CN114029078B - Catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater and preparation and application methods thereof - Google Patents
Catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater and preparation and application methods thereof Download PDFInfo
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- CN114029078B CN114029078B CN202111423199.5A CN202111423199A CN114029078B CN 114029078 B CN114029078 B CN 114029078B CN 202111423199 A CN202111423199 A CN 202111423199A CN 114029078 B CN114029078 B CN 114029078B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 45
- 230000003213 activating effect Effects 0.000 title claims abstract description 37
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 93
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052709 silver Inorganic materials 0.000 claims abstract description 70
- 239000004332 silver Substances 0.000 claims abstract description 70
- 150000001621 bismuth Chemical class 0.000 claims abstract description 56
- 239000002096 quantum dot Substances 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 55
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
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- 239000000203 mixture Substances 0.000 claims abstract description 6
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 claims 5
- 230000000694 effects Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 60
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 24
- 229960004306 sulfadiazine Drugs 0.000 description 24
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- 229910021642 ultra pure water Inorganic materials 0.000 description 12
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
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- -1 neodymium modified bismuth Chemical class 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 229960003405 ciprofloxacin Drugs 0.000 description 5
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 5
- 229960001259 diclofenac Drugs 0.000 description 5
- 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 description 5
- 229960001180 norfloxacin Drugs 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229960005404 sulfamethoxazole Drugs 0.000 description 4
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 239000000598 endocrine disruptor Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 229940126575 aminoglycoside Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
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- 210000003734 kidney Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 229940041033 macrolides Drugs 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 210000000056 organ Anatomy 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
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- 229940040944 tetracyclines Drugs 0.000 description 1
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- 150000003952 β-lactams Chemical class 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B01J35/33—
-
- 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
-
- 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
-
- 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 catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater and a preparation method and an application method thereof, wherein the catalyst is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: adding silver nitrate and a bismuth ferrite precursor into water, mixing and dissolving, dropwise adding a sodium hydroxide solution, uniformly stirring, adding black phosphorus quantum dots, and stirring; then transferring the mixture to a hydrothermal reaction kettle for synthesis; after the reaction, the synthesized substance is washed and dried. The invention has the advantages of excellent degradation effect, recoverability and the like.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, relates to a catalyst for degrading antibiotic wastewater, and particularly relates to a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, and preparation and application methods thereof.
Background
The antibiotic-containing wastewater mainly comes from livestock and poultry breeding wastewater, medical wastewater, pharmaceutical wastewater and other industries, the wastewater mainly comprises eight compounds of macrolides, tetracyclines, sulfonamides, quinolones, beta-lactams, aminoglycosides, chloramphenicol and polypeptides, and the pollutants can enter human bodies in various ways, have certain damage effects on organs such as liver and kidney, can cause allergic reaction to damage nervous systems, can change the functions or tissue structures of organisms, and can cause cancers in severe cases. Therefore, the rapid and efficient removal of the antibiotics in the water environment has important ecological safety significance for human health and environmental safety.
Persulfate has low cost, wide pH application range, long half-life period, good oxidation performance on organic pollutants and strong mineralization capability, and becomes a hotspot for research in advanced oxidation technology. Persulfate systems, however, often require the generation of strongly oxidizing hydroxyl radicals (. OH), sulfate radicals (SO), by means of external conditions such as light, heat, electricity, etc4-A) and singlet oxygen: (1O2) And the like (for example, CN 111533234A discloses a method for degrading antibiotic wastewater by activating persulfate through an external field light source in cooperation with a perovskite material). The practical application of the persulfate advanced oxidation technology is also restricted by the additional conditions, so that the development prospect of rapidly activating persulfate at normal temperature and efficiently oxidizing and degrading antibiotics is good, but the reports are few.
