CN108950521A - Red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization - Google Patents
Red phosphorus-ZnO heterojunction film preparation method of 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
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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
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Abstract
A kind of red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization, include the following steps: step 1, titanium sheet mechanical polishing processing, successively titanium sheet is polished, it is smooth to surface, polishing titanium sheet is sequentially placed into acetone, dehydrated alcohol and deionized water and is respectively cleaned by ultrasonic 15 minutes, is spontaneously dried at room temperature, it is spare；Step 2 prepares red phosphorus film, and the polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus film as substrate, with chemical vapor deposition；Step 3, prepares nano-ZnO thin film, plates one layer of uniform nano-ZnO thin film with atomic layer deposition in the substrate obtained in step 2 for being deposited with red phosphorus film.Its advantage is that: red phosphorus-ZnO heterojunction film can all kill bacterium in 20 minutes under the irradiation of visible light, and have broad spectrum antibacterial.In addition, red phosphorus-ZnO heterojunction film has preferable biocompatibility.
Description
Technical field
The present invention relates to photocatalysis, heterojunction semiconductor, biological antibiotic field of material technology is specifically a kind of quick
The red phosphorus of photo-catalyst-ZnO heterojunction film preparation method.
Background technique
In order to cope with pandemic caused by the pathogenic microorganisms such as polluted source, Medical Devices and food poisoning and bacterium,
Demand of the people to novel antibacterial coating is increasingly increasing.Wherein, drinking water safety be in world wide one it is urgent and important
The problem of, especially in most of developing countries for lacking drinking water supply.In developing country due to containing in drinking water
Bacterium, the pathogenic microorganisms such as fungi have resulted in the disease of 80% water.For example, only in 2012, since drinking water is asked
Topic just has 1,500,000 people to die of diarrhoeal diseases related with pathogenic microorganisms.In addition, with industrialized fast development, environmental pollution
It is further exacerbated by water pollution, to be easier to infect waterborne disease.
The solar disinfection (SODIS) of drinking water is one of most important means of disinfection water in world wide.However,
SODIS depends primarily on ultraviolet light (only account for total solar spectrum energy 4%), this causes processing speed slow and time-consuming (exposure
Time 6-48 hour).Therefore, quickly, energy conservation, environmentally friendly, inexpensive processing route for effective and safe carries out water and disappears for exploitation
Poison is of great significance to visible light in capture solar energy to accelerate to purify water source.
Various antibacterial strategies, such as antibiotic filling structure, all there are many disadvantage and potential risks for silver-based system etc..Specifically
For, abuse of antibiotics will lead to the appearance of antibiotic resistant bacteria or even the appearance of superbacteria.In addition, silver-based system pair
Human health (i.e. argyrism) and environment have significant toxic effect, and silver natural abundance in the earth's crust is only
0.075ppm。
Phosphorus is rich content and widely distributed element in the earth, there is about 100,000,000,000 tons on earth.There are three by element P
Kind allotrope, including white phosphorus, black phosphorus and red phosphorus, wherein red phosphorus (amorphous state and crystalline state) has been used for the light under visible light
Catalysis produces hydrogen and decomposes water.Importantly, red phosphorus is nontoxic, it is relatively stable, economical and environmentally friendly.Fiber phase red phosphorus is direct band gap
Semiconductor, forbidden bandwidth 1.5eV, therefore there are huge applications potentiality in the photo-catalyst of Driven by Solar Energy.
Zinc oxide is the important semiconductor material of direct band gap (3.37eV) at room temperature, non-toxic because its is at low cost, in light
Catalytic field has obtained extensive research.However, the broad-band gap of ZnO limits it in the work of the visible light region of solar spectrum
Property.In addition, since the light induced electron of one-component optical catalyst and hole are easy to recombine, separation of charge efficiency is lower and charge
Quickly the compound photocatalysis efficiency for leading to ZnO is poor for carrier.
