CN114956191A - Flake Bi for catalysis of peroxymonosulfate 2 Fe 4 O 9 And preparation method and application thereof - Google Patents
Flake Bi for catalysis of peroxymonosulfate 2 Fe 4 O 9 And preparation method and application thereof Download PDFInfo
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- CN114956191A CN114956191A CN202210417545.7A CN202210417545A CN114956191A CN 114956191 A CN114956191 A CN 114956191A CN 202210417545 A CN202210417545 A CN 202210417545A CN 114956191 A CN114956191 A CN 114956191A
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 70
- 239000011259 mixed solution Substances 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000012266 salt solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 33
- 230000015556 catabolic process Effects 0.000 abstract description 32
- 239000003814 drug Substances 0.000 abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 229940079593 drug Drugs 0.000 abstract description 26
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 241000894006 Bacteria Species 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 113
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 56
- 229960005489 paracetamol Drugs 0.000 description 34
- 239000010865 sewage Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 16
- 229960005404 sulfamethoxazole Drugs 0.000 description 16
- 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 16
- 230000001590 oxidative effect Effects 0.000 description 13
- 241000588724 Escherichia coli Species 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000000872 buffer Substances 0.000 description 7
- 230000001788 irregular Effects 0.000 description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 4
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229960001948 caffeine Drugs 0.000 description 4
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 4
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 4
- 229960000623 carbamazepine Drugs 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 229960001259 diclofenac Drugs 0.000 description 4
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 4
- 229960001680 ibuprofen Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003640 drug residue Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910001412 inorganic anion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- ISEUFVQQFVOBCY-UHFFFAOYSA-N prometon Chemical compound COC1=NC(NC(C)C)=NC(NC(C)C)=N1 ISEUFVQQFVOBCY-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- 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 flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 And a preparation method and application thereof, belonging to the technical field of water body deep treatment. The invention successfully prepares the flaky Bi by using KOH as a mineralizer through a one-step hydrothermal method 2 Fe 4 O 9 The flake Bi 2 Fe 4 O 9 Has high specific surface area and excellent catalytic performanceCan be used for improving the stability. The bismuth ferrite is used together with peroxymonosulfate, is applied to degradation of water medicines or bacteria, has wide applicable pH value range and high stability, and is flaky Bi 2 Fe 4 O 9 The technology for removing pollutants in water by catalyzing the peroxymonosulfate to oxidize by the catalyst can obviously improve the utilization efficiency of the peroxymonosulfate, can be recycled, does not generate secondary pollution, and is a very efficient water advanced treatment technology. Provides a new way for solving the problem of degradation of various drug pollutants in water in the prior art.
Description
Technical Field
The invention belongs to the technical field of water advanced treatment, and relates to a flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 And a preparation method and application thereof.
Background
In recent years, with the development of industry and the improvement of living standard of people, the problem of drug pollution in water is highlighted. Although the concentration of drugs is low compared to other pollutants in sewage wastewater, they are discharged into the nature through long-term accumulation, and finally pose a threat to the survival of organisms. The traditional sewage treatment process is difficult to effectively remove the medicines, so that the finding of a method for effectively removing the medicines in the water body has important significance for the ecological environment.