At present, the key factor for activating the persulfuric acid at normal temperature is a catalyst, and most of the catalysts have the problems of difficult recovery, low activation efficiency, long time for removing pollutants and the like. Perovskite materials have attracted much attention because of their excellent photoelectric properties, such as wide spectral absorption range, low defect density, low carrier recombination rate, etc. There are few reports on the use of bismuth ferrite, a perovskite structure material, for activating persulfates. Only the grant publication No. CN 108640249B introduces a method for removing residual endocrine disruptors in water based on boron and neodymium modified bismuth ferrite catalysis persulfate, but the method is used for removing endocrine disruptors with lower concentration and needs longer reaction time, and the practical application of the method is also limited. Therefore, a technology capable of rapidly activating persulfate at normal temperature and efficiently removing antibiotic pollutants is urgently needed to be developed so as to ensure the ecological safety of the water environment.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst which has high catalytic performance, is easy to recover and is applied to rapidly activate persulfate to oxidize and degrade antibiotic wastewater at normal temperature.
In order to achieve the above object, the present invention provides a catalyst for rapidly activating persulfate to oxidatively degrade antibiotic wastewater, which has the following characteristics: the catalyst is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and is a composite catalyst in which silver and black phosphorus quantum dots are doped and modified to bismuth ferrite.
The invention provides a preparation method of the catalyst for quickly activating persulfate to oxidize and degrade antibiotic wastewater, which is characterized in that: adding silver nitrate and a bismuth ferrite precursor into water, mixing and dissolving, dropwise adding a sodium hydroxide solution, uniformly stirring, adding black phosphorus quantum dots, and stirring for 12 hours; then transferring the mixture to a hydrothermal reaction kettle for synthesis, wherein the synthesis reaction time is 60-600 min, and the reaction temperature is 150-200 ℃; and after the reaction is finished, washing and drying the synthesized substance to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
Further, the invention provides a preparation method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which can also have the following characteristics: wherein the bismuth ferrite precursor is ferric nitrate and bismuth nitrate.
Further, the invention provides a preparation method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which can also have the following characteristics: wherein the dosage ratio of the ferric nitrate, the bismuth nitrate, the silver nitrate, the sodium hydroxide and the black phosphorus quantum dots is 4.04g to 2.425g (0.3374-0.839g) to (0.084-0.1mol) to (2-5 mg).
Further, the invention provides a preparation method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which can also have the following characteristics: wherein the washing method comprises the following steps: and alternately washing the mixture for 2-6 times by using absolute ethyl alcohol and deionized water.
Further, the invention provides a preparation method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which can also have the following characteristics: wherein the drying temperature is 60-80 ℃, and the drying time is 2-6 h.
The invention also provides an application method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is characterized in that: and (2) putting the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst into the wastewater to be treated, stirring, adding persulfate to start reaction after adsorption balance is achieved, wherein the reaction temperature is 10-25 ℃, and the reaction time is 0.5-6 min.
Further, the invention provides an application method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, and the catalyst can also have the following characteristics: the mass ratio of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst to the persulfate is 1: 1-10.
Further, the invention provides an application method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, and the catalyst can also have the following characteristics: wherein the persulfate is potassium persulfate or sodium persulfate.
Further, the invention provides an application method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, and the catalyst can also have the following characteristics: wherein the stirring time is 10-30 min.
The synthetic material of the invention is a bismuth ferrite composite catalyst co-modified by magnetic silver and black phosphorus quantum dots, wherein the doping of silver element causes the lattice defect of bismuth ferrite, and accelerates the electron transfer on the surface of the catalyst while generating simple substance silver, so that the oxidation capacity and the mineralization degree of the system are improved.
The invention has the beneficial effects that:
the catalyst for rapidly activating the persulfate to oxidize and degrade the wastewater containing the antibiotics, which is prepared by the invention, is characterized in that the morphology of bismuth ferrite is modified by doping silver element and black phosphorus quantum dots, the structure of the bismuth ferrite is strengthened, and the persulfate activating capability of the bismuth ferrite is improved.
