CN115138395A - 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 PDF

Info

Publication number
CN115138395A
CN115138395A CN202210842498.0A CN202210842498A CN115138395A CN 115138395 A CN115138395 A CN 115138395A CN 202210842498 A CN202210842498 A CN 202210842498A CN 115138395 A CN115138395 A CN 115138395A
Authority
CN
China
Prior art keywords
black phosphorus
composite material
photocatalytic composite
based photocatalytic
polyvinyl alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210842498.0A
Other languages
Chinese (zh)
Other versions
CN115138395B (en
Inventor
魏丽丹
张文斌
刘美多
王艳梅
汪宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heilongjiang University of Science and Technology
Original Assignee
Heilongjiang University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Heilongjiang University of Science and Technology filed Critical Heilongjiang University of Science and Technology
Priority to CN202210842498.0A priority Critical patent/CN115138395B/en
Publication of CN115138395A publication Critical patent/CN115138395A/en
Application granted granted Critical
Publication of CN115138395B publication Critical patent/CN115138395B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • 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
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • 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
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

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 problem that the existing black phosphorus has low dispersibility in water, so that the effective absorption of the black phosphorus to sunlight is influenced, and the photocatalytic performance is poor. The method comprises the following steps: 1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid; 2. preparing a spinning solution; 3. electrostatic spinning; 4. dipping in a metal phthalocyanine solution; 5. and (6) circulating. The method is used for preparing the black phosphorus-based photocatalytic composite material.

