CN114950498B - Recyclable efficient photocatalytic material and preparation method and application thereof - Google Patents
Recyclable efficient photocatalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114950498B CN114950498B CN202210531858.5A CN202210531858A CN114950498B CN 114950498 B CN114950498 B CN 114950498B CN 202210531858 A CN202210531858 A CN 202210531858A CN 114950498 B CN114950498 B CN 114950498B
- Authority
- CN
- China
- Prior art keywords
- photocatalytic material
- preparation
- recyclable
- agcl
- efficiency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 33
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000001768 cations Chemical group 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 6
- 239000005017 polysaccharide Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000012412 chemical coupling Methods 0.000 claims abstract description 5
- 150000004676 glycans Chemical class 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 13
- 229940043267 rhodamine b Drugs 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 11
- 229940012189 methyl orange Drugs 0.000 claims description 11
- 235000010413 sodium alginate Nutrition 0.000 claims description 11
- 239000000661 sodium alginate Substances 0.000 claims description 11
- 229940005550 sodium alginate Drugs 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- 239000004098 Tetracycline Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229960002180 tetracycline Drugs 0.000 claims description 8
- 229930101283 tetracycline Natural products 0.000 claims description 8
- 235000019364 tetracycline Nutrition 0.000 claims description 8
- 150000003522 tetracyclines Chemical class 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 235000010408 potassium alginate Nutrition 0.000 claims description 4
- 239000000737 potassium alginate Substances 0.000 claims description 4
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- -1 alginate ions Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229940072056 alginate Drugs 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a recyclable efficient photocatalytic material, a preparation method and application thereof, wherein the recyclable efficient photocatalytic material is prepared by introducing graphene oxide material, utilizing the property that an anionic natural high polymer polysaccharide aqueous solution and divalent cations form stable gel, adopting a chemical coupling and in-situ deposition method to load AgCl, and then adopting a photo-induced reduction method to prepare the Ag@AgCl/GO photocatalytic material. The photocatalytic material has great application potential in actual photocatalyst production.
Description
Technical Field
The invention relates to a photocatalytic material and a preparation method and application thereof, in particular to a recyclable efficient photocatalytic material and a preparation method and application thereof.
Background
In recent years, ag@AgCl plasma photocatalysts have attracted a great deal of attention. Ag@AgCl refers to the single-state Ag decomposed by AgCl under the illumination condition 0 The Ag@AgCl photocatalyst is a novel visible light catalytic material based on the nano metal surface plasma effect and the semiconductor photocatalytic effect. Although Ag@AgCl plasma has good photocatalytic activity, the AgCl has poor photochemical stability, is easy to agglomerate, and has high photo-generated electron-hole recombination rate. Therefore, its application in photocatalytic research is limited.
Graphene Oxide (GO) is a novel carbon-based material, is a single-layer graphene sheet composed of oxygen-containing functional groups such as carboxyl, hydroxyl and epoxy groups, has a wrinkled surface, is a derivative of graphene, has excellent hydrophilicity, larger specific surface area, low toxicity and other characteristics, and a composite material formed by the Graphene Oxide (GO) and a photocatalyst is greatly concerned in the fields of photocatalysis and the like, such as GO and TiO 2 、Ag 3 PO 4 、BiOI、BiVO 4 、ZnO。
2018 patent CN201410492455.X discloses a method for preparing Ag@AgCl/GO self-cleaning surface Raman enhanced substrate. The Ag@AgCl sol is obtained after the AgCl sol is insulated for 12-36 hours at 160-180 ℃ in an autoclave, and then the Ag@AgCl/GO composite film is obtained by self-assembling Ag@AgCl nano particles with positive charges by utilizing the characteristic that GO is negatively charged and strong adsorption function and template effect and is applied to a self-cleaning Raman enhanced substrate. The 2020 patent CN111905774A discloses a method for preparing a photocatalyst for degrading methyl orange, which comprises the steps of adding a certain amount of TiO 2 At the height of the tube furnace Wen Dedao C-TiO 2 Then a proper amount of silver nitrate is addedAmmonia water, C-TiO 2 Adding GO into a container, adding an acidic solution and an alcohol solution successively, and obtaining a catalyst Ag/AgCl/C-TiO through visible light irradiation 2 /GO。
At present, some of the prepared GO-supported Ag@AgCl composite photocatalytic materials are complex in preparation process, some of the prepared GO-supported Ag@AgCl composite photocatalytic materials are required to be calcined at high temperature, some of the prepared GO-supported Ag@AgCl composite photocatalytic materials are difficult to separate from water, recycling is difficult, and secondary pollution is easy to cause.