Advanced oxidation technology, also known as deep oxidation technology, is a sewage treatment process for mineralizing organic pollutants by generating high-activity free radicals. The method has good removal effect on organic pollutants and high reaction efficiency, and gradually becomes a mainstream method for removing the organic pollutants. The conventional feedwater treatment and sewage treatment process has very limited capability of removing drug and bacteria pollutants. Therefore, the water quality safety must be further ensured by means of advanced treatment technology. Wherein the radicals are based on sulfate radicals (SO) 4 ·- ) Advanced oxidation technology has been developed in the field of water pollution treatment in recent years. SO (SO) 4 ·- Is produced by activating persulfates (peroxomonosulfate (PMS) and Peroxodisulfate (PS)). The solid persulfate is easy to transport, store and add, so that the operation process is more convenient, and compared with H 2 O 2 The applicable pH value range of the method is wider. The conventional methods for activating persulfate at present include heating, ultraviolet radiation, ultrasonic wave, nonmetal activation, metal catalyst activation and the like. Wherein, the method of using the catalyst for activation is more economical than other methods, and the catalyst can be reused. Because other methods have additional energy consumption and are difficult to recycle. The iron-based catalyst has low cost, wide raw material source and noIs toxic and harmless, and is widely applied to the research of preparing the catalyst by doping with other elements. However, the catalysts used at present have some problems, such as low catalytic efficiency and certain selectivity. In the face of complex and various pollutants, the catalysts are difficult to meet the actual requirements. Therefore, it is urgently needed to develop and prepare a catalyst which is used in the heterogeneous catalysis persulfate technology, is economical, efficient and has a wide application range, so as to solve the problem of degradation of various drug pollutants in water.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 The preparation method and the application thereof can obviously strengthen the activation of the peroxymonosulfate on the surface of the catalyst to generate SO with high oxidation activity 4 ·- Finally, the hard-to-degrade drug pollutants and bacterial pollutants are removed in an enhanced manner.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention provides a flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 The material comprises the following raw material components in percentage by volume: 80-84% of 6M KOH solution, 2-5% of concentrated nitric acid and 13-15% of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 And (3) a mixed solution of O.
Preferably, the Fe (NO) is 13-15% 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 In O mixed solution, Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: 1.
Preferably, the flake Bi 2 Fe 4 O 9 Has a catalyst specific surface area of 13.32m 2 G, the aperture is 1 nm-10 nm.
The present invention provides the above-mentioned flaky Bi 2 Fe 4 O 9 The preparation method comprises the following steps:
step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution;
step 2) adding the prepared Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding concentrated nitric acid into the O mixed solution, and uniformly mixing to obtain a metal salt solution;
step 3) preparing 6M KOH solution;
step 4) uniformly mixing the metal salt solution and the 6M KOH solution to ensure that the metal salt solution and the KOH solution completely react to obtain a mixed solution;
step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing the solution;
step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 。
Preferably, the specific operation of step 4) is: and dropwise adding the prepared metal salt solution into a KOH solution under the condition of stirring, and continuously stirring for 30-60 min after the dropwise addition is finished to obtain a uniformly mixed solution.
Preferably, in the step 5), the hydrothermal reaction is carried out under the condition of 140 ℃ to 200 ℃.
Preferably, the hydrothermal reaction time is 12h to 24 h.
Preferably, the drying temperature in the step 6) is 60-80 ℃, and the drying time is 4-8 h.
The flaky Bi 2 Fe 4 O 9 The catalyst is used for catalyzing peroxymonosulfate.
Preferably, Bi in flake form 2 Fe 4 O 9 The concentration of (b) is 0.05-0.2 g/L, and the concentration of the peroxymonosulfate is 0.4 mM-0.5 mM.
Compared with the prior art, the invention has the following beneficial effects:
the flaky Bi prepared by the invention for catalyzing peroxymonosulfate 2 Fe 4 O 9 Wide source of raw material, low cost and no poison, the test shows that the flake Bi 2 Fe 4 O 9 The catalyst has the advantages of high specific surface area, high self-stability, wide application range, high catalytic efficiency, high recovery efficiency and no pollution, and is more suitable for solving the problem of water body drug pollution in the technical field of water body deep treatment.
The invention takes ferric nitrate nonahydrate and bismuth nitrate pentahydrate as main raw materials and adopts a uniform and controllable hydrothermal method to prepare irregular flaky Bi 2 Fe 4 O 9 A catalyst. Furthermore, compared to the prior art (Wen-Da Oh, Victor W.C.Chang, Teik-Thye Lim.environmental Science&Pollution Research,2019,26: 1026- 4 ·- The method can remove pollutants such as difficultly degraded drugs and bacteria, remarkably improve water quality and ensure water quality safety. The preparation method is simple and low in cost.
