CN108950521B - Preparation method of red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization - Google Patents
Preparation method of red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization Download PDFInfo
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
Abstract
A preparation method of a red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization comprises the following steps: step one, carrying out mechanical polishing treatment on a titanium sheet, sequentially grinding the titanium sheet until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively carrying out ultrasonic cleaning for 15 minutes, and naturally drying at room temperature for later use; step two, preparing a red phosphorus film, taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by chemical vapor deposition; and step three, preparing a nano ZnO film, and plating a layer of uniform nano ZnO film on the substrate deposited with the red phosphorus film obtained in the step two by atomic layer deposition. The advantages are that: the red phosphorus-zinc oxide heterojunction film can kill bacteria completely within 20 minutes under the irradiation of visible light, and has broad-spectrum antibacterial property. In addition, the red phosphorus-zinc oxide heterojunction film has better biocompatibility.
Description
Technical Field
The invention relates to the technical field of photocatalysis, semiconductor heterojunction and biological antibacterial materials, in particular to a preparation method of a red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization.
Background
In order to cope with epidemic diseases caused by pathogenic microorganisms and bacteria such as contaminated water sources, medical equipment, food poisoning, etc., people are increasingly demanding on novel antibacterial coatings. Among these, drinking water safety is an urgent and important issue worldwide, especially in most developing countries where there is a shortage of drinking water supply. In developing countries, 80% of water-borne diseases have been caused by the presence of pathogenic microorganisms such as bacteria and fungi in drinking water. For example, in 2012 alone, 150 million people died from diarrhea associated with pathogenic microorganisms due to drinking water problems. In addition, with the rapid development of industrialization, water quality pollution is further aggravated by environmental pollution, so that water-borne diseases are more easily infected.
Solar disinfection (SODIS) of drinking water is one of the most important means of disinfecting water worldwide. However, SODIS depends mainly on ultraviolet light (only 4% of the total solar spectral energy), which results in slow and time consuming processing (exposure time 6-48 hours). Therefore, a processing route with rapidness, energy conservation, environmental protection and low cost is developed, and the method has important significance for effectively and safely carrying out water disinfection and capturing visible light in solar energy to accelerate water source purification.
Various antimicrobial strategies, such as antibiotic loaded structures, silver-based systems, etc., have many drawbacks and potential risks. Specifically, abuse of antibiotics can lead to the emergence of antibiotic-resistant bacteria, and even superbacteria. In addition, silver-based systems have significant toxic effects on human health (i.e., silver poisoning) and the environment, and the natural abundance of silver in the earth's crust is only 0.075 ppm.
Phosphorus is an abundant and widely distributed element in the earth, with about 1000 million tons on earth. Element P exists in three allotropes including white phosphorus, black phosphorus and red phosphorus, of which red phosphorus (amorphous and crystalline) has been used for photocatalytic hydrogen production under visible light and water decomposition. More importantly, the red phosphorus is non-toxic, relatively stable, economical and environment-friendly. The fiber phase red phosphorus is a direct band gap semiconductor, and the forbidden band width is 1.5eV, so the fiber phase red phosphorus has great application potential in solar-driven photocatalytic sterilization.
Zinc oxide is an important semiconductor material with direct band gap (3.37eV) at room temperature, and has been widely studied in the field of photocatalysis due to its low cost and nontoxicity. However, the wide bandgap of ZnO limits its activity in the visible region of the solar spectrum. In addition, because the photoproduction electron and the hole of the single-component photocatalyst are easy to recombine, the charge separation efficiency is low, and the charge carrier is quickly recombined, so that the photocatalytic efficiency of ZnO is poor.
Disclosure of Invention
In this study, an RP/ZnO heterojunction film was described that absorbs visible light to drive water splitting reactions to achieve rapid photocatalytic water disinfection. At the RP/ZnO heterojunction interface, the light-excited carrier transport process can be efficiently realized, so that ROS (reactive oxygen species) generated by visible light photocatalysis can be used for quickly killing bacteria (staphylococcus aureus and escherichia coli).
The invention aims to solve the technical defects and problems, and provides a preparation method of a red phosphorus-zinc oxide heterojunction film with efficient antibacterial effect and broad-spectrum rapid photocatalytic sterilization, which specifically comprises the following steps:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Plating a layer of uniform red phosphorus film on the polished titanium sheet obtained in the step one as a substrate by Chemical Vapor Deposition (CVD),
and the concrete steps are as follows:
1) placing red phosphorus powder at 200 deg.C, performing hydrothermal treatment for 9-15 hr, slowly cooling to room temperature, vacuum drying, and grinding to uniform powder below 100 μm;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 1-10sccm, heating to 550-750 ℃ at the rate of 5-15 ℃/min, and preserving heat for 4-6 h;
3) cooling to 250-450 deg.C at 5-10 deg.C/min, maintaining for 1-3h, and slowly cooling to room temperature.
