CN115318315A - Magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst and preparation method and application thereof - Google Patents
Magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst and a preparation method and application thereof, relating to the technical field of photocatalytic materials. The carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst comprises: a red phosphorus/carbon nitride heterojunction composed of carbon nitride stacked in layers and red phosphorus particles fixed on the carbon nitride; magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunctions. The simple substance 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 and a magnetic carbon nanotube are combined by an ultrasonic-hydrothermal two-step method to obtain the magnetic recyclable carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst. The ternary nonmetal photocatalyst can realize photocatalytic sterilization under wide-spectrum visible light and can be fully recycled.
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 nonmetal photocatalyst and a preparation method and application thereof.
Background
Red phosphorus is an abundant, 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 structures of red phosphorus and carbon nitride suitably compensate for the respective defects. The absorption wave band of the red phosphorus is wider, and the defect of low utilization rate of the carbon nitride to visible light is overcome. Meanwhile, after the red phosphorus sterilization agent is combined with carbon nitride, the sterilization efficiency of the red phosphorus is also improved.
Most visible-light-driven photocatalyst is powder, is not easy to recover in a water body, and is a feasible solution through magnetic separation. Most of the recyclable magnetic photocatalysts use various ferrites, such as CoFe 2 O 4 、NiFe 2 O 4 And so on. However, the ferrite has high preparation cost, is easy to cause heavy metal ion leakage in the operation process, causes secondary pollution to the environment, and is not an optimal solution.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Studies have shown that carbon nanotubes have intrinsic magnetic properties. Therefore, the magnetic carbon nano tube is extracted from the carbon nano tube by using the permanent magnet and hybridized with the red phosphorus/carbon nitride heterojunction, and a recyclable magnetic carbon nano tube/red phosphorus/carbon nitride ternary photocatalytic system is constructed. The magnetic carbon nanotube is environment-friendly, green and recyclable, is easy to conduct electricity, improves the migration and separation rate of red phosphorus/carbon nitride photocarriers, and can greatly improve the photocatalytic quantum efficiency and the sterilization efficiency.
One of the purposes of the invention is to provide a magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst, which overcomes the defect that the traditional red phosphorus/carbon nitride is not beneficial to recovery, greatly expands the visible light response range of the catalyst and improves the photocatalytic sterilization efficiency.
The second objective of the present invention is to provide a method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride three-element non-metal photocatalyst.
The invention also aims to provide the application of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst in broad-spectrum photocatalytic sterilization, wherein the photoresponse wavelength range of the broad-spectrum photocatalysis is 420-800 nm.
In order to realize the purpose, the following technical scheme is adopted:
in a first aspect, the present invention provides a magnetic carbon nanotube/red phosphorus/carbon nitride three-element non-metal photocatalyst, comprising:
a red phosphorus/carbon nitride heterojunction composed of carbon nitride stacked in layers and red phosphorus particles fixed on the carbon nitride;
and magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunctions;
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 carbon nanotubes using a permanent magnet.
In some embodiments, in the magnetic carbon nanotube/red phosphorus/carbon nitride three-element nonmetal 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; in one example, the C element is 42.10%, the N element is 19.04%, the O element is 11.02%, and the P element is 27.83%.
In a second aspect, the invention provides a method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride three-element non-metal photocatalyst, which comprises the following steps:
(a) Obtaining the magnetic carbon nano tube: dispersing carbon nanotubes into a solvent, extracting magnetic carbon nanotubes by using a permanent magnet for multiple times of attraction, 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 mixing uniformly, transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain a primary red phosphorus/carbon nitride heterojunction; transferring the obtained preliminary red phosphorus/carbon nitride heterojunction into a vacuum quartz tube, placing the quartz tube into a muffle furnace for high-temperature calcination, and naturally cooling to obtain the red phosphorus/carbon nitride heterojunction;
(c) Preparing a magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal 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 ultrasonically dispersing the obtained powder in water to form a primary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride; and transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst.
The respective steps will be described in detail.
Step (a)
In this step, specifically, the method includes: dispersing 1g of carbon nano tube into 200ml of ethanol by ultrasonic and stirring, and then extracting the carbon nano tube 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 at 60 ℃ overnight and ground to a powder for use.
Step (b)
In the step, the carbon nitride material is prepared and the red phosphorus is purified before the red phosphorus/carbon nitride heterojunction is prepared.
