CN103638960A - Polymer photocatalyst as well as preparation method and application thereof - Google Patents
Polymer photocatalyst as well as preparation method and application thereof Download PDFInfo
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- CN103638960A CN103638960A CN201310698321.9A CN201310698321A CN103638960A CN 103638960 A CN103638960 A CN 103638960A CN 201310698321 A CN201310698321 A CN 201310698321A CN 103638960 A CN103638960 A CN 103638960A
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- photochemical catalyst
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Abstract
The invention discloses a polymer photocatalyst as well as a preparation method and an application thereof. The preparation method comprises the following steps of firstly preparing an organic polymer carbon nitride catalyst, and using the organic polymer carbon nitride catalyst to kill bacteria in a water phase. Compared with the conventional ultraviolet light catalyst TiO2, a visible-light-driven photocatalyst TiO2-xNx, metal nitrides, metal nitric oxides and the like, the carbon nitride catalyst is more efficient and stable, the preparation method of the carbon nitride catalyst is simple and is easy to implement, the carbon nitride catalyst does not contain any metal elements and is a cheap catalyst, by-products such as the chlorine-containing compound in a sterilization process are not generated, and the polymer photocatalyst is beneficial to large-scale application in industrial sterilization.
Description
Technical field
The invention belongs to surround lighting catalytic field, be specifically related to the method for kill bacteria in a kind of polymer photochemical catalyst preparation and water thereof.
Background technology
The morbid substance containing in water produces serious harm to human body, particularly from the pathogenic microorganisms in water as bacterium, virus etc.According to the report of the World Health Organization, there is every year the people over 3,400,000 to die from the relevant disease that water body carries, become one of sick and dead first cause of the mankind.Although current various chemical oxidizing agent such as chlorine, chlorine dioxide, chloramines etc. for sterilization, and can effectively be removed the germ in water in water treatment, these methods face produces some carcinogenic oxidized byproducts as chloroform; Physical method, as ultraviolet disinfection is also employed and water treatment sterilization, is still only used ultraviolet disinfection can not kill some uvioresistant bacteriums in water in addition.The limitation of these methods, makes researcher need to develop the method for more efficient, healthy water sterilization.
1985, Matsunaga report photocatalysis technology can effectively kill the bacterium in water, and a new sterilizing approach has been started in this discovery.Compare with traditional sterilizing methods, photocatalysis sterilization has the features such as economy, efficient, strong oxidizing property, and the organic pollution in can oxidize water in sterilizing, has therefore attracted numerous researchers to launch further investigation.Mostly early stage photocatalysis sterilization technology is to launch around titanium dioxide and modified product thereof, yet because titanium dioxide can only utilize in solar energy the energy less than 4%, sterilization process quantum efficiency is not high, these have limited the large-scale promotion application of photocatalysis sterilization technology, in addition some non-titania-based photochemical catalysts are as ZnO, AgBr-Ag-Bi
2wO
6, CdIn
2o
4deng being also applied to photocatalysis sterilization field, however these catalyst exist and contain the shortcomings such as heavy metal, catalytic performance be unstable, limited their large-scale promotion application.Therefore exploitation energy responding to visible light, efficient, cheap, nontoxic and stable photochemical catalyst are still the cores in photocatalysis sterilization field.
In recent years, the friendly type of a kind of nonmetal environment photochemical catalyst---graphite-phase carbonitride enjoys the extensive concern of domestic and international scientists, it is at photolysis water hydrogen (Nat. Mater. 2009,8,76), light degradation organic pollution (Adv. Mater. 2009,21,1609) become (J. Am. Chem. Soc. 2010 with organic photosynthetic, 132,16299) etc. aspect has a wide range of applications, yet does not receive publicity as its sterilization ability of a kind of photochemical catalyst.Therefore, we are applied to photocatalysis by this polymer semiconductor and kill disease caused by infectious water bacterium, experiment showed, that this novel polymer semiconductor has very high sterilizing activity and stability.
Summary of the invention
The object of the present invention is to provide a kind of polymer photochemical catalyst and its preparation method and application, for conventional TiO
2catalyst is low in the efficiency of water sterilizing, the shortcomings such as solar energy utilization ratio is low, selected cheap and there is visible light-responded polymer photochemical catalyst carbonitride, its suitable position of energy band makes it to improve significantly the utilization rate of solar energy, photochemical catalyst prepared by the present invention has high-specific surface area, can kill efficiently and stably the bacterium in water.Technique of the present invention is simple, and cost is low, and productive rate is high, and realistic need of production has larger application potential.
