CN114377712A - CN/NCD/ZFL photocatalyst, application thereof and antibiotic wastewater treatment method - Google Patents
CN/NCD/ZFL photocatalyst, application thereof and antibiotic wastewater treatment method Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 13
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 239000004098 Tetracycline Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229960002180 tetracycline Drugs 0.000 claims abstract description 9
- 229930101283 tetracycline Natural products 0.000 claims abstract description 9
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 9
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 9
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 239000002800 charge carrier Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a CN/NCD/ZFL photocatalyst, application thereof and an antibiotic wastewater treatment method. The CN/NCD/ZFL photocatalyst is prepared by an in-situ deposition-calcination method, the charge carrier transfer capability of the catalyst is enhanced by forming a Z-type graphite-phase carbon nitride/zinc-iron layered double-metal hydroxide heterojunction, the photoresponse range is increased, and the visible light utilization rate and the charge transfer capability are further improved by nitrogen-doped carbon points. The nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-shaped heterojunction photocatalyst prepared by the method can effectively respond to visible light and generate related active species, and can efficiently degrade tetracycline in water.
Description
Technical Field
The invention belongs to the technical field of composite catalysts, and particularly relates to a CN/NCD/ZFL photocatalyst, application thereof and an antibiotic wastewater treatment method.
Background
Advanced Oxidation Processes (AOPs) to generate active species (h) with strong oxidizing power+、·OH、·O2 -) The method is characterized in that under the reaction conditions of high temperature and high pressure, electricity, sound, light irradiation, catalysts and the like, the organic matters which are difficult to degrade are oxidized into low-toxicity or non-toxic micromolecule substances, thereby degrading pollutants. The semiconductor photocatalysis can not cause secondary pollution and can thoroughly degrade pollutants (generate CO)2、H2O) and is thus considered to be the most feasible method for solving environmental pollutants in sewage.
A great deal of research finds that the single semiconductor photocatalyst has the defects of high photoelectron-hole pair recombination speed, low visible light utilization rate and the like. In recent years, a novel semiconductor photocatalyst, namely a Z-type heterojunction photocatalyst, is widely applied to the field of photocatalysis due to excellent photocatalytic performance. Compared with the traditional II-type heterojunction photocatalyst, the Z-type heterojunction photocatalyst shows excellent photocatalytic activity and can keep higher redox capacity, so that the photocatalytic efficiency is improved.
Graphite-like phase carbon nitride, as a metal-free semiconductor material, has attracted extensive attention in the field of photocatalysis due to its excellent optical properties, but still has the problems of easy electron-hole recombination, small specific surface area, low electrical conductivity, poor visible light absorption and the like. It has been reported that the photocatalytic activity of graphite-like phase carbon nitride can be enhanced when it is combined with layered double hydroxide. The carbon dots have up-conversion photoluminescence properties, so that not only can charge transfer be improved, but also the utilization rate of visible light can be improved. When the carbon dots are doped with nitrogen atoms, electrons in a semiconductor conduction band are transferred to the nitrogen-doped carbon dots, so that the recombination of photoinduced electron-hole pairs is inhibited. In addition, nitrogen atoms can lower the work function of the carbon dots to further improve photocatalytic performance.
So far, no report is found on the research on the degradation of tetracycline wastewater by a nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-shaped heterojunction photocatalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a CN/NCD/ZFL photocatalyst, application thereof and an antibiotic wastewater treatment method, and solves the problems in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a CN/NCD/ZFL photocatalyst which is a Z-type heterojunction photocatalyst of nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide.
The second technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a CN/NCD/ZFL photocatalyst is provided, which comprises the following steps:
1) preparing a nitrogen-doped carbon dot solution;
2) preparing nitrogen-doped carbon dot composite graphite-like phase carbon nitride;
3) preparing a Z-type heterojunction photocatalyst:
adding calcined solid materials into deionized water, uniformly mixing by ultrasonic waves, adding zinc sulfate and ferrous sulfate, adjusting the pH value to 7.5-8 by using a sodium hydroxide solution, and stirring for 1-2 hours;
② adding H2O2Aging for 3-4 h at 40-45 ℃ to obtain a mixed material;
and thirdly, washing the mixed material until the pH value is 7, carrying out solid-liquid separation, cleaning, drying and grinding the separated solid to obtain the CN/NCD/ZFL Z-type heterojunction photocatalyst.