Description

Preparation method and application of black phosphorus-based photocatalytic composite material
Technical Field
The invention relates to a preparation method of a photocatalytic composite material.
Background
In the world, energy shortage and environmental pollution are two issues which can not be avoided, the influence on human beings is the deepest, and the photocatalysis technology can utilize solar energy to degrade organic pollutants, and an intermediate product is non-toxic and harmless and cannot cause secondary pollution, so that the photocatalysis technology is paid more and more attention.
Photocatalysis is based on the redox ability of a photocatalyst under the condition of illumination, when light with energy equal to or larger than the forbidden bandwidth of the catalyst is irradiated, electrons in the valence band are excited to jump 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 the electrons and holes from recombining again. These trapped electrons and holes diffuse to the surface of the particles, respectively, and a strong redox potential is generated.
The black phosphorus is a nonmetal photocatalyst, has excellent carrier mobility, can improve carrier separation efficiency, has a wide ultraviolet-visible-near infrared light absorption range, and is beneficial to improving the light absorption efficiency of the catalytic material. In the more numerous morphologies, black phosphorus includes multiple layers, similar to graphite. However, the dispersibility of the black phosphorus in water is low, which affects the effective absorption of the black phosphorus to sunlight, resulting in poor photocatalytic performance.
Disclosure of Invention
The invention aims to solve the problem that the existing black phosphorus has low dispersibility in water, so that the effective absorption of the black phosphorus to sunlight is influenced, and the photocatalytic performance is poor. 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 the black phosphorus powder into a polyvinyl alcohol solution for homogenization, and then adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion liquid; 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 percent;
2. preparing a spinning solution:
dissolving polyethyleneimine in N-methylpyrrolidone, 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 20-50%;
3. electrostatic spinning:
under the conditions that the receiving distance is 12 cm-15 cm, the voltage is 10 kV-15 kV and the flow rate of spinning solution is 0.5 mL/h-0.65 mL/h, carrying out electrostatic spinning, and finally drying to obtain an electrostatic spinning film;
4. adding metal phthalocyanine into absolute ethyl alcohol, and uniformly stirring to obtain a metal phthalocyanine solution; then dipping the electrostatic spinning membrane obtained in the third step into a metal phthalocyanine solution, evaporating the solvent to dryness under the heating condition, and drying to obtain a reaction product;
5. and step four, obtaining the black phosphorus-based photocatalytic composite material.
The invention has the beneficial effects that:
black phosphorus exhibits many unique properties such as a large specific surface area, high carrier mobility, an excellent on/off ratio, in-plane anisotropy, and an adjustable forbidden bandwidth based on the number of layers. It is these excellent characteristics that make black phosphorus materials ideal in many respects. According to the invention, the black phosphorus can be stripped into a few black phosphorus layers by homogenizing the polyvinyl alcohol and the black phosphorus under high pressure, and the added polyvinyl alcohol can play a role of a stabilizer to improve the catalytic efficiency. The black phosphorus fiber membrane formed by electrostatic spinning is in a fiber mesh structure, the black phosphorus is well dispersed on the fibers, and then the fiber membrane is placed in sewage, so that the problem of low dispersibility of the black phosphorus in the sewage is solved, and the high 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 effect of the polyvinyl alcohol can be utilized to effectively improve the light absorption conversion rate of the black phosphorus-based photocatalytic composite material, and further improve the photocatalytic efficiency. And moreover, the black phosphorus-based photocatalytic composite material which is porous and can be accurately regulated and controlled in size can be prepared by electrostatic spinning, and the strength and the water resistance of the black phosphorus-based photocatalytic composite material are improved by the added polyvinyl alcohol and the black phosphorus through electrostatic spinning.
Drawings
Fig. 1 is a graph showing the effect of degrading methylene blue by using the black phosphorus-based photocatalytic composite material prepared in the first embodiment.
Detailed Description
The first embodiment is as follows: the preparation method of the black phosphorus-based photocatalytic composite material of the embodiment is carried out according to the following steps:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding the black phosphorus powder into a polyvinyl alcohol solution for homogenization, and then adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion liquid; 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 percent;
2. preparing a spinning solution:
dissolving polyethyleneimine in N-methylpyrrolidone, 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 20-50%;
3. electrostatic spinning:
under the conditions that the receiving distance is 12 cm-15 cm, the voltage is 10 kV-15 kV and the flow rate of spinning solution is 0.5 mL/h-0.65 mL/h, carrying out electrostatic spinning, and finally drying to obtain an electrostatic spinning film;
4. adding metal phthalocyanine into absolute ethyl alcohol, and uniformly stirring to obtain a metal phthalocyanine solution; then dipping the electrostatic spinning membrane obtained in the third step into a metal phthalocyanine solution, evaporating the solvent to dryness under the heating condition, and drying to obtain a reaction product;
5. and step four, obtaining the black phosphorus-based photocatalytic composite material.
The beneficial effects of the embodiment are as follows:
black phosphorus exhibits many unique properties such as a large specific surface area, high carrier mobility, an excellent on/off ratio, in-plane anisotropy, and an adjustable forbidden bandwidth based on the number of layers. It is these excellent characteristics that make black phosphorus materials ideal in many respects. According to the embodiment, the polyvinyl alcohol and the black phosphorus are homogenized under high pressure, the black phosphorus can be peeled into few black phosphorus layers, and the added polyvinyl alcohol can play a role of a stabilizer to improve the catalysis efficiency. The black phosphorus fiber membrane formed by electrostatic spinning is in a fiber net structure, the black phosphorus is well dispersed on the fibers, and then the fiber membrane is placed in sewage, so that the problem of low dispersibility of the black phosphorus in the sewage is solved, and the high 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 effect of the polyvinyl alcohol can be utilized, the light absorption conversion rate of the black phosphorus-based photocatalytic composite material is effectively improved, and the photocatalytic efficiency is further improved. And moreover, the black phosphorus-based photocatalytic composite material which is porous and can be accurately regulated and controlled in size can be prepared by electrostatic spinning, and the strength and the water resistance of the black phosphorus-based photocatalytic composite material are improved by the added polyvinyl alcohol and the black phosphorus through electrostatic spinning.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, the particle size of the black phosphorus powder is 0.5-2.0 μm. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: in the first step, the homogenizing pressure is 60-80 MPa, and the homogenizing time is 30-60 min. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the mass ratio of the polyethyleneimine to the black phosphorus in the second step is (3-4) to 1. The others are the same as the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and one of the first to fourth embodiments is: the spinning temperature in the spinning process of the third step is 15-20 ℃. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is: and in the third spinning step, the relative humidity of the environment is 7-10%. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the metal phthalocyanine in the step four is one or a mixture of several 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 step four is 0.1g (400 mL-500 mL); the stirring speed in the fourth step is 100 r/min-300 r/min; in the fourth step, the heating temperature is 70-80 ℃, and the drying temperature is 70-80 ℃. The others are the same as the first to sixth embodiments.
The specific implementation mode eight: the present embodiment differs from one of the first to seventh embodiments in that: and step five, circulating the step four for 3-5 times to obtain the black phosphorus-based photocatalytic composite material. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the black phosphorus-based photocatalytic composite material of the embodiment is used for degrading methylene blue.
The specific implementation mode is ten: the ninth 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 the methylene blue content of 10-50 mg/L, adjusting the pH value of the wastewater to 6.5-7.5, and irradiating for 4-10 min by using a xenon lamp as a light source under the condition that the power is 200-400W to obtain water from which the methylene blue is removed; the mass ratio of the black phosphorus-based photocatalytic composite material to the volume of the waste water is (1 g-5 g): 100mL.
The rest is the same as the embodiment nine.
The following examples were employed to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
the preparation method of the black phosphorus-based photocatalytic composite material of the embodiment is as follows:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding the black phosphorus powder into a polyvinyl alcohol solution, homogenizing for 45min under the condition that the pressure is 80MPa, and adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion solution; 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 percent;
2. preparing a spinning solution:
dissolving polyethyleneimine in N-methylpyrrolidone, 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;
3. electrostatic spinning:
under the conditions that the receiving distance is 14cm, the voltage is 12kV, the flow rate of a spinning solution is 0.5mL/h, the spinning temperature is 15-17 ℃, and the relative humidity of the environment is 7-10%, carrying out electrostatic spinning, and finally drying to obtain an electrostatic spinning film;
4. adding iron phthalocyanine into absolute ethyl alcohol, and uniformly stirring at a stirring speed of 100r/min to obtain an iron phthalocyanine solution, wherein the volume ratio of the mass of the iron phthalocyanine to the absolute ethyl alcohol is 0.1g 400mL; then dipping the electrostatic spinning film obtained in the third step into an iron phthalocyanine solution, evaporating the solvent to dryness under the heating condition, and drying again to obtain a reaction product;
5. and the step is circulated for four times and 4 times to obtain the black phosphorus-based photocatalytic composite material.
The average grain diameter of the black phosphorus powder is 1.0 μm.
In the fourth step, the heating temperature is 80 ℃, and the drying temperature is 80 ℃.
The black phosphorus-based photocatalytic composite material prepared in the embodiment is irradiated for 20min by 980nm laser with the power of 2W, and the loss amount of evaporated water is 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 photothermal conversion efficiency is about 50%.
Adding the black phosphorus-based photocatalytic composite material into wastewater with the methylene blue content of 30mg/L, adjusting the pH value of the wastewater to 7, and irradiating for 0-8 min under the condition of the power of 300W by using a xenon lamp as a light source to obtain water from which the methylene blue is removed; the mass ratio of the black phosphorus-based photocatalytic composite material to the waste water is 1g.
Taking 5mL of wastewater every 2min, measuring the absorbance of the obtained wastewater by using a spectrophotometer, wherein the wavelength is 665nm, taking the wastewater without the black phosphorus-based photocatalytic composite material as a blank control group, and obtaining the concentration ratio of methylene blue in the wastewater before and after by using the linear relation between the absorbance and the concentration, wherein the concentration 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 the first embodiment. As can be seen from the figure, after 6min, the degradation rate of the black phosphorus-based photocatalytic composite material to methylene blue in the methylene blue solution is 100%.