Disclosure of Invention
The invention aims to: the invention aims to provide a recyclable efficient photocatalytic material, a preparation method and application thereof, and the problem that a powder catalyst is difficult to separate and recycle is effectively solved. The invention also aims to provide a preparation method of the recyclable efficient photocatalytic material. The invention also aims to provide the application of the recyclable high-efficiency photocatalytic material in preparing water body cleaning agents.
The technical scheme is as follows: the recyclable efficient photocatalytic material is prepared by introducing graphene oxide material, utilizing the property that an anionic natural high molecular polysaccharide aqueous solution and divalent cations form stable gel, adopting a chemical coupling and in-situ deposition method to load AgCl, and adopting a photo-induced reduction method to prepare the Ag@AgCl/GO photocatalytic material.
The anionic natural high molecular polysaccharide is sodium alginate or potassium alginate.
The recyclable high-efficiency photocatalytic material, and the divalent cations are selected from Ca 2+ 、Cu 2+ Or Zn 2+ Preferably Ca 2+ 。
The preparation method of the recyclable efficient photocatalytic material comprises the following steps of:
(1) Adding sodium alginate or potassium alginate solution into graphene oxide dispersion liquid, and performing ultrasonic dispersion to fully mix;
(2) Adding cetyltrimethylammonium bromide into the mixed solution obtained in the step (2), and performing ultrasonic dispersion; due to the action of hydrogen bonds and the surfactant action of CTAB, alginate ions will be adsorbed on GO.
(3) AgNO is slowly added dropwise under stirring 3 After the solution is added, stirring is continued; positively charged silver ions (Ag due to electrostatic attraction + ) Will attract negatively charged alginate ions and carboxylate groups (-COO-) on GO, thereby making Ag + Is tightly enclosed inside the GO.
(4) Slowly dropwise adding CaCl into the mixed suspension obtained in the step (3) under stirring 2 Forming insoluble small particles from the solution, stirring and standing; by Ca 2+ And AgCl precipitates to form insoluble small particles.
(5) Filtering the product obtained in the step (4) by using gauze, washing the obtained small-particle precipitate by using water, adding the small-particle precipitate into a container, adding water, stirring, placing under the irradiation of sun light or under the irradiation of a xenon lamp light source, filtering by using gauze, washing by using water, and performing vacuum freeze-drying to obtain the Ag@AgCl/GO photocatalytic material.
The preparation method of the recyclable efficient photocatalytic material comprises the step of preparing the gauze from double layers of gauze.
The recyclable efficient photocatalytic material is applied to preparation of water body cleaning agents.
The recyclable efficient photocatalytic material is applied to preparation of a photocatalyst.
The recyclable high-efficiency photocatalytic material is applied to degradation of rhodamine B, methylene blue and methyl orange.
The recyclable high-efficiency photocatalytic material is applied to the degradation of tetracycline.
The high-efficiency visible light catalytic material which is easy to separate and capable of being recycled, prepared by the invention, effectively solves the problem that the powder catalyst is difficult to separate and recycle. Aiming at the problems of poor light stability and difficult recovery of AgCl, the invention introduces Graphene Oxide (GO) material and utilizes anionic natural polymer polysaccharide Sodium Alginate (SA) aqueous solution and divalent cations (such as Ca) 2+ ) Can form stable gel, adopts chemical coupling and in-situ deposition to load AgCl, and adopts a photo-induced reduction methodThe Ag@AgCl/GO insoluble particle photocatalytic material is prepared and then used for treating pollutants such as dye wastewater, antibiotic wastewater and the like. The photocatalytic material is in a small particle shape, has high photocatalytic efficiency, wide visible light wave response range, is easy to separate from water phase and can be recycled.
The invention mainly solves the problems of poor photochemical stability, easy agglomeration, insufficient adsorption capacity and difficult recycling of AgCl. By introducing Graphene Oxide (GO) material and using Sodium Alginate (SA) aqueous solution and divalent cations (such as Ca 2+ ) Can form stable gel, adopts chemical coupling and in-situ deposition method to load AgCl, and prepares Ag@AgCl/GO insoluble particle photocatalytic material by a photo-induced reduction method. The photocatalytic material is in a small particle shape, has the advantages of simple preparation process, strong adsorption capacity, short photocatalytic degradation time, high catalytic efficiency, easy recycling, and the like, and can be used for degrading various organic pollution wastewater in practice.