The present invention provides a method for producing a bismuth alloy using the above flaky Bi 2 Fe 4 O 9 Use as catalyst for the catalysis of peroxymonosulfates by utilizing Bi in flake form 2 Fe 4 O 9 The high-efficiency activation of the catalyst on the surface of the peroxymonosulfate ensures that a reaction system generates SO with strong oxidizing property 4 ·- And the enhanced removal of the drug and bacteria pollutants is realized. Wide applicable pH value range, high stability and flaky Bi 2 Fe 4 O 9 The technology for removing pollutants in water by catalyzing the peroxymonosulfate through oxidation by the catalyst can obviously improve the utilization efficiency of the peroxymonosulfate, can be recycled, does not produce secondary pollution, and is a very efficient water deep treatment technology.
Drawings
In order to more clearly explain the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows a sheet Bi of the present invention 2 Fe 4 O 9 Wherein the image a is an SEM image at a magnification of 25000 and the image b is an SEM image at a magnification of 80000.
FIG. 2 shows a sheet Bi of the present invention 2 Fe 4 O 9 XRD pattern of (a).
FIG. 3 shows a sheet Bi of the present invention 2 Fe 4 O 9 A TEM image of (a).
FIG. 4 shows a Bi sheet of the present invention 2 Fe 4 O 9 Graph of the degradation effect on AMP at different pH values.
FIG. 5 shows a Bi sheet according to the present invention 2 Fe 4 O 9 Graph of the degradation effect of AMP in the presence of different inorganic anions.
FIG. 6 shows a sheet Bi of the present invention 2 Fe 4 O 9 For the total phosphorus content in the AMP solution and the total phosphorus content in the secondary effluent (0.2 mg. L) -1 ) Degradation effect graph when consistent.
FIG. 7 shows a Bi sheet according to the present invention 2 Fe 4 O 9 The experimental results are repeated as recovery of the catalyst.
FIG. 8 shows a sheet-like Bi of the present invention 2 Fe 4 O 9 The degradation effect of different drugs is shown.
FIG. 9 shows Bi in the prior art 2 Fe 4 O 9 Graph of the degradation effect on different pH values of SMX.
FIG. 10 shows a Bi sheet according to the present invention 2 Fe 4 O 9 Graph of the degradation effect on SMX.
FIG. 11 shows a Bi sheet according to the present invention 2 Fe 4 O 9 The bactericidal effect on bacteria (Escherichia coli) is shown.
Detailed Description
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, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the embodiments of the present invention, it should be noted that if the terms "upper", "lower", "horizontal", "inner", etc. are used for indicating the orientation or positional relationship based on the orientation or positional relationship shown in the drawings or the orientation or positional relationship which is usually arranged when the product of the present invention is used, the description is merely for convenience and simplicity, and the indication or suggestion that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, cannot be understood as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
Furthermore, the term "horizontal", if present, does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should be further noted that unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The invention is described in further detail below with reference to the accompanying drawings:
referring to FIGS. 1 to 3, the present invention provides a flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 The material comprises the following raw material components in percentage by volume: 80-84% of 6MKOH, 2-5% of concentrated nitric acid and 13-15% of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Mixed solution of O, 13-15% of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 In O mixed solution, Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: 1.
Example one
The invention also provides the flaky Bi 2 Fe 4 O 9 The preparation method comprises the following steps:
step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution: the invention prepares the mixed solution of ferric nitrate nonahydrate and bismuth nitrate pentahydrate according to the molar ratio of 1:1 to prepare Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution 13.5 mL.
Step 2) adding the prepared Fe (NO) 3 ) 3 · 9 H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding concentrated nitric acid into the O mixed solution, and uniformly mixing to obtain a metal salt solution: namely, to the above Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 4.5mL of concentrated nitric acid was added to the O-mixed solution to prepare 18mL of a metal salt solution.
Step 3) preparing a 6M KOH solution: taking 72mL of 6MKOH solution;
step 4), uniformly mixing the metal salt solution with the 6M KOH solution to completely react to obtain a mixed solution: and dropwise adding the prepared metal salt solution into the prepared KOH solution under the stirring condition, and continuously stirring for 60min to fully mix and react.