The bismuth ferrite composite catalyst co-modified by the synthetic material silver and the black phosphorus quantum dots has certain magnetism, and is beneficial to recycling and recovering of the composite catalyst.
The leaching rates of iron, bismuth and silver ions in the stability test of the catalyst for rapidly activating persulfate to oxidize and degrade the antibiotic wastewater prepared by the invention are lower than the national wastewater discharge standard.
The composite material of the invention, which is the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, can rapidly activate persulfate at normal temperature, and can completely degrade water distribution containing antibiotics within 5 min.
Fifthly, the composite material magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst quickly activates persulfate at normal temperature, and has a good removal effect on sulfadiazine contained in different water bodies within 60 min.
Drawings
FIG. 1 is an SEM image of a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst in example 1;
FIG. 2 is an XRD (X-ray diffraction) pattern of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst in example 1;
FIG. 3 is an XPS plot of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst in example 1;
FIG. 4 is a diagram illustrating the effect of the different reaction systems in example 1 on rapidly activating persulfate to oxidatively degrade sulfadiazine;
FIG. 5 is a graph showing the effect of the magnetic silver and black phosphorus quantum dots co-modified bismuth ferrite composite catalyst in example 1 in removing sulfadiazine and TOC;
FIG. 6 is a graph showing the effect of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst in example 1 in removing sulfadiazine from different water bodies;
FIG. 7 is a diagram of the effect of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst in example 1 in removing sulfadiazine for 5 times of repeated use.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps:
4.04g of ferric nitrate, 2.425g of bismuth nitrate and 0.839g of silver nitrate are respectively added into 10mL of ultrapure water to be dissolved by ultrasonic treatment for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, 5mL of 1 mg/mL of black phosphorus quantum dots are added after uniform mixing by magnetic stirring, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with deionized water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst is characterized, and an SEM image, an XRD image and an XPS image are shown in figures 1-3.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst is placed into wastewater to be treated, stirring is carried out, persulfate is added after adsorption balance is achieved, reaction treatment is started, and treatment time is 0.5-6 min.
Specifically, the following application comparisons were made with the control group:
respectively comparing the system with the system added with only potassium persulfate (PDS group, 2mmol/L), bismuth ferrite (BFO group, 0.2g/L) and black phosphorus quantum dots (BPQDs group, 0.2g/L), and bismuth ferrite modified by potassium persulfate and black phosphorus quantum dots (BPQDs/BiFeO)3Group, PDS: 2mmol/L, BPQDs/BiFeO3: 0.2g/L, sulfadiazine: 60mg/L-100mL), potassium persulfate and silver modified bismuth ferrite catalyst (Ag-BiFeO)3Group, PDS: 2mmol/L, Ag-BiFeO3: 0.2g/L, sulfadiazine: 60mg/L-100mL), potassium persulfate, magnetic silver and black phosphorus quantum dots co-modified bismuth ferrite composite catalyst (BPQDs/Ag-BiFeO)3Group, PDS: 2mmol/L, BPQDs/Ag-BiFeO 3: 0.2g/L, sulfadiazine: 60mg/L-100mL) is removed by the application method60mg/L sulfadiazine solution (wastewater to be treated) is reacted for 5min, then the solution is filtered by 0.22 mu m filter membranes respectively, and then the concentration of the remaining sulfadiazine is tested by HPLC, different reaction systems have different sulfadiazine removal effects, and the result is shown in figure 4, wherein the magnetic silver and black phosphorus quantum dots co-modified bismuth ferrite composite catalyst activates potassium persulfate to completely remove sulfadiazine, and the mineralization rate reaches 65%. The effect graph of the bismuth ferrite composite catalyst with the co-modified magnetic silver and black phosphorus quantum dots for removing sulfadiazine and TOC is shown in FIG. 5.