Claims (10)

1. A preparation method of a black phosphorus-based photocatalytic composite material is characterized by comprising the following steps:
1. preparing a polyvinyl alcohol-black phosphorus dispersion liquid:
adding the black phosphorus powder into a polyvinyl alcohol solution for homogenization, and then adding N-methyl pyrrolidone to prepare a polyvinyl alcohol-black phosphorus dispersion liquid; 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 percent;
2. preparing a spinning solution:
dissolving polyethyleneimine in N-methylpyrrolidone, and then adding polyvinyl alcohol-black phosphorus dispersion liquid to obtain spinning liquid;
the total mass percentage of polyethyleneimine and black phosphorus in the spinning solution is 20-50%;
3. electrostatic spinning:
under the conditions that the receiving distance is 12 cm-15 cm, the voltage is 10 kV-15 kV, and the flow rate of a spinning solution is 0.5 mL/h-0.65 mL/h, carrying out electrostatic spinning, and finally drying to obtain an electrostatic spinning film;
4. adding metal phthalocyanine into absolute ethyl alcohol, and uniformly stirring to obtain a metal phthalocyanine solution; then dipping the electrostatic spinning membrane obtained in the third step into a metal phthalocyanine solution, evaporating the solvent to dryness under the heating condition, and drying to obtain a reaction product;
5. and step four, obtaining the black phosphorus-based photocatalytic composite material.
2. The method of claim 1, wherein the particle size of the black phosphorus powder in step one is 0.5 μm to 2.0 μm.
3. The method for preparing a black phosphorus-based photocatalytic composite material as claimed in claim 1, wherein the pressure for homogenization in step one is 60 to 80MPa, and the time for homogenization is 30 to 60min.
4. The method for preparing the black phosphorus-based photocatalytic composite material as recited in claim 1, wherein the mass ratio of polyethyleneimine to black phosphorus in the second step is (3-4): 1.
5. The method for preparing the black phosphorus-based photocatalytic composite material as claimed in claim 1, wherein the spinning temperature in the spinning process of the third step is 15 ℃ to 20 ℃.
6. The method for preparing the black phosphorus-based photocatalytic composite material as claimed in claim 1, wherein the relative humidity of the environment in the third spinning step is 7-10%.
7. The method for preparing a photocatalytic composite material based on black phosphorus according to claim 1, wherein the metal phthalocyanine in step four is one or a mixture of several 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 step four is 0.1g (400 mL-500 mL); the stirring speed in the fourth step is 100 r/min-300 r/min; in the fourth step, the heating temperature is 70-80 ℃, and the drying temperature is 70-80 ℃.
8. The method for preparing a black phosphorus-based photocatalytic composite material according to claim 1, wherein the step five is repeated for four 3 to 5 times to obtain the black phosphorus-based photocatalytic composite material.
9. Use of a black phosphorus based photocatalytic composite material prepared by the preparation method as claimed in claim 1, characterized in that it is used for degrading methylene blue.
10. The use of the black phosphorus-based photocatalytic composite material as set forth in claim 9, wherein the black phosphorus-based photocatalytic composite material is used for degrading methylene blue by the following steps:
adding the black phosphorus-based photocatalytic composite material into wastewater with the methylene blue content of 10-50 mg/L, adjusting the pH value of the wastewater to 6.5-7.5, using a xenon lamp as a light source, and irradiating for 4-10 min under the condition that the power is 200-400W to obtain water from which the methylene blue is removed; the mass ratio of the black phosphorus-based photocatalytic composite material to the volume of the waste water is (1 g-5 g): 100mL.
CN202210842498.0A 2022-07-18 2022-07-18 Preparation method and application of black phosphorus-based photocatalytic composite material Active CN115138395B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210842498.0A CN115138395B (en) 2022-07-18 2022-07-18 Preparation method and application of black phosphorus-based photocatalytic composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210842498.0A CN115138395B (en) 2022-07-18 2022-07-18 Preparation method and application of black phosphorus-based photocatalytic composite material

Publications (2)

Publication Number Publication Date
CN115138395A true CN115138395A (en) 2022-10-04
CN115138395B CN115138395B (en) 2023-06-30

Family

ID=83411241

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210842498.0A Active CN115138395B (en) 2022-07-18 2022-07-18 Preparation method and application of black phosphorus-based photocatalytic composite material

Country Status (1)

Country Link
CN (1) CN115138395B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012023100A1 (en) * 2010-08-17 2012-02-23 Mintek Polymer bound metallophthalocyanines
CN103526539A (en) * 2013-10-23 2014-01-22 东华大学 Preparation method of functional gold-silver core-shell nanoparticle/electrostatic spun composite nano-fiber felt
WO2017191887A1 (en) * 2016-05-04 2017-11-09 재단법인차세대융합기술연구원 Method for producing graphene oxide/carbon nanotube composite fiber, graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber using wet spinning process
US20180277832A1 (en) * 2017-03-22 2018-09-27 Toyota Jidosha Kabushiki Kaisha Method of manufacturing negative electrode for non-aqueous electrolyte secondary battery, and method of manufacturing non-aqueous electrolyte secondary battery
CN109370127A (en) * 2018-09-30 2019-02-22 华南理工大学 A kind of two-dimensional layer material-polyvinyl alcohol hydrogel and preparation method thereof
CN109487438A (en) * 2018-11-09 2019-03-19 上海理工大学 A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine
CN110103560A (en) * 2019-04-09 2019-08-09 上海大学 Improve the black phosphorus preparation method of composite film of black phosphorus stability
CN113019401A (en) * 2021-03-11 2021-06-25 黑龙江工业学院 Preparation method, application and application method of graphene-based photocatalytic composite material
CN113042030A (en) * 2021-03-31 2021-06-29 中南大学 Flexible film for degrading organic pollution in wastewater under natural condition
CN113731503A (en) * 2021-09-08 2021-12-03 河南师范大学 Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012023100A1 (en) * 2010-08-17 2012-02-23 Mintek Polymer bound metallophthalocyanines
CN103526539A (en) * 2013-10-23 2014-01-22 东华大学 Preparation method of functional gold-silver core-shell nanoparticle/electrostatic spun composite nano-fiber felt
WO2017191887A1 (en) * 2016-05-04 2017-11-09 재단법인차세대융합기술연구원 Method for producing graphene oxide/carbon nanotube composite fiber, graphene oxide/graphene composite fiber or graphene oxide/graphene/carbon nanotube composite fiber using wet spinning process
US20180277832A1 (en) * 2017-03-22 2018-09-27 Toyota Jidosha Kabushiki Kaisha Method of manufacturing negative electrode for non-aqueous electrolyte secondary battery, and method of manufacturing non-aqueous electrolyte secondary battery
CN109370127A (en) * 2018-09-30 2019-02-22 华南理工大学 A kind of two-dimensional layer material-polyvinyl alcohol hydrogel and preparation method thereof
CN109487438A (en) * 2018-11-09 2019-03-19 上海理工大学 A method of multi-functional PVA nanosphere is prepared with electrostatic spinning machine
CN110103560A (en) * 2019-04-09 2019-08-09 上海大学 Improve the black phosphorus preparation method of composite film of black phosphorus stability
CN113019401A (en) * 2021-03-11 2021-06-25 黑龙江工业学院 Preparation method, application and application method of graphene-based photocatalytic composite material
CN113042030A (en) * 2021-03-31 2021-06-29 中南大学 Flexible film for degrading organic pollution in wastewater under natural condition
CN113731503A (en) * 2021-09-08 2021-12-03 河南师范大学 Preparation method of metal phthalocyanine complex-titanium dioxide composite photocatalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XUEFEI ZHOU ET AL.: "Enhanced photocatalytic activity in metal phthalocyanine‑sensitized TiO2 nanorods" *
任春华: "静电纺丝技术中使用的聚合物" *