For achieving the above object, the present invention adopts following technical scheme:
Polymer photochemical catalyst is a macromolecule organic polymer semiconducting nitride C catalyst, and chemical formula is CN
xh
y, 0.67 < x< 0.7,0.45 < y< 0.55 wherein.
The method of preparing polymer photochemical catalyst as above is that take containing cyanamide, cyanamid dimerization or melamine is raw material, use thermal copolymerization method, in different atmosphere, prepare body phase carbon nitride, or introduce again the carbonitride that silica nanosphere is the synthesising mesoporous structure of template.
The preparation process of described body phase carbon nitride comprises: predecessor is from normal temperature process constant heating rates sintering 4 hours to 550 ℃ in the Muffle furnace of nitrogen atmosphere, and then constant temperature 4 h at 550 ℃, naturally cool to room temperature, obtain body phase carbon nitride CN
xh
y; Described predecessor is cyanamide, cyanamid dimerization or melamine.The specific area of synthetic body phase carbon nitride is 12 m
2/ g.
The preparation process of the carbonitride of described meso-hole structure comprises: 5 g cyanamides or cyanamid dimerization are dissolved in 12.5 g Ludox (volume content is 40%, the silica of 12 nm) in the aqueous solution, be stirred to cyanamide or cyanamid dimerization all dissolves, then 80-100 ℃ of oil bath, be stirred to dry, obtain white powder, in blanket of nitrogen, in 550 ℃ of insulation 4 h, heating-up time is 4 h, obtain yellow powder, join in 4 mol/L HF solution and stir 24 h, filter, washing, stir again 12 h, filter, washing, ethanol is washed, 60 ℃ of vacuum drying ovens are dry, obtain the carbonitride JK-CN of meso-hole structure
xh
y.The specific area of the carbonitride of meso-hole structure is 100～230 m
2/ g, and the abundant amino functional group that not yet participates in polymerisation is contained on surface.
The evaluation method of polymer photochemical catalyst water photo-catalyst efficiency as above comprises the steps: in the aqueous solution that contains finite concentration bacterium, adds polymer photochemical catalyst CN
xh
y, at room temperature in daylight, reaction time 4～8 h, reaction finishes the rear dull and stereotyped situation of killing that counting method detects bacterium in water of cultivating of using, and wherein said light source is sunshine or artificial light source, and wherein the illumination wavelength of artificial light source is 400～800 nm.
Remarkable advantage of the present invention is:
(1) the present invention is applied to photocatalysis sterilization field by macromolecule organic polymer semiconducting nitride carbon first, has large specific area, and photo-generated carrier can be effectively separated, is a kind of novel photocatalysis sterilization catalyst.
(2) whole technical process of the present invention is simple and easy to control, and energy consumption is low, and productive rate is high, and cost is low, and realistic need of production is conducive to large-scale popularization.
(3) carbonitride that the present invention uses can be killed the bacterium in water efficiently, has good activity stability simultaneously.In light-catalyzed reaction system, can carry out easily separating treatment, recycling rate of waterused is high, has very high practical value and application prospect widely.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the mesoporous carbonitride of macromolecule organic polymer semiconductor of embodiment 5,6.
Fig. 2 is the N of the mesoporous carbonitride of macromolecule organic polymer semiconductor of embodiment 5,6
2adsorption-desorption isothermal curve figure.
Fig. 3 be embodiment 5,6 the mesoporous carbonitride of macromolecule organic polymer semiconductor ultraviolet-spectrogram diffuses.
The specific embodiment
In a kind of polymer photochemical catalyst preparation of the present invention and water thereof, the method for kill bacteria comprises the steps: that 50 mg～200 mg carbonitrides or other metal oxide, metal oxynitride are catalyst, catalyst is joined in 50～200 mL reactant liquors that contain germ, reaction temperature is room temperature, open light source, reaction time 1～10 h.After reaction finishes, adopt the effect of colony counting method evaluate catalysts photocatalysis sterilization: the reactant liquor of drawing 0.1 mL, after suitably diluting, make the germ in water fully be dispersed into individual cells, getting a certain amount of diluted sample liquid is applied on flat board, through cultivating, by each unicellular growth and breeding, form macroscopic bacterium colony, statistics clump count, according to its extension rate and sampling inoculum concentration can converse in sample containing bacterium number, the result of measuring with have neither part nor lot in bacterial population contrast in the stoste of light-catalyzed reaction, determine the effect of photochemical catalyst sterilization.
