CN111389469A - Preparation method of photocatalytic heterojunction nano composite material for removing algae in water body - Google Patents
Preparation method of photocatalytic heterojunction nano composite material for removing algae in water body Download PDFInfo
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 46
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000013207 UiO-66 Substances 0.000 claims abstract description 22
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- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 17
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
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- 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 6
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method of a photocatalytic heterojunction nano composite material for removing algae in a water body, which utilizes UIO-66 (NH)2) Multiple aromatic rings of the organic ligand with g-C3N4The two are tightly combined to form a heterojunction, and simultaneously an in-situ growth method is utilized on the binary heterojunction substrate to introduce an Ag-AgCl semiconductor into the heterojunction to construct Ag-AgCl/g-C3N4/UIO‑66（NH2) Of ternary heterostructuresThe nano composite photocatalyst is used for effectively removing harmful algae in water under visible light. The photocatalytic heterojunction nano-composite prepared by the method has the characteristics of large specific surface area, good visible light response, high separation efficiency of photon-generated carriers and good stability, and can be applied to removal of algae in water to realize photocatalytic inactivation of algae cells in water.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method of a photocatalytic heterojunction nano composite material for removing eutrophic water algae.
Background
With the global warming becoming worse, the eutrophication problem of water body becomes more serious, and toxic and harmful algal blooms appear in lakes, rivers and reservoirs more and more frequently. The rapid propagation of harmful algae in eutrophic water bodies will cause serious damage to aquatic ecosystems, and in addition, most of the harmful algae, such as microcystis aeruginosa in eutrophic water bodies, can produce algal toxins, which will also bring about the problem of water environmental safety. Currently, in order to deal with cyanobacterial bloom, many conventional physical and chemical methods such as mechanical fishing, biological algae removal, ultrasonic algae removal, etc. have been developed. However, these conventional methods have limited their application due to corresponding drawbacks. For example, the mechanical fishing method needs a large amount of manpower and material resources, has higher cost and is not easy to be used as a long-term algae removal method; the biological algae removal method is usually longer in treatment period, is not suitable for the blue algae bloom which is rapidly burst, is more complex in subsequent treatment and has the risk of aggravating damage to an ecological system; the ultrasonic method is only suitable for small-scale treatment in water plants at present because of limited algae removal effect. Therefore, how to effectively control the cyanobacterial bloom so as to further solve the problem of water eutrophication becomes a hotspot of research in the field of water treatment.
In recent years, the photocatalytic technology has been gradually applied to environmental studies such as pollution control and antibiosis due to its advantages of high efficiency, low cost, environmental protection, and the like. The photocatalysis technology applies the nano photocatalyst, and provides a new idea for solving the problem of eutrophication of water bodies due to the advantages of high photocatalytic activity, good environmental sustainability, low cost, no toxicity and the like. The nanometer photocatalyst can be combined with microorganisms to induce and generate active substances with strong oxidation capacity to destroy algae cells, so that the growth of algae is inhibited, and corresponding cytotoxins are degraded. The method for controlling the outbreak of the cyanobacterial bloom by applying the photocatalytic reaction of the nano photocatalyst is an effective and environment-friendly treatment method. However, there are still some problems to apply the nano photocatalyst to the removal of algae in practical water: on one hand, most of the current photocatalytic algae removal materials can only be activated under the irradiation of ultraviolet light to realize the photocatalytic process, and the ultraviolet light only accounts for about 4% of the whole spectrum in terms of solar spectrum, which means that the energy conversion efficiency of the photocatalyst is low, thereby causing the reduction of the algae removal efficiency. On the other hand, the existing photocatalyst generally has the defects of fast recombination of photoproduction holes and electrons, short service life of photoproduction electrons and the like, and further limits the application of the photocatalyst in removing algae in practical water bodies. In contrast, the heterostructure formed by combining the metal-organic framework material and the graphite-like carbonitride can realize the close contact between the materials, accelerate the charge transfer across the interface and improve the separation rate of photoinduced electrons and holes. In addition, the noble metal is deposited on the binary heterojunction material, so that the visible light response capability of the material can be improved, the separation efficiency of photon-generated carriers can be further improved, and the recombination of electron hole pairs can be effectively inhibited.
Thus, by constructing heterostructures of Ag-AgCl/g-C3N4/UIO-66（NH2) The photocatalytic nanocomposite material can remarkably improve the utilization capacity of a catalyst on visible light, accelerate interface electron transfer and reduce the recombination rate of electron hole pairs, thereby effectively improving the photocatalytic capacity of the photocatalyst and realizing the effective removal of cyanobacterial bloom in a water body.