In a preferred embodiment of the present invention, in the step 3), Zn2+With Fe3+The ratio of (A) to (B) is 3: 1.
In a preferred embodiment of the present invention, in the third step of step 3), the separated solid is dried at 40-60 ℃ for 5-6 hours after being washed with absolute ethyl alcohol and deionized water for several times.
In a preferred embodiment of the present invention, the step 1) includes:
dissolving citric acid and urea in deionized water, uniformly mixing, and carrying out hydrothermal reaction for 5 hours at 180-200 ℃;
and secondly, centrifuging the solution at a high speed, drying the supernatant and dissolving the supernatant in deionized water to prepare a nitrogen-doped carbon dot solution with the mass concentration of 1-2 mg/mL.
In a preferred embodiment of the invention, in the step 1), the mass ratio of the citric acid to the urea is 2: 1-1.5: 1, and the total mass fraction of the solute in the solution is 17-21%.
In a preferred embodiment of the present invention, the step 2) includes:
adding melamine into absolute ethyl alcohol and stirring for 2 hours, then dropwise adding the nitrogen-doped carbon dot solution, continuously stirring for 2-3 hours to obtain a mixed solution, stirring under a water bath heating condition of 60-70 ℃ until the solvent volatilizes, and realizing solid-liquid separation to obtain a solid material;
and secondly, calcining the solid material for 2-4 hours at 530-550 ℃ after grinding.
In a preferred embodiment of the present invention, in the step 2), the mass concentration of the melamine in the mixed solution is 60g/L, and the volume ratio of the absolute ethyl alcohol to the nitrogen-doped carbon dot solution is 50: 30-50.
The third technical scheme adopted by the invention for solving the technical problems is as follows: provides an application of a CN/NCD/ZFL photocatalyst in antibiotic wastewater treatment.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows: the method comprises the steps of carrying out photocatalytic degradation treatment by adopting the CN/NCD/ZFL photocatalyst and a 300W xenon lamp light source loaded with a 420nm optical filter; the concentration of the CN/NCD/ZFL photocatalyst in the antibiotic wastewater is 0.2-1.0 g/L, and the antibiotic wastewater comprises tetracycline wastewater.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention utilizes the performance enhancement effect of the layered double hydroxide on the graphite-like phase carbon nitride, not only strengthens the charge transfer capability of the catalyst by forming the Z-shaped heterojunction of the graphite-like phase carbon nitride/zinc-iron layered double hydroxide, increases the photoresponse range, but also further improves the visible light utilization rate and the charge transfer capability through the nitrogen-doped carbon dots;
2. the photocatalyst prepared by the invention can effectively respond to visible light, electrons positioned on a valence band of graphite-like carbon nitride and zinc-iron layered double hydroxide can jump to a corresponding conduction band position under the excitation of corresponding energy of the visible light, and further undergo an oxidation-reduction reaction with oxygen to generate active species, thereby efficiently degrading tetracycline in water;
3. the photocatalyst prepared by the invention has higher stability, and repeated experiments show that the photocatalyst has stable catalytic effect, can realize the recycling of the catalyst and reduce secondary pollution;
4. the photocatalyst of the invention is additionally provided with a 300W xenon lamp light source loaded with a 420nm optical filter under the conditions of normal temperature and normal pressure, so that the conditions required by the reaction can be achieved, and active species can be continuously generated under the irradiation of the light source, thereby continuously degrading tetracycline wastewater.
Drawings
FIG. 1 is a TEM photograph of the CN/NCD/ZFL photocatalyst prepared in example 1, wherein (a) is at a magnification of 200nm and (b) is at 5 nm.
FIG. 2 is a UV-VIS diffuse reflectance spectrum of the CN/NCD/ZFL photocatalyst prepared in example 1.
Fig. 3 shows photoluminescence spectra of different photocatalysts.
FIG. 4 is a graph showing the photocatalytic effect of four replicates of the CN/NCD/ZFL photocatalyst prepared in example 1.
FIG. 5 is a graph showing the effect of different photocatalysts on treating tetracycline in water.