Summary of the invention
During this investigation it turned out, describing a kind of RP/ZnO hetero-junction thin-film absorption visible light so that water decomposition reaction be driven
Realize rapid photocatalytic water sterilization.At RP/ZnO heterojunction boundary, photoexcitation carrier transport process can be realized efficiently,
So the ROS (active oxygen) that visible light photocatalysis generates can be used for quickly killing bacterium (staphylococcus aureus and large intestine bar
Bacterium).
The purpose of the present invention is to solve above-mentioned technological deficiency and problem, a kind of antibacterial effect for providing is efficiently and wide spectrum
Rapid photocatalytic sterilization red phosphorus-ZnO heterojunction film preparation method, specifically comprise the following steps:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until surface is smooth, successively by polishing titanium sheet
It is placed in acetone, dehydrated alcohol and deionized water and is respectively cleaned by ultrasonic 15 minutes, spontaneously dry at room temperature, it is spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film,
And specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 9-15h, is slowly dropped to room temperature, is ground to after vacuum drying
100 microns of uniform powders below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas are first passed through with 1-10sccm rate, then 5-15
DEG C/min heating rate to 550-750 DEG C, keep the temperature 4-6h；
3) with 5-10 DEG C/min rate of temperature fall to 250-450 DEG C, then 1-3h is kept the temperature, is finally slowly dropped to room temperature.
Preferably, 1 described in step 2) red phosphorus powder pre-treating temperature be 200 DEG C, the processing time be 12h；
2 described in step 2) argon gas be passed through rate be 2sccm, heating rate be 10 DEG C/min, holding temperature be 650 DEG C,
Soaking time is 5h；
3 described in step 2) rate of temperature fall be 5 DEG C/min, holding temperature be 350 DEG C, soaking time 2h.
Step 3 prepares nano-ZnO thin film
One layer of uniform nanometer is plated with ALD (atomic layer deposition) in the substrate for being deposited with red phosphorus film that step 2 is obtained
ZnO film.
Preferably, the specific steps of step 3 are as follows: it is thin that nano-ZnO as zinc source and oxygen source is prepared with diethyl zinc and water
Film is 80-120 DEG C, deposition pressure 20-40Pa in depositing temperature, under conditions of deposition flow is 10-20sccm, with water vein
It rushes 0.1s, High Purity Nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s to be deposited as a circulation, recycle
Number is 200-400, and nano-ZnO thin film is obtained in substrate, i.e. Ti-RP/ZnO hetero-junction thin-film is successfully prepared.
Preferably, reactive deposition temperature is 100 DEG C in step 3, deposition pressure 40Pa, deposition flow are 20sccm, reaction
Cycle-index is 300.
Red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization, its advantage is that:
(1) can be visibly homogeneous using the film that the method for CVD plates one layer of fiber phase red phosphorus in substrate, while can pass through
Regulate and control the thickness of relevant parameter control red phosphorus.Compared to amorphous red phosphorus, fiber phase red phosphorus has better photocatalysis effect.It is fine
It is nontoxic to tie up phase red phosphorus, there is good biocompatibility.
(2) the thickness controllable precise for being plated one layer of nano-ZnO thin film in substrate using the method for ALD is resisted with excellent
Bacterium effect.The organic antibacterial agents such as antibiotic are compared to, nano-ZnO thin film has quick, wide spectrum under light illumination and efficiently resists
Bacterium property, and there is certain biocompatibility.
(3) preparation method is simple, and no toxic and harmful gas generates, economic and environment-friendly, prepares table using the technology of the present invention
Face has the zinc oxide heterogeneous junction thin film material of red phosphorus-of rapid photocatalytic sterilization, and enforcement difficulty is small, and equipment investment is few, consumption money
Source is few.
(4) red phosphorus-ZnO heterojunction film has wide spectrum and quick antibiotic property；Red phosphorus-ZnO heterojunction film
With preferable biocompatibility；So that the heterojunction type photocatalytic system of preparation can effectively improve photoexcited electron and hole
Separation, and significantly widen material in the visible absorption range of entire solar spectrum；Efficient light excitation on heterojunction boundary
Charge transport plays effect outstanding in terms of improving photocatalytic activity；Pass through hetero-junctions circle to heterojunction type photocatalytic system
Face regulates and controls to realize that high-efficiency solar decomposes water.