Step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing liquid: and transferring the mixed solution into a reaction kettle, sealing properly, and carrying out hydrothermal reaction in an electrothermal blowing dry box under the reaction condition of 160 ℃ for 24 hours.
Step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 : after the reaction is finished, washing the reaction product for a plurality of times by using ethanol and deionized water to remove impurities in the product, drying the reaction product for 6 hours at 70 ℃ to remove water, and grinding the dried sample to obtain irregular flaky Bi 2 Fe 4 O 9 And (3) powder.
Example two
Step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution: the invention prepares the mixed solution of ferric nitrate nonahydrate and bismuth nitrate pentahydrate according to the molar ratio of 1:1 to prepare Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution 12.6 mL.
Step 2) adding the prepared Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding concentrated nitric acid into the O mixed solution, and uniformly mixing to obtain a metal salt solution: namely, to the above Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 1.8mL of concentrated nitric acid was added to the O-mixed solution to prepare 14.4mL of a metal salt solution.
Step 3) preparing a 6M KOH solution: taking 75.6mL of 6M KOH solution;
step 4), uniformly mixing the metal salt solution with the 6M KOH solution to completely react to obtain a mixed solution: and dropwise adding the prepared metal salt solution into the prepared KOH solution under the stirring condition, and continuously stirring for 30min to fully mix and react.
Step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing liquid: and transferring the mixed solution into a reaction kettle, sealing properly, and carrying out hydrothermal reaction in an electrothermal blowing dry box under the reaction condition of 200 ℃ for 12 hours.
Step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 : after the reaction is finished, washing the reaction product for a plurality of times by using ethanol and deionized water to remove impurities in the product, drying the reaction product for 4 hours at 80 ℃ to remove water, and grinding the dried sample to obtain irregular flaky Bi 2 Fe 4 O 9 And (3) powder.
EXAMPLE III
The invention also provides the flaky Bi 2 Fe 4 O 9 The preparation method comprises the following steps:
step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution: the invention prepares the mixed solution of ferric nitrate nonahydrate and bismuth nitrate pentahydrate according to the molar ratio of 1:1 to prepare Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution 11.7 mL.
Step 2) adding prepared Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding concentrated nitric acid into the O mixed solution, and uniformly mixing to obtain a metal salt solution: i.e. to the above Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 3.6mL of concentrated nitric acid was added to the O-mixed solution to prepare 15.3mL of a metal salt solution.
Step 3) preparing a 6M KOH solution: taking 74.7mL of 6M KOH solution;
step 4), uniformly mixing the metal salt solution with the 6M KOH solution to completely react to obtain a mixed solution: and dropwise adding the prepared metal salt solution into the prepared KOH solution under the stirring condition, and continuously stirring for 50min to fully mix and react.
Step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing liquid: and transferring the mixed solution into a reaction kettle, sealing properly, and carrying out hydrothermal reaction in an electrothermal blowing dry box under the reaction condition of 180 ℃ for 18 hours.
Step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 : after the reaction is finished, washing the reaction product for a plurality of times by using ethanol and deionized water to remove impurities in the product, drying the reaction product for 8 hours at the temperature of 60 ℃ to remove water, and grinding the dried sample to obtain irregular flaky Bi 2 Fe 4 O 9 And (3) powder.
Example four
The invention also provides the flaky Bi 2 Fe 4 O 9 The preparation method comprises the following steps:
step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution: according to the method, a mixed solution of ferric nitrate nonahydrate and bismuth nitrate pentahydrate is prepared according to a molar ratio of 1:1, 4.04g of ferric nitrate nonahydrate and 4.8507g of bismuth nitrate pentahydrate are weighed respectively, the weighed materials are added into a beaker together, deionized water is added into the beaker to dissolve the mixture to 13mL, and Fe (NO) is prepared 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 And (4) mixing the components.
Step 2) adding the prepared Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding concentrated nitric acid into the O mixed solution, and uniformly mixing to obtain a metal salt solution: namely, to the above Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 2mL of concentrated nitric acid is added into the O mixed solution to prepare 15mL of metal salt solution.
