CN113318771A - Magnetic nano carbon nitride photocatalyst capable of removing algae and preparation method thereof - Google Patents
Magnetic nano carbon nitride photocatalyst capable of removing algae and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 241000195493 Cryptophyta Species 0.000 title claims abstract description 34
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
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- 238000001035 drying Methods 0.000 claims description 7
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
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- 239000007790 solid phase Substances 0.000 claims description 4
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- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
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- 229930002868 chlorophyll a Natural products 0.000 description 5
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 5
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- 241000192710 Microcystis aeruginosa Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000010451 perlite Substances 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
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- 230000001603 reducing effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005422 algal bloom Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- 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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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
The invention discloses a magnetic nano carbon nitride photocatalyst capable of removing algae and a preparation method thereof. The photocatalyst takes graphite-phase carbon nitride as a carrier, and noble metal palladium Pd is loaded, so that the photocatalytic activity of the photocatalyst is improved. The noble metal palladium Pd can improve the separation efficiency of photo-generated charge carriers of the semiconductor photocatalyst by capturing electrons, and the Surface Plasmon Resonance (SPR) effect of palladium atoms can greatly improve the visible light absorption rate of the photocatalyst, accelerate the generation of free radicals and catalyze the photocatalystThe growth of the chemical oxidation algae is promoted. Meanwhile, the photocatalyst provided by the invention is loaded with nano Fe3O4The photocatalyst has good magnetism and is recovered under the action of magnetic attraction. Therefore, the development of the photocatalyst has important significance on the removal work of harmful algae.
Description
Technical Field
The invention belongs to a preparation technology of a nano catalytic material, is applied to the field of photocatalytic algae removal, and particularly relates to a magnetic nano carbon nitride photocatalyst capable of removing algae and a preparation method thereof.
Background
With the development of social economy, industrial wastewater, domestic sewage and farmland runoff bring a large amount of nitrogen and phosphorus into a water body for enrichment, so that the water body is eutrophicated. Under the influence of environmental factors such as proper temperature and the like, blue algae in water body grow in large quantity to form macroscopic cyanobacterial bloom, which causes adverse effect on the ecological environment of the water body, generates huge economic loss and directly or indirectly affects human health, and becomes one of the main environmental problems ubiquitous in the world.
The photocatalytic oxidation technology has been drawing attention as an environmental purification technology with great potential due to its characteristics of high oxidation capacity, environmental friendliness, low cost and the like. In the photocatalytic oxidation process, the semiconductor material can be excited by light to generate hydroxyl radicals (OH) with strong oxidation capacity, and the radicals can degrade organic pollutants in water and inactivate microorganisms in water, so that many researchers apply the technology to the control of algal bloom.
As a novel semiconductor material with visible light response, the graphite-phase carbon nitride has the advantages of excellent thermal and chemical stability, low raw material cost and the like, so that the graphite-phase carbon nitride shows a good application prospect. However, the material is limited by conditions of large forbidden band width (2.7eV), narrow response range to visible light (generally less than 460nm), high recombination rate of photo-generated electron-hole pairs, small specific surface area and the like in practical application. In order to enhance the photocatalytic activity of a semiconductor photocatalyst under visible light, it is essential to improve the separation efficiency of charge carriers and enhance the responsiveness thereof to visible light. By combining noble metals with existing semiconductor photocatalysts, effective separation of the optical carriers can be achieved. The noble metal palladium Pd can improve the separation efficiency of photo-generated charge carriers of the semiconductor photocatalyst by capturing electrons, and the visible light absorption rate of the photocatalyst can be greatly improved by the Surface Plasmon Resonance (SPR) effect of palladium atoms, so that the generation of free radicals is accelerated, and the growth of photocatalytic oxidation algae is promoted.
However, the photocatalyst itself is expensive in cost and low in recovery rate, which limits its application range. Therefore, the problem that the photocatalyst is difficult to recover is solved, and the photocatalytic algae removal process is very important to be put into practical application.
Disclosure of Invention
The invention aims to provide a magnetic nano carbon nitride photocatalyst capable of removing algae and a preparation method thereof aiming at the existing problems.
