CN109926064A - Responding to visible light is thoroughly degraded the narrowband catalysis material and preparation method of tetracycline - Google Patents

Responding to visible light is thoroughly degraded the narrowband catalysis material and preparation method of tetracycline Download PDF

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CN109926064A
CN109926064A CN201910122883.6A CN201910122883A CN109926064A CN 109926064 A CN109926064 A CN 109926064A CN 201910122883 A CN201910122883 A CN 201910122883A CN 109926064 A CN109926064 A CN 109926064A
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tetracycline
visible light
narrowband
responding
catalysis material
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CN109926064B (en
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何琴玉
莫熙
余小燕
胡佳敏
何俊峰
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South China Normal University
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South China Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The present invention is that a kind of responding to visible light is thoroughly degraded the narrowband catalysis material and preparation method of tetracycline.Responding to visible light thoroughly degrade tetracycline narrowband catalysis material ingredient be La2‑ xSrxNiMnO6(x=0.01-0.20).1) preparation method, which comprises the following steps that, will analyze pure La2O3,MnO2, SrO and dehydrated alcohol are mixed, are dried after ball milling；2) powder of drying is suppressed, pressure is 10MPa-100MPa；3) by the block of compacting in 800 DEG C of -1150 DEG C of sintering；4) block by step 3) sintering carries out ball milling；5) by the tabletting again of the powder of ball milling in step 4), pressure is 10MPa-100MPa；6) piece being pressed into step 5) is sintered again, sintering temperature is 800 DEG C -1250 DEG C；7) ball milling is carried out again by step 6) sintered, obtain required powder.Responding to visible light of the present invention thoroughly degrade tetracycline narrowband catalysis material can thoroughly degrade under the irradiation of visible light tetracycline to safety minerals.

Description

Responding to visible light is thoroughly degraded the narrowband catalysis material and preparation method of tetracycline
Technical field
The present invention is a kind of narrowband catalysis material and preparation method, and especially a kind of responding to visible light is thoroughly degraded Fourth Ring The narrowband catalysis material and preparation method of element belong to responding to visible light and thoroughly degrade the narrowband catalysis material and system of tetracycline The innovative technology of Preparation Method.
Background technique
The abuse of present antibiotic enters animal and plant body by crop so that there are a large amount of tetracyclines in environment water It is interior.And the presence of tetracycline makes animal and plant gene change.Therefore, the tetracycline in environment is completely degraded into such as dioxy Change the minerals such as carbon and water, has very important significance.
Since water body is very huge, therefore the degradation of tetracycline needs the method using energy conservation, green in environment.Photocatalysis can benefit With sun light degradation, without additional energy.But the material for the tetracycline that can degrade in present catalysis material is nearly all broadband Semiconductor generates high energy active material under the ultraviolet light of sunlight come tetracycline of degrading.Because the degradation of tetracycline is very Difficulty, especially A ring.And ultraviolet light only accounts for the energy of sunlight about 5%.Therefore it is not high to the utilization rate of sunlight.It is used to degrade at present Although the narrow-band semiconductor of tetracycline can absorb visible light, the utilization rate of solar energy is improved, the activity generated due to it Matter energy is inadequate, and cannot thoroughly degrade tetracycline, can generate intermediate product.And these intermediate products have bigger toxicity. Therefore so that tetracycline degradation pathway is avoided intermediate product using special catalysis material, being completely degraded into minerals is very must It wants.
Summary of the invention
The narrowband that a kind of responding to visible light thoroughly degrades tetracycline is provided it is an object of the invention to consider the above problem Catalysis material.The present invention can thoroughly degrade tetracycline to the minerals of safety under the irradiation of visible light.
It thoroughly degrades the narrowband catalysis material of tetracycline another object of the present invention is to provide a kind of responding to visible light Preparation method.
The narrowband catalysis material of tetracycline the technical scheme is that responding to visible light of the invention is thoroughly degraded, Ingredient is La2-xSrxNiMnO6(x=0.01-0.20).