The beneficial effects are that: (1) The preparation process is simple, excessive equipment investment is not required, and the preparation process can be obtained without complex technical means and process conditions. (2) The absorption band is wider in response to both ultraviolet and visible light, especially in visible light. (3) Has better catalytic effect on various organic pollutants, high catalytic efficiency and short catalytic time, and the first-order reaction dynamics fitting shows that the photocatalytic degradation rate constants (k) of the catalytic material on rhodamine B (RhB), methylene Blue (MB) and Methyl Orange (MO) are 0.5381min respectively -1 、0.4989min -1 0.2573min -1 . (4) The catalytic material is in a small particle shape, is easy to recycle and has good stability, and the composite material still has a decoloration rate of more than 91.0% for RhB after being recycled for 5 times. The catalyst material has good photocatalytic stability and reusability, and has great potential in practical production as a visible light catalyst.
Drawings
FIG. 1 is a diagram of the morphology of a catalyst catalytic material as observed by a high resolution field emission Scanning Electron Microscope (SEM);
FIG. 2 is a view of a morphology of a catalyst catalytic material as observed by a Transmission Electron Microscope (TEM);
FIG. 3 is an EDS diagram of a catalytic material;
FIG. 4 is an infrared spectrum of a catalytic material;
FIG. 5 is a Raman spectrum of the catalytic material;
FIG. 6 is a graph of the specific surface area of a catalytic material;
FIG. 7 is a graph of pore size distribution of a catalytic material;
FIG. 8 is an ultraviolet-visible spectrum of photocatalytic material for RhB degradation;
FIG. 9 is an ultraviolet-visible spectrum of photocatalytic material versus MB degradation;
FIG. 10 is an ultraviolet-visible spectrum of photocatalytic material for MO degradation;
FIG. 11 is a cycle stability test curve for photocatalytic material RhB degradation;
FIG. 12 is an ultraviolet-visible spectrum of a photocatalytic material for tetracycline degradation.
Detailed Description
Example 1
Preparation of Ag@AgCl/GO
1. 60mL of Graphene Oxide (GO) dispersion liquid with the concentration of 1g/L is taken, 3mL of Sodium Alginate (SA) solution with the concentration of 4g/L is added, and ultrasonic dispersion is carried out for 15min to fully mix the GO dispersion liquid and the SA solution.
2. 1.5mL of cetyltrimethylammonium bromide (CTAB) with the concentration of 10g/L is added into the mixed solution, and ultrasonic dispersion is carried out for 30min, so that alginate ions can be adsorbed on GO due to the action of hydrogen bonds and the action of a surfactant of CTAB.
3. Slowly dropwise adding AgNO with the concentration of 50g/L under magnetic stirring 3 9mL of solution, after the dripping is finished, continuing to magnetically stir for 20min. Positively charged silver ions (Ag due to electrostatic attraction + ) Will attract negatively charged alginate ions and carboxylate groups (-COO-) on GO, thereby making Ag + Is tightly enclosed inside the GO.
4. Slowly dropwise adding 9mLCaCl into the mixed suspension under magnetic stirring 2 Solution using Ca 2+ Is further formed into insoluble small particles, caCl, by cross-linking and AgCl precipitation 2 The concentration of the solution is 20g/L, and the solution is kept stand for 24 hours after being magnetically stirred for 30 min.
5. Filtering with double-layer gauze, washing the obtained small particle precipitate with deionized water for 5 times, adding the small particle precipitate into a 250mL triangular flask, adding 50mL deionized water, and irradiating under magnetic stirring for 30min under sun light or under 350W xenon lamp light source for 1h. Filtering with double-layer gauze, washing the obtained particles with deionized water for 3 times, and vacuum freeze-drying to obtain the Ag@AgCl/GO photocatalytic material.
Example 2
The photocatalytic material obtained in example 1 was observed by a high-resolution field emission Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), respectively, and the results are shown in fig. 1 and 2. FIG. 3 shows the result of EDS measurement of the photocatalytic material prepared in example 1, and FIG. 3 shows the result of IR spectrum measurement of the photocatalytic material prepared in example 1, and FIG. 4 shows the result of Raman spectrum measurement of the photocatalytic material prepared in example 1, and FIG. 5 shows the result of Raman spectrum measurement. The specific surface area of the catalytic material was measured, and the result is shown in fig. 6. The pore size distribution of the catalytic material was measured and the result is shown in fig. 7.