The preparation method of each catalyst in the control group is as follows:
the pure bismuth ferrite method comprises the following steps: 4.04g of ferric nitrate and 4.85g of bismuth nitrate were added to 10mL of ultrapure water, respectively, and dissolved by sonication for 20min, followed by dropwise addition of 10mL of 10mol/L sodium hydroxide and magnetic stirring for 12 hours to mix them uniformly. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the pure bismuth ferrite catalyst.
The method for modifying the bismuth ferrite by silver comprises the following steps: 4.04g of ferric nitrate, 2.425g of bismuth nitrate and 0.839g of silver nitrate were added to 10mL of ultrapure water respectively and dissolved by ultrasonic treatment for 20min, followed by dropwise addition of 10mL of 10mol/L sodium hydroxide and magnetic stirring for 12h to mix them uniformly. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the silver modified bismuth ferrite catalyst.
The method for modifying bismuth ferrite by black phosphorus quantum dots comprises the following steps: 4.04g of ferric nitrate and 4.85g of bismuth nitrate are respectively added into 10mL of ultrapure water to be dissolved by ultrasonic treatment for 20min, 10mL of 10mol/L sodium hydroxide is then added dropwise, after uniform mixing by magnetic stirring, 5mL of 1 mg/mL of black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the black phosphorus quantum dot modified bismuth ferrite catalyst.
Comparing the removal effects of ultrapure water or deionized water, tap water and Nenjiang water containing 60mg/L sulfadiazine in a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst (0.2g/L) activated potassium persulfate (2mmol/L) system, the sulfadiazine in different water bodies has better removal effect after reacting for 60min, as shown in FIG. 6.
And (3) testing the stability of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst: the bismuth ferrite composite material modified by the silver and black phosphorus quantum dots is put into 100mL of a 60mg/L sulfadiazine solution for degradation experiment, the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst is recovered for regeneration, the degradation experiment is continued, and the removal effect on sulfadiazine is still more than 85% after repeating for 5 times, as shown in FIG. 7.
Example 2
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.839g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic treatment for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, after uniform mixing by magnetic stirring, 5mL of 1 mg/mL of black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: taking 100mL of 60mg/L sulfamethoxazole solution, adding 0.2g/L of catalyst (bismuth ferrite, silver modified bismuth ferrite, black phosphorus quantum dot modified bismuth ferrite, silver and black phosphorus quantum dot modified bismuth ferrite), placing the solution in a magnetic stirrer at 350rpm, stirring the solution for 30min, then adding 2mmol/L of potassium persulfate to start reaction, sampling 1.5mL at 0.5, 1, 2, 3, 4 and 5min, filtering the solution by using a 0.22 mu m filter membrane, and testing the residual sulfamethoxazole concentration by using HPLC (high performance liquid chromatography), wherein after the reaction is carried out for 5min, the degradation rate of the sulfamethoxazole by the silver and black phosphorus quantum dot modified bismuth ferrite reaches 99.95%, the mineralization rate reaches 65%, and the degradation rate of the sulfamethoxazole after the pure bismuth ferrite, the silver modified bismuth ferrite and the black phosphorus quantum dot modified bismuth ferrite are reacted for 5min is only 5.07%, 12.21% and 7.05% respectively.
Example 3
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.5061g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic wave for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, after uniform mixing by magnetic stirring, 3mL of 1 mg/mL of black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 180 ℃ for 8h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: taking 0.1g of dried silver and black phosphorus quantum dot modified bismuth ferrite, adding the dried silver and black phosphorus quantum dot modified bismuth ferrite into a reaction bottle filled with 100mL of ciprofloxacin solution with the concentration of 20mg/L, stirring for 10min to reach adsorption balance, adding 0.5 g of potassium persulfate, starting reaction for 5min, taking a sample every minute, and taking the removal rate and the mineralization degree of ciprofloxacin as evaluation indexes. And detecting the concentration of the ciprofloxacin by adopting HPLC, and detecting the total organic carbon in the ciprofloxacin solution by adopting a TOC analyzer. After the reaction is carried out for 5min, the removal rate of the ciprofloxacin reaches more than 95 percent, and the mineralization rate reaches 62 percent.