Detailed Description
Example 1
The CN/NCD/ZFL photocatalyst is a nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-shaped heterojunction photocatalyst, and the preparation method comprises the following steps:
(1) under magnetic stirring, adding 3g of citric acid and 1g of urea into 15mL of deionized water, uniformly mixing, transferring to a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 5 hours at 180 ℃;
(2) centrifuging the solution obtained in the step (1) at a high speed to remove impurities, drying the supernatant, and dissolving the supernatant in deionized water to prepare a nitrogen-doped carbon dot solution with the concentration of 1mg/mL for later use;
(3) adding 3g of melamine into 50mL of absolute ethyl alcohol, stirring for 2h, then dropwise adding the nitrogen-doped carbon dot solution obtained in the step (2), continuously stirring for 2h, and continuously stirring in a water bath at 70 ℃ until the solvent is volatilized;
(4) grinding the material obtained in the step (3), transferring the ground material into a muffle furnace, calcining for 4 hours at 550 ℃, cooling to room temperature, grinding, transferring the ground material into the muffle furnace again, and calcining for 2 hours at 530 ℃;
(5) adding 0.2109g of the material obtained in the step (4) into 50mL of deionized water while stirring, uniformly stirring, then adding 0.1078g of zinc sulfate and 0.0348g of ferrous sulfate, stirring until the solid is completely dissolved, dropwise adding 1.0mol/L of NaOH solution into the beaker, and adjusting the pH to 7.5-8;
(6) adding H into the solution obtained in the step 5)2O2And aging at 40 deg.C for 4 h;
(7) and (3) washing the material obtained in the step (6) until the pH value is 7, carrying out solid-liquid separation, washing the material for several times by using absolute ethyl alcohol, drying the material at 60 ℃, and grinding the material to obtain a CN/NCD/ZFL powder catalyst, namely the nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-shaped heterojunction photocatalyst shown in figure 1. In fig. 1(b), the lattice stripes d ═ 0.222nm and d ═ 0.206nm correspond to the crystal plane of ZFL and the (100) crystal plane of the nitrogen-doped carbon dots, indicating successful preparation of the photocatalyst.
Comparison experiment of antibiotic wastewater degradation efficiency
Experimental groups: the nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-type heterojunction photocatalyst prepared in the embodiment 1 is marked as CN/NCD/ZFL;
control group: graphite-like carbon nitride powder, noted CN;
the nitrogen-doped carbon quantum dot composite graphite-like phase carbon nitride powder is marked as CN/NCD;
the experimental procedure was as follows:
the preparation method of CN comprises the following steps:
transferring 3g of melamine into an alumina crucible, transferring the alumina crucible into a muffle furnace, calcining for 4 hours at 550 ℃, grinding after cooling to room temperature, transferring the melamine crucible into the muffle furnace again, calcining for 2 hours at 530 ℃, and grinding to obtain the CN powder catalyst.
The preparation method of CN/NCD comprises the following steps:
(1) adding 3g of melamine into 50mL of absolute ethyl alcohol, stirring for 2h, then dropwise adding a nitrogen-doped carbon dot solution, continuously stirring for 2h, and continuously stirring in a water bath at 70 ℃ until the solvent is volatilized;
(2) grinding the material obtained in the step (1), transferring the ground material into a muffle furnace, calcining for 4 hours at 550 ℃, cooling to room temperature, grinding, transferring the ground material into the muffle furnace again, and calcining for 2 hours at 530 ℃;
under the conditions of normal temperature and normal pressure, 50mL of tetracycline solution containing 30mg/L is added into a reactor, a 300W visible light source loaded with a 420nm filter is added for irradiation, and the nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide Z-type heterojunction photocatalyst prepared in the example 1, control group graphite-like carbon nitride powder and nitrogen-doped carbon quantum dot composite graphite-like carbon nitride powder are respectively added to enable the concentration to be 0.6 g/L.
An ultraviolet spectrophotometer is used for detecting the treatment effect, as shown in figure 2, the CN/NCD/ZFL photocatalyst prepared in the example 1 has a red shift phenomenon compared with graphite-like phase carbon nitride in the absorption of a visible light region, and the fact that the Z-type graphite-like phase carbon nitride/zinc-iron layered double metal hydroxide Z-type heterojunction is formed strengthens the charge transfer capability of the catalyst, enhances the photoresponse range and improves the utilization rate of visible light.