Example 3
0.2g of the prepared photocatalytic material is taken and added into a triangular flask containing 50mL of deionized water, rhodamine B (RhB) is added to enable the concentration of the photocatalytic material to be 10mg/L, the pH value is adjusted to be 6.5, the temperature is controlled to be 40 ℃, the photocatalytic material is firstly adsorbed for 30min under magnetic stirring in dark, then the photocatalytic material is placed at a visible light position of a 350W xenon lamp and is irradiated for 10min under magnetic stirring, the distance from a light source to the liquid level is 2cm, and the adsorption and degradation conditions of the photocatalytic material to RhB are shown in figure 8. The characteristic absorption of RhB at 554nm (electron transition of N- & gtpi- & gton C=O, C=N) and 270nm (electron transition of pi- & gtpi- & gton benzene ring) in ultraviolet region, the maximum absorption peak in the visible region is rapidly reduced along with the extension of reaction time, which shows that the chromogenic groups of phenylamino and carbonyl bond are gradually destroyed, and the main structural substances of RhB are completely decomposed after 10 min.
Example 4
0.2g of the prepared photocatalytic material is taken and added into a triangular flask containing 50mL of deionized water, methylene Blue (MB) is added to ensure that the concentration of the photocatalytic material is 10mg/L, the pH value is regulated to 6.5, the temperature is controlled to be 40 ℃, the photocatalytic material is firstly adsorbed for 30min under magnetic stirring at the dark place, then the photocatalytic material is placed at a visible light place of a 350W xenon lamp, the photocatalytic material is irradiated for 10min under magnetic stirring, the light source is 2cm away from the liquid level, and the degradation condition is shown in figure 9.MB has characteristic absorption peaks at 664, 609, 291.8 and 246.4nm, wherein 664nm and 291.8nm respectively correspond to absorption peaks generated by super-large conjugated structure of MB and pi-pi transition of benzene ring. After 10min, these characteristic absorption peaks disappeared, indicating that MB in the wastewater had been degraded after the reaction.
Example 5
0.2g of the prepared photocatalytic material is taken and added into a triangular flask containing 50mL of deionized water, methyl Orange (MO) is added to ensure that the concentration is 10mg/L, the pH value is regulated to 6.5, the temperature is controlled to be 40 ℃, the photocatalytic material is firstly adsorbed for 30min under magnetic stirring at the dark place, then the photocatalytic material is placed at a visible light place of a 350W xenon lamp, the photocatalytic material is irradiated for 12min under magnetic stirring, the light source is 2cm away from the liquid level, and the degradation condition is shown in figure 10.MO has characteristic absorption peaks at 465.2nm and 271.6nm, which are respectively absorption peaks generated by-n=n-azo chromogenic groups of MO and benzene ring conjugated systems. Along with the extension of the catalytic degradation reaction time, 2 absorption peaks are continuously weakened, and after 12 minutes, no obvious absorption peaks exist in the visible region and the ultraviolet region, which indicates that MO is subjected to catalytic degradation.
Example 6
0.1g of the prepared photocatalytic material is taken and added into a triangular flask containing 50mL of deionized water, rhB is added to ensure that the concentration of the photocatalytic material is 10mg/L, the pH value is regulated to 6.5, the temperature is controlled to 40 ℃, and the photocatalytic material is magnetically stirred and placed under the irradiation of a 350W xenon lamp visible light for 20min. The particles obtained after filtration were washed with deionized water 2 times, and the above-mentioned operations were repeated, and the degradation effect after 5 cycles of use was as shown in fig. 11. After 5 times of recycling, the photocatalytic material still has a degradation rate of more than 90.0% to RhB, which indicates that the photocatalytic material has good photocatalytic stability and reusability.
