CN114768846A - Preparation method and application of visible light catalytic material for efficiently degrading enoxacin - Google Patents
Preparation method and application of visible light catalytic material for efficiently degrading enoxacin Download PDFInfo
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- CN114768846A CN114768846A CN202210299063.6A CN202210299063A CN114768846A CN 114768846 A CN114768846 A CN 114768846A CN 202210299063 A CN202210299063 A CN 202210299063A CN 114768846 A CN114768846 A CN 114768846A
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- 229960002549 enoxacin Drugs 0.000 title claims abstract description 26
- IDYZIJYBMGIQMJ-UHFFFAOYSA-N enoxacin Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 IDYZIJYBMGIQMJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 7
- 230000000593 degrading effect Effects 0.000 title description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- 238000006731 degradation reaction Methods 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002555 FeNi Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000011941 photocatalyst Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000003933 environmental pollution control Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 239000000969 carrier Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
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- 238000010170 biological method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of environmental pollution control engineering, and provides a preparation method and application of a visible light high-efficiency degradation enoxacin catalytic material. With lamellar iron-nickel double hydroxide and modified g-C3N4For the precursor, g-C was constructed by calcination phosphating3N4the/FeNi/P heterojunction photocatalyst is applied to the visible light efficient degradation of enoxacin in a water body. The spectral response range under visible light can be enlarged by constructing a heterojunction structure, and the band gap structure can be regulated and controlled. The bridging effect of P can be utilized to strengthen the photon-generated carrier migration capability of the heterojunction catalyst and improve the photocatalytic reduction capability. The degradation rate of enoxacin in the prepared heterojunction material within 40min can reach 99%. The photocatalyst has simple preparation method, wide raw material source and low priceLow cost and easy large-scale production.
Description
Technical Field
The invention belongs to the technical field of environmental pollution control engineering, relates to the technical research on preparation of heterojunction photocatalytic materials, in particular to preparation of iron-nickel diphosphide and graphite-phase carbon nitride heterojunction photocatalytic materials, and particularly relates to innovation of a method for degrading enoxacin by applying the catalyst with high visible light efficiency and low consumption.
Background
Enoxacin (ENO) is a third-generation fluoroquinolone antibiotic, has a good treatment effect, is low in allergy rate, can be used for bacterial infection diseases of human without selectivity, but is difficult to completely decompose in a human body, can exist in a water body for a long time after entering the environment through a metabolic process, and has potential risks to an ecosystem and human health.
The catalytic method achieves the purpose of degrading organic pollutants in water by converting solar energy into chemical energy, and has the advantages of greenness, sustainability, no secondary pollution and the like compared with the traditional methods such as a biological method, chemical reduction and the like. The method is suitable for removing ENO in the environmental water body. In recent years, a non-metallic semiconductor-graphite phase carbon nitride (g-C)3N4) The photocatalyst has a proper energy band structure and excellent catalytic activity, and is a photocatalytic material with potential practical application value. However, conventional methods such as "Zhou et al Novel double-effective Z-scheme heterojunction with g-C3N4, Ti3C2 MXene and black phosphor for improving visual light-induced degradation of ciprofloxacin3N4The problems of low light utilization rate, narrow spectral response range, easy recombination of photon-generated carriers, low specific surface area, few reaction sites and the like caused by serious pi-pi stacking phenomenon exist, so that the g-C is greatly limited3N4Practical application of[1]. Based on the above problems, the articles "meso Carbon Nitride-silicon composites by a combined sol-gel/thermal condensation and reaction as photocatalysts", "Stabilization of Single atom on graphical Carbon Nitride", "A surface Band Alignment of Polymeric Carbon Nitride Semiconductors to structural isotope interconnections" can respectively improve g-C Carbon composites by morphology control, Metal or nonmetal doping, and structure of the junction heterogeneity3N4Although the photocatalytic performance can be improved to a certain extent and the recombination of photogenerated carriers is inhibited, the photocatalytic performance cannot meet the requirement of a photocatalytic degradation technology on the photocatalytic performance. Therefore, the patent adopts a morphology regulation and control and heterostructure building cooperation strategy and adopts a soft templateIn the modification of g-C by auxiliary phosphorization calcination method3N4Constructing a ternary heterojunction on the substrate, and bridging iron-nickel diphosphide and modified g-C by P3N4The mobility of photogenerated carriers between heterojunction interface electric fields is enhanced, the photogenerated carrier recombination is inhibited, and the formed heterojunction can effectively improve the redox capability of the photogenerated carriers and broaden the spectrum absorption range, so that the purpose of improving the degradation performance of the photocatalytic material is achieved, and the purpose of degrading ENO in the environmental water with high efficiency and low consumption is realized.
