CN110841672A - Method for treating antibiotic wastewater by utilizing graphite alkyne modified silver phosphate composite photocatalyst - Google Patents
Method for treating antibiotic wastewater by utilizing graphite alkyne modified silver phosphate composite photocatalyst Download PDFInfo
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- CN110841672A CN110841672A CN201911207096.8A CN201911207096A CN110841672A CN 110841672 A CN110841672 A CN 110841672A CN 201911207096 A CN201911207096 A CN 201911207096A CN 110841672 A CN110841672 A CN 110841672A
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- graphite alkyne
- silver phosphate
- composite photocatalyst
- phosphate composite
- modified silver
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- -1 graphite alkyne modified silver phosphate Chemical class 0.000 title claims abstract description 68
- 239000010439 graphite Substances 0.000 title claims abstract description 66
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 66
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 31
- 229960001180 norfloxacin Drugs 0.000 claims abstract description 38
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 13
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 11
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 7
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 230000001699 photocatalysis Effects 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006731 degradation reaction Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000013032 photocatalytic reaction Methods 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000005997 Calcium carbide Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005192 partition Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 3
- 239000005341 toughened glass Substances 0.000 claims description 3
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims description 2
- 229960003405 ciprofloxacin Drugs 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- 229960003376 levofloxacin Drugs 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical class [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 206010040872 skin infection Diseases 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 210000001635 urinary tract Anatomy 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst, which is used for treating antibiotic wastewater by using the graphite alkyne modified silver phosphate composite photocatalyst, wherein the graphite alkyne modified silver phosphate composite photocatalyst takes graphite alkyne nanosheets as a carrier, and silver phosphate particles are loaded on the graphite alkyne nanosheets. In the method, the adopted graphite alkyne modified silver phosphate composite photocatalyst has high-efficiency catalytic activity, can degrade and remove antibiotics in water in a short time under visible light, has the advantages of low cost, high treatment efficiency, good removal effect and the like, and has a very good application prospect. By taking norfloxacin as an example, when the norfloxacin wastewater is degraded by using the graphite alkyne modified silver phosphate composite photocatalyst, the norfloxacin wastewater can be completely degraded and removed after being irradiated for 12min, and the treatment efficiency is high and the treatment effect is good.
Description
Technical Field
The invention belongs to the technical field of photocatalytic application and environmental protection of semiconductor materials, and relates to a method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst.
Background
Antibiotics have been frequently detected in natural water bodies around the world and in and out water of sewage treatment plants in cities and towns since the antibiotics were detected in rivers in the 80 s of the last century, wherein norfloxacin is an effective antibacterial drug widely used in clinical treatment, for example, for treating urinary tract, gastrointestinal tract, skin infection and the like. Currently, norfloxacin is detected in various water bodies at different concentrations, with the highest concentration detected in hospital wastewater exceeding 100 mg/L. The environmental residue of norfloxacin can destroy the original ecological balance of natural water body, and induce the generation of drug-resistant bacteria and resistance genes, thereby indirectly harming the health of human and animals. Extensive ecological and health risk studies have shown that prolonged ingestion of norfloxacin in minute quantities can lead to heart disease, stroke, and decreased body resistance. However, norfloxacin cannot be effectively degraded and removed by most organisms, so that the traditional water treatment process has difficulty in realizing complete degradation and removal of norfloxacin. Therefore, there is an urgent need to develop a new strong oxidation technology to degrade and remove such pollutants.
