CN103521224A - Nano-composite photocatalyst material and preparation method thereof - Google Patents
Nano-composite photocatalyst material and preparation method thereof Download PDFInfo
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- CN103521224A CN103521224A CN201310496092.2A CN201310496092A CN103521224A CN 103521224 A CN103521224 A CN 103521224A CN 201310496092 A CN201310496092 A CN 201310496092A CN 103521224 A CN103521224 A CN 103521224A
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Abstract
The invention relates to an all-weather nano-composite photocatalyst material with photocatalysis memory effect based on electron capture and storage and a preparation method thereof. The nano-composite photocatalyst material takes a semiconductor nanomaterial with sunlight response as a matrix, a modification substance is a nano-structure with valence variation property in photoproduction electron flow direction, so as to realize capturing and storing the electron to obtain the all-weather nano-composite photocatalyst material with photocatalysis memory effect. The nano-composite photocatalyst material can be directly used for solving problems of decomposition of organic substance under sunlight, inactivation of microorganism pathogene and efficient utilization of solar energy; due to the 'photocatalysis memory effect' induced in material design, the photocatalyst still retains certain activity after illumination is off, so that all-weather photocatalysis is realized, and the problem that the photocatalysis material has no activity after illumination is off is solved.
Description
Technical field
The invention belongs to inorganic nonmetallic nanometer material preparation, environmental protection technology and technical field of solar utilization technique, relate in particular to a kind of round-the-clock nano composite photo-catalyst material with " photocatalysis memory effect " based on electron capture and storage and preparation method thereof.This nano composite photo-catalyst material can be directly used in the problem that solves organic decomposition and the deactivation of microbial pathogens and the efficient utilization of solar energy under sunshine, especially, " the photocatalysis memory effect " introduced by design of material, make this material after illumination is closed, still retain certain activity, realize round-the-clock photocatalysis, solved catalysis material deactivated difficult problem after illumination is closed.
Background technology
Since titanium dioxide in 1972 be found under the effect of ultraviolet light can decomposition water since, semi-conducting material is widely used as photochemical catalyst aspect environment remediation.Photocatalytic semiconductor material is under the exciting of the light of certain wavelength, produce electronics-hole pair, catch catalyzed dose of surperficial material in electronics-hole, reaction produces active specy, these active species have very high oxidation-reduction quality, can further react with the organic pollution in environment, mineralising is carbon dioxide and inorganic ions.The right effective separation in electronics-hole wherein producing is considered to restrict a committed step of photochemical catalyst effect, if electronics-hole to the separation that can not be hunted down in time, will occur compound and emit heat, reduces the quantum efficiency of photochemical catalyst.
In addition, light-catalyzed reaction can only be carried out operation having under the condition of light, and this feature is also seriously restricting development and the industrialization of photocatalysis technology.
For a long time, photoelectronic catching is considered to reduce semiconductor electronic and hole to compound main cause.Therefore, by compound means, building nano composite photo-catalyst material, from structure, match guiding, realize catching and storing of electronics with being with, is the important directions that photocatalysis technology is studied.
Summary of the invention
The object of the present invention is to provide a kind of round-the-clock nano composite photo-catalyst material and preparation and application with " photocatalysis memory effect " based on electron capture and storage.This material is the nanostructured that is modified to electron stream to side and has the character of appraising at the current rate on the semiconductor nano material matrix with sunshine response, to realize catching and storing of electronics.This nano composite photo-catalyst material has illumination memory effect, and catalysis material, after illumination, even if light extinguished after a few hours, still shows obvious photocatalytic effect, thereby obtains the nano composite photo-catalyst material of the row of holding concurrently round the clock.This nano composite photo-catalyst material can be directly used in the deactivation of organic degraded and microbial pathogens under sunshine, especially, this nano composite photo-catalyst material with " photocatalysis memory effect " still retains certain activity after illumination is closed, realize round-the-clock photocatalysis, solved catalysis material deactivated difficult problem after illumination is closed.
technical scheme of the present invention is:
A kind of nano composite photo-catalyst material and preparation method thereof, this composite photo-catalyst for have on the semiconductor nano material matrix of sunshine response, modify light induced electron can the side of flow direction and there is the nanostructured of the character of appraising at the current rate, to realize catching and storing of electronics, thereby obtain the round-the-clock nano composite photo-catalyst material with " photocatalysis photocatalysis memory effect ".