In some embodiments, a thermal polymerization method is used to prepare carbon nitride material by selecting a suitable precursor;
preferably, the precursor is urea or melamine;
preferably, the thermal polymerization method is used for heating for 2-6 hours at a constant temperature of 500-600 ℃ at a heating rate of 1-5 ℃/min;
in some embodiments, the carbon nitride is prepared as follows: 40 grams of urea was heated at a ramp rate of 2 deg.C/min in 550 deg.C air for 4 hours. The prepared yellowish block is cooled to room temperature and then ground into carbon nitride powder for subsequent use.
In some embodiments, red phosphorus is purified by a hydrothermal method;
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 di 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, and specifically comprising the following steps:
adding water into carbon nitride and the purified red phosphorus for mixing, performing ultrasonic treatment, transferring the mixture 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;
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 naturally cooling to obtain the final red phosphorus/carbon nitride heterojunction.
In some embodiments, the mass ratio of red phosphorus to carbon nitride is 0.5;
in some embodiments, the amount of water added is 25 to 70mL per 100mg of carbon nitride.
In some embodiments, the sonication time is 1 to 6 hours.
In some embodiments, the hydrothermal reaction is carried out at a reaction temperature of 100 to 180 ℃ for 6 to 12 hours.
In some embodiments, the high temperature calcination has a calcination temperature of 300 to 500 ℃ and 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 varying weights of red phosphorus (50, 100, 150 mg) were added to 65mL of DI water and mixed well. The suspension was transferred to a 100mL autoclave, heated to 180 ℃ for 12 hours, centrifuged (10000rpm, 5min), washed with ethanol and deionized water several times, and dried at 60 ℃ overnight. The temperature then provides further control over the growth of the red phosphorus/carbon nitride heterojunction. During the heating process, the pink sample was heated gradually to 500 ℃ and stored in a vacuum quartz tube for 2 hours in order to make the red phosphorus and carbon nitride bond more tightly. Finally obtaining pink product, namely the red phosphorus/carbon nitride heterojunction.
Step (c)
In the step, an ultrasonic-hydrothermal two-step method is adopted to combine the magnetic carbon nano tube and the red phosphorus/carbon nitride heterojunction to obtain the magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst, and the method 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 ultrasonically dispersing the obtained powder in water to form a primary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride;
and transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst.
In some embodiments, the mass ratio of the magnetic carbon nanotube to the red phosphorus/carbon nitride heterojunction is 0.25;
in some embodiments, the time of sonication is between 2 and 6 hours.
In some embodiments, the hydrothermal reaction is carried out at a reaction temperature of 100 to 180 ℃ for a reaction time of 6 to 12 hours.
In some embodiments, the magnetic carbon nanotube/red phosphorus/carbon nitride ternary non-metal photocatalyst is prepared by the following steps:
100mg of red phosphorus/carbon nitride heterojunction and different weights of magnetic carbon nanotubes (25, 50 and 100 mg) were ground with an agate mortar for half an hour. The resulting powder was ultrasonically dispersed in 65mL of 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, it was washed several times with deionized water and ethanol and centrifuged, and the resulting product was air-dried at 60 ℃ overnight. The dried sample is ground into powder to obtain the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal 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 nonmetal photocatalyst is prepared by a two-step method, and the obtained catalyst has the special structure and composition of the first aspect.
In a third aspect, the invention provides an application of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst in broad spectrum photocatalytic sterilization, wherein the photoresponse wavelength range of the broad spectrum photocatalysis is 420-800 nm.
The catalyst has the advantages of recyclable and wide-spectrum response photocatalytic sterilization application, and the sterilization efficiency of the catalyst is higher than that of pure red phosphorus and carbon nitride.
The invention firstly uses simple substance red phosphorus and carbon nitride as raw materials, prepares a stable red phosphorus/carbon nitride heterojunction by an ultrasonic-hydrothermal-high temperature calcination three-step method, and combines the heterojunction with a magnetic carbon nanotube by an ultrasonic-hydrothermal two-step method to obtain a magnetic recyclable carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst. The ternary nonmetal photocatalyst can realize the application of photocatalytic sterilization under wide-spectrum visible light, and has the advantage that magnetism can be fully recovered. The load of the carbon nano tube and the red phosphorus greatly expands the visible light response range of the catalyst, improves the photocatalytic sterilization efficiency, does not contain any metal component, solves the problem of recoverability of the photocatalyst only 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.
Has the advantages that:
the invention not only prepares the stable and high-efficiency 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 nonmetal photocatalyst. The magnetic recyclable carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst prepared by the invention has the application of recyclable and wide-spectrum response photocatalysis sterilization, and the sterilization efficiency is higher than that of pure red phosphorus and carbon nitride.