The photocatalysis technology has mild reaction conditions and can directly utilize solar energy to convert into chemical compoundsThe advantage of chemical energy becomes a green technology with great application prospect in the fields of energy and environment, and the key point is how to obtain a proper photocatalyst. However, the photocatalytic activity of the existing photocatalytic materials, such as most semiconductor photocatalysts, in the visible light region is still not ideal, which hinders the further development and application of photocatalytic technology. Therefore, research and development of efficient visible light photocatalysts are the key to solving the technical bottleneck. Among the numerous catalysts having visible light activity, silver phosphate (Ag)3PO4) Exhibits excellent organic pollutant degrading capacity. Ag3PO4The unique energy band position ensures that a photoproduction cavity in a valence band has strong oxidizing capability and can directly oxidize and degrade pollutants, but Ag3PO4The photocatalytic efficiency of the monomer needs to be further improved, and in addition, the photo-corrosion is serious, and the root cause of the photo-corrosion is that the recombination process of photo-generated electron-hole pairs is far faster than the capture-transfer process, so that the Ag is obtained+Photo-generated electrons are reduced into silver simple substance to destroy Ag3PO4The crystal structure reduces the light absorption performance, thereby reducing the photocatalytic activity and deteriorating the reusability, which seriously hinders the popularization and application of the photocatalyst. Therefore, how to overcome the problems of low separation efficiency, poor photocatalytic activity, poor reusability and the like of the photo-generated electron-hole pair in the existing silver phosphate material has very important significance. At present, there are many studies on the treatment of antibiotic wastewater by photocatalytic technology, for example, patent CN2015100193719, "a catalyst for photocatalytic degradation of antibiotics in water, and a preparation method and application thereof," a photocatalyst is prepared by using strontium acetate and antimony pentoxide as raw materials and adopting a hydrothermal method. And the photocatalyst is placed in a photocatalytic reactor consisting of ultraviolet lamp tubes to degrade and remove tetracycline hydrochloride. The invention patent CN2012100861618 'a method for removing antibiotic resistance genes in sewage', wherein in the step (5), high-pressure CO2 sterilized effluent obtained in the step (4) is sent into a nano titanium dioxide (TiO2) photocatalytic oxidation pond for photocatalytic reaction, and TiO2 is adopted to further remove the antibiotic resistance genes in the water body. However, the existing photocatalytic technology still has a plurality of defects: (1) an ultraviolet light source must be providedThe direct utilization rate of sunlight is low because visible light cannot be directly utilized; (2) the required illumination time is long, and the problem of low treatment efficiency exists; (3) the photocatalyst has large dosage, low pollutant load and small wastewater treatment capacity; (4) the recycling and reutilization of the photocatalyst are not arranged, and the recycling of the photocatalyst cannot be realized. Therefore, the graphite alkyne modified silver phosphate composite photocatalyst with good photocatalytic activity and good reutilization property is obtained, and has very important significance for effectively treating antibiotic wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the method for treating the antibiotic wastewater by using the graphite alkyne modified silver phosphate composite photocatalyst, which has the advantages of low cost, high treatment efficiency and good removal effect.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst is characterized in that the antibiotic wastewater is treated by using the graphite alkyne modified silver phosphate composite photocatalyst; the graphite alkyne modified silver phosphate composite photocatalyst takes graphite alkyne nanosheets as carriers; and silver phosphate particles are loaded on the graphite alkyne nanosheets.
In the method, the particle size of the silver phosphate particles is 0.1-0.4 μm.
In a further improvement of the above method, the preparation method of the graphite alkyne modified silver phosphate composite photocatalyst comprises the following steps:
(1) mixing calcium carbide, benzene and absolute ethyl alcohol, and grinding under a vacuum condition;
(2) calcining the milled material in the step (1) under the protection of inert gas;
(3) sequentially placing the product obtained after calcination in the step (2) in a dilute nitric acid solution and a glacial acetic acid solution for ultrasonic treatment, washing, centrifuging and drying to obtain the graphdiyne;
(4) adding the graphyne obtained in the step (3) into ultrapure water, and performing ultrasonic treatment to obtain a graphyne dispersion liquid;
(5) mixing Ag with water+Dropwise adding the solution into the graphyne dispersion liquid obtained in the step (4), and stirring under the condition of keeping out of the sun to obtain the graphyne/Ag+A dispersion liquid;
(6) introducing HPO4 2-Dropwise adding the solution into the graphyne/Ag obtained in the step (5)+And stirring, washing, centrifuging and drying the dispersion under the condition of keeping out of the sun to obtain the graphite alkyne modified silver phosphate composite photocatalyst.
In the above method, further improvement, the step (1) is: placing calcium carbide, benzene, absolute ethyl alcohol and a stainless steel ball in a stainless steel sealing tank, and vacuumizing the sealing tank; placing the sealed tank after vacuum-pumping treatment in an omnibearing planetary ball mill, and milling for 10-20 h at the rotating speed of 400-700 r/min; cooling treatment is carried out for 3min to 5min every 6min to 10min in the grinding process; the mass ratio of the calcium carbide to the benzene is 3.5-6.5: 1; the volume ratio of the absolute ethyl alcohol to the benzene is 15-20: 1; the diameter of the stainless steel ball is 5 mm-20 mm; the mass ratio of the calcium carbide to the stainless steel ball is 1: 35-45.