The invention relates to a magnetic nano carbon nitride photocatalyst capable of removing algae, which is characterized in that: by supporting Pd on Fe3O4/g-C3N4Obtained on the composite material.
Preferably, the doping molar concentration of Pd in the magnetic nano carbon nitride photocatalyst is 5%;
preferably, said Fe3O4/g-C3N4In composite materials, Fe is in the nanometer range3O4And g-C3N4The mass ratio of (A) to (B) is 1: 4.
Preferably, step one, nanometer-scale Fe3O4Mixing with carbon nitride, and adding into anhydrous ethanol for ultrasonic treatment; drying the mixture after the ultrasonic treatment is finished, grinding, sieving and calcining to obtain Fe3O4/g-C3N4A composite material.
Step two, adding Fe3O4/g-C3N4Dispersing the composite material into a mixed solution of deionized water and a methanol solution, and dropwise adding Na into the obtained dispersion system2PdCl4And (3) solution.
And step three, introducing nitrogen into the dispersion system obtained in the step two, removing dissolved oxygen, and respectively keeping the anoxic and constant-temperature environments of the dispersion system in a nitrogen continuous cleaning and cooling water circulation mode.
And step four, performing xenon lamp illumination. And after the illumination is finished, filtering and drying the solid phase to obtain the magnetic nano carbon nitride photocatalyst capable of removing algae.
The preparation method of the magnetic nano carbon nitride photocatalyst capable of removing algae comprises the following steps:
the preparation process of the graphite phase carbon nitride in the first step is as follows: feeding the ground dicyandiamide into a box-type atmosphere furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, calcining for 2h at 500 ℃, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining for 2h at 550 ℃; cooling and grinding to obtain the yellowish granular graphite-phase carbon nitride.
Preferably, the calcination in the first step is carried out at 450 ℃ for 2 hours.
Preferably, the xenon lamp is irradiated under visible light conditions with an optical power density of 2W/cm2。
Preferably, in the second step, Na is used2PdCl4The dropping rate of the solution was 5 ml/min.
Preferably, in step two, every 0.6g of Fe3O4/g-C3N440.16ml of Na is added into the composite material dropwise2PdCl4And (3) solution.
Preferably, in the second step, the volume ratio of the deionized water to the methanol solution is 4: 1. The solid phase is filtered out in the fourth step by suction filtration and washing with deionized water for 3 times.
The invention has the beneficial effects that:
1. the invention loads noble metal Pd on Fe3O4/g-C3N4The particle is used as a photocatalytic material for inhibiting algae, the noble metal palladium Pd is used for improving the separation efficiency of a photo-generated charge carrier of the semiconductor photocatalyst by capturing electrons, and the visible light absorption rate of the photocatalyst can be greatly improved by the Surface Plasmon Resonance (SPR) effect of palladium atoms, so that the generation of free radicals is accelerated, and the growth of the photocatalytic oxidation algae is promoted. Therefore, compared with the existing algae inhibiting photocatalyst, the invention has Fe3O4-Pd/g-C3N4The photocatalyst can improve the activity of the photocatalyst and has more obvious algae inhibiting effect in shorter time.
2. The catalyst provided by the invention contains nano Fe3O4This makes the synthesized catalyst magneticAnd the catalyst is convenient to recycle after the reaction is finished, so that the secondary pollution is reduced.
Drawings
FIG. 1 shows Fe obtained in example 1 of the present invention3O4-Pd/g-C3N4An energy spectrum of the particulate matter;
FIG. 2 shows Fe in example 2 of the present invention3O4-Pd/g-C3N4A comparative line plot of the effect of the particulate matter on reduction of algal cell density;
FIG. 3 shows Fe in example 2 of the present invention3O4-Pd/g-C3N4A comparative line graph of the effect of the particles on the reduction of chlorophyll a content in algal cells.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1:
a preparation method of a magnetic nano carbon nitride photocatalyst capable of removing algae comprises the following specific steps:
weighing 10.0g of dicyandiamide, uniformly grinding the dicyandiamide, putting the ground dicyandiamide into a 50mm crucible, covering the crucible, sending the mixture into a box-type atmosphere furnace, heating the mixture to 500 ℃ at a heating rate of 10 ℃/min, calcining the mixture at 500 ℃ for 2 hours, heating the mixture to 550 ℃ at a heating rate of 5 ℃/min, calcining the mixture at 550 ℃ for 2 hours, taking out the crucible, and naturally cooling the crucible to room temperature; and grinding the sample in the crucible uniformly to obtain light yellow carbon nitride particles. And in the preparation process of the carbon nitride particles, nitrogen is introduced to isolate oxygen.