Step 3) preparing a 6M KOH solution: weighing 25.2g KOH solid, adding deionized water into a beaker to dissolve the KOH solid to 75mL, and preparing into 6 mol.L -1 KOH solution ofLiquid;
step 4), uniformly mixing the metal salt solution with the 6M KOH solution to completely react to obtain a mixed solution: and dropwise adding the prepared metal salt solution into the prepared KOH solution under the stirring condition, and continuously stirring for 30-60 min to fully mix and react.
Step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing liquid: and transferring the mixed solution into a reaction kettle, sealing properly, and carrying out hydrothermal reaction in an electrothermal blowing dry box under the reaction condition of 180 ℃ for 24 hours.
Step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 : after the reaction is finished, washing the reaction product for a plurality of times by using ethanol and deionized water to remove impurities in the product, drying the reaction product for 8 hours at the temperature of 80 ℃ to remove water, and grinding the dried sample to obtain irregular flaky Bi 2 Fe 4 O 9 And (3) powder.
Referring to FIG. 1, the Bi 2 Fe 4 O 9 The catalysts are all in irregular flake shapes, and the sizes of the flakes are uniform; referring to FIG. 2, the substance is identified as Bi 2 Fe 4 O 9 And the crystallization is good; see FIG. 3, Bi 2 Fe 4 O 9 The nano-sheet is very thin and has irregular shape and size, and the lattice stripes presented on the surface are obvious; calculated as the flake Bi 2 Fe 4 O 9 Has a catalyst specific surface area of 13.32m 2 The pore diameter is 1 nm-10 nm.
The flake Bi 2 Fe 4 O 9 Use of bismuth as a catalyst for the catalysis of peroxymonosulfate, wherein the bismuth is in the form of flakes 2 Fe 4 O 9 The concentration of (b) is 0.05-0.2 g/L, and the concentration of peroxymonosulfate is 0.4 mM-0.5 mM.
The application method comprises the following steps:
bi in sheet form 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into sewage containing drug residue or bacteria residue, and mixing to obtain the final productReaction solution; flake Bi in the reaction solution 2 Fe 4 O 9 The concentration of the peroxymonosulfate oxidant is 0.05-0.2 g/L, and the concentration of the peroxymonosulfate oxidant is 0.5 mM;
na at a concentration of 0.1g/L 2 B 4 O 7 ·7H 2 O is used as a buffering agent, and the pH value of the reaction solution is adjusted to 7.0 +/-0.5 so as to carry out the reaction;
sampling and filtering the reaction solution every 1-5 min;
detecting the drug concentration of the sampled reaction solution by high performance liquid chromatography;
the degradation rate is calculated by the following specific method:
wherein C is the concentration of drug or bacteria residue in the sampled reaction solution, C 0 Is the concentration of drug or bacteria remaining in the initial wastewater;
after the degradation rate calculated by sampling for several times is not changed, the flaky Bi is treated 2 Fe 4 O 9 And (5) recovering to finish the degradation process of the drug residue in the sewage.
Preferably, the concentration of the drug in the water body to be treated is 0.025-0.125 mM, and the pH value of the water body to be treated is 3.0-9.0.
EXAMPLE five
Referring to FIG. 4, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into sewage containing AMP (acetaminophen), and mixing to obtain reaction solution; wherein, Bi 2 Fe 4 O 9 The concentration of (A) is 0.1g/L, the concentration of AMP (acetaminophen) in the wastewater is 0.025mM, the concentration of peroxymonosulfate is 0.5mM, and the buffer Na is 2 B 4 O 7 ·7H 2 The concentration of O is 0.1g/L, and the reaction liquid is divided into 4 groups;
correspondingly adjusting the pH values of the four groups of reaction liquid to 3, 5, 7 and 10 to react;
sampling and filtering the reaction solution every 0min, 0.5min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the AMP concentration of the reaction solution by high performance liquid chromatography;
calculating the degradation rate;
thus, the flaky Bi can be seen 2 Fe 4 O 9 The method can be applied to the environment of drug residue or bacteria residue degradation under different pH values, wherein the degradation effect on AMP (acetaminophen) is the best in the environment with the pH value of 7.