Example 7
Adding 0.2g of the prepared photocatalytic material into 2 triangular flasks containing 50mL of deionized water, adding tetracycline to a concentration of 10mg/L, adjusting pH to 6.5, and controlling the temperature at 40deg.C before darkeningAfter 30min of adsorption under magnetic stirring, 1 bottle of hydrogen peroxide (H) with the concentration of 30% (w/w) is added 2 O 2 ) 0.2mL, and the other bottle is not added with hydrogen peroxide and is simultaneously placed at the visible light position of a 350W xenon lamp, and is irradiated for 20min under magnetic stirring, the light source is 2cm away from the liquid level, and the adsorption and degradation conditions are shown in figure 12. When the light is irradiated for 20min, H is not added 2 O 2 The tetracycline showed a weak absorption peak at 267nm, indicating that a small amount of aromatic ring A structure was still present, while a small amount of H was added to the system 2 O 2 Peaks at 267nm and 355nm (aromatic rings B-D with chromophores attached thereto) for tetracycline disappeared, indicating complete degradation of the tetracycline.
Claims (7)
1. The preparation method of the recyclable efficient photocatalytic material is characterized by comprising the steps of introducing graphene oxide material, utilizing the property that an anionic natural high-molecular polysaccharide aqueous solution and divalent cations form stable gel, adopting chemical coupling and in-situ deposition to load AgCl, and preparing the Ag@AgCl/GO photocatalytic material through photo-induced reduction; the anionic natural high molecular polysaccharide is sodium alginate or potassium alginate; the divalent cation is Ca 2+ The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the following steps:
(1) Adding sodium alginate or potassium alginate solution into graphene oxide dispersion liquid, and performing ultrasonic dispersion to fully mix;
(2) Adding cetyltrimethylammonium bromide into the mixed solution obtained in the step (1), and performing ultrasonic dispersion;
(3) AgNO is slowly added dropwise under stirring 3 After the solution is added, stirring is continued;
(4) Slowly dropwise adding CaCl into the suspension obtained in the step (3) under stirring 2 Forming insoluble small particles from the solution, stirring and standing;
(5) Filtering the product obtained in the step (4) by using gauze, washing the obtained small-particle precipitate by using water, adding the small-particle precipitate into a container, adding water, stirring, placing under the irradiation of sun light or under the irradiation of a xenon lamp light source, filtering by using gauze, washing by using water, and performing vacuum freeze-drying to obtain the Ag@AgCl/GO photocatalytic material.
2. The method for preparing a recyclable efficient photocatalytic material according to claim 1, wherein the gauze is a double-layered gauze.
3. The use of the recyclable high-efficiency photocatalytic material obtained by the preparation method of the recyclable high-efficiency photocatalytic material in the preparation of a water body cleaner.
4. The use of the recyclable high-efficiency photocatalytic material obtained by the preparation method of the recyclable high-efficiency photocatalytic material in the preparation of a photocatalyst.
5. The application of the recyclable high-efficiency photocatalytic material obtained by the preparation method of the recyclable high-efficiency photocatalytic material in the degradation of rhodamine B, methylene blue and methyl orange.
6. The use of the recyclable high-efficiency photocatalytic material obtained by the preparation method of the recyclable high-efficiency photocatalytic material in the degradation of tetracycline.
7. The application of the recyclable high-efficiency photocatalytic material obtained by the preparation method of the recyclable high-efficiency photocatalytic material in combination with hydrogen peroxide in the degradation of tetracycline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210531858.5A CN114950498B (en) | 2022-05-16 | 2022-05-16 | Recyclable efficient photocatalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210531858.5A CN114950498B (en) | 2022-05-16 | 2022-05-16 | Recyclable efficient photocatalytic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114950498A CN114950498A (en) | 2022-08-30 |
