CN115301267A - Porous tubular carbon nitride catalyst suitable for visible light catalysis and preparation method and application thereof - Google Patents
Porous tubular carbon nitride catalyst suitable for visible light catalysis and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 229960001180 norfloxacin Drugs 0.000 claims description 10
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
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- 239000011259 mixed solution Substances 0.000 claims description 9
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003242 anti bacterial agent Substances 0.000 claims description 6
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 229960003405 ciprofloxacin Drugs 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 3
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 2
- XUBOMFCQGDBHNK-JTQLQIEISA-N (S)-gatifloxacin Chemical compound FC1=CC(C(C(C(O)=O)=CN2C3CC3)=O)=C2C(OC)=C1N1CCN[C@@H](C)C1 XUBOMFCQGDBHNK-JTQLQIEISA-N 0.000 claims 1
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims 1
- KYGZCKSPAKDVKC-UHFFFAOYSA-N Oxolinic acid Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC2=C1OCO2 KYGZCKSPAKDVKC-UHFFFAOYSA-N 0.000 claims 1
- 229960002549 enoxacin Drugs 0.000 claims 1
- 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 claims 1
- 229960003923 gatifloxacin Drugs 0.000 claims 1
- 229960003376 levofloxacin Drugs 0.000 claims 1
- 229960003702 moxifloxacin Drugs 0.000 claims 1
- FABPRXSRWADJSP-MEDUHNTESA-N moxifloxacin Chemical compound COC1=C(N2C[C@H]3NCCC[C@H]3C2)C(F)=CC(C(C(C(O)=O)=C2)=O)=C1N2C1CC1 FABPRXSRWADJSP-MEDUHNTESA-N 0.000 claims 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
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- 231100000719 pollutant Toxicity 0.000 description 9
- 239000004098 Tetracycline Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 229960002180 tetracycline Drugs 0.000 description 7
- 229930101283 tetracycline Natural products 0.000 description 7
- 235000019364 tetracycline Nutrition 0.000 description 7
- 150000003522 tetracyclines Chemical class 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 6
- -1 carbon nitride compound Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004298 light response Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IQPSEEYGBUAQFF-UHFFFAOYSA-N Pantoprazole Chemical compound COC1=CC=NC(CS(=O)C=2NC3=CC=C(OC(F)F)C=C3N=2)=C1OC IQPSEEYGBUAQFF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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- 238000004832 voltammetry Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- 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
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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
- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention relates to a porous tubular carbon nitride catalyst suitable for visible light catalysis, and a preparation method and application thereof 3 N 4 Raw materials, a precursor with a regular structure is generated through a hydrothermal reaction, and the wall of the precursor collapses through high-temperature calcination, so that the porous tubular g-C is obtained 3 N 4 . The preparation method has the advantages of simple process, strong operability and easy realization of industrial production. The porous tubular shape can improve the utilization efficiency of visible light of the catalyst, improve the electron transmission performance and increase the g-C 3 N 4 Specific surface area ofThereby improving the visible light catalytic performance of the catalyst.
Description
Technical Field
The invention relates to a porous tubular carbon nitride catalyst suitable for visible light catalysis and a preparation method thereof, belongs to the field of preparation of catalytic materials and relates to the field of visible light catalytic degradation of antibiotic pollutants.
Technical Field
Currently, the water environment in China faces serious pollution problems, and the residual problem of novel pollutants of medicines and personal care products (PPCPs) in the environment is increasingly serious. The antibiotic pollutants are widely enriched in the surface water environment due to the large use and the difficult degradation property of the antibiotic pollutants, and seriously threaten the ecological system and the human health. Therefore, the development of an efficient antibiotic pollutant treatment technology is the key to solve the current water environment pollution problem. Compared with the traditional wastewater treatment technology, the visible light catalysis technology has the advantages of low energy consumption, simple operation, low cost, mild reaction condition, wide treatment range and the like when being applied to the aspect of wastewater treatment, so that the visible light catalysis technology has wide prospect in practical application. However, in the prior art, the visible light catalysis technology still has the problems of slow reaction rate, incomplete mineralization of pollutants, insufficient visible light response of the catalyst and volatile activity.