As can be seen from fig. 3, the CN/NCD/ZFL photocatalyst prepared in example 1 has the lowest electron-hole pair recombination rate and higher charge transfer efficiency.
As can be seen from fig. 4, the CN/NCD/ZFL photocatalyst prepared in example 1 has stable catalytic effect after four repeated experiments, and can realize recycling of the catalyst and reduce secondary pollution.
As shown in FIG. 5, after 80min, the degradation efficiency of tetracycline in the group using CN/NCD/ZFL photocatalyst was 83.7%, and the degradation efficiency of CN and CN/NCD was 54.6% and 63.6%, respectively, at room temperature and under normal pressure.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A CN/NCD/ZFL photocatalyst is characterized in that: is a Z-shaped heterojunction photocatalyst of nitrogen-doped carbon dot composite graphite-like carbon nitride/zinc-iron layered double hydroxide.
2. The method of claim 1, wherein the method comprises the steps of: the method comprises the following steps:
1) preparing a nitrogen-doped carbon dot solution;
2) preparing nitrogen-doped carbon dot composite graphite-like phase carbon nitride;
3) preparing a Z-type heterojunction photocatalyst:
adding calcined solid materials into deionized water, uniformly mixing by ultrasonic waves, adding zinc sulfate and ferrous sulfate, adjusting the pH value to 7.5-8 by using a sodium hydroxide solution, and stirring for 1-2 hours;
② adding H2O2Aging for 3-4 h at 40-45 ℃ to obtain a mixed material;
and thirdly, washing the mixed material until the pH value is 7, carrying out solid-liquid separation, cleaning, drying and grinding the separated solid to obtain the CN/NCD/ZFL Z-type heterojunction photocatalyst.
3. The method of claim 2The preparation method of the CN/NCD/ZFL photocatalyst is characterized by comprising the following steps: in the step 3), Zn2+With Fe3+The ratio of (A) to (B) is 3: 1.
4. The method for preparing CN/NCD/ZFL photocatalyst as claimed in claim 2, wherein: and in the third step of the step 3), the separated solid is dried for 5-6 hours at 40-60 ℃ after being washed for a plurality of times by absolute ethyl alcohol and deionized water.
5. The method for preparing CN/NCD/ZFL photocatalyst as claimed in claim 2, wherein: the step 1) comprises the following steps:
dissolving citric acid and urea in deionized water, uniformly mixing, and carrying out hydrothermal reaction for 5 hours at 180-200 ℃;
and secondly, centrifuging the solution at a high speed, drying the supernatant and dissolving the supernatant in deionized water to prepare a nitrogen-doped carbon dot solution with the mass concentration of 1-2 mg/mL.
6. The method for preparing CN/NCD/ZFL photocatalyst according to claim 5, wherein: in the step 1), the mass ratio of citric acid to urea is 2: 1-1.5: 1, and the total mass fraction of solutes in the solution is 17-21%.
7. The method for preparing CN/NCD/ZFL photocatalyst as claimed in claim 2, wherein: the step 2) comprises the following steps:
adding melamine into absolute ethyl alcohol and stirring for 2 hours, then dropwise adding the nitrogen-doped carbon dot solution, continuously stirring for 2-3 hours to obtain a mixed solution, stirring under a water bath heating condition of 60-70 ℃ until the solvent volatilizes, and realizing solid-liquid separation to obtain a solid material;
and secondly, calcining the solid material for 2-4 hours at 530-550 ℃ after grinding.
8. The method for preparing CN/NCD/ZFL photocatalyst according to claim 7, wherein: in the step 2), the mass concentration of melamine in the mixed solution is 60g/L, and the volume ratio of the absolute ethyl alcohol to the nitrogen-doped carbon dot solution is 50: 30-50.
9. Use of a CN/NCD/ZFL photocatalyst as claimed in claim 1 in the treatment of antibiotic wastewater.
10. An antibiotic wastewater treatment method is characterized in that: the CN/NCD/ZFL photocatalyst is adopted to carry out photocatalytic degradation treatment by a 300W xenon lamp light source loaded with a 420nm optical filter under the conditions of normal temperature and normal pressure; the concentration of the CN/NCD/ZFL photocatalyst in the antibiotic wastewater is 0.2-1.0 g/L, and the antibiotic wastewater comprises tetracycline wastewater.
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