EXAMPLE six
Referring to FIG. 5, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into sewage containing AMP (acetaminophen), and mixing to obtain reaction solution; wherein, Bi 2 Fe 4 O 9 The concentration of (A) is 0.1g/L, the concentration of AMP drug in the sewage is 0.025mM, and the concentration of peroxymonosulfate is 0.5 mM;
with Na 2 B 4 O 7 ·7H 2 Adjusting the pH value of the reaction solution to 7.0 +/-0.5 by using an O buffer agent to perform reaction;
sampling and filtering the reaction solution every 0min, 0.5min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the AMP concentration of the reaction solution by high performance liquid chromatography;
calculating the degradation rate;
thus, the flaky Bi 2 Fe 4 O 9 The method can be applied to the degradation effect of AMP in the presence of different inorganic anions, and proves that except for phosphate ions with high concentration, other anions have no obvious influence on the AMP, which is beneficial to the practical application of materials.
EXAMPLE seven
Referring to FIG. 6, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into sewage containing AMP (acetaminophen), and mixing to obtain reaction solution; wherein, Bi 2 Fe 4 O 9 The concentration of (A) is 0.1g/L,the concentration of AMP drug in the sewage is 0.025mM, and the concentration of peroxymonosulfate is 0.5 mM;
with Na 2 B 4 O 7 ·7H 2 Adjusting the pH value of the reaction solution to 7 by using an O buffer so as to perform reaction;
sampling and filtering the reaction solution every 0min, 0.5min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the drug concentration of the sampled reaction solution by high performance liquid chromatography;
calculating degradation rate;
is Bi 2 Fe 4 O 9 Catalyst for the total phosphorus content in AMP (acetaminophen) solution and the total phosphorus content in secondary effluent (0.2 mg. L) -1 ) The consistent degradation effect shows that in actual sewage treatment, the degradation effect of the whole system on AMP (acetaminophen) is not greatly influenced due to the low content of phosphate ions, and the catalyst can still keep excellent catalytic efficiency, so that the degradation efficiency of AMP (acetaminophen) can reach more than 98% within 2 min.
Example eight
Referring to FIG. 7, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into sewage containing AMP (acetaminophen), and mixing to obtain reaction solution; wherein, Bi 2 Fe 4 O 9 The concentration of (A) is 0.15g/L, the concentration of AMP drug in the sewage is 0.025mM, and the concentration of peroxymonosulfate is 0.5 mM;
with Na 2 B 4 O 7 ·7H 2 Adjusting the pH value of the reaction solution to 7 by using an O buffer to perform reaction;
sampling and filtering the reaction solution every 0min, 0.5min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the drug concentration of the sampled reaction solution by high performance liquid chromatography;
calculating the degradation rate;
it was found that Bi flakes after use as a catalyst 2 Fe 4 O 9 The catalyst is recycled and repeatedly used as a catalyst, and the result shows that the degradation effect of the catalyst on AMP (acetaminophen) after 5 times of recycling can reach more than 98 percent after 5min, and only the flaky Bi is not proved 2 Fe 4 O 9 The material has high catalytic effect and stability as a catalyst.
Example nine
Referring to FIG. 8, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and a peroxymonosulfate oxidant into sewage containing IBP (ibuprofen), DCF (diclofenac), PMD (prometone), AMP (acetaminophen), SMX (sulfamethoxazole), CBZ (carbamazepine) and CAF (caffeine) medicines respectively, and mixing uniformly to form reaction liquid respectively; wherein, Bi 2 Fe 4 O 9 The concentration of the compound is 0.1g/L, the concentration of the medicine in the sewage is 0.0025mM, and the concentration of the peroxymonosulfate is 0.5 mM;
with Na 2 B 4 O 7 ·7H 2 Adjusting the pH value of the reaction solution to 7.0 +/-0.5 by using an O buffer agent to perform reaction;
sampling and filtering each reaction solution every 0min, 0.5min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the drug concentration of the sampled reaction solution by high performance liquid chromatography;
calculating the degradation rate;
it was found that the flaky Bi 2 Fe 4 O 9 Material, the flake Bi 2 Fe 4 O 9 The material as a catalyst can be used for treating different antibiotic drugs including IBP (ibuprofen), DCF (diclofenac), PMD (prometone), AMP (acetaminophen), SMX (sulfamethoxazole), CBZ (carbamazepine), CAF (caffeine) and the like, and the degradation rate of the material can reach more than 90% when the material reacts for 2min, and the degradation of the material on SMX (sulfamethoxazole) is particularly obvious.