Many researchers in this field have focused their attention on the development of photocatalysts, commonly used catalyst substrates such as: titanium dioxide, zinc oxide, molybdates, ferrites, and the like. However, the traditional photocatalyst has the defects of insufficient visible light response capability, high electron hole recombination rate, low stability and the like.
Graphene-like carbon nitride compound (g-C) 3 N 4 ) As a two-dimensional pi conjugated polymer semiconductor material, the two-dimensional pi conjugated polymer semiconductor material has the advantages of simple synthesis method, low preparation cost, high chemical stability, no metal, no pollution and band gap potentialUnique characteristics, and the like, is particularly suitable for the fields of photocatalytic degradation of organic pollutants, hydrolysis hydrogen production, carbon dioxide reduction, organic synthesis and the like, and is a photocatalytic material with great application prospect [1-3] 。g-C 3 N 4 The band gap width is about 2.7eV, partial visible light can be absorbed, and the material has better acid and alkali resistance and photo-corrosion resistance [4] Good stability and unique energy band structure, so that the photocatalyst is introduced into the field of photocatalytic degradation of organic pollutants as a visible light photocatalyst without metal components [5,6] 。Raha [7] Study g-C 3 N 4 /Fe 3 O 4 the/ZnO composite photocatalyst degrades pantoprazole, and g-C in the composite photocatalyst is found 3 N 4 Effectively trapping visible light and generating abundant electron-hole pairs. Sun [8] The Ag @ AgCl/g-C is successfully prepared 3 N 4 Photocatalyst, highly dispersed Ag @ AgCl active component and g-C 3 N 4 The effective photoresponse enables efficient removal of tetracycline under visible light.
However, g-C 3 N 4 The photocatalytic material has the following defects in practical application: (1) g-C 3 N 4 The band gap width of the photocatalytic material is about 2.7eV, the absorption side band is about 460nm, and only a very small amount of visible light in sunlight can be utilized, so the solar energy utilization efficiency is low; (2) The pi-pi conjugated electron structure of the material enables the catalyst to generate light to generate electrons and holes with high recombination rate after being irradiated by light; (3) g-C obtained by conventional thermal polymerization 3 N 4 The photocatalytic material has small specific surface area, few active sites and lower photocatalytic activity.
The above work shows that g-C 3 N 4 The material has excellent performance in the aspect of photocatalysis, but the defects of insufficient visible light response capability, poor electron transfer performance and small specific surface area are caused by the traditional preparation method. Therefore, a g-C with simple preparation process, low cost, large specific surface area, and strong visible light response and electron transfer performance is developed 3 N 4 Catalyst, improving the degradation efficiency and mineralization rate of photocatalytic degradation antibiotics for promoting visible light catalysisThe application of the technology in the aspect of water environment treatment has important significance.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a porous tubular carbon nitride catalyst suitable for visible light catalysis and a preparation method thereof.
In one aspect, the invention provides a porous tubular carbon nitride catalyst suitable for visible light catalysis, and the surface micro-morphology of the prepared catalyst presents a porous tubular shape. In the preparation process, melamine and cyanuric acid are subjected to hydrothermal reaction to generate a precursor, and further subjected to thermal polymerization to generate a tubular structure with a regular structure and a porous pipe wall, wherein the porous tubular g-C 3 N 4 Denoted as HNCN.
The invention also aims to provide a preparation method of the porous tubular carbon nitride catalyst suitable for visible light catalysis, which is based on a supermolecular self-assembly method and takes melamine and cyanuric acid as g-C 3 N 4 Raw materials are subjected to hydrothermal reaction to generate a precursor with a regular structure, and the wall of the precursor is collapsed through high-temperature calcination, so that porous tubular g-C is obtained 3 N 4 . The porous tubular shape can improve the utilization efficiency of visible light of the catalyst, improve the electron transmission performance and increase the g-C 3 N 4 Thereby improving the visible light catalytic performance of the catalyst.
A preparation method of a porous tubular carbon nitride catalyst suitable for visible light catalysis comprises the following steps:
1) Certain mass of melamine and cyanuric acid are added into a certain amount of deionized water, and the mixture is subjected to ultrasonic treatment and magnetic stirring to obtain a mixed solution.
2) Adding the mixed solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oil bath kettle with magnetic stirring, reacting for 8-12h at 120-200 ℃, centrifuging, collecting the obtained product, fully washing, and drying at 60 ℃ to obtain a precursor.
3) And (3) placing the precursor in a ceramic crucible with a cover, placing the ceramic crucible in a tubular furnace, introducing nitrogen, heating to a certain temperature at the speed of 5 ℃/min, keeping the temperature for 4-6h, and naturally cooling to obtain the HNCN.
As a preferable mode of the present invention, the concentration of melamine and cyanuric acid in deionized water in the step 1) is 1.5-7.5g/100mL.
As a preferable preference of the invention, the ultrasonic time in the step 1) is 10-30min, and the magnetic stirring time is 20-60min.
As a preferred method of the invention, the solution used in the washing in step 2) is deionized water and methanol, and the number of washing times is 3-5.
The porous tubular carbon nitride catalyst HNCN prepared by the preparation method is provided.
The porous tubular carbon nitride catalyst HNCN disclosed by the invention is applied to visible light catalytic degradation of antibiotic pollutants.
The main characteristic pollutant applied to the degradation of the antibiotics is tetracycline antibiotics or quinolone antibiotics; preferably tetracycline, norfloxacin, ofloxacin and ciprofloxacin.
The characteristic pollutant concentration applied to the degradation of antibiotics is 5-20mg/L.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
the preparation method of the porous tubular carbon nitride catalyst suitable for visible light catalysis is a hydrothermal-thermal polymerization method, and has the advantages of simple preparation process, high yield, easiness in industrial production and the like; the hydrothermal reaction in the preparation process realizes the shape regulation of the catalyst, so that the catalyst presents a regular shape; the porous tubular structure of HNCN increases the specific surface area and pore volume of the catalyst (fig. 4), ensuring sufficient exposure of active sites in the catalytic reaction; the tubular structure of the HNCN improves the charge transmission efficiency of the catalyst (figure 5) and ensures the directional high-efficiency transfer of electrons; the porous tubular structure of HNCN improves the reflection of incident light inside the catalyst, improving the efficiency of visible light utilization (fig. 6). The enhanced visible light utilization efficiency, electron transfer and enlarged specific surface area promote the e under the catalysis of visible light - ，h + OH and O 2 - The generation of active species (fig. 7), effectively increases the efficiency of contaminant degradation.
Drawings
FIG. 1 SEM characterization of HNCN precursor prepared in example 4
As can be seen from fig. 1, the HNCN precursor presents a regular cylindrical cavity composed of polyhedrons;
FIG. 2 SEM representation of HNCN-4 prepared in example 4
It can be seen from fig. 2 that HNCN-4 exhibits a regular porous nanotube-like structure;
FIG. 3 TEM-EDS characterization of HNCN-4 prepared in example 4
a is HNCN-4HAADF diagram; b, total HNCN-4EDS diagram; c, cu-mapping; d, N-mapping; e, O-mapping;
it can be seen from fig. 3 that Cu is uniformly distributed in the C, N-rich carbon nitride matrix.
FIG. 4N of HNCN-4 prepared in example 4 2 Adsorption desorption attached figure
a N 2 Adsorption-desorption curve, it can be seen that HNCN-4 has a larger N than CN 2 Adsorption volume, indicating a larger specific surface area;
b pore size distribution curve; the HNCN is larger in pore size distribution and increased in pore volume compared with the CN;
FIG. 5 electrochemical test chart of HNCN-4
a transient photocurrent response shows that HNCN-4 has stronger charge separation and transfer capability than CN; b, alternating current impedance spectrum, and HNCN-4 is lower than CN in charge transfer resistance; c, a voltammetry characteristic curve shows that HNCN-4 has stronger charge transfer efficiency than CN;
FIG. 6 diffuse reflectance UV-VIS map of HNC-4N
It can be seen from FIG. 6 that HNCN has stronger visible light absorption property than CN;
FIG. 7 EPR representation of HNCN-4 catalyst photocatalytic degradation
a is DMPO-OH, visible HNCN, the photocatalytic system generates OH
b:DMPO-·O 2 - It can be seen that the photocatalytic system of HNCN produces O 2 - ；
The HNCN prepared in the other examples has the above result chart similar to that of HNCN-4, and it can be seen that the HNCN prepared in each example has a regular porous nanotube-shaped structure and has the same physicochemical properties.
Detailed Description
The present invention is further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
40mL of deionized water, 1g of melamine and 3g of cyanuric acid are sequentially added into 100mL of polytetrafluoroethylene lining, ultrasonic treatment is carried out for 10min at normal temperature, and then magnetic stirring is carried out for 20min to obtain mixed solution. And then adding the mixed solution into a 100mL hydrothermal reaction kettle, placing the kettle into an oil bath kettle with magnetic stirring, reacting for 8 hours at 120 ℃, centrifuging and collecting the obtained product, and fully washing the product with deionized water and methanol. Drying at 60 ℃ to obtain a precursor. And placing the precursor in a ceramic crucible with a cover in a tubular furnace, introducing nitrogen, heating to 450 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain HNCN-1.
The prepared catalyst is used for visible light catalytic degradation of tetracycline, and the reaction conditions are as follows: the concentration of tetracycline is 10mg/L, and the optical density is 120mW/cm 2 The amount of the catalyst added was 0.2g/L. Before the reaction, a dark adsorption experiment is carried out for 30min to reach adsorption-desorption balance, and then a lamp source is turned on to start catalytic degradation reaction. Samples were taken every 10min and the residual concentration of tetracycline was determined after passage through a 0.22 μm filter. The result shows that the tetracycline removal rate within 80min reaches 94.9 percent, and the mineralization rate reaches 49.6 percent. The tetracycline removal effect of the catalyst after 5 times of cyclic use can still reach 92.2%.
Example 2
50mL of deionized water, 2g of melamine and 2g of cyanuric acid are sequentially added into 100mL of polytetrafluoroethylene lining, ultrasonic treatment is carried out for 20min at normal temperature, and then magnetic stirring is carried out for 40min. And then adding the mixed solution into a 100mL hydrothermal reaction kettle, placing the kettle in an oil bath kettle with magnetic stirring, reacting for 10 hours at 160 ℃, centrifuging and collecting the obtained product, and fully washing the product by using deionized water and methanol. Drying at 60 ℃ to obtain a precursor. And (3) placing the precursor in a ceramic crucible with a cover in a tubular furnace, introducing nitrogen, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 5 hours, and naturally cooling to obtain HNCN-2.
The catalyst prepared by the method is used for preparing the catalystDegrading norfloxacin by photocatalysis under the reaction conditions of: norfloxacin concentration of 5mg/L and optical density of 120mW/cm 2 The amount of catalyst added was 0.2g/L. Before the reaction, a dark adsorption experiment is carried out for 30min to reach adsorption-desorption balance, and then a lamp source is turned on to start catalytic degradation reaction. Samples were taken every 10min and the residual norfloxacin concentration was determined after passage through a 0.22 μm filter. The result shows that the norfloxacin removal rate within 80min reaches 95.9 percent, and the mineralization rate reaches 54.9 percent. The norfloxacin removal effect of the catalyst after 5 times of cyclic use can still reach 93.4%.
Example 3
60mL of deionized water, 1g of melamine and 3g of cyanuric acid are sequentially added into 100mL of polytetrafluoroethylene lining, and magnetic stirring is carried out for 60min after ultrasonic treatment is carried out for 30min at normal temperature. And then adding the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixture into an oil bath kettle with magnetic stirring, reacting for 10 hours at 180 ℃, centrifuging and collecting the obtained product, and fully washing the product by using deionized water and methanol. Drying at 60 ℃ to obtain the precursor. And (3) placing the precursor in a ceramic crucible with a cover in a tubular furnace, introducing nitrogen, heating to 650 ℃ at the speed of 5 ℃/min, preserving heat for 6 hours, and naturally cooling to obtain HNCN-3.
