CN115318315B - Magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst and preparation method and application thereof - Google Patents
Magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst and preparation method and application thereof Download PDFInfo
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Classifications
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- B01J35/33—
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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
-
- 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
- A01N59/26—Phosphorus; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/08—Radiation
- A61L2/088—Radiation using a photocatalyst or photosensitiser
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
Abstract
The invention provides a carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, a preparation method and application thereof, and relates to the technical field of photocatalytic materials. The carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst comprises: a red phosphorus/carbon nitride heterojunction composed of layered stacked carbon nitride and red phosphorus particles fixed on the carbon nitride; magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunction. The method comprises the steps of taking elemental red phosphorus and carbon nitride as raw materials, preparing a stable red phosphorus/carbon nitride heterojunction through an ultrasonic-hydrothermal-high-temperature calcination three-step method, and combining the heterojunction with a magnetic carbon nano tube through an ultrasonic-hydrothermal two-step method to obtain the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst. The ternary nonmetallic photocatalyst can realize photocatalysis sterilization under wide spectrum visible light and can be fully recovered.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, and a preparation method and application thereof.
Background
Red phosphorus is a rich, environmentally friendly substance that has been used in a variety of industries including organic degradation, energy storage, disinfection, and the like. Carbon nitride is considered one of the most promising metal-free photocatalysts for various photocatalytic applications due to its small band gap, strong thermochemical stability and low toxicity. The heterojunction structure of red phosphorus and carbon nitride appropriately compensates for the respective defects. The red phosphorus has wider absorption wave band and makes up the defect of low utilization rate of the carbon nitride to visible light. Meanwhile, after the red phosphorus is combined with the carbon nitride, the sterilization efficiency of the red phosphorus is also improved.
Most of the visible light catalysts are powder, are not easy to recycle in water, and magnetic separation is a viable solution. Most recoverable magnetic photocatalysts use various ferrites, such as CoFe 2 O 4 、NiFe 2 O 4 Etc. However, the ferrite has high preparation cost, is easy to leak heavy metal ions in the operation process, causes secondary pollution to the environment, and is not an optimal solution.
In view of this, the present invention has been made.
Disclosure of Invention
Research has shown that carbon nanotubes have inherent magnetic properties. Therefore, the magnetic carbon nano tube is extracted from the carbon nano tube by the permanent magnet and hybridized with the red phosphorus/carbon nitride heterojunction, and a recyclable magnetic carbon nano tube/red phosphorus/carbon nitride ternary photocatalysis system is constructed. The magnetic carbon nano tube is environment-friendly, environment-friendly and recyclable, is easy to conduct, improves the migration and separation rate of red phosphorus/carbon nitride photocarriers, and can greatly improve the photocatalysis quantum efficiency and the sterilization efficiency.
The invention aims to provide a magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, which overcomes the defect that the traditional red phosphorus/carbon nitride is unfavorable for recycling, greatly expands the visible light response range of the catalyst and improves the photocatalytic sterilization efficiency.
The second object of the present invention is to provide a method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst.
The third object of the present invention is to provide an application of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst in broad spectrum photocatalytic sterilization, wherein the light response wavelength range of the broad spectrum photocatalysis is 420-800 nm.
In order to achieve the above purpose, the following technical scheme is adopted:
in a first aspect, the present invention provides a magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, comprising:
a red phosphorus/carbon nitride heterojunction composed of layered stacked carbon nitride and red phosphorus particles fixed on the carbon nitride;
and magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunction;
wherein the particle size range of the red phosphorus particles is 50-100nm;
the diameter of the magnetic carbon nano tube is 3-5nm.
In some embodiments, the magnetic carbon nanotubes are extracted from the carbon nanotubes using a permanent magnet.
In some embodiments, the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst comprises the following elements in mass percent: 40-45% of C element, 18-20% of N element, 10-15% of O element and 25-30% of P element; in one embodiment, element C is 42.10%, element N is 19.04%, element O is 11.02%, and element P is 27.83%.