In described nano composite photo-catalyst material, matrix is the semiconductor nano material that has sunshine response, specifically refer to: the wide bandgap semiconductor nano material with ultraviolet light response, there is visible light-responded low-gap semiconductor material, there is semiconductor nano material and the doped semiconductor nanocrystal material of sunshine local spectra and full spectrum response.
In described nano composite photo-catalyst material, trim is light induced electron flow direction side, and there is the nanostructured of the character of appraising at the current rate, specifically refer to: can, as matrix material electron stream to square semiconductor nano material, comprise conductor oxidate, chalcogenide semiconductor compound, doped semiconductor oxide, doped semiconductor sulfide, titanate, bismuthates; Can, as the metal nano material of the matrix material light induced electron side of flow direction, comprise noble metal, transition metal and multi-element metal compound.
The matrix of described nano composite photo-catalyst material and the complex method of trim can be both orderly, can be also unordered.
Described nano composite photo-catalyst material can be directly used in the deactivation of organic degraded and microbial pathogens under sunshine, especially, this nano composite photo-catalyst material with " photocatalysis memory effect " still retains certain activity after illumination is closed, realize round-the-clock photocatalysis, solved catalysis material deactivated difficult problem after illumination is closed.
Described nano composite photo-catalyst material, after illumination, by appraising at the current rate of element in trim, has been realized the storage of electronics, and then has realized all weather operations of photochemical catalyst.
Described composite photo-catalyst, concrete preparation process is as follows,
Cuprous oxide-titanic oxide nano compound photocatalyst material of take is example:
1. preparation dispersiveness is semiconductor substrate cuprous oxide preferably, first, and by 0.2 g polyethylene glycol (molecular weight is 10000), 0.5～1.0 mmol CuSO
45H
2o is dissolved in 100～200 mL deionized waters, then, under the effect of magnetic agitation, by the sodium hydrate aqueous solution of 40 g/L of 1.8～3.6 mL, with the speed of one per second, be added drop-wise in above-mentioned solution, stir 5 min, subsequently the 88 g/L aqueous ascorbic acids of 1.8～3.6 mL are added drop-wise in above-mentioned solution with the three seconds speed of one, stir 5 min;
2. by obtaining cuprous oxide powder in step 1, with deionized water and absolute ethyl alcohol, alternately wash 5 times, the cuprous oxide powder having washed is distributed in 10 mL absolute ethyl alcohols, ultrasonic dispersion 10 min, are designated as solution A.
3. titanium tetrafluoride is mixed with to the aqueous solution B of 2.5 g/L, in the effect of magnetic agitation, the B solution of 1.2～2.4 mL is added drop-wise in A solution, stir 1 h.
4. the suspension obtaining in step 3 is diluted to 32 mL by deionized water, drips the aqueous ascorbic acid of 0.2 mL, transfer to subsequently in 50 mL teflon-lined stainless steel autoclaves, Water Under heat 0.5 h of 180～220 ℃.
5. by the suspension centrifugation of hydro-thermal gained, the material of gathering in the crops with deionized water and absolute ethanol washing 5 times.Finally be placed in vacuum tank at 50～70 ℃ dry 10 h.
" photocatalysis memory effect " to kill colibacillary specific experiment step as follows:
First, take material 10 mg of synthesized, be dispersed in the culture dish that is of a size of 50 * 10 mm, being placed in wavelength is 400～700 nm, strong approximately 23 mW/cm
2visible ray under irradiate 3 h more than; Then, close after light source material is placed respectively to 0 h, 8h in the dark in advance, then moving into 10 mL concentration is 10
7the colibacillary buffer solution of cfu/mL, in above-mentioned culture dish, carries out sterilization experiment under dark condition, every 20 min samplings, dilution, painting flat board, then at 37 ℃, cultivates 24 h, and number goes out obtained bacterium colony number.