Also Published As

Publication number Publication date
CN115138395B (en) 2023-06-30

Similar Documents

Publication Publication Date Title
CN108686639B (en) Metal organic framework derivative material-three-dimensional reticular carbon-based composite photocatalyst and preparation method and application thereof
CN109231204A (en) A kind of method of biomass substep activation preparation porous charcoal
CN102505403A (en) Method for preparing hierarchically porous activated carbon fiber membrane
CN112076785B (en) Carbon nitride/lanthanum hydroxide nanofiber membrane and preparation method and application thereof
CN108892138A (en) One kind is based on biomass derived nitrogen/oxygen codope hierarchical porous structure carbon material and preparation method thereof
CN108339544B (en) Photocatalyst/super-hydrophobic membrane composite material modified by fullerene carboxyl derivative
CN114300702A (en) Fuel cell gas diffusion layer structure containing cerium oxide modified carbon nanofiber and preparation method thereof
CN112619684A (en) Functional attapulgite loaded NiO-g-C3N4The photocatalytic-adsorbent and the preparation method
CN113181949A (en) Cobalt-iron alloy/nitrogen-sulfur co-doped carbon nano composite material and preparation method and application thereof
CN111111638B (en) Preparation method of fly ash photocatalytic material
CN103349971B (en) Porous carbon loaded titanium dioxide composite manufactured by utilizing ionic liquid/polyaniline and method and application thereof
Peng et al. In situ growth of carbon nitride on titanium dioxide/hemp stem biochar toward 2D heterostructured photocatalysts for highly photocatalytic activity
CN115138395B (en) Preparation method and application of black phosphorus-based photocatalytic composite material
CN104368369B (en) A kind of preparation method of silver phosphate-cadmium sulfide compounded visible light photocatalyst
CN112452165A (en) Ag/AgBr/AgVO3Composite nanofiber filtering membrane and preparation method and application thereof
CN111135812A (en) Preparation method of carbon-based photocatalyst
Zeng et al. Sargassum horneri‐based carbon‐doped TiO2 and its aquatic naphthalene photodegradation under sunlight irradiation
CN107973367B (en) Fe-doped coated TiO2Process for degrading wastewater by using photocatalyst
CN111063876B (en) Graphene/tannin extract furfuryl alcohol resin derived carbon negative electrode material, and preparation method and application thereof
Cui et al. Core–shell carbon colloid sphere@ phosphotungstic acid/CdS as a Z-scheme heterojunction with synergistic adsorption, photothermal and photocatalytic performance
CN114405468A (en) Preparation method of sphagnum charcoal adsorbent
CN113181912A (en) Cu2O-TiO2Composite photocatalyst and preparation method and application thereof
CN111747747A (en) Preparation method, product and application of carbon-based material with bionic fractal structure based on shaddock peel
Anantachaisilp et al. Activated carbon derived from glutinous rice via gamma radiolysis for lithium–sulfur battery cathodes
CN113667044B (en) Organic polymer material, preparation method and photocatalytic application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant