CN117358281A - MnFe-LDH/g-C antibiotics in water can be removed rapidly 3 N 4 Preparation of composite catalyst - Google Patents
MnFe-LDH/g-C antibiotics in water can be removed rapidly 3 N 4 Preparation of composite catalyst Download PDFInfo
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- CN117358281A CN117358281A CN202311306582.1A CN202311306582A CN117358281A CN 117358281 A CN117358281 A CN 117358281A CN 202311306582 A CN202311306582 A CN 202311306582A CN 117358281 A CN117358281 A CN 117358281A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 16
- 229940088710 antibiotic agent Drugs 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 9
- 238000001994 activation Methods 0.000 abstract description 9
- 239000004098 Tetracycline Substances 0.000 abstract description 8
- 229960002180 tetracycline Drugs 0.000 abstract description 8
- 229930101283 tetracycline Natural products 0.000 abstract description 8
- 235000019364 tetracycline Nutrition 0.000 abstract description 8
- 150000003522 tetracyclines Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000007210 heterogeneous catalysis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- RHVUIKVRBXDJSX-ZLELNMGESA-N (2s)-2-azanyl-3-(1h-imidazol-5-yl)propanoic acid Chemical compound OC(=O)[C@@H](N)CC1=CNC=N1.OC(=O)[C@@H](N)CC1=CNC=N1 RHVUIKVRBXDJSX-ZLELNMGESA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- -1 transition metal activated Peroxymonosulfate Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a high-activity MnFe-LDH/g-C3N4 composite catalyst, and the MnFe-LDH/g-C3N4 can efficiently activate Peroxomonosulfate (PMS) to rapidly remove antibiotics in water. The method mainly comprises the following two steps: in the first step, a two-step calcination method is adopted to prepare the ultrathin g-C3N4 nanosheets. The second step is to prepare MnFe-LDHs/g-C3N4 by adopting a coprecipitation method: the molar ratio was set to 2:1 Mn (NO 3) 2.4H2O and Fe (NO 3) 3.9H2O and x mg g-C3N4 (x=0, 30, 60, 90), is denoted as A solution; the mixed solution of NaOH and Na2CO3 was designated as solution B. Dropwise adding the solution B into the solution A, heating at 65 ℃ for 4 hours, centrifuging, washing, drying and grinding the obtained precipitate to obtain the MnFe-LDH/g-C3N4 composite catalyst. The MnFe-LDH/g-C3N4 composite catalyst provided by the invention has excellent PMS adsorption activation performance, and can rapidly remove antibiotics in water through a non-radical path dominant by an electron transfer path, and the removal efficiency of tetracycline can reach 86.2% within 20 min; the raw materials are low in price, nontoxic and harmless, and have high practical value and application prospect.
Description
Technical Field
The invention relates to a high-activity MnFe-LDH/g-C 3 N 4 Preparation method of composite catalyst and MnFe-LDH/g-C 3 N 4 The Peroxymonosulfate (PMS) can be activated with high efficiency, and antibiotics in water can be removed rapidly through a direct electron transfer dominant non-radical pathway.
Background
Antibiotics are widely used for treating diseases of humans and animals, but they are difficult to metabolize and are discharged into water in the form of excretions, which pose serious threats to sustainable development of the environment and public health care, and thus, there is an urgent need to adopt effective antibiotic repair strategies in aquatic environments. Advanced oxidation techniques (AOPs), including photocatalytic oxidation, persulfate (PS) oxidation, fenton oxidation, ozone oxidation, electrochemical oxidation, and the like, are considered as a series of effective technological means for treating antibiotics in wastewater. Among them, PS oxidation technology has the advantages of fast oxidation rate, large treatment flux, high reaction selectivity, etc., and has been widely paid attention to, and its activation methods include uv activation, thermal activation, electrochemical activation, carbon material activation, photocatalytic activation, and transition metal ion activation.
Among them, the treatment of antibiotics with transition metal activated Peroxymonosulfate (PMS) is an effective method, and according to the activation method, it is classified into homogeneous catalysis and heterogeneous catalysis. The homogeneous catalysis is to directly react with PMS by using transition metal ions, the method is easy to leak the metal ions, and improper treatment can cause a large amount of metal ions to remain in solution, thereby causing secondary pollution and affecting circulation; in addition, metal ions in homogeneous catalysis tend to form hydrates with water in an acidic environment and precipitate in an alkaline environment, which all affect catalytic efficiency. Heterogeneous catalysis exists in a solid particle form, so that the defects are basically overcome, and the catalyst has the advantages of high catalytic activity, good chemical stability and the like, and currently researchers usually adopt heterogeneous catalysis to treat pollutants.
The hydrotalcite (LDHs) material is a two-dimensional layered clay, is composed of metal cation laminates and interlayer anions, has the advantages of simple preparation, high stability, adjustable structural energy bands, low price and the like, and in addition, among a plurality of LDHs materials, mnFe-LDH is a rare environment-friendly hydrotalcite without heavy metals and is widely used for treating water environment, so that MnFe-LDH is used as a carrier of transition metal to activate PMS, and a heterogeneous catalysis process is adopted to treat antibiotics in water. However, currently reported MnFe-LDH uses transition metal ions to activate PMS, degrading antibiotics in the free radical way, but the free radicals (. OH,. SO) 4 - ) The defects of low steady-state concentration, short half-life period, high consumption and poor anti-interference performance exist, so that the effect of catalyzing and degrading antibiotics is poor. Compared with the free radical approach, the non-free radical approach has the advantages of high selectivity, good anti-interference performance, high PMS utilization rate and the like. Thus, by introducing g-C in MnFe-LDH 3 N 4 The chemical environment of Mn and Fe elements in hydrotalcite is effectively improved, the adsorption of metal sites to PMS is improved, a complex of metal and PMS is further formed, and antibiotics in water are rapidly removed through a non-radical path dominant by an electron transfer path.
Disclosure of Invention
The aim of the embodiment of the invention is to provide a high-activity MnFe-LDH/g-C 3 N 4 The preparation method of the composite catalyst is characterized in that the composite catalyst can efficiently activate PMS, antibiotics in water can be rapidly removed through a direct electron transfer dominant non-free radical approach, the removal efficiency of the composite catalyst for tetracycline in 20 minutes can reach 86.2%, the removal efficiency of pure MnFe-LDH for tetracycline only reaches 59.1%, and the removal efficiency of the composite catalyst is greatly improved.
To achieve the above object, an embodiment of the present invention provides a MnFe-LDH/g-C 3 N 4 The preparation method of the composite catalyst comprises the following steps:
(1) Adopting a two-step calcination method, taking melamine as a raw material, placing the raw material into a crucible, then transferring the crucible into a muffle furnace for calcination, and carrying out heat preservation treatment for 4 hours at 550 ℃ at a heating rate of 2.3 ℃/min;
(2) Grinding the powder obtained in the step (1), transferring into a muffle furnace again for calcination, and carrying out heat preservation treatment for 2 hours at 550 ℃ at a heating rate of 5 ℃/min to obtain ultrathin g-C 3 N 4 A nanosheet;
(3) Weighing manganese nitrate tetrahydrate (Mn (NO) according to the molar ratio of manganese (Mn) to iron (Fe) of 2:1 3 ) 2 ·4H 2 O) and ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) dissolving in water, followed by the g-C obtained in step (2) 3 N 4 The nano-sheets are dispersed in the solution and stirred for 30 minutes;
(4) Weighing sodium hydroxide (NaOH) and sodium carbonate (Na) 2 CO 3 ) Dissolving in water, and stirring for 30 min;
(5) Dropwise adding the solution obtained in the step (4) into the solution obtained in the step (3), carrying out ultrasonic treatment on the mixed solution for 30 minutes, and then carrying out heating treatment at 65 ℃ for 4 hours;
(6) Centrifuging, washing, drying and grinding the precipitate obtained in the step (5) to obtain MnFe-LDH/g-C 3 N 4 A composite catalyst.
The embodiment of the invention has the following advantages:
the embodiment of the invention provides MnFe-LDH/g-C 3 N 4 The composite catalyst has excellent PMS adsorption activation performance, can rapidly remove antibiotics in water through a non-radical path leading by an electron transfer path, has the removal efficiency of 86.2% on tetracycline within 20 minutes, and solves the defects of low steady-state concentration of free radicals, poor anti-interference performance, short half-life, high consumption and the like existing in the prior MnFe-LDH for degrading antibiotics through the radical path; and MnFe-LDH/g-C 3 N 4 The raw materials of the composite catalyst are low in price, nontoxic and harmless, and have high practical value and application prospect.
Drawings
FIG. 1 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 X-ray diffraction pattern of the composite catalyst.
FIG. 2 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 Transmission electron microscope image of the composite catalyst.
FIG. 3 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 And (3) a performance diagram of the composite catalyst for degrading tetracycline.
FIG. 4 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 Capture experimental performance graph of the composite catalyst.
FIG. 5 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 Open circuit potential diagram of the composite catalyst.
FIG. 6 shows a MnFe-LDH/g-C according to an embodiment of the present invention 3 N 4 Degradation mechanism diagram of composite catalyst.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
3g of melamine is placed in a muffle furnace, a controller is regulated to heat to 550 ℃ at a heating rate of 2.3 ℃/min, the melamine is preserved for 4 hours at the current temperature, and the melamine is taken out when the temperature is reduced to room temperature. Grinding the obtained solid powder, then continuously placing the ground solid powder into a muffle furnace, heating the ground solid powder to 500 ℃ at a heating rate of 5 ℃/min by a regulating controller, preserving the temperature at the current temperature for 2 hours, and taking out the ground solid powder when the temperature is reduced to room temperature. The resulting powder was ground for use.
Example 2
MnFe-LDHs/g-C is prepared by adopting a coprecipitation method 3 N 4 : 1mmol Fe (NO) 3 ) 3 ·9H 2 O、2mmol Mn(NO 3 ) 2 ·4H 2 O was dissolved in 100mL of water and stirring was continued for 30min, followed by 30mg g-C 3 N 4 Adding the mixture into the solution, and marking the mixture as A solution; 0.035mol of NaOH and 0.015mol of Na 2 CO 3 Dissolved in 100mL of water and stirred for 30min to give solution B. Dropwise adding the solution B into the solution A, controlling the pH value of the solution to be between 10.4 and 10.7 by using a pH meter in the dropwise adding process, and after the dropwise adding is finishedThe mixed solution containing the brown flocculent precipitate was sonicated for 30min. After ultrasonic treatment is uniform, the mixture is transferred into a three-neck flask, a heating sleeve is arranged, and the mixture is heated for 4 hours at 65 ℃. After the reaction is finished, the three-neck flask is naturally cooled to room temperature, and the liquid is centrifugally washed for 10min by using absolute ethyl alcohol and deionized water at the rotating speed of 8000r/min by using a high-speed centrifuge, and the process is repeated for 4 times. The obtained precipitate is dried and ground. The MnFe-LDHs/g-C 3 N 4 A composite catalyst, labeled LCN30.
Example 3
The experimental procedure was the same as in example 2, except that 60mg g-C was weighed 3 N 4 Adding the solution A. Obtaining corresponding MnFe-LDHs/g-C 3 N 4 A composite catalyst, labeled LCN60.
Example 4
The experimental procedure was the same as in example 2, except that 90mg g-C was weighed 3 N 4 Adding the solution A. Obtaining corresponding MnFe-LDHs/g-C 3 N 4 A composite catalyst, labeled LCN90.
Example 5
The experimental procedure is the same as in example 2, except that no g-C is added to solution A 3 N 4 . Obtaining granular MnFe-LDH.
Example 6
The MnFe-LDH/g-C3N4 composite catalyst was subjected to phase characterization by using a D8ADVANCE X-ray diffractometer manufactured by Bruker AXS, germany, and FIG. 1 is an X-ray diffraction pattern of the prepared MnFe-LDH/g-C3N4 composite catalyst. As can be seen from fig. 1, the characteristic diffraction peaks at 2θ of MnFe-LDH correspond to (012), (104), (110), (113), (202) and (018) crystal planes, respectively, at 24.2 °, 31.4 °, 37.5 °, 41.4 °, 45.1 ° and 51.5 °. Meanwhile, the 13.0 ° and 27.6 ° characteristic diffraction peaks at 2θ of g—c3n4 may be indexed to (100) and (002) crystal planes, respectively. Characteristic diffraction peaks of MnFe-LDH and g-C3N4 can be simultaneously observed in the composite sample, and the diffraction intensity of g-C3N4 gradually increases with the increase of the mass content, which indicates successful preparation of the composite catalyst.
Example 7
Microcosmic morphological characterization of the MnFe-LDH/g-C3N4 composite catalyst was performed by using a transmission electron microscope manufactured by Japanese Hitachi Co., ltd. And FIG. 2 is a transmission electron microscope image of the prepared MnFe-LDH/g-C3N4 composite catalyst. As can be seen from FIG. 2, the granular MnFe-LDH is uniformly distributed on the lamellar ultrathin g-C3N4 surface.
Example 8
Degradation experiment is performed by using Phchem type photocatalytic reactor manufactured by Beijing New York bit science and technology company, and FIG. 3 shows the prepared MnFe-LDH/g-C 3 N 4 Performance diagram of composite catalyst for degrading tetracycline. Wherein the dosage of the catalyst is 10mg, the concentration of the degradable tetracycline is 50mg/L, and the concentration of PMS is 0.4mM. As can be seen from FIG. 3, with pure MnFe-LDH and g-C 3 N 4 In comparison, all MnFe-LDH/g-C 3 N 4 The performance of the composite catalyst in the aspect of tetracycline degradation is improved. Wherein, LCN60 has the highest catalytic activity, and the degradation efficiency of TC can reach 86.2% within 20 min.
Example 9
Capturing experiments were performed using a Phchem type photocatalytic reactor manufactured by Beijing New York bit technology company, FIG. 4 shows the prepared MnFe-LDH/g-C 3 N 4 Capture experimental performance graph of the composite catalyst. Respectively selecting Tertiary Butanol (TBA), ethanol (EtOH), p-benzoquinone (p-BQ) and L-Histidine (L-Histidine) to capture OH and SO in the solution 4 - 、·O 2 - And 1 O 2 . In addition, nitrobenzene (NB) is selected to capture the OH of the catalyst surface, phenol (Phenols) is selected to capture both OH and SO of the catalyst surface 4 - 。
Example 10
Adopts CHI-760E electrochemical workstation pair MnFe-LDH/g-C produced by Shanghai Chen Hua Co 3 N 4 The composite catalyst was subjected to Open Circuit Potential (OCP) test, and FIG. 5 shows the prepared MnFe-LDH/g-C 3 N 4 OCP diagram of the composite catalyst. As can be seen from fig. 5, the OCP of the composite sample was significantly increased after PMS addition and decreased after TC addition, indicating that a direct electron transfer process exists between the catalyst, PMS and TC, which is a non-radical degradation pathway.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (5)
1. A preparation method of a MnFe-LDH/g-C3N4 composite catalyst comprises the following specific steps:
(1) Adopting a two-step calcination method, taking melamine as a raw material, placing the raw material into a crucible, then transferring the crucible into a muffle furnace for calcination, and carrying out heat preservation treatment for 4 hours at 550 ℃ at a heating rate of 2.3 ℃/min;
(2) Grinding the powder obtained in the step (1), transferring into a muffle furnace again for calcination, and carrying out heat preservation treatment for 2 hours at 550 ℃ at a heating rate of 5 ℃/min to obtain ultrathin g-C 3 N 4 A nanosheet;
(3) Weighing manganese nitrate tetrahydrate (Mn (NO) according to the molar ratio of manganese (Mn) to iron (Fe) of 2:1 3 ) 2 ·4H 2 O) and ferric nitrate nonahydrate (Fe (NO) 3 ) 3 ·9H 2 O) dissolving in water, followed by the g-C obtained in step (2) 3 N 4 The nano-sheets are dispersed in the solution and stirred for 30 minutes;
(4) Weighing sodium hydroxide (NaOH) and sodium carbonate (Na) 2 CO 3 ) Dissolving in water, and stirring for 30 min;
(5) Dropwise adding the solution obtained in the step (4) into the solution obtained in the step (3), carrying out ultrasonic treatment on the mixed solution for 30 minutes, and then carrying out heating treatment at 65 ℃ for 4 hours;
(6) Centrifuging, washing, drying and grinding the precipitate obtained in the step (5) to obtain MnFe-LDH/g-C 3 N 4 A composite catalyst.
2. MnFe-LDH/g-C as claimed in claim 2 3 N 4 The preparation method of the composite catalyst is characterized in that g-C is added in the step (3) 3 N 4 The amount of (2) is 0-90mg.
3. MnFe-LDH/g-C as claimed in claim 2 3 N 4 The preparation method of the composite catalyst is characterized in that the final concentration of sodium hydroxide in the step (4) is 0.35mol/L, and the final concentration of sodium carbonate is 0.15mol/L.
4. MnFe-LDH/g-C as claimed in claim 2 3 N 4 The preparation method of the composite catalyst is characterized in that the final concentration of sodium hydroxide in the step (4) is 0.35mol/L, and the final concentration of sodium carbonate is 0.15mol/L.
5. A MnFe-LDH/g-C prepared by the method of claim 1-4 3 N 4 The composite catalyst is characterized by being capable of effectively adsorbing and activating Peroxomonosulfate (PMS) and being used for rapidly degrading antibiotics in water, wherein the degradation path is mainly non-radical degradation leading to an electron transfer path.
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