Example ten
Referring to FIGS. 9 and 10, the sheet Bi 2 Fe 4 O 9 Adding the catalyst and peroxymonosulfate oxidant into SMX (sulfamethoxazole) medicine sewage, and mixingHomogenizing to form a reaction solution; wherein, Bi 2 Fe 4 O 9 The concentration of the compound is 0.1g/L, the concentration of the medicine in the sewage is 0.002mM, and the concentration of the peroxymonosulfate is 0.4 mM;
with Na 2 B 4 O 7 ·7H 2 Adjusting the pH value of the reaction solution to 7 by using an O buffer so as to perform reaction;
sampling and filtering each reaction solution every 0min, 1min, 2min, 3min, 4min, 5min, 7.5min and 10min respectively;
detecting the drug concentration of the sampled reaction solution by high performance liquid chromatography;
calculating the degradation rate;
through comparison, the results of the experiments were found to be comparable to the prior study (Wen-Da Oh, Victor W.C. Chang, Teik-thin Lim.A comprehensive performance evaluation of heterologous Bi 2 Fe 4 O 9 /peroxymonosulfate system for sulfamethoxazole degradation[J].Environmental Science&Polarization Research,2019,26: 1026-: in the literature, a two-step method is adopted and NaOH is used as a mineralizer, while the patent successfully prepares flaky Bi with the thickness of dozens of nanometers by using a one-step hydrothermal method and KOH as the mineralizer 2 Fe 4 O 9 Bi prepared in the literature 2 Fe 4 O 9 The morphology of the nano-plate is regular with a thickness of hundreds of nanometers. And compared with the research, the flaky Bi prepared by the invention 2 Fe 4 O 9 The catalytic peroxymonosulfate has better removal effect on organic matters. In the prior art, Bi 2 Fe 4 O 9 The catalyst catalyzes the Sulfamethoxazole (SMX) to be degraded by peroxymonosulfate to react for 5min under the condition that the pH value is 7, the SMX is degraded by 75 percent, even under the optimal condition, the degradation efficiency reaches 80 percent, the SMX is not completely degraded after reacting for 30 min. The flake Bi prepared by the invention 2 Fe 4 O 9 Under the condition that the pH value of the catalyst is 7 and other conditions are the same, the SMX can be completely degraded within 3min, and a remarkable degradation effect is shown.