0.3g of nanoscale Fe3O4And 1.2g of carbon nitride particles are put into a crucible with the thickness of 50mm, 10ml of absolute ethyl alcohol is added for ultrasonic treatment for 30min, after the ultrasonic treatment is finished, the mixture is put into a drying oven with the temperature of 60 ℃ for drying for 2h, then the mixture is uniformly ground, and after the mixture is sieved by a sieve with 80 meshes, the mixture is put into a muffle furnace with the temperature of 450 ℃ for calcining for 2h to obtain Fe3O4/g-C3N4(ii) particulate matter. 0.3g of Fe3O4/g-C3N4Dispersed in a quartz reactor containing a mixed solution of 60ml of deionized water and 15ml of methanol solution. The quartz reactor is a jacket beaker, which is convenient for the circulation of cooling water during the illumination reaction. After thoroughly mixing and stirring, 40.16mL of the solution was added dropwiseNa after completion of the preparation of (3)2PdCl4And (3) solution. Na (Na)2PdCl4The solution preparation method comprises weighing 1g Na2PdCl4(Pd ═ 36.05%), 2ml of concentrated hydrochloric acid was added dropwise until it was completely dissolved, and then diluted with ultrapure water to 500ml of a solution. After continuously stirring for 2h, introducing high-purity nitrogen to remove dissolved oxygen, continuously cleaning the suspension with nitrogen and circulating cooling water to respectively maintain oxygen deficiency and constant temperature, and introducing air into a 250ml container for 30 min. The suspension was illuminated with a xenon lamp. After the illumination is finished, filtering and washing the solution for 3 times by deionized water, and drying the solution in a 60 ℃ oven until the solution is completely dried to obtain the magnetic nano carbon nitride photocatalyst (specifically magnetic Fe)3O4-Pd/g-C3N4Particulate matter) whose spectrum is shown in fig. 1.
Example 2
The magnetic nano carbon nitride photocatalyst prepared in example 1 is used for algae inhibition test, and the specific process is as follows:
magnetic nano carbon nitride photocatalyst (0.5g Fe)3O4-Pd/g-C3N4Pellets) was put into a beaker containing 250ml of an algal solution (OD680 with an initial value of 0.3), and a 500W xenon lamp was placed 15cm from the beaker as a light source, and the light intensity was set at 2mW/cm2An ultraviolet filter is arranged on a xenon lamp, and the photocatalytic reaction is carried out for 6 hours under the condition that the rotating speed of a magnetic stirrer is 200 r/min. 10ml of algae liquid samples are collected every 1h and used for measuring the cell density and the chlorophyll a content of algae.
Comparative example 1
This comparative example differs from example 2 only in that: the particulate matter added into the algae liquid is graphite phase carbon nitride particulate matter (g-C)3N4)。
The comparison of the cell density reducing effect of algae of the present comparative example and example 2 is shown in FIG. 2; addition of photocatalyst Fe3O4-Pd/g-C3N4In the embodiment 2, the microcystis aeruginosa cells are quickly damaged within 6 hours, so that the reduction ratio of the cell density of the microcystis aeruginosa cells reaches 95 percent; and g-C is added3N4Comparative example 1 the algal cell density of the treated group was decreased after 6 hours of photocatalytic reactionThe ratio is only 50.94%. The comparison of the effect of reducing chlorophyll a content in algal cells of the comparative example and example 2 is shown in FIG. 3; addition of photocatalyst Fe3O4-Pd/g-C3N4After the treated algae liquid is subjected to photocatalytic reaction for 6 hours, the content of chlorophyll a is reduced by 98 percent; and g-C3N4After the treatment group is subjected to photocatalytic reaction for 6 hours, the chlorophyll a content of the treatment group is only reduced by 43.34 percent.