In a further improvement of the above method, in the step (2), the inert gas is nitrogen; the heating rate is 2-6 ℃/min in the calcining process; the calcination is carried out at a temperature of 200-300 ℃; the calcining time is 2-5 h.
In the step (3), the ultrasonic treatment of the product in the dilute nitric acid solution and the glacial acetic acid solution is carried out for 30-90 min; the concentration of the dilute nitric acid solution is 0.05 mol/L-0.2 mol/L; the concentration of the glacial acetic acid solution is 1-3 mol/L; the washing is to wash the product after ultrasonic treatment to be neutral by adopting ultrapure water; the drying is carried out under vacuum.
In the above method, further improvement is provided, in the step (4), the time of the ultrasonic treatment is 1h to 3 h.
In the above method, further improvement, in the step (5), the Ag+The solution is AgNO3A solution; the graphoyne/Ag+AgNO in dispersion3The mass ratio of the graphite alkyne to the graphite alkyne is 3500: 1-150: 1; the Ag is+The dropping speed of the solution is 0.2mL/min to 0.5 mL/min; the stirring time is 6-20 h.
In a further improvement of the above method, in the step (6), the HPO4 2-The solution is Na2HPO4·12H2O solution; the HPO4 2-HPO in solution4 2-With graphyne/Ag+Ag in the dispersion+The molar ratio of (A) to (B) is 1: 3; the HPO4 2-The dropping speed of the solution is 0.05mL/min to 0.2 mL/min; the stirring time is 1-6 h; the washing adopts water and ethanol; the drying is carried out under vacuum conditions; the drying temperature is 40-70 ℃.
In a further refinement of the above method, the method comprises the steps of: mixing the graphite alkyne modified silver phosphate composite photocatalyst with antibiotic wastewater, and carrying out degradation reaction under the illumination condition to complete the treatment of the antibiotic wastewater.
In the method, the addition amount of the graphite alkyne-modified silver phosphate composite photocatalyst is further improved, and 0.1 g-0.5 g of the graphite alkyne-modified silver phosphate composite photocatalyst is added into each liter of antibiotic wastewater; the antibiotics in the antibiotic wastewater are at least one of norfloxacin, levofloxacin, tetracycline hydrochloride and ciprofloxacin; the concentration of the antibiotic wastewater is 5 mg/L-100 mg/L.
In the method, the time of the degradation reaction is further improved to 10-40 min; the light source adopted in the degradation reaction process is sunlight, a 300W xenon lamp or an LED energy-saving lamp.
In the above method, further improvement, the degradation reaction is carried out in a photocatalytic reaction device; the photocatalytic reaction device comprises a reaction tank, a light source chamber is arranged around the reaction tank, and the reaction tank and the light source chamber are separated by a light-transmitting partition plate; the reaction tank is internally provided with a plurality of stirrers, the stirrers are transversely arranged at positions 20cm, 40cm, 70cm and 110cm away from the bottom of the reaction tank, and each stirring shaft of each stirrer is provided with 8-15 groups of stirring blades; and a 300W xenon lamp or an LED energy-saving lamp is arranged in the light source chamber.
In the method, the light-transmitting partition plate is made of polymethyl methacrylate or toughened glass; the stirrer is a three-blade stirrer, and the installation mode is a side-in type; the stirring blades are made of polytetrafluoroethylene.
In the above method, further improvement, the degradation reaction further comprises the following steps: conveying the reaction solution to a sedimentation tank, and naturally settling for 20-60 min to obtain supernatant and a sedimentation material; conveying the supernatant to a filter tank for filtering treatment to obtain water and a photocatalytic material; the precipitation material and the photocatalytic material are returned to the reaction tank for continuously catalyzing the antibiotic wastewater; the sedimentation tank is a double-bucket horizontal flow sedimentation tank; the filter membrane material adopted in the filter tank is a water-based polyether sulfone filter membrane; the aperture of the water system polyethersulfone filter membrane is 0.22-0.45 μm.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst, wherein the graphite alkyne modified silver phosphate composite photocatalyst has high-efficiency catalytic activity, can degrade and remove antibiotics in a water body in a short time under visible light, and has the advantages of low cost, high treatment efficiency, good removal effect and the like, thereby having good application prospect. By taking norfloxacin as an example, when the norfloxacin wastewater is degraded by using the graphite alkyne modified silver phosphate composite photocatalyst, the norfloxacin wastewater can be completely degraded and removed after being irradiated for 12min, and the treatment efficiency is high and the treatment effect is good.