Preferably, the pretreatment temperature of the red phosphorus powder 1) in the second step is 200 ℃, and the treatment time is 12 h;
the argon gas introducing rate of 2) in the step two is 2sccm, the heating rate is 10 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 5 hours;
the cooling rate of 3) in the second step is 5 ℃/min, the heat preservation temperature is 350 ℃, and the heat preservation time is 2 h.
Step three, preparing the nano ZnO film
And (4) plating a layer of uniform nano ZnO film on the substrate deposited with the red phosphorus film obtained in the step two by using ALD (atomic layer deposition).
Preferably, the specific steps of step three are: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle with the cycle frequency of 200-400 under the conditions that the deposition temperature is 80-120 ℃, the deposition pressure is 20-40Pa and the deposition flow is 10-20sccm, so as to obtain the nano ZnO film on the substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
Preferably, in the third step, the deposition temperature of the reaction is 100 ℃, the deposition pressure is 40Pa, the deposition flow is 20sccm, and the reaction cycle number is 300.
The preparation method of the red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization has the advantages that:
(1) the fiber phase red phosphorus film is plated on the substrate by adopting a CVD method, so that the uniformity can be realized, and the thickness of the red phosphorus can be controlled by regulating and controlling related parameters. Compared with amorphous red phosphorus, fiber phase red phosphorus has better photocatalysis effect. The fiber phase red phosphorus is nontoxic and has good biocompatibility.
(2) The thickness of the nano ZnO film plated on the substrate by the ALD method is accurate and controllable, and the nano ZnO film has an excellent antibacterial effect. Compared with organic antibacterial agents such as antibiotics and the like, the nano ZnO film has quick, broad-spectrum and efficient antibacterial property under illumination and has certain biocompatibility.
(3) The preparation method is simple and feasible, does not generate toxic and harmful gases, is economic and environment-friendly, and the red phosphorus-zinc oxide heterojunction film material with the surface having rapid photocatalytic sterilization is prepared by adopting the technology of the invention, so the implementation difficulty is low, the equipment investment is low, and the resource consumption is low.
(4) The red phosphorus-zinc oxide heterojunction film has broad-spectrum and quick antibacterial property; the red phosphorus-zinc oxide heterojunction film has better biocompatibility; the prepared heterojunction type photocatalytic system can effectively improve the separation of a light-induced electron and a hole, and obviously broadens the visible light absorption range of the material in the whole solar spectrum; the high-efficiency photo-excited charge transport on the heterojunction interface plays an outstanding role in improving the photocatalytic activity; the high-efficiency solar energy water decomposition is realized by regulating and controlling the heterojunction interface of the heterojunction type photocatalytic system.
Drawings
The following figures are all characterization graphs performed for example 2, with the control group being Ti — ZnO (which is a zinc oxide nano-film obtained by ALD on pure titanium);
FIG. 1 is a comparison of crystal planes of a red phosphorus film obtained in step 2 of example 2 and a fiber phase red phosphorus as a control under a transmission electron microscope;
FIG. 2 is a Raman spectrum of the product of FIG. 1;
FIG. 3 is an Electron Spin Resonance (ESR) spectrum showing that Ti, Ti-RP, Ti-ZnO and Ti-RP/ZnO generate hydroxyl radicals (. OH) and singlet Oxygen (OH) under xenon lamp irradiation1O2) The relative strength of (d);
FIG. 4 and FIG. 5 are graphs showing the coating pattern of the flat plate and the calculation of the corresponding antibacterial ratio, respectively, which show that 100mg L is used-1The amorphous red phosphorus has no obvious antibacterial rate under the illumination of 20min or 10 min;
FIGS. 6 and 7 are respectively a flat plate coating diagram and a corresponding antibacterial ratio calculation diagram, which show the antibacterial property of Ti-RP/ZnO (Escherichia coli: E.coli, Staphylococcus aureus: S.aureus) under sunlight and xenon lamp with the illumination time;
FIG. 8 and FIG. 9 are respectively a flat plate coating layout and a corresponding antibacterial ratio calculation chart, which show the antibacterial property of Ti-RP, Ti-ZnO and Ti-RP/ZnO compared with Ti under dark condition and irradiation of xenon lamp. (Escherichia coli: E.coli, Staphylococcus aureus: S.aureus)
FIGS. 10 and 11 are cytotoxicity tests showing the cell fluorescence and cell viability of Ti-RP, Ti-ZnO and Ti-RP/ZnO, respectively, compared to Ti.
The specific implementation mode is as follows:
for a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples shown.
Example 1:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by Chemical Vapor Deposition (CVD), wherein the method comprises the following specific steps:
1) placing red phosphorus powder at 200 ℃, carrying out hydrothermal treatment for 12h, slowly cooling to room temperature, carrying out vacuum drying, and grinding to obtain uniform powder with the particle size of less than 100 microns;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 2sccm, heating to 650 ℃ at the rate of 10 ℃/min, and preserving heat for 5 hours;
3) cooling to 350 deg.C at 5 deg.C/min, maintaining for 2 hr, and slowly cooling to room temperature.
Step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the substrate deposited with the red phosphorus film obtained in the step two by ALD. The method comprises the following specific steps: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle under the conditions that the deposition temperature is 100 ℃, the deposition pressure is 40Pa and the deposition flow is 20sccm, wherein the cycle number is 200, so that the nano ZnO film is obtained on a substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
Example 2:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by Chemical Vapor Deposition (CVD), wherein the method comprises the following specific steps:
1) placing red phosphorus powder at 200 ℃, carrying out hydrothermal treatment for 12h, slowly cooling to room temperature, carrying out vacuum drying, and grinding to obtain uniform powder with the particle size of less than 100 microns;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 2sccm, heating to 650 ℃ at the rate of 10 ℃/min, and preserving heat for 5 hours;
3) cooling to 350 deg.C at 5 deg.C/min, maintaining for 2 hr, and slowly cooling to room temperature.
Step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the substrate deposited with the red phosphorus film obtained in the step two by ALD. The method comprises the following specific steps: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle with the cycle number of 300 under the conditions that the deposition temperature is 100 ℃, the deposition pressure is 40Pa and the deposition flow is 20sccm, so as to obtain the nano ZnO film on a substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
Example 3:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by Chemical Vapor Deposition (CVD), wherein the method comprises the following specific steps:
1) placing red phosphorus powder at 200 ℃, carrying out hydrothermal treatment for 12h, slowly cooling to room temperature, carrying out vacuum drying, and grinding to obtain uniform powder with the particle size of less than 100 microns;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 2sccm, heating to 650 ℃ at the rate of 10 ℃/min, and preserving heat for 5 hours;
3) cooling to 350 deg.C at 5 deg.C/min, maintaining for 2 hr, and slowly cooling to room temperature.
Step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the pure titanium or the substrate deposited with the red phosphorus film obtained in the step two by ALD. The method comprises the following specific steps: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle under the conditions that the deposition temperature is 100 ℃, the deposition pressure is 40Pa and the deposition flow is 20sccm, wherein the cycle number is 400, so that the nano ZnO film is obtained on a substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
Example 4:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by Chemical Vapor Deposition (CVD), wherein the method comprises the following specific steps:
1) placing red phosphorus powder at 200 ℃, carrying out hydrothermal treatment for 12h, slowly cooling to room temperature, carrying out vacuum drying, and grinding to obtain uniform powder with the particle size of less than 100 microns;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 2sccm, heating to 650 ℃ at the rate of 10 ℃/min, and preserving heat for 5 hours;
3) cooling to 350 deg.C at 5 deg.C/min, maintaining for 1 hr, and slowly cooling to room temperature.
Step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the pure titanium or the substrate deposited with the red phosphorus film obtained in the step two by ALD. The method comprises the following specific steps: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle with the cycle number of 300 under the conditions that the deposition temperature is 100 ℃, the deposition pressure is 40Pa and the deposition flow is 20sccm, so as to obtain the nano ZnO film on a substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
Example 5:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by Chemical Vapor Deposition (CVD), wherein the method comprises the following specific steps:
1) placing red phosphorus powder at 200 ℃, carrying out hydrothermal treatment for 12h, slowly cooling to room temperature, carrying out vacuum drying, and grinding to obtain uniform powder with the particle size of less than 100 microns;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 2sccm, heating to 650 ℃ at the rate of 10 ℃/min, and preserving heat for 5 hours;
3) cooling to 350 deg.C at a rate of 5 deg.C/min, maintaining for 3 hr, and slowly cooling to room temperature.
