the same procedure as above.
FIG. 4 is a sample of CFR@UiO-66 (NH) prepared in example 1 2 )@Ag 2 Photocatalytic antibacterial performance diagram of S hybrid material after 60min of visible light irradiation: FIG. (a) represents E.coli and FIG. (b) represents Staphylococcus aureus. FIG. 4a shows that the materials CFR, uiO-66 (NH) 3 )、Ag 2 S has a certain activity against E.coli, but is less than 50%, and under the same experimental conditions CFR@UiO-66 (NH 2 )@Ag 2 The S antibacterial property reaches more than 99%, and meanwhile, the comparison of the light group and the Dark group shows that the CFR@UiO-66 (NH 2) @Ag2S nano material has almost no antibacterial activity under the Dark condition. FIG. 4b shows that the materials CFR, uiO-66 (NH) 3 )、Ag 2 S has a certain anti-staphylococcus aureus activity, but is lower than 40%, and under the same experimental conditions, CFR@UiO-66 (NH 2 )@Ag 2 The antibacterial activity of S reaches more than 99 percent. Meanwhile, the light group is compared with the Dark group, and the CFR@UiO-66 (NH 2) @Ag2S nanomaterial has almost no antibacterial activity under Dark conditions.
The foregoing is only illustrative of the preferred embodiments of the present invention, but the scope of the invention is not limited thereto, and any equivalent or modified embodiments according to the technical scheme and the inventive concept of the present invention are still included in the scope of the present invention without departing from the technical scope of the present invention disclosed in the present invention.
Claims (10)
1. The preparation method of the catechol-formaldehyde resin microsphere photocatalysis hybridization material is characterized by comprising the following steps:
step one: adding catechol, formaldehyde and ammonia water into water, uniformly mixing, and performing hydrothermal treatment to obtain CFR nano microspheres;
step two: dissolving zirconium tetrachloride and 2-amino terephthalic acid in a solvent, adding the CFR nano microsphere obtained in the first step into the solution, performing ultrasonic dispersion, and stirring for reaction to obtain CFR@UiO-66 (NH) 2 ) Particles;
step three: CFR@UiO-66 (NH) 2 ) Dispersing particles in ethanol by ultrasonic, adding mercaptoethylamine hydrochloride, regulating the pH value of the solution, carrying out reflux reaction, adding silver nitrate, continuing the reflux reaction, and adding an ethanol solution of thioacetamide, and continuing the reflux reaction to obtain the catechol-formaldehyde resin microsphere photocatalysis hybrid material.
2. The preparation method of the catechol-formaldehyde resin microsphere photocatalysis hybridization material according to claim 1, characterized in that in the step one, the mass ratio of catechol, formaldehyde and ammonia water is 1 (1.5-2.5): (0.6-1.6), and the concentration of catechol in aqueous solution is 2-4 mg/mL.
3. The method for preparing catechol-formaldehyde resin microsphere photocatalytic hybrid material of claim 1, wherein the temperature of the hydrothermal treatment in the step one is 120-160 ℃, and the time of the hydrothermal treatment is 4-8 hours.
4. The preparation method of the catechol-formaldehyde resin microsphere photocatalysis hybridization material according to claim 1, which is characterized in that the mass ratio of the 2-amino terephthalic acid, zirconium tetrachloride and CFR nanometer microsphere in the second step is 1 (1.2-1.4): 0.4-2.
5. The method for preparing catechol-formaldehyde resin microsphere photocatalytic hybrid material of claim 1, wherein the temperature of the stirring reaction in the second step is 120 ℃, and the stirring reaction time is 2-4 hours.
6. The method for preparing catechol-formaldehyde resin microsphere photocatalytic hybrid material of claim 1, wherein the silver nitrate, thioacetamide, mercaptoethylamine hydrochloride and cfr@uio-66 (NH 2 ) The mass ratio of the particles is 1 (0.2-0.8): 2: (2-10).
7. The method for preparing catechol-formaldehyde resin microsphere photocatalysis hybridization material according to claim 1, characterized in that the temperature of the reflux reaction carried out by adding mercaptoethylamine hydrochloride in the step three is 80-120 ℃, and the reaction time is 2-4h.
8. The catechol-formaldehyde resin microsphere photocatalytic hybrid material obtained by the preparation method of claim 1.
9. The catechol-formaldehyde resin microsphere photocatalytic hybrid material of claim 8, wherein the catechol-formaldehyde resin microsphere photocatalytic hybrid material has a diameter of 100-600 nm, uio-66 (NH 2 ) Coating the surface of the CFR nano microsphere with the thickness of 10-60 nm, and generating Ag in situ in MOFs pore canal 2 The nano-size of the S nano-crystal is smaller than 10nm.
10. Use of the catechol-formaldehyde resin microsphere photocatalytic hybrid material of claim 8 as an antibacterial material.
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