Detailed description of the invention
Following figures be using embodiment 2 as object, and control group be Ti-ZnO (be on pure titanium by ALD method acquisition
Zinc oxide nano film), the phenogram of progress；
Fig. 1 be in the step 2 of embodiment 2 the red phosphorus film that obtains and the fiber phase red phosphorus as control in transmission electricity
Crystal face comparison diagram under sub- microscope；
Fig. 2 is the Raman spectrogram in Fig. 1 product；
Fig. 3 is electron spin resonance (ESR) spectrum, illustrates Ti, Ti-RP, Ti-ZnO and Ti-RP/ZnO and shines in xenon lamp
Penetrate lower generation hydroxyl radical free radical (OH) and singlet oxygen (1O2) relative intensity；
Fig. 4, Fig. 5 are respectively that plate applies Butut, corresponding antibiotic rate calculating figure, illustrate 100mg L-1Amorphous red phosphorus exist
Without obvious antibiotic rate under the illumination of 20min or 10min；
Fig. 6, Fig. 7 be plate apply Butut, corresponding antibiotic rate calculating figure, show under sunlight and xenon lamp with
The antibiotic property (Escherichia coli: E.coli, staphylococcus aureus: S.aureus) of light application time Ti-RP/ZnO；
Fig. 8, Fig. 9 are that plate applies Butut, corresponding antibiotic rate calculating figure, show to irradiate in dark condition and xenon lamp
The lower antibiotic property of Ti-RP, Ti-ZnO and Ti-RP/ZnO compared to Ti.(Escherichia coli: E.coli, staphylococcus aureus:
S.aureus)
Figure 10, Figure 11 are cytotoxicity test, show that Ti-RP, Ti-ZnO and Ti-RP/ZnO are thin compared to Ti respectively
Born of the same parents' fluorescence and cell survival rate.
Specific embodiment:
To be best understood from the present invention, the present invention is done further be described in detail with reference to the accompanying drawings and examples, still
The scope of protection of present invention is not limited to the range of embodiment expression.
Embodiment 1:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until after surface is smooth, will polishing titanium sheet according to
Secondary be placed in acetone, dehydrated alcohol and deionized water is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film, specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 12h, is slowly dropped to room temperature, is ground to 100 after vacuum drying
Micron uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 2sccm rate, then 10 DEG C/
Min heating rate keeps the temperature 5h to 650 DEG C；
3) with 5 DEG C/min rate of temperature fall to 350 DEG C, then 2h is kept the temperature, is finally slowly dropped to room temperature.
Step 3 prepares nano-ZnO thin film
One layer of uniform nano-ZnO thin film is plated with ALD in the substrate for being deposited with red phosphorus film that step 2 is obtained.It has
Body step are as follows: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 100 DEG C in depositing temperature, deposition pressure
By force it is 40Pa, under conditions of deposition flow is 20sccm, 20s, diethyl zinc pulse is cleaned with aquapulse 0.1s, High Purity Nitrogen
0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, and cycle-index 200 obtains nano-ZnO thin film in substrate,
That is Ti-RP/ZnO hetero-junction thin-film is successfully prepared.
Embodiment 2:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until after surface is smooth, will polishing titanium sheet according to
Secondary be placed in acetone, dehydrated alcohol and deionized water is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film, specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 12h, is slowly dropped to room temperature, is ground to 100 after vacuum drying
Micron uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 2sccm rate, then 10 DEG C/
Min heating rate keeps the temperature 5h to 650 DEG C；
3) with 5 DEG C/min rate of temperature fall to 350 DEG C, then 2h is kept the temperature, is finally slowly dropped to room temperature.
Step 3 prepares nano-ZnO thin film
One layer of uniform nano-ZnO thin film is plated with ALD in the substrate for being deposited with red phosphorus film that step 2 is obtained.It has
Body step are as follows: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 100 DEG C in depositing temperature, deposition pressure
By force it is 40Pa, under conditions of deposition flow is 20sccm, 20s, diethyl zinc pulse is cleaned with aquapulse 0.1s, High Purity Nitrogen
0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, and cycle-index 300 obtains nano-ZnO thin film in substrate,
That is Ti-RP/ZnO hetero-junction thin-film is successfully prepared.
Embodiment 3:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until after surface is smooth, will polishing titanium sheet according to
Secondary be placed in acetone, dehydrated alcohol and deionized water is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film, specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 12h, is slowly dropped to room temperature, is ground to 100 after vacuum drying
Micron uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 2sccm rate, then 10 DEG C/
Min heating rate keeps the temperature 5h to 650 DEG C；
3) with 5 DEG C/min rate of temperature fall to 350 DEG C, then 2h is kept the temperature, is finally slowly dropped to room temperature.
Step 3 prepares nano-ZnO thin film
It is thin with ALD one layer of uniform nano-ZnO of plating in the substrate for being deposited with red phosphorus film that pure titanium or step 2 are obtained
Film.The specific steps are that: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 100 in depositing temperature
DEG C, deposition pressure 40Pa under conditions of deposition flow is 20sccm, cleans 20s, diethyl with aquapulse 0.1s, High Purity Nitrogen
Zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, and cycle-index 400 obtains nanometer in substrate
ZnO film, i.e. Ti-RP/ZnO hetero-junction thin-film are successfully prepared.
Embodiment 4:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until after surface is smooth, will polishing titanium sheet according to
Secondary be placed in acetone, dehydrated alcohol and deionized water is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film, specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 12h, is slowly dropped to room temperature, is ground to 100 after vacuum drying
Micron uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 2sccm rate, then 10 DEG C/
Min heating rate keeps the temperature 5h to 650 DEG C；
3) with 5 DEG C/min rate of temperature fall to 350 DEG C, then 1h is kept the temperature, is finally slowly dropped to room temperature.
Step 3 prepares nano-ZnO thin film
It is thin with ALD one layer of uniform nano-ZnO of plating in the substrate for being deposited with red phosphorus film that pure titanium or step 2 are obtained
Film.The specific steps are that: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 100 in depositing temperature
DEG C, deposition pressure 40Pa under conditions of deposition flow is 20sccm, cleans 20s, diethyl with aquapulse 0.1s, High Purity Nitrogen
Zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, and cycle-index 300 obtains nanometer in substrate
ZnO film, i.e. Ti-RP/ZnO hetero-junction thin-film are successfully prepared.
Embodiment 5:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until after surface is smooth, will polishing titanium sheet according to
Secondary be placed in acetone, dehydrated alcohol and deionized water is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus as substrate, using chemical vapor deposition (CVD)
Film, specific steps are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 12h, is slowly dropped to room temperature, is ground to 100 after vacuum drying
Micron uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 2sccm rate, then 10 DEG C/
Min heating rate keeps the temperature 5h to 650 DEG C；
3) with 5 DEG C/min rate of temperature fall to 350 DEG C, then 3h is kept the temperature, is finally slowly dropped to room temperature.
Step 3 prepares nano-ZnO thin film
It is thin with ALD one layer of uniform nano-ZnO of plating in the substrate for being deposited with red phosphorus film that pure titanium or step 2 are obtained
Film.The specific steps are that: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 100 in depositing temperature
DEG C, deposition pressure 40Pa under conditions of deposition flow is 20sccm, cleans 20s, diethyl with aquapulse 0.1s, High Purity Nitrogen
Zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, and cycle-index 300 obtains nanometer in substrate
ZnO film, i.e. Ti-RP/ZnO hetero-junction thin-film are successfully prepared.
In following table, the thickness of product is corresponded to for embodiment one step 2 or step 3 into embodiment five, wherein CVD is protected
The warm time refers in step 2 soaking time described in 3)；
It is summarized for the parameter of different case study on implementation:
As seen from the above table, ALD cycle number is adjusted and can control the corresponding thickness of ZnO film, and CVD is kept the temperature
Time, which is adjusted, can control the corresponding thickness of RP (red phosphorus) film.
The following are the corresponding Analysis of test results of embodiment 2: (wherein, plating one layer of uniform nanometer with ALD on pure titanium
ZnO film, to obtain Ti-ZnO, as a control group)
In example 2, the red phosphorus film (Ti- obtained in titanium substrate by the titanium (Ti) that is obtained to step 1, step 2
RP), the zinc oxide nano that control group zinc oxide nano film (Ti-ZnO) and step 3 obtain in the substrate for being deposited with red phosphorus film
Rice film (Ti-RP/ZnO) these four samples have carried out a series of characterizations.
As shown in Figure 1, being detected by high resolution transmission electron microscopy (HRTEM), it is shown that the interplanar of red phosphorus film
Away from for(001) crystal face corresponding to fiber phase red phosphorus.Meanwhile Fig. 2 is Raman spectrum, and it is thin to further demonstrate red phosphorus
Successful synthesis of the film in titanium substrate.
If Fig. 3 shows electron spin resonance (ESR) spectrum, illustrates Ti, Ti-RP, Ti-ZnO and Ti-RP/ZnO and exist
Xenon lamp irradiation is lower generate hydroxyl radical free radical (OH) and singlet oxygen (1O2) relative intensity.It is compared with Ti, Ti-RP and Ti-
ZnO can generate more OH and1O2, illustrate that red phosphorus film and nano-ZnO thin film have certain photocatalysis effect.In addition,
Ti-RP/ZnO can generate most OH and1O2, hence it is evident that higher than the intensity of Ti-RP and Ti-ZnO, show that red phosphorus-is zinc oxide heterogeneous
Knot film has the effect of Photocatalytic enhancement.
Fig. 4, Fig. 5 are respectively that plate applies Butut and corresponding antibiotic rate calculating figure, illustrate 100mg L-1It is amorphous red
Phosphorus (compares blank group, antimicrobial efficiency is less than 8%) without obvious antibiotic rate under the illumination of 20min or 10min.
Fig. 6, Fig. 7 are respectively that plate applies Butut and corresponding antibiotic rate calculating figure, it is known that Ti-RP/ZnO is in sunlight and xenon
As light application time antibiotic property is continuously increased under light lamp, and Ti-RP/ZnO obviously compares S.auerus to the antibacterial effect of E.coli
It is good.When using fluorescent lamp, 99.92 ± 0.02% are reached to 15 minutes antibiotic rates of S.auerus illumination, to E.coli illumination 7
Minute antibiotic rate reaches 99.86 ± 0.10%.When using fluorescent lamp, 20 minutes antibiotic rates of S.auerus illumination are reached
99.63 ± 0.24%, 99.72 ± 0.12% are reached to 10 minutes antibiotic rates of E.coli illumination.The result shows that fiber phase red phosphorus ratio
Amorphous red phosphorus has better antibacterial effect.In addition, Ti-RP/ZnO has very S.auerus and E.coli in a short time
Good photo-catalyst effect and broad-spectrum sterilization.
Fig. 8, Fig. 9 are respectively that plate applies Butut and corresponding antibiotic rate calculating figure, show to shine in dark condition and xenon lamp
Penetrate the antibiotic property of lower Ti-RP, Ti-ZnO and Ti-RP/ZnO compared to Ti.Figure is seen it is found that under dark condition, Ti-RP, Ti-
ZnO and Ti-RP/ZnO is substantially without antibacterial effect, and when xenon lamp irradiation, and Ti-RP/ZnO is (to S.auerus antibiotic rate 99.63
± 0.24% and to E.coli antibiotic rate 99.72 ± 0.12) antibiotic rate much larger than Ti-RP (to S.auerus antibiotic rate 35.12 ±
3.30% and to E.coli antibiotic rate 34.92 ± 4.50%) and Ti-ZnO (to 43.32 ± 2.10% He of S.auerus antibiotic rate
To E.coli antibiotic rate 51.14 ± 3.55%), wherein error bar indicates average value ± standard deviation: P < 0.001 * * * (t inspection
It tests).These results further demonstrate the effect that red phosphorus-ZnO heterojunction film has photocatalytic to enhance, and produce more
More active oxygens carry out quick sterilization.