Step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the pure titanium or the substrate deposited with the red phosphorus film obtained in the step two by ALD. The method comprises the following specific steps: preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle with the cycle number of 300 under the conditions that the deposition temperature is 100 ℃, the deposition pressure is 40Pa and the deposition flow is 20sccm, so as to obtain the nano ZnO film on a substrate, namely the Ti-RP/ZnO heterojunction film is successfully prepared.
In the following table, the thickness of the product corresponding to the second step or the third step in the first to fifth examples is shown, wherein the CVD holding time refers to the holding time in step 3) in the second step;
summary of parameters for different implementation cases:
as can be seen from the above table, the thickness of the ZnO film can be controlled by adjusting the number of ALD cycles, and the thickness of the RP (red phosphorus) film can be controlled by adjusting the CVD incubation time.
The corresponding assay results of example 2 were analyzed as follows: (wherein a uniform nano ZnO film was deposited on pure titanium by ALD to obtain Ti-ZnO as a control)
In example 2, a series of characterizations were performed on four samples of titanium (Ti) obtained in step 1, a red phosphorus thin film (Ti-RP) obtained on a titanium substrate in step 2, a control zinc oxide nano-thin film (Ti-ZnO), and a zinc oxide nano-thin film (Ti-RP/ZnO) obtained on a substrate on which a red phosphorus thin film was deposited in step 3.
As shown in FIG. 1, the interplanar spacing of the red phosphorus thin film was shown to be
Corresponding to the (001) crystal face of the red phosphorus of the fiber phase. Meanwhile, fig. 2 is a raman spectrum, which further confirms the successful synthesis of a red phosphorus thin film on a titanium substrate.
FIG. 3 shows an Electron Spin Resonance (ESR) spectrum showing that Ti, Ti-RP, Ti-ZnO and Ti-RP/ZnO generate hydroxyl radicals (. OH) and singlet oxygen under irradiation of a xenon lamp (R) ((R))1O2) Relative strength of (d). Ti-RP and Ti-ZnO produce more OH and1O2the red phosphorus film and the nano ZnO film have certain photocatalysis effect. In addition, Ti-RP/ZnO can generate the most OH and1O2the strength of the film is obviously higher than that of Ti-RP and Ti-ZnO, which shows that the red phosphorus-zinc oxide heterojunction film has the photocatalysis enhancement effect.
FIGS. 4 and 5 are graphs of plate coating patterns and corresponding antibacterial ratios calculation, respectively, illustrating 100mg L-1The amorphous red phosphorus has no obvious antibacterial rate under the illumination of 20min or 10min (compared with a blank group, the antibacterial efficiency is less than 8 percent).
Fig. 6 and 7 are a flat plate coating diagram and a corresponding antibacterial ratio calculation diagram, respectively, and it is known that the antibacterial property of Ti-RP/ZnO is continuously increased with the illumination time under the sunlight and xenon lamp, and the antibacterial effect of Ti-RP/ZnO on e.coli is obviously better than that of s.auerus. When a fluorescent lamp is used, the antibacterial rate of the fluorescent lamp reaches 99.92 +/-0.02% for S.auerus illumination for 15 minutes, and the antibacterial rate of the fluorescent lamp reaches 99.86 +/-0.10% for E.coli illumination for 7 minutes. When a fluorescent lamp is used, the antibacterial rate of the fluorescent lamp reaches 99.63 +/-0.24% for S.auerus illumination for 20 minutes, and the antibacterial rate of the fluorescent lamp reaches 99.72 +/-0.12% for E.coli illumination for 10 minutes. The results show that the fiber phase red phosphorus has better antibacterial effect than amorphous red phosphorus. In addition, Ti-RP/ZnO has good photocatalytic sterilization effect and broad-spectrum sterilization performance on S.auerus and E.coli in a short time.
FIGS. 8 and 9 are a flat plate coating diagram and a corresponding antibacterial ratio calculation diagram, respectively, showing the antibacterial properties of Ti-RP, Ti-ZnO and Ti-RP/ZnO compared with Ti under dark conditions and irradiation of a xenon lamp. As can be seen, in the dark, Ti-RP, Ti-ZnO and Ti-RP/ZnO have substantially no antibacterial effect, while the antibacterial ratio of Ti-RP/ZnO (99.63. + -. 0.24% for S.aueruus and 99.72. + -. 0.12% for E.coli) is much greater than that of Ti-RP (35.12. + -. 3.30% for S.aueruus and 34.92. + -. 4.50% for E.coli) and that of Ti-ZnO (43.32. + -. 2.10% for S.aueruus and 51.14. + -. 3.55% for E.coli) under xenon irradiation, wherein the error bars indicate the mean. + -. standard deviation: p <0.001 (t-test). These results further confirm that the red phosphorus-zinc oxide heterojunction film has photocatalytic enhancement effect and generates more active oxygen to sterilize rapidly.