The test shows that the concentration of the staphylococcus aureus is 10 7 cfu·mL -1 In the bacterial solution, the highest removal rate of staphylococcus aureus in water treated by the catalyst can reach 100 percent, and the rate is improved by 2 to 5 times compared with the rate of pure carbon nitride and red phosphorus, thereby achieving the ideal purification purpose.
Drawings
FIG. 1 is a transmission electron microscope image of the magnetic carbon nanotube/red phosphorus/carbon nitride three-element non-metal photocatalyst prepared in example 1.
FIG. 2 is the surface micro-area composition analysis chart of the EDS spectrum of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary non-metallic photocatalyst prepared in example 1.
Fig. 3 is an XPS chart 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 the photocatalytic sterilization efficiency of the magnetic recyclable carbon nanotube/red phosphorus/carbon nitride ternary non-metallic photocatalyst of the present invention with that of pure red phosphorus and carbon nitride.
Fig. 5 shows the charge transfer performance of carbon nitride, red phosphorus/carbon nitride, magnetic carbon nanotube/red phosphorus/carbon nitride photocatalyst in a three-electrode system, where a is the photocurrent response curve and b is the electrochemical impedance spectrum.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.
Reagent: LB broth, nutrient agar purchased from Qingdao Haibo Biotech limited; staphylococcus aureus was purchased from Hangzhou Baosu Biotech limited; red phosphorus, ethanol and urea are purchased from Tianjin Yu Fine chemical Co., ltd in China; carbon nanotubes were purchased from Shanghai Maxin Biotechnology, inc.
The instrument comprises: transmission electron microscope (TEM, JEM-2100F); scanning electron microscope (SEM, sigma 300), equipped with EDS; x-ray photoelectron spectroscopy (ESCALB 250).
The preparation method of the magnetic carbon nanotube in the embodiment is as follows: dispersing 1g of carbon nano tube into 200mL of ethanol by ultrasonic and stirring, and then extracting the carbon nano tube 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
A preparation method of a magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst comprises the following steps:
(1) Putting 40g of urea into a crucible, heating at the constant temperature of 550 ℃ for 4 hours (the heating rate is 2 ℃/min), and after the temperature is cooled, grinding a sample into yellow powder to obtain a carbon nitride material for later use;
(2) 8g of elemental red phosphorus was added to a 100mL polytetrafluoroethylene-lined reaction vessel, 60mL of water was added, and the reaction vessel 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 powdered 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, and the suspension was transferred to a 100mL autoclave, heated to 180 ℃ for 12 hours, centrifuged (10000rpm, 5 min), washed with ethanol and deionized water several times, and dried at 60 ℃ overnight. Thereafter, the pink sample was gradually heated to 500 ℃ and stored in a vacuum quartz tube for 2 hours. Finally obtaining pink product, namely the 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 using an agate mortar, and ultrasonically dispersing the obtained powder in 65mL of deionized water for 2 hours to form a primary 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, it was washed several times with deionized water and ethanol, and dried at 60 ℃ overnight. The dried sample was milled to a powder to yield a magnetic carbon nanotube/red phosphorus/carbon nitride ternary non-metallic photocatalyst (noted as MCNT/CN/RP-2).
Example 2
This example differs from example 1 in that the weight of red phosphorus in step (3) is 50mg.
Example 3
This example differs from example 1 in that the weight of red phosphorus in step (3) is 150mg.
Example 4
This example differs from example 1 in that the weight of the magnetic carbon nanotubes in step (4) is 25mg (noted as MCNT/CN/RP-1).
Example 5
This example differs from example 1 in that the weight of the magnetic carbon nanotubes in step (4) is 100mg (noted as MCNT/CN/RP-3).
Comparative example 1 Red phosphorus/carbon nitride heterojunction
This example differs from example 1 in that step (4) is not included and a red phosphorus/carbon nitride heterojunction is obtained, designated as RP/CN-2.
Comparative example 2 Red phosphorus/carbon nitride heterojunction
This example differs from example 4 in that step (4) is not included and a red phosphorus/carbon nitride heterojunction is obtained, designated as RP/CN-1.
Comparative example 3 Red phosphorus/carbon nitride heterojunction
This example differs from example 5 in that step (4) is not included and a red phosphorus/carbon nitride heterojunction is obtained, denoted as RP/CN-3.