(2) According to the invention, the graphite alkyne modified silver phosphate composite photocatalyst is adopted, graphite alkyne nanosheets are used as carriers, and silver phosphate particles are loaded on the graphite alkyne nanosheets. The graphite alkyne modified silver phosphate composite photocatalyst has the advantages of good photocatalytic activity, good reusability and the like, is a novel efficient visible light photocatalyst, can effectively remove antibiotic pollutants in water in a short time under the condition of visible light, and has high use value and good application prospect.
(3) The preparation method of the graphite alkyne modified silver phosphate composite photocatalyst comprises the following steps: sequentially adding AgNO3Solution, Na2HPO4·12H2And adding the O solution into the graphite alkyne dispersion liquid, stirring under a dark condition to generate silver phosphate particles, and loading the silver phosphate particles on the graphite alkyne nanosheet to obtain the graphite alkyne modified silver phosphate composite photocatalyst with good photocatalytic activity and good reutilization property. The preparation method has the advantages of simple process, easy operation, low requirements on preparation conditions and preparation equipment, low cost, high yield, greenness, no pollution and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a graph showing the degradation effect of the graphite alkyne-modified silver phosphate composite photocatalyst on norfloxacin under different time conditions in example 1 of the present invention.
Fig. 2 is a process flow chart of treating antibiotic wastewater by using the graphite alkyne-modified silver phosphate composite photocatalyst in embodiment 2 of the present invention.
Fig. 3 is a graph showing the degradation effect of the graphite alkyne-modified silver phosphate composite photocatalyst on norfloxacin under different time conditions in example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the processes used were conventional processes, the equipment used were conventional equipment, and the data obtained were average values of three or more experiments.
Example 1
A method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst, in particular to a method for treating norfloxacin wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst, which comprises the following steps:
50mg of graphite alkyne modified silver phosphate composite photocatalyst (Ag) is weighed3PO4@5.0mL of gamma-G), adding into 100mL of norfloxacin solution with the concentration of 20mg/L, carrying out ultrasonic treatment for 1min, and stirring and reacting for 30min in the dark to enable the norfloxacin solution to reach adsorption equilibrium. Then, at 300W xenon lamp (lambda)>420nm) under irradiation.
Blank group: treating the norfloxacin wastewater under the condition of not adding a photocatalytic material, wherein other conditions are the same.
In the degradation reaction process, reaction solutions under different reaction times are taken, the content of norfloxacin in the reaction solutions is measured by using a high performance liquid chromatography, and the degradation effect of the graphite alkyne modified silver phosphate composite photocatalyst on the norfloxacin solutions in different times is obtained by calculation, and the result is shown in fig. 1.
Fig. 1 is a graph showing the degradation effect of the graphite alkyne-modified silver phosphate composite photocatalyst on norfloxacin under different time conditions in example 1 of the present invention. As can be seen from fig. 1, under the condition of no addition of the photocatalytic material, the concentration of norfloxacin hardly changes, and the norfloxacin cannot be degraded by itself under the illumination condition; after the photocatalytic material (the graphite alkyne modified silver phosphate composite photocatalyst) is added, stirring is carried out for 30min under the dark condition, about 20% of norfloxacin is adsorbed by the photocatalyst, then norfloxacin is rapidly degraded and removed by the catalyst under the visible light condition (lambda is more than 420nm), after 8min of illumination, the norfloxacin removal rate reaches 99%, and after 12min of illumination, the norfloxacin removal rate reaches 100%.
In this embodiment, the graphite alkyne-modified silver phosphate composite photocatalyst is prepared by using a graphite alkyne nanosheet as a carrier, and the graphite alkyne nanosheet is loaded with silver phosphate particles. The particle size of the silver phosphate particles is 0.1-0.4 μm.
In this embodiment, the preparation method of the graphite alkyne-modified silver phosphate composite photocatalyst includes the following steps:
(1) 10.0g of calcium carbide, 2mL of benzene and 35mL of absolute ethyl alcohol are placed in a 250mL stainless steel tank, and 375g of stainless steel balls with the diameters of 15mm, 12mm, 10mm, 8mm and 5mm are added, wherein the mass ratio of the steel balls with the diameters is 2: 1. And after the charging is finished, carrying out vacuum-pumping treatment on the stainless steel tank.
(2) And (2) placing the vacuum sealed tank filled with the materials in the step (1) in an all-directional planetary ball mill to be sequentially subjected to grinding treatment at 600 rpm/min and 450rpm/min for 8h, and cooling treatment for 3min every 6min in the operation process to prevent the materials from being overheated.
(3) And (3) calcining the material ground in the step (2) at 260 ℃ for 3h in a nitrogen atmosphere at the heating rate of 5 ℃/min, and performing ultrasonic treatment on the obtained solid material by using 0.1mol/L dilute nitric acid solution and 2mol/L glacial acetic acid solution respectively, wherein the ultrasonic treatment time is 60min respectively.
(4) And (4) washing the material obtained in the step (3) to be neutral by using ultrapure water, performing centrifugal separation to obtain a solid part, and performing vacuum drying to obtain the grapyne which is named as gamma-G.
(5) And (3) weighing 0.2g of the graphyne obtained in the step (4), adding the graphyne into 400mL of ultrapure water, and carrying out ultrasonic treatment for 2h to obtain a graphyne dispersion liquid.
(6) 5mL of the graphdine dispersion obtained in step (5) was diluted with ultrapure water to 100 mL.
(7) 20mL of AgNO3Solution (9 mmol AgNO in the solution)3) Dropwise adding the mixture into the graphite alkyne dispersion liquid obtained in the step (6) at a rate of 0.3mL/min, and stirring for 12 hours in a dark place to obtain graphite alkyne/AgNO3And (3) dispersing the mixture.
(8) 20mL of Na2HPO4·12H2O solution (3 mmol Na in this solution)2HPO4·12H2O) dropwise adding the graphdiyne/AgNO obtained in the step (7) at the dropwise adding speed of 0.1mL/min3Stirring in dark for 6h, washing with water and ethanol for several times, centrifuging to obtain solid part, vacuum drying at 60 deg.C to obtain graphite alkyne modified silver phosphate composite photocatalyst, named as Ag3PO4@5.0mLγ-G。
Example 2
A method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst is specifically used for treating norfloxacin wastewater, and a treatment process flow diagram is shown in figure 2 and comprises the following steps:
(1) 2kg of the graphdine-modified silver phosphate composite photocatalyst (Ag) prepared in example 13PO4@5.0 mL. gamma. -G) added into a reaction tank (containing 20m of catalyst) of a photocatalytic reaction device3Norfloxacin wastewater with a concentration of 20 mg/L).
(2) And opening a stirrer in the reaction tank, and uniformly mixing the graphite alkyne modified silver phosphate composite photocatalyst with the norfloxacin wastewater.
(3) And carrying out photocatalytic reaction for 24min under the sunlight under the condition of continuous stirring of a stirrer.
(4) After the photocatalytic reaction is finished, introducing the wastewater in the reaction tank into a sedimentation tank, naturally settling for 30min, discharging supernatant into a filter tank, and recycling materials in the sedimentation zone to the reaction tank again by using a pump.
(5) And (3) filtering the supernatant in the filter tank by adopting a water system polyether sulfone filter membrane with the aperture of 0.45 mu m to obtain the clear water river photocatalytic material, directly discharging the clear water after the clear water reaches the standard or performing other resource utilization, and recycling the obtained photocatalytic material into the reaction tank by using a pump.
Blank group: treating the norfloxacin wastewater under the condition of not adding a photocatalytic material, wherein other conditions are the same.
In this embodiment, the adopted photocatalytic reaction device includes a reaction tank, a light source chamber is arranged around the reaction tank, and the reaction tank and the light source chamber are separated by a light-transmitting partition plate (both polymethyl methacrylate and toughened glass); the reaction tank is internally provided with a plurality of stirrers (the number of the stirrers is selected according to actual needs), the stirrers are transversely arranged at positions 20cm, 40cm, 70cm and 110cm away from the bottom of the reaction tank, and a stirring shaft of each stirrer is provided with 10 groups of stirring blades; A300W xenon lamp or an LED energy-saving lamp (as a light source for photocatalytic reaction in rainy days or at night) is installed in the light source chamber.
In this embodiment, the stirrer is a three-blade stirrer, and the stirring blade is made of teflon.
In this embodiment, the sedimentation tank used is a double-bucket horizontal flow sedimentation tank.
In this embodiment, in the photocatalytic reaction process, reaction solutions at different reaction times are taken, the content of norfloxacin in the reaction solutions is measured by using a high performance liquid chromatography, and the degradation effect of the graphdiyne-modified silver phosphate composite photocatalyst on the norfloxacin solution at different times is obtained by calculation, and the result is shown in fig. 3.
Fig. 3 is a graph showing the degradation effect of the graphite alkyne-modified silver phosphate composite photocatalyst on norfloxacin under different time conditions in example 2 of the present invention. As can be seen from fig. 3, the concentration of norfloxacin hardly changed with the increase in the solar light irradiation time without adding the photocatalytic material. After the graphite alkyne-modified silver phosphate composite photocatalyst prepared in example 1 is added, the concentration of norfloxacin is rapidly reduced along with the increase of illumination time, and when the illumination time reaches 16min, norfloxacin is degraded and removed by 100%.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A method for treating antibiotic wastewater by using a graphite alkyne modified silver phosphate composite photocatalyst is characterized in that the method comprises the steps of treating the antibiotic wastewater by using the graphite alkyne modified silver phosphate composite photocatalyst; the graphite alkyne modified silver phosphate composite photocatalyst takes graphite alkyne nanosheets as carriers; and silver phosphate particles are loaded on the graphite alkyne nanosheets.
2. The method of claim 1, wherein the silver phosphate particles have a particle size of 0.1 μm to 0.4 μm.
3. The method as claimed in claim 2, wherein the preparation method of the graphite alkyne-modified silver phosphate composite photocatalyst comprises the following steps:
(1) mixing calcium carbide, benzene and absolute ethyl alcohol, and grinding under a vacuum condition;
(2) calcining the milled material in the step (1) under the protection of inert gas;
(3) sequentially placing the product obtained after calcination in the step (2) in a dilute nitric acid solution and a glacial acetic acid solution for ultrasonic treatment, washing, centrifuging and drying to obtain the graphdiyne;
(4) adding the graphyne obtained in the step (3) into ultrapure water, and performing ultrasonic treatment to obtain a graphyne dispersion liquid;
(5) mixing Ag with water+Dropwise adding the solution into the graphyne dispersion liquid obtained in the step (4), and stirring under the condition of keeping out of the sun to obtain the graphyne/Ag+A dispersion liquid;
(6) introducing HPO4 2-Dropwise adding the solution into the graphyne/Ag obtained in the step (5)+And stirring, washing, centrifuging and drying the dispersion under the condition of keeping out of the sun to obtain the graphite alkyne modified silver phosphate composite photocatalyst.
4. The method of claim 3, wherein the step (1) is: placing calcium carbide, benzene, absolute ethyl alcohol and a stainless steel ball in a stainless steel sealing tank, and vacuumizing the sealing tank; placing the sealed tank after vacuum-pumping treatment in an omnibearing planetary ball mill, and milling for 10-20 h at the rotating speed of 400-700 r/min; cooling treatment is carried out for 3min to 5min every 6min to 10min in the grinding process; the mass ratio of the calcium carbide to the benzene is 3.5-6.5: 1; the volume ratio of the absolute ethyl alcohol to the benzene is 15-20: 1; the diameter of the stainless steel ball is 5 mm-20 mm; the mass ratio of the calcium carbide to the stainless steel ball is 1: 35-45;
in the step (2), the inert gas is nitrogen; the heating rate is 2-6 ℃/min in the calcining process; the calcination is carried out at a temperature of 200-300 ℃; the calcining time is 2-5 h;
in the step (3), the ultrasonic treatment of the product in the dilute nitric acid solution and the glacial acetic acid solution is carried out for 30-90 min; the concentration of the dilute nitric acid solution is 0.05 mol/L-0.2 mol/L; the concentration of the glacial acetic acid solution is 1-3 mol/L; the washing is to wash the product after ultrasonic treatment to be neutral by adopting ultrapure water; the drying is carried out under vacuum conditions;
in the step (4), the ultrasonic treatment time is 1-3 h;
in the step (5), the Ag+The solution is AgNO3A solution; the graphoyne/Ag+AgNO in dispersion3The mass ratio of the graphite alkyne to the graphite alkyne is 3500: 1-150: 1; the Ag is+The dropping speed of the solution is 0.2mL/min to 0.5 mL/min; the stirring time is 6-20 h;
in the step (6), the HPO4 2-The solution is Na2HPO4·12H2O solution; the HPO4 2-HPO in solution4 2-With graphyne/Ag+Ag in the dispersion+The molar ratio of (A) to (B) is 1: 3; the HPO4 2-The dropping speed of the solution is 0.05mL/min to 0.2 mL/min; the stirring time is 1-6 h; the washing adopts water and ethanol; the drying is carried out under vacuum conditions; the drying temperature is 40-70 ℃.