As shown in fig. 10, the cytotoxicity assay was characterized by cell fluorescence and cell viability. The cell fluorescence shows that the cells are well spread and take the shape of a polygon (the scale is 50 mu m), and reflects that the four materials of Ti, Ti-RP, Ti-ZnO and Ti-RP/ZnO have no obvious cytotoxicity.
In addition, FIG. 11 shows that Ti-RP has the best cell viability in the cell viability assay and reaches a maximum at 1 day (138.36%), while Ti-ZnO shows the greatest toxicity and reaches a maximum at 7 days (58.53%). However, Ti-RP, Ti-ZnO and Ti-RP/ZnO have no obvious cytotoxicity and have better biocompatibility on the whole.
The verification steps of each test function, which are not described in detail above, are obtained in a conventional manner (for example, the steps of fig. 1 to fig. 11 and the parameter summary table are obtained in a conventional manner, and thus, the process thereof is not described in detail).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The preparation method of the red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization is characterized by comprising the following steps:
step one, mechanical polishing treatment of titanium sheet
Sequentially polishing the titanium sheet on a polishing machine by using 240-mesh and 800-mesh carborundum until the surface is smooth, sequentially placing the polished titanium sheet in acetone, absolute ethyl alcohol and deionized water, respectively ultrasonically cleaning for 15 minutes, and naturally drying at room temperature for later use;
step two, preparing the red phosphorus film
Taking the polished titanium sheet obtained in the step one as a substrate, and plating a layer of uniform red phosphorus film by adopting a chemical vapor deposition method, which comprises the following specific steps:
1) placing red phosphorus powder at 200 deg.C, performing hydrothermal treatment for 9-15 hr, slowly cooling to room temperature, vacuum drying, and grinding to uniform powder below 100 μm;
2) placing the pretreated red phosphorus and titanium sheets in a CVD furnace, introducing argon at the rate of 1-10sccm, heating to 550-750 ℃ at the rate of 5-15 ℃/min, and preserving heat for 4-6 h;
3) cooling to 250-450 deg.C at a rate of 5-10 deg.C/min, maintaining for 1-3h, and slowly cooling to room temperature;
step three, preparing the nano ZnO film
And D, plating a layer of uniform nano ZnO film on the substrate deposited with the red phosphorus film obtained in the step two by using ALD (atomic layer deposition) to obtain the red phosphorus-zinc oxide heterojunction film.
2. The method for preparing a red phosphorus-zinc oxide heterojunction thin film for rapid photocatalytic sterilization according to claim 1, wherein the pretreatment time in the step two of 1) is 12 hours.
3. The method for preparing a red phosphorus-zinc oxide heterojunction thin film for rapid photocatalytic sterilization as claimed in claim 1, wherein in step 2), the argon gas is introduced at a rate of 2sccm, the temperature rise rate is 10 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 5 hours.
4. The method for preparing a red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization according to claim 1, wherein in the step two, the temperature reduction rate is 5 ℃/min, the heat preservation temperature is 350 ℃, and the heat preservation time is 2h in the step 3).
5. The method for preparing the red phosphorus-zinc oxide heterojunction film with the rapid photocatalytic sterilization function according to claim 1, wherein the preparation process of the nano ZnO film in the third step is as follows:
preparing a nano ZnO film by taking diethyl zinc and water as a zinc source and an oxygen source, and depositing by taking water pulse 0.1s, high-purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s and high-purity nitrogen cleaning 20s as a cycle with the cycle frequency of 200-400 under the conditions that the deposition temperature is 80-120 ℃, the deposition pressure is 20-40Pa and the deposition flow is 10-20sccm to obtain the nano ZnO film on a substrate.
6. The method for preparing a red phosphorus-zinc oxide heterojunction thin film with rapid photocatalytic sterilization according to claim 5, wherein the reaction deposition temperature is 100 ℃, the deposition pressure is 40Pa, the deposition flow is 20sccm, and the reaction cycle times are 300 in the preparation process of the nano ZnO thin film.
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