The business titanium dioxide P25 of take is matrix, and the preparation process of the composite photo-catalyst of surface finish nano metallic (gold, silver, palladium, copper etc.) is as follows:
1. take in the ultrasonic quartz ampoule that is dispersed in the absolute ethyl alcohol that 100 mL are housed of 0.1 g business titanium dioxide P25, a certain amount of slaine, obtain suspension A.
By suspension A under the effect of magnetic agitation, first pass into nitrogen 30 min, with being placed under the uviol lamp that wavelength is 365 nm, in the time of illumination, continue to pass into nitrogen, time remaining 2～3 h.
Reacted suspension is centrifugal 3., with alcohol washing 3 times, be finally placed in vacuum tank at 60 ℃ dry 10 h.
" photocatalysis memory effect " to kill colibacillary specific experiment step as follows:
First, take material 10 mg of synthesized, be dispersed in the culture dish that is of a size of 50 * 10 mm, being placed in wavelength is 400～700 nm, strong approximately 23 mW/cm
2visible ray under irradiate 3 h more than; Then, close after light source material is placed respectively to 0 h, 8h in the dark in advance, then moving into 10 mL concentration is 10
7the colibacillary buffer solution of cfu/mL, in above-mentioned culture dish, carries out sterilization experiment under dark condition, every 20 min samplings, dilution, painting flat board, then at 37 ℃, cultivates 24 h, and number goes out obtained bacterium colony number.
Design principle of the present invention is as follows:
As shown in Figure 4, the present invention is the basic principle according to light-catalyzed reaction, by building on the semiconductor that sunshine absorbs that to build the nanostructured with electron capture and storage capacity be trim having, realized the right effective separation in electronics-hole, when improving photocatalysis efficiency, make catalyst after illumination is closed, still retain certain activity, realized round-the-clock photocatalysis operation.
The invention has the advantages that:
1. the present invention, by compound means, has realized catching and storing of electronics, has improved photocatalysis efficiency and solar energy utilization ratio;
2. in the present invention, the complex method of matrix and trim can be both orderly, can be also unordered.
3. trim of the present invention has electron capture or storage effect, after making like this illumination close, can also under dark, discharge electronics, continues catalytic reaction occurs, and shows a kind of " photocatalysis memory effect "
4. nano composite photo-catalyst material of the present invention can be directly used in the deactivation of organic degraded and microbial pathogens under sunshine, especially, this nano composite photo-catalyst material with " photocatalysis memory effect " still retains certain activity after illumination is closed, and has realized round-the-clock photocatalysis operation.
Accompanying drawing explanation
Fig. 1 is at Cu
2load 12%TiO on O matrix
2the TEM figure of composite;
Fig. 2 is at Cu
2load 12%TiO on O matrix
2the bactericidal effect figure of composite;
Fig. 3 is at Cu
2load 12%TiO on O matrix
2composite illumination 3h after the high-resolution spectrogram of Ti 2p track of xps;
Fig. 4 is the principle schematic of the present invention's " photocatalysis memory effect ".
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
embodiment (one)
Take Nano balls of cuprous oxide as matrix, other titanium dioxide of decorated nanometer level, and the preparation process that Ti:Cu mol ratio is 12% is as follows:
1. preparation dispersiveness is semiconductor substrate cuprous oxide preferably, first, and by 0.2 g polyethylene glycol (molecular weight is 10000), 0.5 mmol CuSO
45H
2o is dissolved in 100 mL deionized waters, then, under the effect of magnetic agitation, by the sodium hydrate aqueous solution of 40 g/L of 1.8 mL, with the speed of one per second, be added drop-wise in above-mentioned solution, stir 5 min, subsequently the 88 g/L aqueous ascorbic acids of 1.8 mL are added drop-wise in above-mentioned solution with the three seconds speed of one, stir 5 min;
2. by obtaining cuprous oxide powder in step 1, with deionized water and absolute ethyl alcohol, alternately wash 5 times, the cuprous oxide powder having washed is distributed in 10 mL absolute ethyl alcohols, ultrasonic dispersion 10 min, are designated as solution A.