Furthermore, F-Ce-TiO in the prior art2The Expanded Perlite (EP) floating photocatalyst has the most remarkable algae inhibiting effect on the growth of algae cells, and the reduction ratio of the cell density of the algae is 88.7 percent, which is lower than that of the invention. However, from the viewpoint of treatment time, F-Ce-TiO2Expanded Perlite (EP) floating photocatalyst takes 9 hours, while Fe used in the present invention3O4-Pd/g-C3N4The photocatalyst can exceed the algae inhibiting effect within 6 hours, thereby saving energy consumption and improving the algae removal efficiency.
Claims (10)
1. A magnetic nanometer carbon nitride photocatalyst capable of removing algae is characterized in that: by supporting Pd on Fe3O4/g-C3N4Obtained on the composite material.
2. The algae-removing magnetic nano carbon nitride photocatalyst as claimed in claim 1, wherein: the doping molar concentration of Pd in the magnetic nano carbon nitride photocatalyst is 5 percent.
3. The algae-removing magnetic nano carbon nitride photocatalyst as claimed in claim 1, wherein: said Fe3O4/g-C3N4In composite materials, Fe is in the nanometer range3O4And g-C3N4The mass ratio of (A) to (B) is 1: 4.
4. The method for preparing the magnetic nano carbon nitride photocatalyst capable of removing algae according to claim 1, wherein the method comprises the following steps:
step one, nano-scale Fe3O4Mixing with carbon nitride, and adding into anhydrous ethanol for ultrasonic treatment; drying the mixture after the ultrasonic treatment is finished, grinding, sieving and calcining to obtain Fe3O4/g-C3N4A composite material;
step two, adding Fe3O4/g-C3N4Dispersing the composite material into a mixed solution of deionized water and a methanol solution, and dropwise adding Na into the obtained dispersion system2PdCl4A solution;
step three, introducing nitrogen into the dispersion system obtained in the step two, removing dissolved oxygen, and respectively keeping the anoxic and constant-temperature environments of the dispersion system in a nitrogen continuous cleaning and cooling water circulation mode;
step four, performing xenon lamp illumination; and after the illumination is finished, filtering and drying the solid phase to obtain the magnetic nano carbon nitride photocatalyst capable of removing algae.
5. The method for preparing the algae-removing magnetic nano carbon nitride photocatalyst according to claim 4, wherein the method comprises the following steps: the preparation process of the graphite phase carbon nitride in the first step is as follows: feeding the ground dicyandiamide into a box-type atmosphere furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, calcining for 2h at 500 ℃, heating to 550 ℃ at a heating rate of 5 ℃/min, and calcining for 2h at 550 ℃; cooling and grinding to obtain the yellowish granular graphite-phase carbon nitride.
6. The method for preparing the algae-removing magnetic nano carbon nitride photocatalyst according to claim 4, wherein the method comprises the following steps: the calcining condition in the step one is calcining for 2 hours at 450 ℃.
7. The method for preparing the algae-removing magnetic nano carbon nitride photocatalyst according to claim 4, wherein the method comprises the following steps: the illumination condition of the xenon lamp is set as visible light, and the optical power density is 2W/cm2。
8. According to claimThe preparation method of the magnetic nano carbon nitride photocatalyst capable of removing algae in the claim 4 is characterized by comprising the following steps: in the second step, Na is added2PdCl4The dropping rate of the solution was 5 ml/min.
9. The method for preparing the algae-removing magnetic nano carbon nitride photocatalyst according to claim 4, wherein the method comprises the following steps: in step two, each 0.6g of Fe3O4/g-C3N440.16ml of Na is added into the composite material dropwise2PdCl4And (3) solution.
10. The method for preparing the algae-removing magnetic nano carbon nitride photocatalyst according to claim 4, wherein the method comprises the following steps: in the second step, the volume ratio of the deionized water to the methanol solution is 4: 1; the solid phase is filtered out in the fourth step by suction filtration and washing with deionized water for 3 times.
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| CN114804283A (en) * | 2022-04-19 | 2022-07-29 | 湖南大学 | Method for treating harmful algae by photocatalysis |
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