Disclosure of Invention
For the current limit g-C3N4The application and development of the base photocatalysis material have low light utilization rate, easy recombination of photon-generated carriers and the like. The invention provides a method for bridging iron-nickel diphosphide and modified g-C by P3N4A method for forming a heterojunction photocatalytic material is applied to efficient visible light degradation of ENO in a water body. With lamellar iron-nickel double hydroxide and modified g-C3N4The heterojunction structure is used as a precursor, the spectral absorption range and the light utilization rate under visible light are increased, the band gap structure is regulated and controlled, the photocatalytic reduction capability is improved, and the photogenerated carrier migration capability of the heterojunction catalyst is enhanced by utilizing the bridging action of P, so that the innovation of the ENO method with high visible light efficiency and low consumption is realized.
The technical scheme of the invention is as follows:
a preparation method of a visible light high-efficiency degradation enoxacin catalytic material comprises the following steps:
step 1: dispersing melamine and cyanuric acid in a mass ratio of 1:10-10:1 in deionized water, wherein the cyanuric acid concentration is 0.15-1.5mol/L, stirring the mixed solution to be uniform, drying in an oven at 60-80 ℃, putting the dried solution into a tubular furnace, and putting the dried solution into a N-type furnace2In the atmosphere, the reaction temperature is 450-650 ℃, the reaction time is 3-6h, the reaction is cooled to room temperature after the reaction is finished, deionized water and ethanol are alternately washed for three times, and the modified g-C is obtained by drying at 60 DEG C3N4。
Step 2: dispersing ferric nitrate, nickel sulfate and urea in 10-100 mL of deionized water, and stirring until the mixture is uniform, wherein the molar ratio of the ferric nitrate to the nickel sulfate is 1:1.5, and the concentrations of the ferric nitrate and the urea are 8-80mmol/L and 40-400mmol/L respectively; transferring the obtained solution into a reaction kettle, maintaining the solution in an oven at the temperature of 130-150 ℃ for 12-24h, cooling, washing and drying to obtain the lamellar FeNi-LDH.
And step 3: the lamellar iron-nickel double hydroxide obtained in the step 2 and the modified g-C obtained in the step 13N4Uniformly mixed (1: 2-1: 40), and added with a phosphorus source, namely sodium hypophosphite (the addition amount of the phosphorus source is g-C)3N45-20 times the mass) are simultaneously placed in a tube furnace, N2The atmosphere, the calcination temperature is 300-500 ℃, the reaction time is 1-4h, and g-C is obtained3N4the/FeNi/P heterojunction photocatalytic material.
g-C obtained by the preparation method3N4the/FeNi/P heterojunction photocatalytic material is used as a photocatalyst to degrade enoxacin, and reacts for 40min at 25 ℃ under the condition of visible light, and the degradation rate of 20ppm enoxacin reaches more than 99%.
Lamellar FeNi-LDH is taken as a precursor of iron-nickel biphosphite, and the PH released by a phosphorus source in the calcining process3The method can carry out in-situ replacement on O atoms in FeNi-LDH, retain the original lamellar structure, effectively inhibit the agglomeration of iron-nickel diphosphides, reduce the formation of new metal phosphide composite centers in a heterojunction catalyst and improve the migration capability of photon-generated carriers.
Iron-nickel phosphide and modified g-C3N4The mobility of photon-generated carriers among the heterojunction structures can be further improved through P bridging, and the recombination rate of the photon-generated carriers is reduced.
The invention has the beneficial effects that: in the invention, g-C is used for the first time3N4the/FeNi/P is used as a photocatalytic material to realize the high-efficiency and low-consumption degradation of the visible light of ENO. Preparation of modified g-C by morphology control method3N4The aggregation of the photo-generated electrons is inhibited, the reactive active sites are increased, and N vacancies are added on the surface of the photo-generated electrons, so that the separation capability of carriers is improved. Then layered FeNi-LDH and modified g-C3N4The raw material, sodium hypophosphite is taken as a phosphorus source, and the g-C is prepared by high-temperature calcination3N4The method has wide raw materials and no precious materialsThe preparation cost is low due to metal doping. After high-temperature calcination, O in FeNi-LDH is replaced by P to form biphosphite, and meanwhile, P can also replace lamellar biphosphite with g-C3N4Bridging, which can further alter the material valence band, conduction band position, and band gap width. In addition, the bridging effect of P can obviously improve the separating capability of photogenerated carriers, and further, g-C is reserved3N4The original photocatalytic oxidation capability is simultaneously enhanced, and the originally weaker photocatalytic reduction capability is further enhanced.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the technical solutions.
Example 1
g-C3N4Preparation method of/FeNi/P
Preparing modified CN: dispersing 5 g of melamine and 5 g of cyanuric acid in 50 mL of deionized water, stirring the mixed solution until the mixed solution is uniform, drying the mixed solution in an oven at 60 ℃, and putting the dried mixed solution into a tube furnace in a N mode2Calcining in atmosphere for 4h, cooling to room temperature after the reaction is finished, alternately washing with deionized water and ethanol for three times, and drying at 60 ℃ to obtain modified g-C3N4. Calcination temperatures of 450, 500, 550 and 600 ℃ respectively to obtain a series of modified g-C3N4Named modified CN-450, modified CN-500, modified CN-550 and modified CN-600. Through the characterization of the appearance, the structure and the optical property, the specific surface area of the modified CN-550 is the largest, and the appearance is a hollow coralliform structure with a large number of holes on the surface. At the same time, by X-ray photoelectron spectroscopy, solid state13C nuclear magnetic resonance and electron spin resonance spectroscopy can know that the N defect structure in the modified CN-550 is the most, and the subsequent heterojunction formation and the capture of photon-generated carriers are facilitated, so that the modified CN-550 can be used as a subsequent heterojunction catalyst substrate. In addition, tests show that the specific surface area of the modified CN series material is gradually increased along with the increase of the temperature, and the number of N defects is increased. However, when the temperature exceeded 550 ℃, the yield of modified CN gradually decreased, and it was known that the yield became 0 at 650 ℃.
Preparing iron-nickel double hydroxide: dispersing ferric nitrate, nickel sulfate and urea in 50 mL of deionized water, and stirring until uniform, wherein the molar ratio of the ferric nitrate to the nickel sulfate is 1:1.5, and the concentrations of the ferric nitrate and the urea are 40 mmol/L and 200 mmol/L respectively. Transferring the obtained solution into a reaction kettle, maintaining the temperature of 150 ℃ in an oven for 12 hours, cooling, washing and drying to obtain the lamellar iron-nickel double hydroxide (FeNi-LDH).
g-C3N4Preparation of/FeNi/P heterojunction catalyst: weighing 1 g of modified CN-550 powder and 0.15 g of FeNi-LDH, uniformly mixing, using sodium hypophosphite as a phosphorus source, transferring the dried sample and the sodium hypophosphite together into a porcelain boat, and adding N in a tube furnace2At 500 ℃ for 1 h, cooling to room temperature to obtain g-C3N4a/FeNi/P heterojunction catalyst powder.
Example 2
Enoxacin degradation test: weighing 0.02 g of prepared g-C3N4the/FeNi/P catalyst was added to a photocatalytic reactor containing 100 mL of enoxacin (initial concentration 20 mg/L). Before the light reaction, the mixture was stirred in the dark for 30 min to reach adsorption equilibrium. And then, carrying out degradation test under the condition of visible light, reacting for 40min at the reaction temperature of 25 ℃, taking the reaction solution once every 10 min, and filtering by using a filter membrane of 0.22 mu m to obtain a test sample.
The concentration of the target pollutants is measured by ultra-high performance liquid chromatography, and the result shows that the degradation efficiency of enoxacin can reach 99.9 percent and the mineralization rate reaches 50 percent in 40 min.
And (3) degradation test comparison: selecting pure modified CN-550, preparing g-C3N4 by traditional method and Ag/AgCl @ ZIF-8/g-C with excellent performance in past research3N4As a reference group, the degradation conditions were unchanged, and after 40min of reaction, the degradation rates of ENO were 41%, 15% and 45%, respectively, and the mineralization rates were 13%, 0% and 20%, respectively.
Example 3
Free radical quenching test: p-Benzoquinone (BQ), EDTA-2Na, L-histidine (L-histidine), t-butanol (TBA), AgNO were used3As superoxide radical (. O) respectively2 -) Hole (h)+) Singlet oxygen (1O)2) Hydroxyl radical (. OH)Electron (e)-) 1 mM quencher was added to a photocatalytic reactor containing 100 mL of enoxacin (initial concentration: 20 mg/L) together with 0.02 g of the prepared composite catalyst. Before the light reaction, the mixture was stirred for 30 min under dark conditions to reach adsorption equilibrium. And then, carrying out degradation test under the condition of visible light, reacting for 40min at the reaction temperature of 25 ℃, taking the reaction solution once every 10 min, and filtering by using a filter membrane of 0.22 mu m to obtain a test sample. The effect of the various free radicals was compared by testing the change in degradation efficiency of enoxacin before and after addition of the quencher.
When AgNO is added into a photocatalytic degradation system3And p-benzoquinone, the degradation rate is completely inhibited, which indicates that e in the reaction system-And O2 -Plays a major role. And the degradation efficiency of enoxacin is slightly influenced by adding EDTA-2Na, L-histidine and TBA, so h+、1O2OH does not play a significant role in the reaction. The results of Electron Spin Resonance (ESR) further demonstrate the presence of active free radicals, O trapped by DMPO2 -The signal is gradually enhanced, which shows that O can be generated under the condition of visible light illumination2 -For electrons, the TEMPO signal peak decreased until it disappeared, demonstrating that e-Are present.
Claims (2)
1. A preparation method of a visible light high-efficiency degradation enoxacin catalytic material is characterized by comprising the following steps:
step 1: dispersing melamine and cyanuric acid in a mass ratio of 1:10-10:1 in deionized water, wherein the cyanuric acid concentration is 0.15-1.5mol/L, stirring the mixed solution to be uniform, drying in an oven at 60-80 ℃, putting the dried solution into a tubular furnace, and putting the dried solution into a N-type furnace2Under the atmosphere, the reaction temperature is 450-650 ℃, the reaction time is 3-6h, the reaction is cooled to room temperature after the reaction is finished, deionized water and ethanol are alternately washed for three times, and the modified g-C is obtained by drying at 60 DEG C3N4；
And 2, step: dispersing ferric nitrate, nickel sulfate and urea in deionized water, and stirring until the mixture is uniform, wherein the molar ratio of the ferric nitrate to the nickel sulfate is 1:1.5, and the concentrations of the ferric nitrate and the urea are 8-80mmol/L and 40-400mmol/L respectively; transferring the obtained solution into a reaction kettle, maintaining for 12-24h at the temperature of 130-150 ℃, cooling, washing and drying to obtain lamellar iron-nickel double hydroxide, FeNi-LDH;
and 3, step 3: the lamella FeNi-LDH obtained in the step 2 and the modified g-C obtained in the step 1 are mixed3N4According to the mass ratio of 1:2-1:40, and then putting the mixture and sodium hypophosphite into a tube furnace at the same time, wherein the adding amount of the sodium hypophosphite is g-C3N45-20 times of mass, N2The atmosphere, the calcination temperature is 300-500 ℃, the reaction time is 1-4h, and g-C is obtained3N4the/FeNi/P heterojunction photocatalytic material.
2. g-C obtained by the preparation method of claim 13N4the/FeNi/P heterojunction photocatalytic material is used as a photocatalyst to degrade enoxacin, and reacts for 40min at 25 ℃ under the condition of visible light, and the degradation rate of 20ppm enoxacin reaches more than 99%.
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| CN115837285A (en) * | 2022-11-25 | 2023-03-24 | 嘉兴学院 | CoP/coralliform carbon nitride heterogeneous composite material and preparation method and application thereof |
| CN117324015A (en) * | 2023-09-19 | 2024-01-02 | 华北电力大学 | FeO (FeO) x Se y Preparation of nano wall catalytic material and application of nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics |
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| CN109092343A (en) * | 2018-09-06 | 2018-12-28 | 滨州学院 | A kind of visible-light response type g-C3N4/BiVO4The preparation method and applications of heterojunction material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115837285A (en) * | 2022-11-25 | 2023-03-24 | 嘉兴学院 | CoP/coralliform carbon nitride heterogeneous composite material and preparation method and application thereof |
| CN115837285B (en) * | 2022-11-25 | 2024-04-19 | 嘉兴学院 | CoP/coralloid carbon nitride heterogeneous composite material, and preparation method and application thereof |
| CN117324015A (en) * | 2023-09-19 | 2024-01-02 | 华北电力大学 | FeO (FeO) x Se y Preparation of nano wall catalytic material and application of nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics |
| CN117324015B (en) * | 2023-09-19 | 2024-04-16 | 华北电力大学 | FeO (FeO)xSeyPreparation of nano wall catalytic material and application of nano wall catalytic material in photo-Fenton degradation of fluoroquinolone antibiotics |
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