Disclosure of Invention
The invention aims to provide a preparation method of a photocatalytic heterojunction nano composite material for removing algae in a water body, which is used for relieving the problem of cyanobacterial bloom. The present invention utilizes UIO-66 (NH)2) Multiple aromatic rings of the organic ligand with g-C3N4The two are closely combined to form a heterojunction through the pi-pi interaction between the triazine rings, and the heterojunction is formed at the same timeThe Ag-AgCl semiconductor is introduced into the binary heterojunction substrate by using an in-situ growth method to construct Ag-AgCl/g-C3N4/UIO-66（NH2) The nano composite photocatalyst with the ternary heterostructure can effectively remove harmful algae in water under visible light.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a photocatalytic heterojunction nano composite material for removing algae in a water body comprises the following steps:
1）g-C3N4the synthesis of (2): placing urea in a crucible with a cover, calcining at 550 ℃ in a muffle furnace, taking out and grinding to obtain yellow g-C3N4Powder;
2）g-C3N4/UIO-66（NH2) The synthesis of (2): g-C prepared in the step 1)3N4Powder and a quantity of ZrCl4With 2-aminoterephthalic acid in dimethylformamide to form a homogeneous suspension. Subsequently, the solution was transferred to a teflon lined reactor, sealed and kept at 120 ℃ for 24 h; the product obtained is filtered, washed several times with dimethylformamide and methanol to give a precipitate, and dried at 80 ℃ for 24 h to give g-C3N4/UIO-66（NH2）;
3）Ag-AgCl/g-C3N4/UIO-66（NH2) Preparation of heterojunction photocatalyst: preparing AgNO with a certain concentration3Solution of a certain amount of g-C obtained in step 2)3N4/UIO-66（NH2) Dissolved in the prepared AgNO3Stirring the solution for 3 hours at room temperature; dropwise adding the solution into NaCl solution with a certain concentration within 20min, and stirring at room temperature for 10h to obtain a bluish purple product; washing the product with deionized water for three times to remove excess NaCl, and drying at 70 ℃ for 12 h to obtain Ag-AgCl/g-C3N4/UIO-66（NH2）。
Further, in the step 1), the temperature rising rate of the muffle furnace is 10 ℃/min, and the high-temperature calcination time is 4 h.
Further, g to C used in step 2)3N4Powder and ZrCl4And 2-amino-terephthalic acid in a mass ratio of 1:3: 2.3; dimethylformamide and g-C used3N4，ZrCl4The mass ratio of the three mixtures to the total mass of the three mixtures of 2-amino-terephthalic acid was 96.3: 1.
Further, AgNO in step 3)3The concentration of the solution is 53.7 mmol/L, the concentration of the NaCl solution is 10.48 mmol/L, AgNO3And g-C3N4/UIO-66（NH2) The mass ratio of (A) to (B) is 1: 2.9; NaCl and AgNO3Is 1.1: 1.
The photocatalytic heterojunction nano composite material prepared by the method can be used for removing algae in water. The prepared nano composite material is powdery, and on one hand, the material has a larger specific surface area and can provide enough active sites for photocatalytic reaction; on the other hand, the material has better visible light response capability, and meanwhile, the heterostructure endows the material with higher photon-generated carrier separation efficiency and lower photon-generated electron hole pair recombination rate, so that the material has higher photocatalytic activity.
Compared with the existing algae removal technology, the invention has the following advantages:
1. the photocatalytic heterojunction nano composite material prepared by the method has the characteristics of high photocatalytic activity, environmental friendliness, strong antibacterial effect, good stability and the like.
2. The photocatalytic heterojunction nano composite material is used for controlling the problem of cyanobacterial bloom in eutrophic water, has large surface area, and can enhance the interaction between reactants and a catalyst by increasing the adsorption performance on a target model; the strong visible light response capability of the photocatalyst can improve the utilization rate of the photocatalyst on visible light, so that the photocatalytic activity of the material is improved.
3. The photocatalytic heterojunction nano composite material prepared by the invention can accelerate charge transfer of an interface and shorten the charge transmission distance through the formed heterojunction, thereby improving the separation rate of photoinduced electron hole pairs, inhibiting the recombination rate of the photoinduced electron hole pairs and obviously improving the photocatalytic activity of the material.
Drawings
FIG. 1 is a schematic representation of Ag-AgCl/g-C prepared in example 13N4/UIO-66（NH2) The algae removal effect of the photocatalyst is compared with that of each single-component photocatalyst under visible light.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
（1）g-C3N4Synthesis of (2)
10g of urea was placed in a crucible with a lid and then heated to 550 ℃ in a muffle furnace, and the temperature was maintained for 4 hours at a heating rate of 10 ℃/min. g-C obtained3N4The flakes are yellow powders, thin and flat nanoplatelets.