3. titanium tetrafluoride is mixed with to the aqueous solution B of 0.02M, in the effect of magnetic agitation, the B solution of 3 mL is added drop-wise in A solution, stir 1 h.
4. the suspension obtaining in step 3 is diluted to 32 mL by deionized water, drips the aqueous ascorbic acid of 0.2 mL, transfer to subsequently in 50 mL teflon-lined stainless steel autoclaves, at Water Under heat 0.5 h of 180 ℃.
5. by the suspension centrifugation of hydro-thermal gained, the material that water and absolute ethanol washing are gathered in the crops 5 times.Finally be placed in vacuum tank at 60 ℃ dry 10 h.
It is as follows that 6 " photocatalysis memory effects " are killed colibacillary specific experiment step:
First, take material 10 mg of synthesized, be dispersed in the culture dish that is of a size of 50 * 10 mm, being placed in wavelength is 400～700 nm, light intensity approximately 23 mW/cm
2visible ray under irradiate 3 h; Then, close after light source material is placed respectively to 0 h, 8h in the dark in advance, then moving into 10 mL concentration is 10
7the colibacillary buffer solution of cfu/mL, in above-mentioned culture dish, carries out sterilization experiment under dark condition, every 20 min samplings, dilution, painting flat board, then at 37 ℃, cultivates 24 h, and number goes out obtained bacterium colony number.
embodiment (two)
The business titanium dioxide P25 of take is matrix, surface finish nano copper, and the preparation process of the Cu:Ti presoma mass ratio composite photo-catalyst that is 25% is as follows:
1. take in the ultrasonic quartz ampoule that is dispersed in the absolute ethyl alcohol that 100 mL are housed of the cupric sulfate pentahydrate of 0.1 g business titanium dioxide P25,25 mg, obtain suspension A.
By suspension A under the effect of magnetic agitation, first pass into nitrogen 30 min, with being placed under the uviol lamp that wavelength is 365 nm, in the time of illumination, continue to pass into nitrogen, time remaining 2 h, can see that suspension becomes aubergine.
Reacted suspension is centrifugal 3., with alcohol washing 3 times, be finally placed in vacuum tank at 60 ℃ dry 10 h.
4. it is as follows that " photocatalysis memory effect " kills colibacillary specific experiment step:
First, take material 10 mg of synthesized, be dispersed in the culture dish that is of a size of 50 * 10 mm, being placed in wavelength is 400～700 nm, light intensity approximately 23 mW/cm
2visible ray under irradiate 3 h; Then, close after light source material is placed respectively to 0 h, 8h in the dark in advance, then moving into 10 mL concentration is 10
7the colibacillary buffer solution of cfu/mL, in above-mentioned culture dish, carries out sterilization experiment under dark condition, every 20 min samplings, dilution, painting flat board, then at 37 ℃, cultivates 24 h, and number goes out obtained bacterium colony number.
Claims (9)
1. a nano composite photo-catalyst material, it is characterized in that: have on the semiconductor nano material matrix of sunshine response, modify light induced electron can the side of flow direction and there is the nanostructured of the character of appraising at the current rate, to realize catching and storing of electronics, thereby obtain the round-the-clock nano composite photo-catalyst material with photocatalysis photocatalysis memory effect.
2. a kind of nano composite photo-catalyst material according to claim 1, it is characterized in that: matrix is the semiconductor nano material that has sunshine response, specifically refer to, the wide bandgap semiconductor nano material with ultraviolet light response, there is visible light-responded low-gap semiconductor material, there is semiconductor nano material and the doped semiconductor nanocrystal material of sunshine local spectra and full spectrum response.
3. a kind of nano composite photo-catalyst material according to claim 1, it is characterized in that: at matrix material light induced electron, flowing to the nanostructured that Fang Zhujian has the character of appraising at the current rate is trim, comprises conductor oxidate, chalcogenide semiconductor compound, doped semiconductor oxide, doped semiconductor sulfide, titanate, bismuthates; Can be trim as the metal nano material of the matrix material light induced electron side of flow direction, comprise noble metal, transition metal and multi-element metal compound.
4. a kind of nano composite photo-catalyst material according to claim 1, is characterized in that: the complex method of matrix and trim can be both orderly, can be also unordered.
5. a kind of nano composite photo-catalyst material according to claim 1, it is characterized in that: this nano composite photo-catalyst material can be directly used in the deactivation of organic degraded and microbial pathogens under sunshine, especially, this photochemical catalyst still retains certain activity after illumination is closed, and has realized round-the-clock photocatalysis.
6. a kind of nano composite photo-catalyst material according to claim 1, it is characterized in that: this nano composite photo-catalyst material has illumination memory effect, be catalysis material after illumination, even if light extinguished after a few hours, still show obvious photocatalytic effect.
7. a kind of nano composite photo-catalyst material preparation method according to claim 1, is characterized in that: it is as follows that photocatalysis memory effect is killed colibacillary specific experiment step:
First, take material 10 mg of synthesized, be dispersed in the culture dish that is of a size of 50 * 10 mm, being placed in wavelength is 400～700 nm, light intensity approximately 23 mW/cm
2visible ray under, more than irradiating 3 h; Then, close after light source material is placed respectively to 0 h, 8 h in the dark in advance, then moving into 10 mL concentration is 10
7the colibacillary buffer solution of cfu/mL, in above-mentioned culture dish, carries out sterilization experiment under dark condition, every 20 min samplings, dilution, painting flat board, then at 37 ℃, cultivates 24 h, and number goes out obtained bacterium colony number.
8. the preparation method of a kind of nano composite photo-catalyst material according to claim 7, it is characterized in that: photocatalysis memory effect is in particular in: close after light source, material is placed to 0 h in the dark in advance and can kill more than 90% Escherichia coli at 80 min; Close after light source, material is placed to the bactericidal effect and illumination in advance after 8 h in the dark in advance, directly the effect under dark is suitable, can kill at 80 min the Escherichia coli of 40% left and right.
9. the preparation method of a kind of nano composite photo-catalyst material according to claim 7, it is characterized in that: described material more than illumination 3 h after, by appraising at the current rate of element in trim, realized the storage of electronics, after closing, illumination still retains certain activity, realize round-the-clock photocatalysis, solved catalysis material deactivated difficult problem after illumination is closed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113289635A (en) * | 2021-06-08 | 2021-08-24 | 深圳市康弘环保技术有限公司 | Quaternary high-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier |
| CN113385190A (en) * | 2021-06-08 | 2021-09-14 | 南方科技大学 | High-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143366A (en) * | 1998-12-24 | 2000-11-07 | Lu; Chung Hsin | High-pressure process for crystallization of ceramic films at low temperatures |
| CN101620935A (en) * | 2009-07-21 | 2010-01-06 | 华中师范大学 | TiO2-based composite film material with functions of solar energy storage and release |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6143366A (en) * | 1998-12-24 | 2000-11-07 | Lu; Chung Hsin | High-pressure process for crystallization of ceramic films at low temperatures |
| CN101620935A (en) * | 2009-07-21 | 2010-01-06 | 华中师范大学 | TiO2-based composite film material with functions of solar energy storage and release |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113289635A (en) * | 2021-06-08 | 2021-08-24 | 深圳市康弘环保技术有限公司 | Quaternary high-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier |
| CN113385190A (en) * | 2021-06-08 | 2021-09-14 | 南方科技大学 | High-efficiency photocatalytic nano material with memory effect, preparation method thereof and air purifier |
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Application publication date: 20140122 |