Be below several embodiments of the present invention, further illustrate the present invention, but the present invention is not limited only to this.
embodiment 1
First take the TiO of 100 mg metal oxide-type
2catalyst is distributed to 100 mL and contains (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, opens visible light source (λ >400 nm), and the reaction time is 4 h, adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 1.
embodiment 2
First take the TiO of 100 mg metal nitrogen oxygen thing classes
2-xn
xcatalyst is distributed to 100 mL and contains (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, opens visible light source (λ >400 nm), and the reaction time is 4 h, adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 1.
embodiment 3
First taking body phase carbon nitride catalyst prepared by 100 mg melamines is distributed to and contains 100 mL and contain (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, opens visible light source (λ >400 nm), and the reaction time is 4 h, adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 1.
embodiment 4
First taking mesoporous carbonitride catalyst prepared by 100 mg cyanamid dimerizations is distributed to and contains 100 mL and contain (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, opens visible light source (λ >400 nm), and the reaction time is 4 h, adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 1.
embodiment 5
First taking mesoporous carbonitride catalyst prepared by 100 mg cyanamides is distributed to and contains 100 mL and contain (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, opens visible light source (λ >400 nm), and the reaction time is 4 h, adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 1.
In table 1, sterilizing is calculated with following formula:
Sterilization rate (%)=(C
o-C
t)/C
o* 100%
C in formula
ofor the initial concentration of Escherichia coli (E. Coli K-12), C
tfor light-catalyzed reaction colibacillary concentration after 4 hours.
embodiment 6
First taking mesoporous carbonitride catalyst prepared by 100 mg cyanamides is distributed to and contains 100 mL and contain (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), controlling reaction temperature is 25 ℃, open visible light source (λ >400 nm), react after 4 hours, by the catalyst centrifugation in reactant liquor and spend ion-cleaning clean after, be re-dispersed into and contain 100 mL and contain (E. Coli K-12, concentration 2.5 * 10 in the colibacillary physiological saline aqueous solution
6cfu/mL), so circulate five times, each result all adopts colony counting method to analyze the effect of photocatalysis sterilization, the results are shown in Table 2.
Fig. 1 is the XRD collection of illustrative plates of the mesoporous carbonitride of embodiment 5,6 macromolecule organic polymer semiconductor.As can be seen from Figure 1 carbonitride occurs that at 13.0o and 27.4o place two obvious diffraction maximums correspond respectively to (002) and (100) crystal face of graphite-phase carbonitride.
Fig. 2 is the N of the mesoporous carbonitride of embodiment 5,6 macromolecule organic polymer semiconductor
2adsorption-desorption isothermal curve figure.As can be seen from Figure 2 synthetic carbonitride, isothermal adsorption curve belongs to IV class, belongs to the indicatrix of mesoporous material, illustrates that macromolecule organic polymer semiconductor has meso-hole structure.
Fig. 3 is embodiment 5, the uv drs collection of illustrative plates of the mesoporous carbonitride of 6 macromolecule organic polymer semiconductor, as can be seen from Figure 3 carbonitride has obvious and precipitous absorption band edge in 465 nm left and right, corresponding energy gap is 2.7 eV, and the mesoporous carbonitride energy of this organic polymer semiconductor responding to visible light is described.
The visible light catalytic sterilizing activity comparison of table 1 different catalysts
Note: JK-CN
xh
y ato take the mesoporous carbonitride that cyanamid dimerization prepared as predecessor; JK-CN
xh
y bto take the mesoporous carbonitride that cyanamide prepared as predecessor
Table 1 is embodiment 1, and embodiment 2, and embodiment 3, and embodiment 4, and in embodiment 5, different photochemical catalysts are in the active result comparison of kill bacteria.By table 1 result, shown and can be found out: with other metal oxide, metal oxynitride is compared, carbonitride and mesoporous carbonitride demonstrate higher photocatalysis sterilization efficiency under visible ray shines.
The mesoporous carbonitride of table 2 repeatedly recycles circulation sterilizing
Table 2 is embodiment 6, the sterilizing activity that the mesoporous carbonitride of preparing for predecessor for use cyanamide is repeatedly recycling.Under visible ray shines, carbonitride can also effectively be killed the bacterium in water after using repeatedly, illustrates that carbonitride has higher activity stability in photocatalysis sterilization process.Trace active in 3-5 round reduces, and is attributable to, in centrifugal collection carbonitride process, to have lost a small amount of carbonitride photochemical catalyst.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. a polymer photochemical catalyst, is characterized in that: described photochemical catalyst is macromolecule organic polymer semiconducting nitride C catalyst.