Example 4
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.3374g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, after uniform mixing by magnetic stirring, 1mL of 2mg/mL black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 190 ℃ for 8h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 70 ℃ for 2h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: taking 0.1g of dried silver and black phosphorus quantum dot modified bismuth ferrite, adding the dried silver and black phosphorus quantum dot modified bismuth ferrite into a reaction bottle filled with 100mL of norfloxacin solution with the concentration of 20mg/L, stirring for 15min to reach adsorption balance, adding 0.6 g of potassium persulfate, starting reaction, wherein the time is 5min, sampling once per minute, and taking the norfloxacin removal rate and the mineralization degree as evaluation indexes. And detecting the concentration of the norfloxacin by adopting HPLC, and detecting the total organic carbon in the norfloxacin solution by adopting a TOC analyzer. The norfloxacin removal rate reaches over 95 percent after 5min of reaction, and the mineralization rate reaches 60 percent.
Example 5
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.839g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic for 20min, then 7mL of 12mol/L sodium hydroxide solution is added dropwise, 2mL of 2mg/mL of black phosphorus quantum dots are added after uniform mixing by magnetic stirring, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 200 ℃ for 6h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 70 ℃ for 2h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: taking 0.2g of dried silver and black phosphorus quantum dot modified bismuth ferrite, adding the dried silver and black phosphorus quantum dot modified bismuth ferrite into a reaction bottle filled with 100mL of diclofenac solution with the concentration of 20mg/L, stirring for 15min to reach adsorption balance, adding 0.6 g of potassium persulfate, starting reaction, wherein the reaction time is 5min, sampling once per minute, and taking the removal rate and the mineralization degree of the diclofenac as evaluation indexes. And detecting the concentration of the diclofenac by HPLC, and detecting the total organic carbon in the diclofenac solution by a TOC analyzer. After the reaction is carried out for 5min, the removal rate of the diclofenac reaches more than 94 percent, and the mineralization rate reaches more than 60 percent.
Example 6
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.839g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic treatment for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, after uniform mixing by magnetic stirring, 5mL of 1 mg/mL of black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 180 ℃ for 10h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 60 ℃ for 6h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: 100mL of 20mg/L of ultrapure water or deionized water of different water bodies, tap water and sulfadiazine solution in Yangjiang water are taken, 0.2g of silver and black phosphorus quantum dot modified bismuth ferrite is added, the mixture is placed in a magnetic stirrer at 350rpm and stirred for 30min, then 2mmol/L of potassium persulfate is added to start reaction, a sample is taken every 10min, and the sulfadiazine removal rate exceeds 70% after the reaction is carried out for 60 min.
Example 7
The embodiment provides a catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater, which is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, and the preparation method comprises the following steps: 0.839g of silver nitrate, 4.04g of ferric nitrate and 2.425g of bismuth nitrate are added into 10mL of ultrapure water and dissolved by ultrasonic treatment for 20min, then 10mL of 10mol/L sodium hydroxide solution is added dropwise, after uniform mixing by magnetic stirring, 5mL of 1 mg/mL of black phosphorus quantum dots are added, and stirring is carried out for 12 h. Carrying out hydrothermal reaction at 150 ℃ for 1h, cooling to room temperature, removing supernatant, alternately washing the precipitate with water and absolute ethyl alcohol for 6 times, drying at 80 ℃ for 2h, and grinding to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst.