Responding to visible light of the present invention thoroughly degrade tetracycline narrowband catalysis material preparation method, include following step It is rapid:
1) pure La will be analyzed2O3, MnO2, SrO and dehydrated alcohol are mixed, are dried after ball milling；
2) powder of drying is suppressed, pressure is 10MPa-100MPa；
3) by the block of compacting in 800 DEG C of -1150 DEG C of sintering；
4) block by step 3) sintering carries out ball milling；
5) by the tabletting again of the powder of ball milling in step 4), pressure is 10MPa-100MPa；
6) piece being pressed into step 5) is sintered again, sintering temperature is 800 DEG C -1250 DEG C；
7) ball milling is carried out again by step 6) sintered, obtain required powder.
Above-mentioned steps 1) ball milling 2-20 hours.
Above-mentioned steps 1) it is dried at 40-90 DEG C of temperature.
Above-mentioned steps 2) pressing time is 1-10 minutes.
Above-mentioned steps 3) sintering time is 1-20 hours.
Above-mentioned steps 4) Ball-milling Time is 1-10 hours.
Above-mentioned steps 5) pressing time is 2-20 minutes.
Above-mentioned steps 6) sintering time is 0.5-3 hours.
Above-mentioned steps 7) Ball-milling Time is 0.5-2 hours.
The present invention is solved the problems, such as using sunlight fast degradation tetracycline, because visible light energy is remote more in sunlight In the energy of ultraviolet light, almost ten times；Energy responding to visible light of the present invention, it is meant that the speed for tetracycline of degrading is accelerated very much, The present invention is that a kind of convenient and practical responding to visible light is thoroughly degraded the narrowband catalysis material and preparation method of tetracycline.
Detailed description of the invention
Fig. 1 is the degradation schematic diagram of the embodiment of the present invention 1；
Fig. 2 is the degradation schematic diagram of the embodiment of the present invention 2；
Fig. 3 is the degradation schematic diagram of the embodiment of the present invention 3；
Fig. 4 is the degradation schematic diagram of the embodiment of the present invention 4.
Specific embodiment
Embodiment 1:
Responding to visible light of the invention is thoroughly degraded the narrowband catalysis material of tetracycline, ingredient La2-xSrxNiMnO6(x= 0.01).Preparation method is in accordance with the following steps:
1) pure La will be analyzed2O3, MnO2, SrO and after dehydrated alcohol mixing and ball milling 2 hours 40 DEG C dry.
2) powder of drying is suppressed 1 minute in 10MPa.
3) block of compacting is sintered 1 hour at 800 DEG C DEG C.
4) by block high-energy ball milling 1 hour of step 3) sintering.
5) powder of ball milling in step 4) is tabletted again, pressure 10MPa, the time 2 minutes.
6) piece suppressed in step 5) is sintered at 800 DEG C of temperature, 800 DEG C keep the temperature 0.5 hour.
7) step 5) sintered is carried out ball milling 0.5 hour again.
Above-mentioned steps 1,5), 6) in ball milling be all high-energy ball milling.
The test method that tetracycline of the present invention is thoroughly degraded is as follows:
0.1 gram of above-mentioned powder is taken, is put into 100 milliliters of tetracyclines (20mg/ liter, 100ml).First allow the photocatalysis material of preparation Material adequately adsorbs tetracycline, carries out visible light illumination to this mixed solution after reaching adsorption-desorption balance.Every certain Time take a certain amount of upper solution to be centrifuged after solution do uv-vis spectra absorption；From the corresponding absorption peak of tetracycline (about in the A functional group of 270nm and the B functional group about near 358nm) and the absorption peak of tetracycline before photocatalysis compare. If two absorption peaks all disappear, degradation is thorough.
As shown in Figure 1, after dark absorption in 1 hour, it is seen that 5 hours tetracyclines of light photocatalysis are thoroughly degraded.
Embodiment 2:
Responding to visible light of the invention is thoroughly degraded the narrowband catalysis material of tetracycline, ingredient La2-xSrxNiMnO6(x= 0.20)。Preparation method is in accordance with the following steps:
1) pure La will be analyzed2O3, MnO2, SrO and after dehydrated alcohol mixing and ball milling 20 hours 90 DEG C dry.