Experimental example 1 Electron microscopy characterization
Test samples: the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst prepared in example 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 a non-uniform block shape with sizes varying from 1 mm to 12 microns. The original carbon nitride shows a unique stacked layered structure, similar to silk. The untreated magnetic carbon nanotubes are easily agglomerated into pellets of various sizes. On the nanometer scale, magnetic carbon nanotubes are significantly elongated tubular structures. The red phosphorus/carbon nitride exhibits a platelet morphology, consisting of a large number of red phosphorus particles and a silk-like carbon nitride. The red phosphorus particles are fixed on the carbon nitride sheet, and the particle size of the red phosphorus after the heterojunction is formed is obviously smaller than that of the untreated red phosphorus. The research shows that the sonochemistry and high-temperature method can not only strip off multiple layers of carbon nitride, but also break up red phosphorus particles with larger particle size. At the same time, the magnetic carbon nanotube coating is smaller in size over the entire surface of the larger-sized red phosphorus/carbon nitride heterojunction. The agglomeration of magnetic carbon nanotubes in the composite material is significantly reduced compared to pure carbon nanotubes, which may be due to strong interactions between different components in sonochemical and hydrothermal processes. Notably, the magnetic carbon nanotubes shuttle between red phosphorus/carbon nitride, which facilitates interfacial charge transfer.
Test example 2 energy Spectroscopy
Test samples: the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst prepared in example 1.
The test process comprises the following steps: the energy spectrum of the scanning electron microscope is used for analyzing the chemical composition of the surface micro-area of the sample of the example 1.
Test results and analysis: the results are shown in FIG. 2.
EDS shows that the main components of the catalyst are C, N, O and P, the C element accounts for 42.10 percent, the N element accounts for 19.04 percent, the O element accounts for 11.02 percent and the P element accounts for 27.83 percent, and the synthesis and the expectation of the material are similar.
Test example 3X-ray photoelectron Spectroscopy (XPS) analysis
Test samples: the magnetic carbon nano tube/red phosphorus/carbon nitride ternary nonmetal photocatalyst MCNT/RP/CN prepared in the embodiment 1; magnetic carbon nanotubes MCNT alone; carbon nitride CN alone (prepared in step (1) of example 1); red phosphorus RP alone (prepared in step (2) of example 1); comparative example 1 the resulting red phosphorus/carbon nitride heterojunction RP/CN was prepared.
The test process comprises the following steps: the 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 the RP/CN and MCNT/RP/CN heterojunctions, the C, N, O and P components are obviously present, the reason that the binding energy of MCNT/RP/CN is enhanced compared with RP/CN is probably that the MNCT and the RP/CN generate tight interface connection, and the abundant carbon nanotube network promotes the charge separation and migration in the RP/CN heterojunctions.
Test example 4 photocatalytic bactericidal performance test
Test samples: the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst prepared in example 1; individual magnetic carbon nanotubes; carbon nitride alone (prepared in example 1, step (1)); red phosphorus alone (prepared in step (2) of example 1); comparative example 1 the resulting red phosphorus/carbon nitride heterojunction was prepared.
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 killed bacteria.
Culturing Escherichia coli in LB broth at 37 deg.C for 16 hr to obtain stationary phase strain, centrifuging, collecting, and adding 0.9%Diluting NaCl solution to 10 concentration 7 cfu/mL of bacterial solution. The test sample (12.5 mg) was added to 50mL of the above bacterial solution, stirred in the dark for 30min, then the xenon lamp light source (equipped with visible light filter =420 nm) was turned on to start the reaction, and the number of colonies was counted by plate counting using a plate made of nutrient agar.
And (3) test results: the results are shown in FIG. 4.
As can be seen from FIG. 4, the red phosphorus/carbon nitride heterojunction is inactivated within 60min 10 7 The disinfection capability of the red phosphorus/carbon nitride heterojunction is obviously improved after the staphylococcus aureus with cfu/mL concentration is introduced into proper MCNT under the irradiation of visible light. The prepared magnetic carbon nano tube/red phosphorus/carbon nitride composite nano sheet can completely kill 10 percent of carbon nano tubes/red phosphorus/carbon nitride composite nano sheets within 45min 7 The effect of cfu/mL bacteria is obviously higher than red phosphorus, carbon nitride and red phosphorus/carbon nitride heterojunction. Experimental results show that the magnetic carbon nanotube/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 Performance analysis (PEC) test
Performance enhancement analysis of ternary versus 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 the working electrode was prepared, the ITO glass was subjected to ultrasonic treatment in acetone, ethanol and deionized water for 20min, respectively, 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 DI water and 0.25mL of isopropyl alcohol and sonicated to give a relatively uniform slurry. 50 μ L of the slurry was dropped on the pretreated ITO glass, and dried at 60 ℃ for 30min to enhance the adhesion. Using a 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.