2. polymer photochemical catalyst according to claim 1, is characterized in that: the chemical formula of described photochemical catalyst is CN
xh
y, 0.67 < x< 0.7,0.45 < y< 0.55 wherein.
3. a method of preparing polymer photochemical catalyst as claimed in claim 1, is characterized in that: take cyanamide, cyanamid dimerization or melamine as raw material, use thermal copolymerization method, in different atmosphere, prepare body phase carbon nitride.
4. the preparation method of polymer photochemical catalyst according to claim 3, it is characterized in that: cyanamide, cyanamid dimerization or melamine are passed through to constant heating rates sintering 4 hours to 550 ℃ from room temperature in the Muffle furnace of nitrogen atmosphere, then constant temperature 4 h at 550 ℃, naturally cool to room temperature, obtain body phase carbon nitride CN
xh
y.
5. the preparation method of polymer photochemical catalyst according to claim 4, is characterized in that: the specific area of synthetic body phase carbon nitride is 12 m
2/ g.
6. a method of preparing polymer photochemical catalyst as claimed in claim 1, it is characterized in that: take cyanamide, cyanamid dimerization or melamine as raw material, using thermal copolymerization method, in different atmosphere, is the carbonitride of the synthesising mesoporous structure of template by introducing silica nanosphere.
7. the preparation method of polymer photochemical catalyst according to claim 6, it is characterized in that: 5 g cyanamides or cyanamid dimerization are dissolved in to 12.5 g Ludox, be stirred to cyanamide or cyanamid dimerization all dissolves, then 80-100 ℃ of oil bath, be stirred to dry, the white powder obtaining is in nitrogen atmosphere Muffle furnace, constant heating rates sintering 4 hours to 550 ℃, and in 550 ℃ of insulation 4 h, obtain yellow powder, join in 4 mol/L HF solution and stir 24 h, filter, washing, stir again 12 h, filter, washing, ethanol is washed, 60 ℃ of vacuum drying ovens are dry, obtain the carbonitride JK-CN of meso-hole structure
xh
y.
8. the preparation method of polymer photochemical catalyst according to claim 7, is characterized in that: the specific area of the carbonitride of meso-hole structure is 100～230 m
2/ g, and the abundant amino functional group that not yet participates in polymerisation is contained on surface.
9. an application for polymer photochemical catalyst as claimed in claim 1, is characterized in that: containing in the germy aqueous solution, add photochemical catalyst CN
xh
y, at room temperature in daylight, reaction time 1～10 h.
10. the application of polymer photochemical catalyst according to claim 9, is characterized in that: described illumination light source is sunshine or artificial light source, and wherein the illumination wavelength of artificial light source is 400～800 nm.
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| CN104311864A (en) * | 2014-10-16 | 2015-01-28 | 扬州喜达屋环保科技有限公司 | High-efficiency visible light antibacterial fresh-keeping plastic packaging material and preparation method thereof |
| CN104722325A (en) * | 2015-02-27 | 2015-06-24 | 清华大学 | Three-dimensional macro-scale porous graphite phase carbon nitride photocatalyst and preparation and application of photocatalyst |
| CN109794277A (en) * | 2019-01-30 | 2019-05-24 | 扬州工业职业技术学院 | A kind of ceria/graphite phase carbon nitride composite material and its application in photocatalysis |
| WO2020010749A1 (en) * | 2018-07-09 | 2020-01-16 | 华南理工大学 | Modified carbon nitride photocatalyst and preparation method therefor, and method for synthesizing xylosic acid by photocatalytic oxidation of xylose |
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| JP2012200698A (en) * | 2011-03-28 | 2012-10-22 | Daicel Corp | Photocatalyst and oxidation method for organic compound using the same |
| CN103127948A (en) * | 2013-02-26 | 2013-06-05 | 福州大学 | Polymer photocatalyst, and method of water-phase photo-catalytic selective alcohol oxidation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311864A (en) * | 2014-10-16 | 2015-01-28 | 扬州喜达屋环保科技有限公司 | High-efficiency visible light antibacterial fresh-keeping plastic packaging material and preparation method thereof |
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| WO2020010749A1 (en) * | 2018-07-09 | 2020-01-16 | 华南理工大学 | Modified carbon nitride photocatalyst and preparation method therefor, and method for synthesizing xylosic acid by photocatalytic oxidation of xylose |
| CN109794277A (en) * | 2019-01-30 | 2019-05-24 | 扬州工业职业技术学院 | A kind of ceria/graphite phase carbon nitride composite material and its application in photocatalysis |
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