CN115138395B - Preparation method and application of black phosphorus-based photocatalytic composite material - Google Patents
Preparation method and application of black phosphorus-based photocatalytic composite material Download PDFInfo
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- CN115138395B CN115138395B CN202210842498.0A CN202210842498A CN115138395B CN 115138395 B CN115138395 B CN 115138395B CN 202210842498 A CN202210842498 A CN 202210842498A CN 115138395 B CN115138395 B CN 115138395B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 17
- 239000002351 wastewater Substances 0.000 claims description 13
- 229920002873 Polyethylenimine Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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Abstract
A preparation method and application of a black phosphorus-based photocatalytic composite material relate to a preparation method and application of a photocatalytic composite material. The invention aims to solve the problems that the existing black phosphorus has low dispersibility in water, influences the effective absorption of sunlight and causes poor photocatalytic performance. The method comprises the following steps: 1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid; 2. preparing spinning solution; 3. carrying out electrostatic spinning; 4. immersing in a metal phthalocyanine solution; 5. and (5) circulating. The preparation method is used for preparing the black phosphorus-based photocatalytic composite material.
Description
Technical Field
The invention relates to a preparation method of a photocatalysis composite material.
Background
The energy shortage and the environmental pollution are two non-bypassing topics in the world, the influence on human beings is the deepest, the photocatalysis technology can utilize solar energy to degrade organic pollutants, and intermediate products are nontoxic and harmless and cannot cause secondary pollution, so that the photocatalysis technology is attracting more and more attention.
Photocatalysis is based on the redox capability of a photocatalyst under illumination, when the energy is equal to or greater than the forbidden bandwidth of the catalyst, electrons in the valence band are excited to transition to the conduction band, negatively charged high-activity electrons are generated on the conduction band, and relatively stable holes are left on the valence band, so that electron-hole pairs are formed. Due to the large number of defects and dangling bonds in the nanomaterial, the defects and dangling bonds can trap electrons or holes and prevent recombination of the electrons and the holes. These trapped electrons and holes diffuse to the surface of the particles, respectively, creating a strong redox potential.
Black phosphorus is a nonmetallic photocatalyst, has excellent carrier mobility, can improve carrier separation efficiency, has a wide light absorption range of ultraviolet, visible and near infrared, and is beneficial to improving the light absorption efficiency of catalytic materials. In larger amounts of morphology, the black phosphorus comprises multiple layers, similar to graphite. However, the dispersibility of black phosphorus in water is low, which affects the effective absorption of sunlight, resulting in poor photocatalytic performance.
Disclosure of Invention
The invention aims to solve the problems that the existing black phosphorus has low dispersibility in water, influences the effective absorption of sunlight and causes poor photocatalytic performance. Further provides a preparation method and application of the black phosphorus-based photocatalytic composite material.
The invention relates to a preparation method of a black phosphorus-based photocatalytic composite material, which comprises the following steps:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding black phosphorus powder into a polyvinyl alcohol solution for homogenization, and then adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion; wherein, the mass concentration of the black phosphorus powder in the polyvinyl alcohol-black phosphorus dispersion liquid is 5-10%; the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-black phosphorus dispersion liquid is 7% -10%;
2. preparation of spinning solution:
dissolving polyethylenimine in N-methyl pyrrolidone, and then adding polyvinyl alcohol-black phosphorus dispersion liquid to obtain spinning solution;
the total mass percentage of the polyethylenimine and the black phosphorus in the spinning solution is 20-50%;
3. and (3) electrostatic spinning:
under the conditions that the receiving distance is 12 cm-15 cm, the voltage is 10 kV-15 kV, the flow rate of the spinning solution is 0.5 mL/h-0.65 mL/h, electrostatic spinning is carried out, and finally drying is carried out, so that an electrostatic spinning film is obtained;
4. adding metal phthalocyanine into absolute ethyl alcohol, and uniformly stirring to obtain a metal phthalocyanine solution; then dipping the electrostatic spinning film obtained in the step three into a metal phthalocyanine solution, evaporating the solvent under the heating condition, and drying to obtain a reaction product;
5. and step four, recycling to obtain the black phosphorus-based photocatalytic composite material.