EXAMPLE eleven
Referring to FIG. 11, the sheet Bi 2 Fe 4 O 9 AsAdding the catalyst and the peroxymonosulfate oxidant into the sewage containing the escherichia coli, and uniformly mixing to form a reaction solution 1; wherein, Bi 2 Fe 4 O 9 The concentration of (2) is 0.1g/L, and the concentration of Escherichia coli in the sewage is 10 5 CFU/mL, the concentration of peroxymonosulfate is 0.5 mM;
adding a peroxymonosulfate oxidant into the sewage containing the escherichia coli, and uniformly mixing to form a reaction liquid 2; wherein the concentration of Escherichia coli in the sewage is 10 5 CFU/mL, the concentration of peroxymonosulfate is 0.5 mM;
bi in sheet form 2 Fe 4 O 9 As a catalyst, independently adding the catalyst into sewage containing escherichia coli, and uniformly mixing to form a reaction solution 3; wherein, Bi 2 Fe 4 O 9 The concentration of (2) is 0.1g/L, and the concentration of Escherichia coli in the sewage is 10 5 CFU/mL；
Will contain Bi 3+ Adding salt into sewage containing escherichia coli, and uniformly mixing to form a reaction solution 4; wherein the concentration of Escherichia coli in the sewage is 10 5 CFU/mL，Bi 3+ The concentration of (A) is 2.5 mg/L;
with Na 2 B 4 O 7 ·7H 2 The O buffer adjusted the pH values of the reaction solution 1, the reaction solution 2, the reaction solution 3, and the reaction solution 4 to 6.5, respectively, to allow them to react;
sampling and filtering the reaction solution every 5 min;
detecting the concentration of escherichia coli in the sampled reaction solution by high performance liquid chromatography;
calculating the degradation rate;
it can be seen that the catalyst, the oxidant and Bi are present separately 3+ Degradation of E.coli, flaky Bi 2 Fe 4 O 9 The catalysis is matched with the peroxymonosulfate, and the sterilization effect on the escherichia coli is obviously better. Therefore, the catalyst obtained by the method is not only limited to organic pollutants in the aspect of catalyzing the degradation of peroxymonosulfate, but also can be applied in the aspects of sterilization and even more.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Flaky Bi for catalyzing peroxymonosulfate 2 Fe 4 O 9 The composite material is characterized by comprising the following raw material components in percentage by volume: 80-84% of 6M KOH solution, 2-5% of concentrated nitric acid and 13-15% of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 And (3) a mixed solution of O.
2. The Bi flakes of claim 1 for catalyzing peroxymonosulfate 2 Fe 4 O 9 Characterized in that 13 to 15% of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 In the O mixed solution, Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: 1.
3. The flake-like Bi for catalyzing peroxymonosulfate of claim 1 or 2 2 Fe 4 O 9 Characterized in that the flake Bi 2 Fe 4 O 9 Has a catalyst specific surface area of 13.32m 2 G, the aperture is 1 nm-10 nm.
4. The flake-like Bi of any one of claims 1 to 3 2 Fe 4 O 9 The preparation method is characterized by comprising the following steps:
step 1) preparation of Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 O mixed solution;
step 2) adding prepared Fe (NO) 3 ) 3 ·9H 2 O and Bi (NO) 3 ) 3 ·5H 2 Adding into O mixed solutionAdding concentrated nitric acid, and uniformly mixing to obtain a metal salt solution;
step 3) preparing 6M KOH solution;
step 4) uniformly mixing the metal salt solution and the 6M KOH solution to ensure that the metal salt solution and the KOH solution completely react to obtain a mixed solution;
step 5) carrying out hydrothermal reaction on the mixed solution to obtain Bi 2 Fe 4 O 9 Mixing the solution;
step 6) adding Bi 2 Fe 4 O 9 Washing the mixed solution to remove impurities, drying and grinding to obtain the flaky Bi 2 Fe 4 O 9 。
5. The Bi flakes of claim 4 2 Fe 4 O 9 The preparation method is characterized in that the specific operation of the step 4) is as follows: and (3) dropwise adding the prepared metal salt solution into the KOH solution under the condition of stirring, and continuously stirring for 30-60 min after the dropwise addition is finished to obtain a uniformly mixed solution.
6. The Bi flakes of claim 4 2 Fe 4 O 9 The preparation method of (1) is characterized in that, in the step 5), the hydrothermal reaction condition is 140-200 ℃.
7. The Bi flakes of claim 6 2 Fe 4 O 9 The preparation method is characterized in that the hydrothermal reaction time is 12-24 h.
8. The Bi flakes of claim 4 2 Fe 4 O 9 The preparation method is characterized in that the drying temperature in the step 6) is 60-80 ℃, and the drying time is 4-8 h.
9. The Bi flakes of any of claims 1 to 3 2 Fe 4 O 9 The catalyst is used for catalyzing peroxymonosulfate.
10. The method of claim 9Bi in a flake form 2 Fe 4 O 9 Use of bismuth as a catalyst for the catalysis of peroxymonosulfate, characterized in that the bismuth is in the form of flakes 2 Fe 4 O 9 The concentration of (b) is 0.05-0.2 g/L, and the concentration of the peroxymonosulfate is 0.4 mM-0.5 mM.
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