A series of PEC experiments were performed in the absence of any sacrificial agent in a typical three-electrode system, very classically demonstrating the improvement in charge transfer performance of the prepared samples (as shown in figure 5). Under the irradiation of visible light, the photocurrent response of red phosphorus/carbon nitride has good reproducibility and stability (photocurrent density of 0.22 muA-cm) -2 ) 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. Meanwhile, the photocurrent response intensity of the carbon nano tube/red phosphorus/carbon nitride (0.46 muA cm) -2 ) Higher than red phosphorus/carbon nitride, 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 radii 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 is more favorable for electron transfer.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A carbon nano tube/red phosphorus/carbon nitride three-element nonmetal photocatalyst is characterized by comprising:
a red phosphorus/carbon nitride heterojunction consisting of carbon nitride stacked in layers and red phosphorus particles fixed on the carbon nitride;
and magnetic carbon nanotubes shuttled between the red phosphorus/carbon nitride heterojunctions;
wherein the particle size range of the red phosphorus particles is 50-100nm;
the diameter of the magnetic carbon nano tube is 3-5nm.
2. The carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst according to claim 1, wherein the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst comprises the following elements in percentage by mass: 40-45% of C element, 18-20% of N element, 10-15% of O element and 25-30% of P element;
preferably, the C element accounts for 42.10%, the N element accounts for 19.04%, the O element accounts for 11.02%, and the P element accounts for 27.83%.
3. A method for preparing the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst of claim 1 or 2, which comprises the following steps:
(a) Obtaining the magnetic carbon nano tube: dispersing carbon nanotubes into a solvent, extracting magnetic carbon nanotubes by using a permanent magnet for multiple times of attraction, 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 mixing uniformly, transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, centrifuging, washing and drying the obtained suspension to obtain a primary red phosphorus/carbon nitride heterojunction; transferring the obtained preliminary red phosphorus/carbon nitride heterojunction into a vacuum quartz tube, placing the quartz tube into a muffle furnace for high-temperature calcination, and naturally cooling to obtain the red phosphorus/carbon nitride heterojunction;
(c) Preparing a magnetic carbon nano tube/red phosphorus/carbon nitride three-element nonmetal 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 ultrasonically dispersing the obtained powder in water to form a primary combination of the magnetic carbon nano tube and the red phosphorus/carbon nitride; and transferring the suspension into a high-pressure reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the obtained suspension to obtain the magnetic carbon nanotube/red phosphorus/carbon nitride ternary nonmetal photocatalyst.
4. The method of claim 3, wherein step (a) comprises: dispersing 1g of carbon nano tubes into 200ml of ethanol by ultrasonic and stirring, and then extracting the carbon nano tubes 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 at 60 ℃ overnight and ground to a powder for use.
5. The method of claim 3, wherein in step (b) the carbon nitride is prepared by thermal polymerization of a precursor;
preferably, the precursor is urea or melamine;
preferably, the thermal polymerization is heated at a constant temperature of 500-600 ℃ for 2-6 hours at a heating rate of 1-5 ℃/min.
6. The method of claim 3, wherein the red phosphorus is purified by hydrothermal method before being used in step (b);
preferably, the reaction temperature of the hydrothermal method is 180-220 ℃, and the reaction time is 6-12 hours.
7. The method according to claim 3, wherein the mass ratio of red phosphorus to carbon nitride in step (b) is 0.5;
preferably, every 100mg of carbon nitride is added with 25-70 mL of water correspondingly;
preferably, the time of the ultrasound is 1 to 6 hours;
preferably, the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 6-12 hours;
preferably, the high-temperature calcination is carried out at a calcination temperature of 300-500 ℃ for 2-6 hours.
8. The method according to claim 3, wherein the mass ratio of the magnetic carbon nanotubes to the red phosphorus/carbon nitride heterojunction in step (c) is 0.25;
preferably, the time of the ultrasonic treatment is 2 to 6 hours;
preferably, the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is 6-12 hours.
9. Use of the magnetic carbon nanotube/red phosphorus/carbon nitride ternary non-metallic photocatalyst according to claim 1 or 2 or the magnetic carbon nanotube/red phosphorus/carbon nitride ternary non-metallic photocatalyst prepared by the method according to any one of claims 3 to 8 in broad-spectrum photocatalytic sterilization.
10. Use according to claim 9, wherein the broad spectrum photocatalytic photoresponse wavelength ranges from 420 to 800nm.
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