（2）g-C3N4/UIO-66（NH2) Synthesis of (2)
0.0777 g g-C3N4，0.2332 g ZrCl4And 0.1812 g of 2-amino-terephthalic acid were ultrasonically dispersed in a 50m L dimethylformamide solution to form a homogeneous suspension, the solution was then transferred to a 100 m L Teflon-lined reaction kettle, sealed and maintained at 120 ℃ for 24 h, the resulting product was filtered, washed three times with dimethylformamide and methanol, and the precipitate was then dried at 80 ℃ for 24 h to give g-C3N4/UIO-66（NH2）。
（3）Ag-AgCl/g-C3N4/UIO-66（NH2) Preparation of heterojunction photocatalyst
53.7 mmol/L AgNO was prepared3The solution was then weighed 0.2 g g-C3N4/UIO-66（NH2) Dissolving in 14 m L of the above AgNO3Stirring at room temperature for 3 hr, adding 98 m L10.48 mmol/L NaCl solution dropwise within 20min, stirring at room temperature for 10 hr to obtain bluish purple product, washing with deionized water three times to remove excess NaClAnd dried for 12 h at 70 ℃ to obtain Ag-AgCl/g-C3N4/UIO-66（NH2）。
Algae removal effect of photocatalytic heterojunction nano composite material under visible light
Selecting initial algae density of 6.48 × 106The microcystis aeruginosa solution with the concentration of the microcystis aeruginosa per m L is taken as a removal object, and the algae removal effect of the photocatalytic heterojunction nano composite material under visible light is researched by taking chlorophyll a as an index in a photocatalytic experiment, wherein 80 m L algae solution is taken and 30 mg/L Ag-AgCl/g-C is added into the algae solution3N4/UIO-66（NH2) Photocatalysts, noted experimental group. The control group did not have any catalyst added, and the remaining conditions were the same as the experimental group. The experimental group and the control group were put together in a photocatalytic reactor (using a cut-off filter to remove ultraviolet light with a wavelength of < 420 nm) for photocatalytic reaction for 180 min, and the chlorophyll a content was measured by sampling every 30 min, and the experimental results are shown in fig. 1.
As can be seen from FIG. 1, the experimental group Ag-AgCl/g-C was observed after 120 min irradiation with visible light3N4/UIO-66（NH2) The heterojunction photocatalyst can remove 96% of chlorophyll a in algae cells, and can achieve near 100% removal of chlorophyll a in algae cells within 180 min. In contrast, the chlorophyll a content of the algal cells of the control group remained relatively stable during the photocatalytic reaction, indicating that Ag-AgCl/g-C3N4/UIO-66（NH2) The heterojunction photocatalyst can effectively degrade chlorophyll in algae cells, so that the algae cells are inactivated.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a photocatalytic heterojunction nano composite material for removing algae in a water body is characterized by comprising the following steps: using multiple aromatic rings with g-C of organic ligands in the aminated UIO-663N4The two are tightly combined to form a heterojunction through pi-pi interaction between the two triazine rings, and meanwhile, an in-situ growth method is utilized on the binary heterojunction substrate,Ag-AgCl semiconductor is introduced into the solution to construct Ag-AgCl/g-C3N4/UIO-66-NH2A nano composite photocatalyst with a ternary heterostructure.
2. The method of claim 1, wherein the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: the method specifically comprises the following steps:
1）g-C3N4the synthesis of (2): placing urea in a crucible with a cover, calcining at 550 ℃ in a muffle furnace, taking out and grinding to obtain yellow g-C3N4Powder;
2）g-C3N4/UIO-66-NH2the synthesis of (2): g-C prepared in the step 1)3N4Powder and a quantity of ZrCl4With 2-amino-terephthalic acid in dimethylformamide to form a homogeneous suspension; then transferring the solution into a reaction kettle with a teflon lining for sealing and reacting at high temperature; filtering the obtained product, washing with dimethylformamide and methanol to obtain precipitate, drying to obtain g-C3N4/UIO-66-NH2；
3）Ag-AgCl/g-C3N4/UIO-66-NH2Preparation of heterojunction photocatalyst: preparing AgNO with a certain concentration3Solution of a certain amount of g-C obtained in step 2)3N4/UIO-66（NH2) Dissolved in the prepared AgNO3Stirring the solution for 3 hours at room temperature; dropwise adding the solution into NaCl solution with a certain concentration within 20min, and stirring at room temperature for 10h to obtain a bluish purple product; washing the product with deionized water for three times to remove excess NaCl, and drying at 70 ℃ for 12 h to obtain Ag-AgCl/g-C3N4/UIO-66-NH2。
3. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: step 1), the temperature rising rate of a muffle furnace is 10 ℃/min, and the high-temperature calcination time is 4 h.
4. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: g-C used in step 2)3N4Powder and ZrCl4And 2-amino-terephthalic acid in a mass ratio of 1:3: 2.3; dimethylformamide and g-C used3N4，ZrCl4The mass ratio of the three mixtures to the total mass of the three mixtures of 2-amino-terephthalic acid was 96.3: 1.
5. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: the high-temperature reaction in the step 2) is specifically kept at 120 ℃ for 24 hours.
6. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: the drying in the step 2) is specifically drying for 24 hours at 80 ℃.
7. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: AgNO in step 3)3The concentration of the solution was 53.7 mmol/L, and the concentration of the NaCl solution was 10.48 mmol/L.
8. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: AgNO in step 3)3And g-C3N4/UIO-66-NH2The mass ratio of (A) to (B) is 1: 2.9.
9. The method of claim 1, wherein the step of preparing the photocatalytic heterojunction nanocomposite material for removing algae in water comprises: NaCl and AgNO in step 3)3Is 1.1: 1.
10. Use of the photocatalytic heterojunction nanocomposite material prepared by the method of claim 1 in the treatment of algae in a water body.
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