In a second aspect, the present invention provides a method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, comprising the following steps:
(a) Obtaining magnetic carbon nanotubes: dispersing the carbon nanotubes into a solvent, attracting and extracting the magnetic carbon nanotubes for a plurality of times by using a permanent magnet, and drying for later use;
(b) Preparing a red phosphorus/carbon nitride heterojunction: adding carbon nitride and red phosphorus into water, performing ultrasonic dispersion and uniform mixing, transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the obtained suspension to obtain a primary red phosphorus/carbon nitride heterojunction; transferring the obtained primary red phosphorus/carbon nitride heterojunction into a vacuum quartz tube, placing the quartz tube into a muffle furnace for high-temperature calcination, and obtaining the red phosphorus/carbon nitride heterojunction after natural cooling;
(c) Preparing a magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst: mixing and grinding the red phosphorus/carbon nitride heterojunction obtained in the step (b) and the magnetic carbon nano tube obtained in the step (a), and then performing ultrasonic dispersion on the obtained powder in water to form a preliminary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride; transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst.
Each step will be described in detail.
Step (a)
In this step, specifically, the method includes: dispersing 1g of carbon nanotubes into 200ml of ethanol by ultrasonic and stirring, and then extracting the carbon nanotubes with stronger magnetism by using a permanent magnet; repeating the steps for a plurality of times to obtain the magnetic carbon nano tube; the resulting magnetic carbon nanotubes were dried overnight at 60 ℃ and ground to a powder for use.
Step (b)
In the step, the carbon nitride material is prepared before the red phosphorus/carbon nitride heterojunction is prepared, and the red phosphorus is purified.
In some embodiments, a suitable precursor is selected and a thermal polymerization process is used to prepare the carbon nitride material;
preferably, the precursor is urea or melamine;
preferably, the thermal polymerization method is heated for 2 to 6 hours at a constant temperature of 500 to 600 ℃ at a heating rate of 1 to 5 ℃/min;
in some embodiments, the method of preparing carbon nitride is as follows: 40g of urea was heated in air at 550℃for 4 hours at a heating rate of 2℃per minute. The prepared light yellow caking is cooled to room temperature and then ground into carbon nitride powder for subsequent use.
In some embodiments, red phosphorus is purified using a hydrothermal process;
preferably, the reaction temperature of the hydrothermal method is 180-220 ℃ and the reaction time is 6-12 hours.
In some embodiments, the red phosphorus purification process is as follows: commercial red phosphorus was added to a 100mL autoclave containing 60mL of ldi water, hydrothermally treated at 200 ℃ for 12 hours to remove the oxide layer, centrifuged, washed, and then dried in a vacuum oven (50 ℃ overnight).
Then preparing the red phosphorus/carbon nitride heterojunction by a hydrothermal method and a high-temperature calcination method, which comprises the following steps:
adding water into the purified red phosphorus, mixing, performing ultrasonic treatment, transferring into a high-pressure reaction kettle, performing hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain a primary red phosphorus/carbon nitride heterojunction;
quantitatively transferring the obtained red phosphorus/carbon nitride heterojunction into a vacuum quartz tube, and placing the quartz tube into a muffle furnace for high-temperature calcination; and obtaining the final red phosphorus/carbon nitride heterojunction after natural cooling.
In some embodiments, the mass ratio of red phosphorus to carbon nitride is from 0.5:1 to 1.5:1, such as 0.5:1, 1:1, 1.5:1;
in some embodiments, the corresponding amount of water added is 25 to 70mL per 100mg of carbon nitride.
In some embodiments, the time of the ultrasound is 1 to 6 hours.
In some embodiments, the hydrothermal reaction is carried out at a reaction temperature of 100 to 180 ℃ and a reaction time of 6 to 12 hours.
In some embodiments, the high temperature calcination is performed at a calcination temperature of 300 to 500 ℃ for a calcination time of 2 to 6 hours.
In some embodiments, the red phosphorus/carbon nitride heterojunction is prepared as follows:
100mg of carbon nitride and red phosphorus (50, 100, 150 mg) of different weights were added to 65mL of DI water and mixed well. The suspension was transferred to a 100mL autoclave, heated to 180deg.C for 12 hours, centrifuged (10000 rpm,5 min), washed multiple times with ethanol and deionized water, and dried overnight at 60deg.C. Thereafter, the temperature further controls the growth of the red phosphorus/carbon nitride heterojunction. During the heating process, to make the red phosphorus and carbon nitride bond more tightly, the pink sample was gradually heated to 500 ℃ and kept in a vacuum quartz tube for 2 hours. Finally obtaining pink product, namely red phosphorus/carbon nitride heterojunction.
Step (c)
In the step, the magnetic carbon nano tube and the red phosphorus/carbon nitride heterojunction are combined by adopting an ultrasonic-hydrothermal two-step method to obtain the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, which specifically comprises the following steps:
mixing and grinding the red phosphorus/carbon nitride heterojunction obtained in the step (b) and the magnetic carbon nano tube obtained in the step (a), and then performing ultrasonic dispersion on the obtained powder in water to form a preliminary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride;
transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst.
In some embodiments, the mass ratio of magnetic carbon nanotubes to red phosphorus/carbon nitride heterojunction is from 0.25:1 to 1:1, such as 0.25:1, 0.5:1, 1:1;
in some embodiments, the time of the ultrasound is 2 to 6 hours.
In some embodiments, the hydrothermal reaction is carried out at a reaction temperature of 100 to 180 ℃ and a reaction time of 6 to 12 hours.
In some embodiments, the preparation process for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst is as follows:
100mg of red phosphorus/carbon nitride heterojunction and different weights of magnetic carbon nanotubes (25, 50 and 100 mg) were milled for half an hour with an agate mortar. The resulting powder was sonicated in 65mL deionized water for 2 hours to form a preliminary combination of magnetic carbon nanotubes and red phosphorus/carbon nitride. The mixed solution was transferred to a 100mL autoclave and heated at 180 ℃ for 12 hours. Subsequently, the resulting product was dried overnight at 60 ℃ by washing with deionized water and ethanol several times and centrifuging. The dried sample is ground into powder to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst.
The stable red phosphorus/carbon nitride heterojunction is prepared by a three-step method, the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst is prepared by a two-step method, and the obtained catalyst has the special structure and composition described in the first aspect.
In a third aspect, the invention provides an application of the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst in wide-spectrum photocatalytic sterilization, wherein the light response wavelength range of the wide-spectrum photocatalysis is 420-800 nm.
The catalyst has the photocatalysis sterilization application with the advantages of recoverability and wide spectral response, and the sterilization efficiency is higher than that of pure red phosphorus and carbon nitride.
According to the invention, firstly, elemental red phosphorus and carbon nitride are used as raw materials, a stable red phosphorus/carbon nitride heterojunction is prepared by an ultrasonic-hydrothermal-high-temperature calcination three-step method, and then the heterojunction is combined with a magnetic carbon nano tube by an ultrasonic-hydrothermal two-step method to obtain the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst. The ternary nonmetallic photocatalyst can realize the application of photocatalytic sterilization under wide-spectrum visible light, and meanwhile, the ternary nonmetallic photocatalyst also has magnetism and can be fully recovered. The load of the carbon nano tube and red phosphorus greatly expands the visible light response range of the catalyst, improves the photocatalysis sterilization efficiency, does not contain any metal component, only solves the problem of recycling the photocatalyst by utilizing the inherent magnetism of the carbon nano tube, has low cost and has potential application value in the fields of environmental protection and clean energy production.
The beneficial effects are that:
the invention not only prepares the stable and efficient red phosphorus/carbon nitride heterojunction, but also further improves the catalytic performance of the red phosphorus/carbon nitride heterojunction through the magnetic carbon nano tube, and prepares the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst. The magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared by the invention has the photocatalysis sterilization application of recyclable and wide spectral response, and the sterilization efficiency is higher than that of pure red phosphorus and carbon nitride.
Experiments show that the concentration of staphylococcus aureus is 10 7 cfu·mL -1 The highest removal rate of staphylococcus aureus in water treated by the catalyst can reach 100 percent, which is 2 to 5 times higher than the speed of pure carbon nitride and red phosphorus, thus achieving the ideal purification purpose.
Drawings
Fig. 1 is a transmission electron microscope image of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared in example 1.
Fig. 2 is an EDS spectrum surface micro-area composition analysis chart of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared in example 1.
FIG. 3 is an XPS diagram of a magnetic carbon nanotube, carbon nitride, red phosphorus/carbon nitride, magnetic carbon nanotube/red phosphorus/carbon nitride photocatalyst, wherein a is an XPS spectrum, b is a high-resolution XPS spectrum of C1s, C is a high-resolution XPS spectrum of N1s, and d is a high-resolution XPS spectrum of P2P.
FIG. 4 is a graph showing the comparison of photocatalytic sterilization efficiency of the magnetic recyclable carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst of the present invention with pure red phosphorus and carbon nitride.
Fig. 5 shows charge transfer performance of carbon nitride, red phosphorus/carbon nitride, magnetic carbon nanotube/red phosphorus/carbon nitride photocatalyst in a three-electrode system, wherein a is a photocurrent response curve, and b is an electrochemical impedance spectrum.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Reagent: LB broth, nutrient agar was purchased from Qingdao sea Bo Biotechnology Co., ltd; staphylococcus aureus was purchased from hangzhou baosier biotechnology limited; red phosphorus, ethanol and urea are purchased from Tianjin rich fine chemical industry limited company in China; carbon nanotubes were purchased from Shanghai Michelia Biochemical technologies Co.
Instrument: transmission electron microscopy (TEM, JEM-2100F); scanning electron microscopy (SEM, sigma 300), equipped with EDS; x-ray photoelectron spectroscopy (ESCALAB 250).
The preparation method of the magnetic carbon nano tube in the embodiment is as follows: dispersing 1g of carbon nanotubes into 200mL of ethanol by ultrasonic and stirring, and then extracting the carbon nanotubes with stronger magnetism by using a permanent magnet; repeating the steps for a plurality of times to obtain the magnetic carbon nano tube; the obtained magnetic carbon nanotubes were dried at 60 ℃ overnight and pulverized into powder for use.
Example 1
The preparation method of the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst comprises the following steps:
(1) Placing 40g of urea into a crucible, heating at a constant temperature of 550 ℃ for 4 hours (heating speed of 2 ℃/min), and grinding a sample into yellow powder after the temperature is cooled to obtain a carbon nitride material for later use;
(2) 8g of elemental red phosphorus was added to a 100mL polytetrafluoroethylene-lined reactor, 60mL of water was added, and the mixture was placed in an oven and heated at a constant temperature of 200℃for 12 hours. Centrifuging, washing and drying the solid product to obtain red powdery purified red phosphorus for later use;
(3) 100mg of carbon nitride and 100mg of red phosphorus were added to 65mL of DI water (deionized water), mixed well, the suspension was transferred to a 100mL autoclave, heated to 180℃for 12 hours, centrifuged (10000 rpm,5 min), washed with ethanol and deionized water multiple times, and dried overnight at 60 ℃. Thereafter, the pink sample was gradually heated to 500 ℃ and stored in a vacuum quartz tube for 2 hours. Finally obtaining pink product, namely red phosphorus/carbon nitride heterojunction.
(4) Grinding 100mg of red phosphorus/carbon nitride heterojunction and 50mg of magnetic carbon nano tube for half an hour by an agate mortar, and ultrasonically dispersing the obtained powder in 65mL of deionized water for 2 hours to form a preliminary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride; after stirring for 30 minutes, the mixed solution was transferred to a 100mL autoclave and heated at 180℃for 12 hours. Subsequently, the mixture was washed several times with deionized water and ethanol, and dried overnight at 60 ℃. The dried sample was ground to a powder to give a magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst (designated MCNT/CN/RP-2).
Example 2
The difference between this example and example 1 is that the weight of red phosphorus in step (3) is 50mg.
Example 3
The difference between this example and example 1 is that the weight of red phosphorus in step (3) is 150mg.
Example 4
The difference between this example and example 1 is that the weight of the magnetic carbon nanotubes in step (4) was 25mg (designated MCNT/CN/RP-1).
Example 5
The difference between this example and example 1 is that the weight of the magnetic carbon nanotube in step (4) was 100mg (designated as MCNT/CN/RP-3).
Comparative example 1 red phosphorus/carbon nitride heterojunction
The difference between this example and example 1 is that step (4) is not included, resulting in a red phosphorus/carbon nitride heterojunction, designated RP/CN-2.
Comparative example 2 red phosphorus/carbon nitride heterojunction
The difference between this example and example 4 is that step (4) is not included, and a red phosphorus/carbon nitride heterojunction, designated RP/CN-1, is obtained.
Comparative example 3 red phosphorus/carbon nitride heterojunction
The difference between this example and example 5 is that step (4) is not included, resulting in a red phosphorus/carbon nitride heterojunction, designated RP/CN-3.
Test example 1 electron microscope characterization
Test sample: the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared in the embodiment 1.
The test process comprises the following steps: the sample of example 1 was observed under a transmission electron microscope.
Test results and analysis: the results are shown in FIG. 1.
Pure red phosphorus has an uneven block shape, varying in size from 1 mm to 12 microns. The original carbon nitride showed a unique stacked layered structure, similar to silk. Untreated magnetic carbon nanotubes are easily agglomerated into pellets of various sizes. On the nano-scale, magnetic carbon nanotubes are significantly elongated tubular structures. The red phosphorus/carbon nitride presents a flaky morphology, consisting of a large number of red phosphorus particles and silk-like carbon nitride. The red phosphorus particles are fixed on the carbon nitride sheet, and the particle size of the red phosphorus after heterojunction formation is obviously smaller than that of untreated red phosphorus. The research shows that the sonochemistry and high temperature method can not only strip multi-layer carbon nitride, but also break red phosphorus particles with larger particle size. Meanwhile, the magnetic carbon nanotube coating is smaller in size over the entire surface of the larger size red phosphorus/carbon nitride heterojunction. The agglomeration of magnetic carbon nanotubes in the composite is significantly reduced compared to pure carbon nanotubes, possibly due to strong interactions between the different components during sonochemistry and hydrothermal processes. Notably, the magnetic carbon nanotubes shuttle between red phosphorus/carbon nitride, which facilitates interfacial charge transfer.
Test example 2 energy spectrum analysis
Test sample: the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared in the embodiment 1.
The test process comprises the following steps: the surface micro-area of the sample of example 1 was analyzed for chemical composition using the energy spectrum of a scanning electron microscope.
Test results and analysis: the results are shown in FIG. 2.
EDS gives a catalyst with main components of C, N, O, P, 42.10% of C element, 19.04% of N element, 11.02% of O element and 27.83% of P element, and the synthesis and the expectation of the materials are similar.
Test example 3X-ray photoelectron Spectrometry (XPS) analysis
Test sample: the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst MCNT/RP/CN prepared in the example 1; magnetic carbon nanotubes MCNTs alone; carbon nitride CN alone (prepared in example 1, step (1)); red phosphorus RP alone (prepared in example 1, step (2)); the red phosphorus/carbon nitride heterojunction RP/CN prepared in comparative example 1.
The test process comprises the following steps: the above samples were analyzed by X-ray photoelectron spectroscopy (XPS).
Test results and analysis: the results are shown in FIG. 3.
As shown in fig. 3, in RP/CN and MCNT/RP/CN heterojunctions, C, N, O and P components are clearly present, and the reason for the enhanced MCNT/RP/CN binding energy compared to RP/CN may be that MNCT and RP/CN create a tight interface connection, and the rich carbon nanotube network promotes charge separation and migration in RP/CN heterojunctions.
Test example 4 photocatalytic sterilizing Performance test
Test sample: the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared in the embodiment 1; individual magnetic carbon nanotubes; carbon nitride alone (prepared in example 1, step (1)); red phosphorus alone (prepared in example 1, step (2)); the red phosphorus/carbon nitride heterojunction prepared in comparative example 1.
The test process comprises the following steps:
the photocatalytic sterilization performance test was performed in a quartz glass reactor. Staphylococcus aureus (s.aureus) was selected as the target inactivating bacteria.
Culturing Escherichia coli in prepared LB broth at 37deg.C for 16 hr to obtain stationary phase strain, centrifuging, collecting, and diluting with 0.9% NaCl solution to concentration of 10 7 cfu/mL of bacterial solution. 12.5mg of the test sample was added to 50mL of the above bacterial solution, stirred in the dark for 30min, and then a xenon lamp light source (equipped with visible light filter) was turned onLight sheet = 420 nm) and the colony count was calculated by plate counting using plates prepared from nutrient agar.
Test results: the results are shown in FIG. 4.
As can be seen from FIG. 4, the red phosphorus/carbon nitride heterojunction is deactivated 10 within 60min 7 After the staphylococcus aureus with the concentration of cfu/mL is introduced into proper MCNT under the irradiation of visible light, the disinfection capability of the red phosphorus/carbon nitride heterojunction is obviously improved. The prepared magnetic carbon nano tube/red phosphorus/carbon nitride composite nano sheet can completely kill 10 in 45min 7 The effect of cfu/mL bacteria is significantly higher than red phosphorus, carbon nitride and red phosphorus/carbon nitride heterojunction. Experimental results show that the magnetic carbon nano tube/red phosphorus/carbon nitride catalyst prepared by the invention is a novel photocatalytic sterilization material with wide spectral response and high activity.
Test example 5 photoelectrochemical analysis (PEC) experiment
Performance enhancement analysis of ternary materials relative to binary materials
Photoelectrochemical experiments were performed on a CHI760E electrochemical workstation using a conventional three electrode system. AgCl electrode, pt electrode and catalyst modified Indium Tin Oxide (ITO) glass are selected as reference electrode, counter electrode and working electrode respectively. Before preparing the working electrode, the ITO glass is respectively treated by ultrasonic for 20min in acetone, ethanol and deionized water, and dried at 60 ℃. The working electrode was prepared as follows: 1mg of photocatalyst (red phosphorus RP, carbon nitride CN, RP/CN-1, RP/CN-2, RP/CN-3, MCNT/CN/RP-1, MCNT/CN/RP-2, MCNT/CN/RP-3) was dispersed in a mixed solution of 0.75mL of LDI water and 0.25mL of isopropyl alcohol, and a relatively uniform slurry was obtained by ultrasonic treatment. 50. Mu.L of the above slurry was dropped on the pretreated ITO glass, and dried at 60℃for 30 minutes to enhance adhesion. Using 300W xenon lamp (PLS-SXE 300) and 0.1 mol.L -1 Na of (2) 2 SO 4 The solution was used as a VL source and electrolyte solution for photocurrent response and electrochemical impedance testing.
In a typical three-electrode system, a series of PEC experiments were performed without any sacrificial agent, very classically confirming the improvement in charge transfer properties of the prepared samples (as shown in fig. 5). At the position ofThe photocurrent response of red phosphorus/carbon nitride has good reproducibility and stability under irradiation of visible light (photocurrent density of 0.22 mu A cm) -2 ) Specific red phosphorus (0.09. Mu.A.cm) -2 ) And carbon nitride (0.05. Mu.A.cm) -2 ) 2.4 times and 4.4 times higher, respectively. At the same time, the photocurrent response strength of the carbon nanotube/red phosphorus/carbon nitride (0.46. Mu.A.cm -2 ) Higher than red phosphorus/carbon nitride, and the charge separation efficiency is highest. Electrochemical impedance tests show that the impedance arc radius of the binary catalyst red phosphorus/carbon nitride is far smaller than the radius of the red phosphorus and the carbon nitride; the carbon nano tube/red phosphorus/carbon nitride has the smallest impedance arc radius, which shows that the charge transfer resistance of the ternary carbon nano tube/red phosphorus/carbon nitride is the lowest, and the transfer of electrons is facilitated.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (11)
1. A carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, characterized by comprising:
a red phosphorus/carbon nitride heterojunction composed of layered stacked carbon nitride and red phosphorus particles fixed on the carbon nitride;
and magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunction;
wherein the particle size of the red phosphorus particles is 50-100nm;
the diameter of the magnetic carbon nano tube is 3-5nm.