| CN114950498B true CN114950498B (en) | 2023-12-22 |
Family
ID=82983429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210531858.5A Active CN114950498B (en) | 2022-05-16 | 2022-05-16 | Recyclable efficient photocatalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114950498B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096578A (en) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | Preparation method for an Ag/AgBr/GO nano-composite photocatalyst |
| CN105223262A (en) * | 2015-10-23 | 2016-01-06 | 上海交通大学 | Based on the biology sensor and preparation method thereof of aptamer specific detection tetracycline |
| CN106423272A (en) * | 2016-09-28 | 2017-02-22 | 中南林业科技大学 | Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof |
| CN106563473A (en) * | 2015-10-08 | 2017-04-19 | 南京理工大学 | A high-efficiency surface plasma visible-light-induced photocatalyst composite material (Ag@AgCl)-Ni/RGO having magnetic responsibility |
| CN106732690A (en) * | 2016-11-15 | 2017-05-31 | 武汉理工大学 | Ag@AgCl/TiO2The preparation method of graphene oxide composite material |
| CN106975499A (en) * | 2017-05-05 | 2017-07-25 | 董可轶 | A kind of Ag@AgCl/rGO sandwich nano composite materials and preparation method and application |
| KR101766590B1 (en) * | 2016-07-06 | 2017-08-10 | 경희대학교 산학협력단 | Hybrid nanostructures photocatalysts and manufacturing method thereof |
| CN108525683A (en) * | 2018-05-16 | 2018-09-14 | 福州大学 | A kind of three-dimensional grapheme aeroge/silver bromide/silver photochemical catalyst and the preparation method and application thereof |
| CN109126647A (en) * | 2018-09-08 | 2019-01-04 | 佛山市森昂生物科技有限公司 | A kind of preparation method of graphene oxide-sodium alginate gel ball |
| CN110102324A (en) * | 2019-03-26 | 2019-08-09 | 广东工业大学 | A kind of new and effective silver carbonate/silver bromide/GO Three-element composite photocatalyst and its preparation method and application |
| WO2020258931A1 (en) * | 2019-06-27 | 2020-12-30 | 童裳慧 | Method for treating organic dye in waste water |
| CN115069302A (en) * | 2022-07-20 | 2022-09-20 | 江苏农林职业技术学院 | Efficient visible light catalytic material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108855191B (en) * | 2018-07-12 | 2020-09-08 | 苏州大学 | Visible light response hybrid aerogel, preparation method thereof and application thereof in waste gas treatment |
-
2022
- 2022-05-16 CN CN202210531858.5A patent/CN114950498B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096578A (en) * | 2014-07-31 | 2014-10-15 | 安徽工业大学 | Preparation method for an Ag/AgBr/GO nano-composite photocatalyst |
| CN106563473A (en) * | 2015-10-08 | 2017-04-19 | 南京理工大学 | A high-efficiency surface plasma visible-light-induced photocatalyst composite material (Ag@AgCl)-Ni/RGO having magnetic responsibility |
| CN105223262A (en) * | 2015-10-23 | 2016-01-06 | 上海交通大学 | Based on the biology sensor and preparation method thereof of aptamer specific detection tetracycline |
| KR101766590B1 (en) * | 2016-07-06 | 2017-08-10 | 경희대학교 산학협력단 | Hybrid nanostructures photocatalysts and manufacturing method thereof |
| CN106423272A (en) * | 2016-09-28 | 2017-02-22 | 中南林业科技大学 | Supported titanium dioxide/graphene oxide pellets and preparation method and application thereof |
| CN106732690A (en) * | 2016-11-15 | 2017-05-31 | 武汉理工大学 | Ag@AgCl/TiO2The preparation method of graphene oxide composite material |
| CN106975499A (en) * | 2017-05-05 | 2017-07-25 | 董可轶 | A kind of Ag@AgCl/rGO sandwich nano composite materials and preparation method and application |
| CN108525683A (en) * | 2018-05-16 | 2018-09-14 | 福州大学 | A kind of three-dimensional grapheme aeroge/silver bromide/silver photochemical catalyst and the preparation method and application thereof |
| CN109126647A (en) * | 2018-09-08 | 2019-01-04 | 佛山市森昂生物科技有限公司 | A kind of preparation method of graphene oxide-sodium alginate gel ball |
| CN110102324A (en) * | 2019-03-26 | 2019-08-09 | 广东工业大学 | A kind of new and effective silver carbonate/silver bromide/GO Three-element composite photocatalyst and its preparation method and application |
| WO2020258931A1 (en) * | 2019-06-27 | 2020-12-30 | 童裳慧 | Method for treating organic dye in waste water |
| CN115069302A (en) * | 2022-07-20 | 2022-09-20 | 江苏农林职业技术学院 | Efficient visible light catalytic material and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| Ag/AgBr/GO复合材料的制备、表征与光催化性能研究;况鹏鹏;《中国优秀硕士学位论文全文数据库 工程科技I辑》(第1期);第B014-467页 * |
| Daxiang Gao et al..Preparation of Ag@AgCl/GO Material with Efficient Visible-Light Photocatalytic Performance.《Mathematerial Problems in Engineering》.2022,第1-12页. * |
| Yuhua Ma et al..Ag2O/Sodium alginate-reduced graphene oxide aerogel beads for efficient visible light driven photocatalysis.《Applied Surface Science》.2017,第430卷第155页第1节，第157页第3.1节及第159页第3.2节. * |
| 褚亮亮等.复合光催化材料Ag-AgCl/石墨烯的制备及性能.《化工环保》.2013,第33卷(第1期),摘要及第81页第2段和第1.2节. * |
| 高大响等.Ag@AgCl/GO/CA的制备及对模拟废水降解性能研究.《工业水处理》.2022,第42卷(第12期),第106-113页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114950498A (en) | 2022-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Leong et al. | Ni (OH) 2 decorated rutile TiO2 for efficient removal of tetracycline from wastewater | |
| Rajaboopathi et al. | Green synthesis of seaweed surfactant based CdO-ZnO nanoparticles for better thermal and photocatalytic activity | |
| Zhu et al. | Efficient decolorization of azo dye solution by visible light-induced photocatalytic process using SnO2/ZnO heterojunction immobilized in chitosan matrix | |
| Zhao et al. | Fabrication of biomaterial/TiO2 composite photocatalysts for the selective removal of trace environmental pollutants | |
| Wang et al. | Construction of β-FeOOH@ tunicate cellulose nanocomposite hydrogels and their highly efficient photocatalytic properties | |
| Heidarpour et al. | In-situ formation and entrapment of Ag/AgCl photocatalyst inside cross-linked carboxymethyl cellulose beads: A novel photoactive hydrogel for visible-light-induced photocatalysis | |
| CN108786812A (en) | A kind of porous carbon/nano bimetallic oxide composite photocatalyst material and preparation method thereof having both absorption and catalytic action | |
| Gomaa et al. | A hybrid mesoporous CuO@ barley straw-derived SiO2 nanocomposite for adsorption and photocatalytic degradation of methylene blue from real wastewater | |
| Mirbagheri et al. | A Ti-doped γ-Fe2O3/SDS nano-photocatalyst as an efficient adsorbent for removal of methylene blue from aqueous solutions | |
| CN110624594A (en) | Magnetic Fe3O4/ZnO/g-C3N4Composite photocatalyst and preparation method thereof | |
| Yang et al. | Enhanced adsorption/photocatalytic removal of Cu (Ⅱ) from wastewater by a novel magnetic chitosan@ bismuth tungstate coated by silver (MCTS-Ag/Bi2WO6) composite | |
| Buu et al. | Three-dimensional ZnO–TiO2/graphene aerogel for water remediation: The screening studies of adsorption and photodegradation | |
| Wang et al. | Preparation and photocatalytic application of magnetic Fe2O3/SBA-15 nanomaterials | |
| Vu et al. | Synthesis of nano-flakes Ag• ZnO• activated carbon composite from rice husk as a photocatalyst under solar light | |
| Chen et al. | Preparation and recycled simultaneous adsorption of methylene blue and Cu2+ co-pollutants over carbon layer encapsulated Fe3O4/graphene oxide nanocomposites rich in amino and thiol groups | |
| Tu et al. | Ultrafast and efficient removal of aqueous Cr (VI) using iron oxide nanoparticles supported on Bermuda grass-based activated carbon | |
| Kaur | Synergistic effect of biochar impregnated with ZnO nano-flowers for effective removal of organic pollutants from wastewater | |
| Yang et al. | Fabrication of carbon nanotube-loaded TiO 2@ AgI and its excellent performance in visible-light photocatalysis | |
| Sanni et al. | Tailored synthesis of Ag/AgBr nanostructures coupled activated carbon with intimate interface interaction for enhanced photodegradation of tetracycline | |
| CN109046421B (en) | It is a kind of to prepare C, N co-doped nano pipe/stick catalysis material method using quaternary ammonium base | |
| Zhang et al. | 3D chitosan/GO/ZnO hydrogel with enhanced photocorrosion-resistance and adsorption for efficient removal of typical water-soluble pollutants | |
| CN114950498B (en) | Recyclable efficient photocatalytic material and preparation method and application thereof | |
| Gupta et al. | Synchronous role of coupled adsorption and photocatalytic oxidation on the hybrid nanomaterials of pectin and nickel ferrite leads to the excellent removal of toxic dye effluents | |
| CN115069302B (en) | Efficient visible light catalytic material and preparation method and application thereof | |
| CN107486203B (en) | Recyclable floating type composite photocatalytic ball and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |