CN117466373A - Novel technology for degrading trace organic phosphorus pesticide in water environment by visible light catalysis - Google Patents
Novel technology for degrading trace organic phosphorus pesticide in water environment by visible light catalysis Download PDFInfo
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- CN117466373A CN117466373A CN202311271814.4A CN202311271814A CN117466373A CN 117466373 A CN117466373 A CN 117466373A CN 202311271814 A CN202311271814 A CN 202311271814A CN 117466373 A CN117466373 A CN 117466373A
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- 239000000575 pesticide Substances 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000000593 degrading effect Effects 0.000 title claims abstract description 26
- 238000005516 engineering process Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 15
- 239000011574 phosphorus Substances 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000011941 photocatalyst Substances 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003987 organophosphate pesticide Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000001782 photodegradation Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 11
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 adjustable structure Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000003911 water pollution Methods 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A new technology for degrading trace organic phosphorus pesticide in water environment by visible light catalysis is characterized in that a high-temperature pyrolysis method is adopted to prepare a functional nitrogen carbide material. Then, zirconium-based MOFs are grown on the surface of the functionalized nitrogen carbide material in situ, and the high-efficiency heterogeneous composite photocatalyst is designed and synthesized. Finally, the trace organic phosphorus pesticide in the water environment is rapidly and stably subjected to visible light catalytic degradation. The invention has the advantages that: the novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis is reasonable in process and easy to implement; the zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst prepared by the method has good visible light responsiveness and stability when used for degrading organophosphorus pesticides, and can realize efficient adsorption and rapid mass transfer of organophosphorus pesticides; the degradation technology has high adsorptivity, multiple catalytic activities and strong practicability, brings great convenience to the visible light degradation of trace organophosphorus pesticides, improves the use efficiency of heterogeneous composite photocatalysts, and widens the application range of functionalized nitrogen carbide materials and zirconium-based MOFs.
Description
[ field of technology ]
The invention relates to a novel technology for degrading trace organophosphorus pesticides in a water environment by visible light catalysis, in particular to a technology for degrading visible light of a high-efficiency catalyst with two-dimensional heterojunction and multiple metal active sites.
[ background Art ]
With the rapid development of agriculture, water pollution caused by pesticides has a serious influence on the environment and human health. Visible light catalysis technology is an effective method for degrading trace organic pollutants in water environment by utilizing sunlight. The technology has the characteristics of simple operation, low energy consumption, high degradation efficiency and no secondary pollution, and the solar energy utilized by the technology is a renewable resource and has important application prospect in the fields of developing clean energy and protecting environmental pollution. The key point of the visible light catalytic technology is research and development of a photocatalyst with high-efficiency, stable and visible light catalytic activity. At present, most of photocatalysts for degrading pesticide residues in water environment are n-type semiconductor materials and three-dimensional nano materials, and the photocatalysts have the limitations of three-dimensional structure, small specific surface area, few catalytic active sites, low adsorption capacity and the like in application research of degrading trace pesticide pollutants in water environment. Therefore, the high-efficiency photocatalyst with a two-dimensional structure, large specific surface area, multiple catalytic active sites and high adsorption capacity is designed and synthesized, and is a core for efficiently, quickly, stably and degrading trace agricultural organophosphorus pesticides.
In recent years, MOFs materials have been developed rapidly, and various metal-organic framework materials with different structures and different properties have been reported successively. The MOFs material has the characteristics of large surface area, easy control of open channels and pores, adjustable structure, composition and functions and the like, and promotes the MOFs material to degrade organic matters in photocatalysis, prepare hydrogen by photocatalytic water splitting and catalyze CO 2 Is widely applied in the fields of transformation, organic photosynthesis and the like. Among them, zirconium-based MOFs are considered as the most widely studied MOFs material in photocatalysts, zr 4+ The strong aerophilic property of (2) makes it show high stability, but has a narrow band gap structure, so that the visible light catalytic activity is limited. The heterojunction composite catalyst with high active sites is formed by interaction with a semiconductor catalyst, a metal catalyst and a nonmetal catalyst, so that the application of the heterojunction composite catalyst in the visible light catalytic technology is improved.
The nitrogen carbide material is a two-dimensional material with larger specific surface area, more surface active sites, strong chemical stability and excellent photocatalytic activity. The catalyst is easy to be hybridized with a metal semiconductor (or a non-metal organic semiconductor) catalyst to form heterojunction structures such as I type, II type, p-n type, schottky, Z-scheme and the like, and can effectively promote migration of charge carriers, facilitate separation of photo-generated carriers and control the number of carriers to enhance photocatalysis performance. The nitrogen carbide is selected as a matrix material of the high-efficiency visible light heterogeneous catalyst, so that active oxygen with high activity can be generated, charge transfer is accelerated, and the photo-generated electron-hole separation efficiency is improved. So that the trace organic phosphorus pesticide in the water environment is rapidly and accurately catalyzed and degraded.
The new technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis is to select functionalized nitrogen carbide as a substrate, and grow zirconium-based MOFs on the surface of the substrate in situ to obtain the efficient heterogeneous composite photocatalyst. The catalyst not only maintains the visible light catalytic activity of the functionalized nitrogen carbide material, but also has the characteristics of high specific surface area, high catalytic activity and the like of the zirconium-based MOFs, and can remarkably improve the enrichment efficiency and catalytic activity of the photocatalyst on organophosphorus pesticides and perform high-efficiency visible light catalytic degradation on trace organophosphorus pesticides in water environment.
[ invention ]
The invention aims to overcome the defects of no visible light catalytic activity, small specific surface area, few catalytic active sites, low adsorption capacity and the like of the conventional photocatalyst for degrading organophosphorus pesticides. The heterogeneous composite photocatalyst based on zirconium-based MOFs modified functional nitrogen carbide is provided and applied to high-efficiency visible light catalytic degradation of trace organic phosphorus pesticides in water environment.
The technical scheme of the invention is as follows:
a new technology for degrading trace organic phosphorus pesticide in water environment by visible light catalysis is characterized in that a high-temperature pyrolysis method is adopted to prepare a functional nitrogen carbide material. Then, zirconium-based MOFs are grown on the surface of the functionalized nitrogen carbide material in situ, and the high-efficiency heterogeneous composite photocatalyst is designed and synthesized. Finally, the trace organic phosphorus pesticide in the water environment is rapidly and stably subjected to visible light catalytic degradation.
Further, the functional nitrogen carbide material is obtained by placing melamine in a tube furnace, grinding the melamine into powder after high-temperature calcination, uniformly mixing the powder with magnesium powder, reacting at high temperature, washing and drying.
Further, the zirconium-based MOFs modified high-efficiency heterogeneous composite photocatalyst is prepared by respectively dissolving a functional nitrogen carbide material, zirconium oxychloride octahydrate and trimesic acid in a mixed solution of formic acid and tetrahydrofuran, reacting at a high temperature, washing and drying.
Further, the synthesized heterogeneous composite photocatalyst of zirconium-based MOFs modified functional nitrogen carbide is placed in a beaker, ultrapure water and organophosphorus pesticide solution are added, ultrasonic dispersion is uniform under dark conditions, photocatalytic degradation reaction is carried out under a visible light source, reaction suspension is taken by a syringe, a filter membrane is used for filtering, each group of samples to be detected is obtained, and the intensity change of absorption peaks of each group of samples is measured by using an ultraviolet-visible spectrophotometer.
A novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis comprises the following steps:
1) Preparation of functional nitrogen carbide material
Weighing 5g of melamine in a ceramic crucible, placing in the center of a tube furnace, heating to 550 ℃ at 2-5 ℃/min under the protection of argon, reacting for 4 hours, cooling to 100 ℃ at 3-6 ℃/min, taking out after natural cooling, and grinding the product obtained by the reaction to obtain light yellow powder g-C3N4.
Weighing 1-3 g g-C 3 N 4 Mixing with 200mg magnesium powder, placing into a ceramic crucible, placing the crucible into a tube furnace, heating to 750 ℃ at 3-5 ℃/min under the protection of argon, reacting for 2 hours, cooling to 100 ℃ at 3-6 ℃/min, taking out after natural cooling, pickling the product with glacial acetic acid for 5 times, and vacuum drying at 60 ℃ to obtain g-C 3 N X 。
2) Preparation of zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst
Taking 100-300 mg g-C 3 N X 300-600 mg of zirconium oxychloride octahydrate and 100-200 mg of trimesic acid are dissolved in 15mL of mixed solution of formic acid and 15mL of tetrahydrofuran, ultrasonic treatment is carried out for 30min, the mixed solution after ultrasonic treatment is put into a 50mL three-neck flask, reaction is carried out for 24h at 130 ℃, products obtained by the reaction are washed 5 times by tetrahydrofuran and absolute ethyl alcohol respectively, and then heterogeneous composite photocatalyst is obtained by vacuum drying at 60 ℃.
The novel technical application of the visible light catalytic degradation of trace organic phosphorus pesticides in water environment is used for high-efficiency, rapid and stable catalytic degradation of trace organic phosphorus pesticides in water environment, and the specific method is as follows: and dissolving the prepared zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst in 100mL of water and 1mL of 1mg/mL of organophosphorus pesticide solution, carrying out catalytic degradation reaction under the irradiation of a xenon lamp light source, and evaluating the visible light catalytic activity of the heterogeneous composite photocatalyst in the process by ultraviolet analysis to detect the concentration of the organophosphorus pesticide solution after photodegradation.
The invention has the advantages that: the novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis is reasonable in process and easy to implement; the zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst prepared by the method has good visible light responsiveness and stability when used for degrading organophosphorus pesticides, and can realize efficient adsorption and rapid mass transfer of organophosphorus pesticides; the degradation technology has high adsorptivity, multiple catalytic activities and strong practicability, brings great convenience to the visible light degradation of trace organophosphorus pesticides, improves the use efficiency of heterogeneous composite photocatalysts, and widens the application range of functionalized nitrogen carbide materials and zirconium-based MOFs.
[ description of the drawings ]:
FIG. 1 is g-C 3 N 4 Is a lens image of the lens.
FIG. 2 is g-C 3 N X Is a lens image of the lens.
FIG. 3 is an electron microscope image of a zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst.
FIG. 4 is a graph showing the comparison of degradation efficiency of zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst.
[ detailed description ] A method for manufacturing a semiconductor device includes:
examples:
a new technology for degrading trace organic phosphorus pesticide in water environment by visible light catalysis is characterized in that a high-temperature pyrolysis method is adopted to prepare a functional nitrogen carbide material. Then, zirconium-based MOFs are grown on the surface of the functionalized nitrogen carbide material in situ, and the high-efficiency heterogeneous composite photocatalyst is designed and synthesized. Finally, the trace organic phosphorus pesticide in the water environment is rapidly and stably subjected to visible light catalytic degradation.
The method comprises the following steps:
1) Preparation of functional nitrogen carbide material
Synthesizing g-C by adopting pyrolysis method 3 N 4 The specific steps of the material are as follows: placing 5g melamine in a ceramic crucible, placing in the center of a tube furnace, heating to 550 ℃ at a speed of 4 ℃/min under the protection of argon, reacting for 4 hours, then cooling to 100 ℃ at a speed of 5 ℃/min, taking out after natural cooling, and grinding the product obtained by the reaction to obtain light yellow powder g-C 3 N 4 。
FIG. 1 is g-C 3 N 4 Electron microscopy of the material. The graph shows the g-C formed by firing melamine 3 N 4 Is a two-dimensional thin-layer structure with good light transmittance.
Synthesizing g-C by adopting a high-temperature calcination method 3 N X The specific steps of the material are as follows: weighing 2g g-C 3 N 4 Mixing with 200mg magnesium powder, placing into a ceramic crucible, placing the crucible into a tube furnace, heating to 750deg.C at 4deg.C/min under the protection of argon, reacting for 2h, cooling to 100deg.C at 5deg.C/min, naturally cooling, taking out, pickling the product with glacial acetic acid for 5 times, and vacuum drying at 60deg.C to obtain g-C 3 N X 。
FIG. 2 is g-C 3 N X Electron microscopy of the material. The graph shows g-C after denitrification treatment of magnesium powder 3 N X Still be sheet structure, and sheet structure thickness becomes thinner, and the light transmissivity is better.
2) Preparation of zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst
200mg g-C 3 N X 400mg of zirconium oxychloride octahydrate and 150mg of trimesic acid are dissolved in 15mL of mixed solution of formic acid and 15mL of tetrahydrofuran, ultrasonic treatment is carried out for 30min, the mixed solution after ultrasonic treatment is placed in a 50mL three-neck flask, reaction is carried out for 24h at 130 ℃, products obtained by the reaction are washed 5 times by tetrahydrofuran and absolute ethyl alcohol respectively, and then heterogeneous composite photocatalyst is obtained by vacuum drying at 60 ℃.
FIG. 3 is an electron microscope image of a zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst. The figure shows: in g-C by in situ growth 3 N X Surface growth of regular octahedron zirconium-based MOFs Single Crystal Structure, g-C 3 N X Still has a lamellar structure, and the zirconium-based MOFs single crystal particles are uniformly loaded.
The novel technical application of the trace organic phosphorus pesticide in the visible light catalytic degradation water environment is used for efficiently, quickly and stably catalyzing and degrading the trace organic phosphorus pesticide in the water environment, and the zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst is subjected to visible light catalytic degradation by taking diazinon as a target substance under the irradiation of a xenon lamp light source;
preparing diazinon aqueous solutions with different concentrations, regulating the pH value of a reaction system, taking 100mL of the diazinon aqueous solution, respectively adding zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalysts with different masses, and carrying out catalytic degradation reaction under the irradiation of a xenon lamp light source. The detection result shows that: g-C 3 N X When the doping amount is 200mg, the catalyst dosage is 5mg, the pH of the reaction system is 7, and the concentration of the diazinon solution is 10mg/L, the visible light catalytic activity of the heterogeneous composite photocatalyst is optimal, and the catalytic efficiency of diazinon reaches 82.8%.
FIG. 4 is a graph showing the comparison of degradation efficiency of zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst. The figure shows that the degradation efficiency of the heterogeneous composite photocatalyst to diazinon is better than that of a single zirconium-based MOFs material and is more obviously higher than that of g-C 3 N 4 And g-C 3 N X Two catalysts. Description of zirconium-based MOFs and g-C 3 N X The heterogeneous photocatalyst after the recombination has a synergistic interaction between tight interfaces, so that the recombination efficiency of the generated photo-generated electron-hole pairs is reduced, the service life of the photo-generated electron-hole pairs is prolonged, and the composite photocatalyst has the highest visible light catalytic activity on diazinon in a water environment.
Claims (6)
1. A novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis is characterized in that: firstly, preparing the functional nitrogen carbide material by adopting a pyrolysis method. Then, zirconium-based MOFs are grown on the surface of the functionalized nitrogen carbide material in situ, and the high-efficiency heterogeneous composite photocatalyst is designed and synthesized. Finally, the trace organic phosphorus pesticide in the water environment is rapidly and stably subjected to visible light catalytic degradation.
2. The novel technique for degrading trace organophosphorus pesticides in water environment by visible light catalysis according to claim 1, which is characterized in that: the functional nitrogen carbide material is prepared through the steps of calcining melamine in a tubular furnace, grinding into powder, mixing with magnesium powder, high temperature reaction, washing and drying.
3. The novel technique for degrading trace organophosphorus pesticides in water environment by visible light catalysis according to claim 1, which is characterized in that: the zirconium-based MOFs modified high-efficiency heterogeneous composite photocatalyst is prepared by respectively dissolving a functional nitrogen carbide material and zirconium oxychloride octahydrate and trimesic acid in a mixed solution of formic acid and tetrahydrofuran, reacting at a high temperature, washing and drying.
4. The novel technique for degrading trace organophosphorus pesticides in water environment by visible light catalysis according to claim 1, which is characterized by comprising the following steps:
1) Preparation of functional nitrogen carbide material
Weighing 5g of melamine, placing in a ceramic crucible, placing in the center of a tube furnace, heating to 550 ℃ at 2-5 ℃/min under the protection of argon, reacting for 4 hours, cooling to 100 ℃ at 3-6 ℃/min, taking out after natural cooling, and grinding the product obtained by the reaction to obtain light yellow powder g-C 3 N 4 。
Weighing 1-3 g g-C 3 N 4 Mixing with 200mg magnesium powder, placing into a ceramic crucible, placing the crucible into a tube furnace, heating to 750 ℃ at 3-5 ℃/min under the protection of argon, reacting for 2 hours, cooling to 100 ℃ at 3-6 ℃/min, taking out after natural cooling, pickling the product with glacial acetic acid for 5 times, and vacuum drying at 60 ℃ to obtain g-C 3 N X 。
2) Preparation of zirconium-based MOFs modified functional nitrogen carbide heterogeneous composite photocatalyst
Taking 100-300 mg g-C 3 N X 300-600 mg of zirconium oxychloride octahydrate and 100-200 mg of benzeneDissolving trimethyl acid in 15mL formic acid and 15mL tetrahydrofuran mixed solution, carrying out ultrasonic treatment for 30min, placing the mixed solution after ultrasonic treatment in a 50mL three-neck flask, reacting for 24h at 130 ℃, washing the obtained product of the reaction with tetrahydrofuran and absolute ethyl alcohol for 5 times respectively, and then carrying out vacuum drying at 60 ℃ to obtain the heterogeneous composite photocatalyst.
5. An application of a novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis, which is constructed by the method of any one of claims 1-4, and is characterized in that: the method is used for efficiently, rapidly and stably catalyzing and degrading trace organophosphorus pesticides in water environment.
6. The application of the novel technology for degrading trace organophosphorus pesticides in water environment by visible light catalysis as claimed in claim 5, which is characterized in that: and dissolving the prepared zirconium-based MOFs modified functionalized nitrogen carbide heterogeneous composite photocatalyst in 100mL of water and 1mL of 1mg/mL of organophosphorus pesticide solution, carrying out catalytic degradation reaction under the irradiation of a xenon lamp light source, and evaluating the visible light catalytic activity of the heterogeneous composite photocatalyst in the process by ultraviolet analysis to detect the concentration of the organophosphorus pesticide solution after photodegradation.
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