2. The carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst according to claim 1, wherein in the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, the mass fractions of the elements are as follows: 40-45% of C element, 18-20% of N element, 10-15% of O element and 25-30% of P element.
3. The carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst according to claim 2, wherein in the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst, the mass fractions of the elements are as follows: the content of C element is 42.10%, the content of N element is 19.04%, the content of O element is 11.02%, and the content of P element is 27.83%.
4. A method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst as defined in any one of claims 1 to 3, comprising the steps of:
(a) Obtaining magnetic carbon nanotubes: dispersing the carbon nanotubes into a solvent, attracting and extracting the magnetic carbon nanotubes for a plurality of times by using a permanent magnet, and drying for later use;
(b) Preparing a red phosphorus/carbon nitride heterojunction: adding carbon nitride and red phosphorus into water, performing ultrasonic dispersion and uniform mixing, transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the obtained suspension to obtain a primary red phosphorus/carbon nitride heterojunction; transferring the obtained primary red phosphorus/carbon nitride heterojunction into a vacuum quartz tube, placing the quartz tube into a muffle furnace for high-temperature calcination, and obtaining the red phosphorus/carbon nitride heterojunction after natural cooling;
(c) Preparing a magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst: mixing and grinding the red phosphorus/carbon nitride heterojunction obtained in the step (b) and the magnetic carbon nano tube obtained in the step (a), and then performing ultrasonic dispersion on the obtained powder in water to form a preliminary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride; transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst.
5. The method of claim 4, wherein step (a) comprises: dispersing 1g of carbon nanotubes into 200ml of ethanol by ultrasonic and stirring, and then extracting the carbon nanotubes with stronger magnetism by using a permanent magnet; repeating the steps for a plurality of times to obtain the magnetic carbon nano tube; the resulting magnetic carbon nanotubes were dried overnight at 60 ℃ and ground to a powder for use.
6. The method of claim 4, wherein the carbon nitride in step (b) is a precursor prepared by thermal polymerization;
the precursor is urea or melamine;
the thermal polymerization is carried out at a constant temperature of 500-600 ℃ for 2-6 hours at a heating rate of 1-5 ℃/min.
7. The method of claim 4, wherein the red phosphorus in step (b) is purified by a hydrothermal method before use;
the reaction temperature of the hydrothermal method is 180-220 ℃, and the reaction time is 6-12 hours.
8. The method of claim 4, wherein the mass ratio of red phosphorus to carbon nitride in step (b) is 0.5:1 to 1.5:1;
every 100mg of carbon nitride, the corresponding water adding amount is 25-70 mL;
the ultrasonic time is 1-6 hours;
the reaction temperature of the hydrothermal reaction is 100-180 ℃ and the reaction time is 6-12 hours;
the high-temperature calcination is carried out at a calcination temperature of 300-500 ℃ for 2-6 hours.
9. The method of claim 4, wherein the mass ratio of the magnetic carbon nanotubes to the red phosphorus/carbon nitride heterojunction in step (c) is 0.25:1 to 1:1;
the ultrasonic time is 2-6 hours;
the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 6-12 hours.
10. Use of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst as defined in any one of claims 1-3 or the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetallic photocatalyst prepared by the method as defined in any one of claims 4-9 in broad spectrum photocatalytic sterilization.
11. The use according to claim 10, characterized in that the broad spectrum photocatalytic light response wavelength range is 420-800 nm.
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