The beneficial effects of the invention are as follows:
black phosphorus exhibits many unique properties such as a large specific surface area, high carrier mobility, excellent on/off ratio, in-plane anisotropy, and an adjustable forbidden bandwidth based on the number of layers. It is these excellent properties that make black phosphorus materials ideal in many respects. According to the invention, through homogenizing the polyvinyl alcohol and the black phosphorus under high pressure, the black phosphorus can be peeled into a few black phosphorus slice layers, and the added polyvinyl alcohol can play a role of a stabilizer to improve the catalytic efficiency. The black phosphorus fiber film formed by electrostatic spinning is in a fiber network structure, the black phosphorus is well dispersed on the fibers, and then the fiber film is placed in sewage, so that the problem of low dispersibility of the black phosphorus in water is solved, and higher photocatalytic performance is realized. According to the invention, the polyvinyl alcohol and the black phosphorus are added to form the composite film through electrostatic spinning, so that the light absorption conversion rate of the black phosphorus-based photocatalytic composite material can be effectively improved by utilizing the action of the polyvinyl alcohol, and the photocatalytic efficiency is further improved. In addition, the electrostatic spinning can prepare the black phosphorus-based photocatalytic composite material which is porous and can be accurately regulated and controlled in size, and the strength and the water resistance of the black phosphorus-based photocatalytic composite material are improved through the electrostatic spinning of the added polyvinyl alcohol and the black phosphorus.
Drawings
FIG. 1 is a graph showing the effect of degrading methylene blue by using the black phosphorus-based photocatalytic composite material prepared in example one.
Detailed Description
The first embodiment is as follows: the preparation method of the black phosphorus-based photocatalytic composite material in the embodiment comprises the following steps:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding black phosphorus powder into a polyvinyl alcohol solution for homogenization, and then adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion; wherein, the mass concentration of the black phosphorus powder in the polyvinyl alcohol-black phosphorus dispersion liquid is 5-10%; the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-black phosphorus dispersion liquid is 7% -10%;
2. preparation of spinning solution:
dissolving polyethylenimine in N-methyl pyrrolidone, and then adding polyvinyl alcohol-black phosphorus dispersion liquid to obtain spinning solution;
the total mass percentage of the polyethylenimine and the black phosphorus in the spinning solution is 20-50%;
3. and (3) electrostatic spinning:
under the conditions that the receiving distance is 12 cm-15 cm, the voltage is 10 kV-15 kV, the flow rate of the spinning solution is 0.5 mL/h-0.65 mL/h, electrostatic spinning is carried out, and finally drying is carried out, so that an electrostatic spinning film is obtained;
4. adding metal phthalocyanine into absolute ethyl alcohol, and uniformly stirring to obtain a metal phthalocyanine solution; then dipping the electrostatic spinning film obtained in the step three into a metal phthalocyanine solution, evaporating the solvent under the heating condition, and drying to obtain a reaction product;
5. and step four, recycling to obtain the black phosphorus-based photocatalytic composite material.
The beneficial effects of this embodiment are:
black phosphorus exhibits many unique properties such as a large specific surface area, high carrier mobility, excellent on/off ratio, in-plane anisotropy, and an adjustable forbidden bandwidth based on the number of layers. It is these excellent properties that make black phosphorus materials ideal in many respects. In the embodiment, the polyvinyl alcohol and the black phosphorus are homogenized under high pressure, so that the black phosphorus is peeled into a few black phosphorus sheets, and the added polyvinyl alcohol can play a role of a stabilizer to improve the catalytic efficiency. The black phosphorus fiber film formed by electrostatic spinning is in a fiber network structure, the black phosphorus is well dispersed on the fibers, and then the fiber film is placed in sewage, so that the problem of low dispersibility of the black phosphorus in water is solved, and higher photocatalytic performance is realized. According to the embodiment, the polyvinyl alcohol and the black phosphorus are added to form the composite film through electrostatic spinning, so that the light absorption conversion rate of the black phosphorus-based photocatalytic composite material can be effectively improved by utilizing the action of the polyvinyl alcohol, and further the photocatalytic efficiency is improved. In addition, the electrostatic spinning can prepare the black phosphorus-based photocatalytic composite material which is porous and can be accurately regulated and controlled in size, and the strength and the water resistance of the black phosphorus-based photocatalytic composite material are improved through the electrostatic spinning of the added polyvinyl alcohol and the black phosphorus.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the particle size of the black phosphorus powder in the first step is 0.5-2.0 mu m. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the homogenizing pressure in the first step is 60-80 MPa, and the homogenizing time is 30-60 min. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the mass ratio of the polyethyleneimine to the black phosphorus in the second step is (3-4) 1. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the spinning temperature in the spinning process of the step three is 15-20 ℃. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: and in the spinning process of the step three, the relative humidity of the environment is 7-10%. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the metal phthalocyanine in the fourth step is one or a mixture of a plurality of cobalt phthalocyanine, iron phthalocyanine and nickel phthalocyanine; the volume ratio of the mass of the metal phthalocyanine to the absolute ethyl alcohol in the fourth step is 0.1g (400 mL-500 mL); the stirring speed in the fourth step is 100 r/min-300 r/min; the heating temperature in the fourth step is 70-80 ℃, and the drying temperature is 70-80 ℃. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and step five, circulating the step four for 3 to 5 times to obtain the black phosphorus-based photocatalytic composite material. The other is the same as in embodiments one to seven.
Detailed description nine: the black phosphorus-based photocatalytic composite material of the present embodiment is used for degrading methylene blue.
Detailed description ten: this embodiment differs from the ninth embodiment in that: the black phosphorus-based photocatalytic composite material is used for degrading methylene blue and is prepared by the following steps:
adding the black phosphorus-based photocatalytic composite material into wastewater with methylene blue content of 10-50 mg/L, regulating the pH value of the wastewater to 6.5-7.5, and irradiating for 4-10 min under the condition of power of 200-400W by taking a xenon lamp as a light source to obtain water for removing the methylene blue; the volume ratio of the mass of the black phosphorus-based photocatalytic composite material to the volume of the wastewater is (1 g-5 g) 100mL.
The other is the same as in the ninth embodiment.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the black phosphorus-based photocatalytic composite material in the embodiment is as follows:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding black phosphorus powder into a polyvinyl alcohol solution, homogenizing for 45min under the pressure of 80MPa, and adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion; wherein, the mass concentration of the black phosphorus powder in the polyvinyl alcohol-black phosphorus dispersion liquid is 6%; the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-black phosphorus dispersion liquid is 10%;
2. preparation of spinning solution:
dissolving polyethylenimine in N-methyl pyrrolidone, and then adding polyvinyl alcohol-black phosphorus dispersion liquid to obtain spinning solution;
the total mass percentage of the polyethyleneimine and the black phosphorus in the spinning solution is 45%; the mass ratio of the polyethyleneimine to the black phosphorus is 3:1;
3. and (3) electrostatic spinning:
under the conditions that the receiving distance is 14cm, the voltage is 12kV, the flow rate of the spinning solution is 0.5mL/h, the spinning temperature is 15-17 ℃, the relative humidity of the environment is 7-10%, electrostatic spinning is carried out, and finally, drying is carried out, so that an electrostatic spinning film is obtained;
4. adding iron phthalocyanine into absolute ethyl alcohol, and uniformly stirring at the stirring speed of 100r/min to obtain an iron phthalocyanine solution, wherein the volume ratio of the iron phthalocyanine to the absolute ethyl alcohol is 0.1g:400mL; then dipping the electrostatic spinning film obtained in the step three into a phthalocyanine iron solution, evaporating the solvent under the heating condition, and drying to obtain a reaction product;
5. and (4) circulating the steps for four times to obtain the black phosphorus-based photocatalytic composite material.
The average particle diameter of the black phosphorus powder is 1.0 mu m.
The heating temperature in the fourth step is 80 ℃, and the drying temperature is 80 ℃.
The black phosphorus-based photocatalytic composite material prepared in the embodiment was irradiated with 980nm laser with a power of 2W for 20min, and the loss of evaporated water was tested to examine the photo-thermal conversion efficiency. The results show that the evaporation rate of this example is 0.79 kg/(m) 2 H), the light-heat conversion efficiency is about 50%.
Adding the black phosphorus-based photocatalytic composite material into wastewater with 30mg/L of methylene blue content, adjusting the pH value of the wastewater to 7, and irradiating for 0-8 min under the condition of 300W of power by taking a xenon lamp as a light source to obtain water with methylene blue removed; the volume ratio of the mass of the black phosphorus-based photocatalytic composite material to the volume of the wastewater is 1g to 100mL.
And 5mL of wastewater is taken every 2min, absorbance of the obtained wastewater is measured by a spectrophotometer, the wavelength is 665nm, the wastewater without black phosphorus-based photocatalytic composite material is used as a blank control group, and the ratio of the concentration of methylene blue in the wastewater before and after the concentration is obtained by utilizing the linear relation between the absorbance and the concentration, and the ratio is shown in figure 1.
FIG. 1 is a graph showing the effect of degrading methylene blue by using the black phosphorus-based photocatalytic composite material prepared in example one. From the graph, the degradation rate of the black phosphorus-based photocatalytic composite material to methylene blue in the methylene blue solution is 100% after 6 min.
Claims (1)
1. The application of the black phosphorus-based photocatalytic composite material is characterized in that the black phosphorus-based photocatalytic composite material is used for realizing 100% degradation of methylene blue in 6 minutes;
the black phosphorus-based photocatalytic composite material is used for degrading methylene blue and is prepared by the following steps:
adding the black phosphorus-based photocatalytic composite material into wastewater with 30mg/L of methylene blue content, adjusting the pH value of the wastewater to 7, and irradiating for 0-8 min under the condition of 300W of power by taking a xenon lamp as a light source to obtain water with methylene blue removed; the volume ratio of the mass of the black phosphorus-based photocatalytic composite material to the volume of the wastewater is 1g to 100mL; after 6min, the degradation rate of the black phosphorus-based photocatalytic composite material to the methylene blue in the methylene blue solution is 100%;
the preparation method of the black phosphorus-based photocatalytic composite material comprises the following steps:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding black phosphorus powder into a polyvinyl alcohol solution, homogenizing for 45min under the pressure of 80MPa, and adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion; wherein, the mass concentration of the black phosphorus powder in the polyvinyl alcohol-black phosphorus dispersion liquid is 6%; the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-black phosphorus dispersion liquid is 10%;
2. preparation of spinning solution:
dissolving polyethylenimine in N-methyl pyrrolidone, and then adding polyvinyl alcohol-black phosphorus dispersion liquid to obtain spinning solution;
the total mass percentage of the polyethyleneimine and the black phosphorus in the spinning solution is 45%; the mass ratio of the polyethyleneimine to the black phosphorus is 3:1;
3. and (3) electrostatic spinning:
under the conditions that the receiving distance is 14cm, the voltage is 12kV, the flow rate of the spinning solution is 0.5mL/h, the spinning temperature is 15-17 ℃, the relative humidity of the environment is 7-10%, electrostatic spinning is carried out, and finally, drying is carried out, so that an electrostatic spinning film is obtained;
4. adding iron phthalocyanine into absolute ethyl alcohol, and uniformly stirring at the stirring speed of 100r/min to obtain an iron phthalocyanine solution, wherein the volume ratio of the iron phthalocyanine to the absolute ethyl alcohol is 0.1g:400mL; then dipping the electrostatic spinning film obtained in the step three into a phthalocyanine iron solution, evaporating the solvent under the heating condition, and drying to obtain a reaction product;
5. the black phosphorus-based photocatalytic composite material is obtained after the steps are circulated for four 4 times;
the average particle diameter of the black phosphorus powder is 1.0 mu m;
the heating temperature in the fourth step is 80 ℃, and the drying temperature is 80 ℃.
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