The embodiment also provides an application method of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst, which comprises the following steps: taking 0.2g of dried silver and black phosphorus quantum dot modified bismuth ferrite, adding the dried silver and black phosphorus quantum dot modified bismuth ferrite into a reaction bottle filled with 100mL of sulfadiazine solution with the concentration of 60mg/L, stirring for 10min to reach adsorption balance, adding sodium persulfate (the addition of the sodium persulfate is 1mmol/L) to start reaction, wherein the reaction time is 6min, taking a sample every minute, and taking the removal rate and the mineralization degree of sulfadiazine as evaluation indexes. And (3) detecting the concentration of sulfadiazine by adopting HPLC, and detecting the total organic carbon in the sulfadiazine solution by adopting a TOC analyzer. After 6min of reaction, the removal rate of sulfadiazine reaches more than 99 percent, and the mineralization rate reaches more than 60 percent.
The invention selects the bismuth ferrite with ferroelectricity and ferromagnetism as the main catalyst body in the technique of rapidly activating the persulfate advanced oxidation at normal temperature, and the bismuth ferrite has important application prospect in the optical field because the Fe atom in the structure has special spinning characteristic and the band gaps of the semiconductors are narrow. The invention relates to a method for preparing a bismuth ferrite composite catalyst, which comprises the steps of preparing a catalyst main body, preparing a persulfate system, preparing pure bismuth ferrite, preparing a persulfate composite catalyst, and carrying out oxidation degradation on antibiotic wastewater by a persulfate system under normal temperature, wherein the pure bismuth ferrite has limited catalytic performance, and the catalytic performance of the pure bismuth ferrite needs to be improved by methods such as doping or loading.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (7)
1. A catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater is characterized in that:
the catalyst is a magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst;
the preparation method of the catalyst for rapidly activating persulfate to oxidize and degrade antibiotic wastewater comprises the following steps: adding silver nitrate and a bismuth ferrite precursor into water, mixing and dissolving, dropwise adding a sodium hydroxide solution, uniformly stirring, adding black phosphorus quantum dots, and stirring; then transferring the mixture to a hydrothermal reaction kettle for synthesis, wherein the synthesis reaction time is 60-600 min, and the reaction temperature is 150-200 ℃; after the reaction is finished, washing and drying the synthesized substance to obtain the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst;
wherein the bismuth ferrite precursor is ferric nitrate and bismuth nitrate;
the dosage ratio of the ferric nitrate, the bismuth nitrate, the silver nitrate, the sodium hydroxide and the black phosphorus quantum dots is 4.04g to 2.425g to (0.3374-0.839g) to (0.084-0.1mol) to (2-5 mg).
2. The catalyst for the rapid activation of persulfate oxidative degradation of antibiotic wastewater as claimed in claim 1, wherein:
wherein the washing method comprises the following steps: and alternately washing the mixture for 2-6 times by using absolute ethyl alcohol and deionized water.
3. The catalyst for the rapid activation of persulfate oxidative degradation of antibiotic wastewater as claimed in claim 1, wherein:
wherein the drying temperature is 60-80 ℃, and the drying time is 2-6 h.
4. The method for applying the catalyst for rapidly activating the persulfate to oxidize and degrade the antibiotic waste water according to any one of claims 1 to 3, wherein the catalyst comprises the following components in percentage by weight:
and (2) putting the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst into the wastewater to be treated, stirring, adding persulfate to start reaction after adsorption balance is achieved, wherein the reaction temperature is 10-25 ℃, and the reaction time is 0.5-6 min.
5. The method for applying the catalyst for the oxidative degradation of antibiotic wastewater by rapidly activating persulfate as claimed in claim 4, wherein:
the mass ratio of the magnetic silver and black phosphorus quantum dot co-modified bismuth ferrite composite catalyst to the persulfate is 1: 1-10.
6. The application method of the catalyst for the oxidative degradation of antibiotic wastewater by rapidly activating persulfate as claimed in claim 4, wherein:
wherein the persulfate is potassium persulfate or sodium persulfate.
7. The method for applying the catalyst for the oxidative degradation of antibiotic wastewater by rapidly activating persulfate as claimed in claim 4, wherein:
wherein the stirring time is 10-30 min.
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