5. A method according to any one of claims 1 to 4, characterized in that the method comprises the steps of: mixing the graphite alkyne modified silver phosphate composite photocatalyst with antibiotic wastewater, and carrying out degradation reaction under the illumination condition to complete the treatment of the antibiotic wastewater.
6. The method according to claim 5, wherein the graphite alkyne-modified silver phosphate composite photocatalyst is added in an amount of 0.1 to 0.5g per liter of antibiotic wastewater; the antibiotics in the antibiotic wastewater are at least one of norfloxacin, levofloxacin, tetracycline hydrochloride and ciprofloxacin; the concentration of the antibiotic wastewater is 5 mg/L-100 mg/L.
7. The method according to claim 6, wherein the time of the degradation reaction is 10min to 40 min; the light source adopted in the degradation reaction process is sunlight, a 300W xenon lamp or an LED energy-saving lamp.
8. The method of claim 5, wherein the degradation reaction is performed in a photocatalytic reaction device; the photocatalytic reaction device comprises a reaction tank, a light source chamber is arranged around the reaction tank, and the reaction tank and the light source chamber are separated by a light-transmitting partition plate; the reaction tank is internally provided with a plurality of stirrers, the stirrers are transversely arranged at positions 20cm, 40cm, 70cm and 110cm away from the bottom of the reaction tank, and each stirring shaft of each stirrer is provided with 8-15 groups of stirring blades; and a 300W xenon lamp or an LED energy-saving lamp is arranged in the light source chamber.
9. The method of claim 8, wherein the light-transmissive separator is polymethylmethacrylate or tempered glass; the stirrer is a three-blade stirrer, and the installation mode is a side-in type; the stirring blades are made of polytetrafluoroethylene.
10. The method of claim 9, further comprising the following steps after the degradation reaction is completed: conveying the reaction solution to a sedimentation tank, and naturally settling for 20-60 min to obtain supernatant and a sedimentation material; conveying the supernatant to a filter tank for filtering treatment to obtain water and a photocatalytic material; the precipitation material and the photocatalytic material are returned to the reaction tank for continuously catalyzing the antibiotic wastewater; the sedimentation tank is a double-bucket horizontal flow sedimentation tank; the filter membrane material adopted in the filter tank is a water-based polyether sulfone filter membrane; the aperture of the water system polyethersulfone filter membrane is 0.22-0.45 μm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958132A (en) * | 2021-02-07 | 2021-06-15 | 广东石油化工学院 | Method for treating antibiotic wastewater by using nitrogen vacancy doped tungsten nitride modified silver phosphate composite photocatalyst |
| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114225947A (en) * | 2021-12-17 | 2022-03-25 | 中国矿业大学 | Photocatalytic CO2Graphite alkyne composite material for preparing fuel by reduction and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110182888A (en) * | 2019-06-13 | 2019-08-30 | 广东石油化工学院 | A kind of photocatalytic reaction device and technique handling rose red b high-salt wastewater |
-
2019
- 2019-11-29 CN CN201911207096.8A patent/CN110841672A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110182888A (en) * | 2019-06-13 | 2019-08-30 | 广东石油化工学院 | A kind of photocatalytic reaction device and technique handling rose red b high-salt wastewater |
Non-Patent Citations (1)
| Title |
|---|
| YAN LIN等: "Gama-graphyne as photogenerated electrons transfer layer enhances photocatalytic performance of silver phosphate", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958132A (en) * | 2021-02-07 | 2021-06-15 | 广东石油化工学院 | Method for treating antibiotic wastewater by using nitrogen vacancy doped tungsten nitride modified silver phosphate composite photocatalyst |
| CN112958132B (en) * | 2021-02-07 | 2022-09-30 | 广东石油化工学院 | Method for treating antibiotic wastewater by using nitrogen vacancy doped tungsten nitride modified silver phosphate composite photocatalyst |
| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN113578362B (en) * | 2021-07-23 | 2023-09-08 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114225947A (en) * | 2021-12-17 | 2022-03-25 | 中国矿业大学 | Photocatalytic CO2Graphite alkyne composite material for preparing fuel by reduction and preparation method thereof |
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