The prepared catalyst is used for catalyzing and degrading ofloxacin by visible light, and the reaction conditions are as follows: the concentration of ofloxacin is 20mg/L, and the optical density is 120mW/cm 2 The amount of catalyst added was 0.2g/L. Before the reaction, a dark adsorption experiment is carried out for 30min to reach adsorption-desorption balance, and then a lamp source is turned on to start catalytic degradation reaction. Samples were taken every 10min and the residual concentration of ofloxacin was determined after passage through a 0.22 μm filter. The result shows that the norfloxacin removal rate within 80min reaches 96.2 percent, and the mineralization rate reaches 52.8 percent. The norfloxacin removal effect of the catalyst after 5 times of cyclic use can still reach 92.5 percent.
Example 4
50mL of deionized water, 2g of melamine and 2g of cyanuric acid are sequentially added into 100mL of polytetrafluoroethylene lining, ultrasonic treatment is carried out for 20min at normal temperature, and magnetic stirring is carried out for 50min. And then adding the mixed solution into a 100mL hydrothermal reaction kettle, placing the mixture into an oil bath kettle with magnetic stirring, reacting for 12 hours at 200 ℃, centrifuging and collecting the obtained product, and fully washing the product by using deionized water and methanol. Drying at 60 ℃ to obtain a precursor. And placing the precursor in a ceramic crucible with a cover in a tubular furnace, introducing nitrogen, heating to 550 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to obtain HNCN-4.
The prepared catalyst is used for catalyzing and degrading ofloxacin by visible light, and the reaction conditions are as follows: the ciprofloxacin concentration is 10mg/L, and the optical density is 120mW/cm 2 The amount of catalyst added was 0.2g/L. Before the reaction starts, a dark adsorption experiment is carried out for 30min to achieve adsorption-desorption balance, and then a lamp source is turned on to start catalytic degradation reaction. Samples were taken every 10min and the residual concentration of ciprofloxacin was determined after passage through a 0.22 μm filter. The result shows that the norfloxacin removal rate within 80min reaches 97.8 percent, and the mineralization rate reaches 52.8 percent. The removal effect of the norciprofloxacin after the catalyst is recycled for 5 times can still reach 94.1%.
The matter described in this specification is only an example of a form of implementation of the inventive concept and the scope of protection of the invention should not be seen as being limited to the specific form set forth in the examples.
Claims (9)
1. A preparation method of a porous tubular carbon nitride catalyst suitable for visible light catalysis is characterized by comprising the following steps:
1) Adding a certain amount of melamine and cyanuric acid into a certain amount of deionized water, performing ultrasonic treatment at 20-28 ℃, and performing magnetic stirring to obtain a mixed solution;
2) Adding the mixed solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oil bath kettle with magnetic stirring, reacting for 8-12h at 120-200 ℃, centrifuging, collecting the obtained product, fully washing, and drying at 55-65 ℃ to obtain a precursor;
3) And placing the precursor in a ceramic crucible with a cover, placing the ceramic crucible in a tubular furnace, introducing nitrogen, heating to 450-650 ℃ at the speed of 2-5 ℃/min, preserving heat for 4-6h, and naturally cooling to obtain the porous tubular carbon nitride catalyst HNCN.
2. The method according to claim 1, wherein the concentration of melamine and cyanuric acid in deionized water in step 1) is 1.5-7.5g/100mL.
3. The preparation method according to claim 1, wherein the ultrasonic time in step 1) is 10-30min, and the magnetic stirring time is 20-60min.
4. The method according to claim 1, wherein the washing solution used in step 2) is deionized water and methanol, and the number of washing is 3 to 5.
5. The porous tubular carbon nitride catalyst HNCN prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the porous tubular carbon nitride catalyst HNCN of claim 5 in visible light photocatalytic degradation of antibiotic contaminants.
7. Use according to claim 6, characterized in that said antibiotic is selected from the group consisting of tetracycline antibiotics or quinolone antibiotics.
8. The use according to claim 7, characterized in that said quinolone antibiotic is selected from the group consisting of norfloxacin, ciprofloxacin, ofloxacin, enoxacin, levofloxacin, moxifloxacin, or gatifloxacin.
9. Use according to any one of claims 6 to 8, characterized in that the concentration of contaminants characteristic of the degradation of antibiotics is between 5 and 20mg/L.
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