As shown in Figure 10, cytotoxicity test is characterized by cell fluorescence and cell survival rate.Cell fluorescence is shown carefully
Born of the same parents, which have, preferably sprawls and presents polygon (scale be 50 μm), reflects Ti, and tetra- kinds of Ti-RP, Ti-ZnO and Ti-RP/ZnO
Material does not have apparent cytotoxicity.
In addition, Figure 11 shows that Ti-RP has best cell survival rate in cell survival rate detection, and reached maximum at 1 day
It is worth (138.36%), and Ti-ZnO shows maximum toxicity, and reaches maximum value (58.53%) at 7 days.But on the whole,
Ti-RP, Ti-ZnO and Ti-RP/ZnO without apparent cytotoxicity, have preferable biocompatibility.
Each examination functional verification step being above not described in detail is obtained using usual manner (for example, Fig. 1 to Figure 11
And the acquisition of parameter conclusive table, it is that usual manner obtains, therefore, its process is not described in detail).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization, which is characterized in that including walking as follows
It is rapid:
Step 1, titanium sheet mechanical polishing processing
Successively titanium sheet is polished with 240 and 800 mesh diamond dust on polishing machine, until surface is smooth, polishing titanium sheet is sequentially placed into
Respectively it is cleaned by ultrasonic in acetone, dehydrated alcohol and deionized water 15 minutes, spontaneously dries at room temperature, it is spare；
Step 2 prepares red phosphorus film
The polishing titanium sheet that step 1 is obtained plates one layer of uniform red phosphorus film, tool as substrate, using chemical vapour deposition technique
Body step are as follows:
1) red phosphorus powder is placed at 200 DEG C, hydro-thermal process 9-15h, is slowly dropped to room temperature, it is micro- to be ground to 100 after vacuum drying
Rice uniform powder below；
2) pretreated red phosphorus and titanium sheet are placed in CVD stove, argon gas is first passed through with 1-10sccm rate, then 5-15 DEG C/
Min heating rate keeps the temperature 4-6h to 550-750 DEG C；
3) with 5-10 DEG C/min rate of temperature fall to 250-450 DEG C, then 1-3h is kept the temperature, is finally slowly dropped to room temperature；
Step 3 prepares nano-ZnO thin film
One layer of uniform nano-ZnO thin film is plated with ALD in the substrate for being deposited with red phosphorus film that step 2 is obtained, it is red to obtain
Phosphorus-ZnO heterojunction film.
2. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization according to claim 1, special
Sign is, described in step 2 1) in pretreatment time be 12h.
3. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization according to claim 1, special
Sign is that described in step 2 2), it is 2sccm that argon gas, which is passed through rate, and heating rate is 10 DEG C/min, and holding temperature is 650 DEG C, protects
The warm time is 5h.
4. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization according to claim 1, special
Sign is that described in step 2 3), rate of temperature fall is 5 DEG C/min, and holding temperature is 350 DEG C, soaking time 2h.
5. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization according to claim 1, special
Sign is,
Specific steps are as follows: nano-ZnO thin film is prepared as zinc source and oxygen source with diethyl zinc and water, is 80-120 in depositing temperature
DEG C, deposition pressure 20-40Pa, deposition flow be 10-20sccm under conditions of, with aquapulse 0.1s, High Purity Nitrogen cleaning 20s,
Diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited as a circulation, cycle-index 200-400, in substrate
Obtain nano-ZnO thin film.
6. red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization according to claim 5, special
Sign is that reactive deposition temperature described in step 3 is 100 DEG C, deposition pressure 40Pa, deposition flow are 20sccm, reaction cycle
Number is 300.
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| CN111170292A (en) * | 2019-11-04 | 2020-05-19 | 湖北大学 | Preparation method and application of fiber-phase red phosphorus nanoparticles |
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