2) powder of drying is suppressed 10 minutes in 100MPa.
3) block of compacting is sintered 20 hours at 1150 DEG C.
4) by block high-energy ball milling 10 hours of step 3) sintering.
5) powder of ball milling in step 4) is tabletted again, pressure 100MPa, the time 20 minutes.
6) piece suppressed in step 5) is sintered at 1250 DEG C of temperature, 1250 DEG C keep the temperature 3 hours.
7) step 6) sintered is carried out ball milling 2 hours again.
Above-mentioned steps 1,5), 6) in ball milling be all high-energy ball milling.
0.1 gram of above-mentioned powder is taken, is put into 100 milliliters of tetracyclines (20mg/ liter, 100ml).The light of preparation is first allowed to be urged Change material adequately to adsorb tetracycline, visible light illumination is carried out to this mixed solution after reaching adsorption-desorption balance.Every Regular hour takes the solution after a certain amount of upper solution centrifugation to do uv-vis spectra absorption；From the corresponding absorption of tetracycline The absorption peak of peak (about in the A functional group of 270nm and B functional group about near 358nm) and tetracycline before photocatalysis carries out pair Than.If two absorption peaks all disappear, degradation is thorough.
As shown in Fig. 2, after dark absorption in 1 hour, it is seen that 3.5 hours tetracyclines of light photocatalysis are thoroughly degraded.
Embodiment 3:
Responding to visible light of the invention is thoroughly degraded the narrowband catalysis material of tetracycline, ingredient La2-xSrxNiMnO6(x =: 0.10)。Preparation method is in accordance with the following steps:
1) pure La will be analyzed2O3, MnO2, SrO and after dehydrated alcohol mixing and ball milling 10 hours 50 DEG C dry.
2) powder of drying is suppressed 5 minutes in 500MPa.
3) block of compacting is sintered 10 hours at 1000 DEG C.
4) by block high-energy ball milling 5 hours of step 3) sintering.
5) powder of ball milling in step 4) is tabletted again, pressure 50MPa, the time 10 minutes.
6) piece suppressed in step 5) is sintered at 950 DEG C of temperature, 950 DEG C keep the temperature 2 hours.
7) step 6) sintered is carried out ball milling 1 hour again.
Above-mentioned steps 1,5), 6) in ball milling be all high-energy ball milling.
0.1 gram of above-mentioned powder is taken, is put into 100 milliliters of tetracyclines (20mg/ liter, 100ml).The light of preparation is first allowed to be urged Change material adequately to adsorb tetracycline, visible light illumination is carried out to this mixed solution after reaching adsorption-desorption balance.Every Regular hour takes the solution after a certain amount of upper solution centrifugation to do uv-vis spectra absorption；From the corresponding absorption of tetracycline The absorption peak of peak (about in the A functional group of 270nm and B functional group about near 358nm) and tetracycline before photocatalysis carries out pair Than.If two absorption peaks all disappear, degradation is thorough.
As shown in figure 3, after dark absorption in 1 hour, it is seen that 3 hours tetracyclines of light photocatalysis are thoroughly degraded.
Embodiment 4:
Responding to visible light of the invention is thoroughly degraded the narrowband catalysis material of tetracycline, ingredient La2-xSrxNiMnO6(x =: 0.13)。Preparation method is in accordance with the following steps:
1) pure La will be analyzed2O3, MnO2, SrO and after dehydrated alcohol mixing and ball milling 6 hours 70 DEG C dry.
2) powder of drying is suppressed 4 minutes in 40MPa.
3) block of cold pressing is sintered 5 hours at 900 DEG C.
4) by block ball milling 3 hours of step 3) sintering.
5) powder of ball milling in step 4) is tabletted again, pressure 80MPa, the time 5 minutes.
6) piece suppressed in step 5) is sintered at 800 DEG C of temperature, 800 DEG C keep the temperature 2 hours.
7) step 6) sintered is carried out ball milling 1.5 hours again.
Above-mentioned steps 1,5), 6) in ball milling be all high-energy ball milling.
0.1 gram of above-mentioned powder is taken, is put into 100 milliliters of tetracyclines (20mg/ liter, 100ml).The light of preparation is first allowed to be urged Change material adequately to adsorb tetracycline, visible light illumination is carried out to this mixed solution after reaching adsorption-desorption balance.Every Regular hour takes the solution after a certain amount of upper solution centrifugation to do uv-vis spectra absorption；From the corresponding absorption of tetracycline The absorption peak of peak (about in the A functional group of 270nm and B functional group about near 358nm) and tetracycline before photocatalysis carries out pair Than.If two absorption peaks all disappear, degradation is thorough.
As shown in figure 4, after dark absorption in 1 hour, it is seen that 4 hours tetracyclines of light photocatalysis are thoroughly degraded.
The present invention is a kind of narrowband catalysis material, can thoroughly degrade under the irradiation of visible light tetracycline to safety mine Substance.

Claims (10)

  1. A kind of narrowband catalysis material of tetracycline 1. responding to visible light is thoroughly degraded, it is characterised in that ingredient La2- xSrxNiMnO6(x=0.01-0.20).
  2. The preparation method of the narrowband catalysis material of tetracycline 2. a kind of responding to visible light is thoroughly degraded, it is characterised in that include Following steps:
    1) pure La will be analyzed2O3, MnO2, SrO and dehydrated alcohol are mixed, are dried after ball milling；
    2) powder of drying is suppressed, pressure is 10MPa-100MPa；
    3) by the block of compacting in 800 DEG C of -1150 DEG C of sintering；
    4) block by step 3) sintering carries out ball milling；
    5) by the tabletting again of the powder of ball milling in step 4), pressure is 10MPa-100MPa；
    6) piece being pressed into step 5) is sintered again, sintering temperature is 800 DEG C -1250 DEG C；
    7) ball milling is carried out again by step 6) sintered, obtain required powder.
  3. The preparation method of the narrowband catalysis material of tetracycline 3. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 1) ball milling 2-20 hours.
  4. The preparation method of the narrowband catalysis material of tetracycline 4. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 1) is dried at 40-90 DEG C of temperature.
  5. The preparation method of the narrowband catalysis material of tetracycline 5. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that the step 2 pressing time is 1-10 minutes.
  6. The preparation method of the narrowband catalysis material of tetracycline 6. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 3) sintering time is 1-20 hours.
  7. The preparation method of the narrowband catalysis material of tetracycline 7. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 4) Ball-milling Time is 1-10 hours.
  8. The preparation method of the narrowband catalysis material of tetracycline 8. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that the step 5) pressing time is 2-20 minutes.
  9. The preparation method of the narrowband catalysis material of tetracycline 9. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 6) sintering time is 0.5-3 hours.
  10. The preparation method of the narrowband catalysis material of tetracycline 10. responding to visible light according to claim 1 is thoroughly degraded, It is characterized in that step 7) Ball-milling Time is 0.5-2 hours.
CN201910122883.6A 2019-02-19 2019-02-19 Narrow-band photocatalytic material for thoroughly degrading tetracycline in response to visible light and preparation method thereof Active CN109926064B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6521202B1 (en) * 1999-06-28 2003-02-18 University Of Chicago Oxygen ion conducting materials
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CN103058285A (en) * 2012-12-04 2013-04-24 内蒙古工业大学 Two-step solid-phase synthesis method of pure-phase LaNiMnO6 powder
CN106390996A (en) * 2016-09-27 2017-02-15 中北大学 Preparation method and synergetic photocatalysis effect of composite oxide La0.7Sr0.3MnO3-delta/TiO2
CN107200378A (en) * 2017-06-23 2017-09-26 华南师范大学 A kind of simple method for preparing of the mix powder of efficient degradation tetracycline
CN107376964A (en) * 2017-07-21 2017-11-24 湘潭大学 A kind of composite photo-catalyst using adulterated with Ca and Ti ore as carrier prepares and its application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6521202B1 (en) * 1999-06-28 2003-02-18 University Of Chicago Oxygen ion conducting materials
US7625835B2 (en) * 2005-06-10 2009-12-01 Gm Global Technology Operations, Inc. Photocatalyst and use thereof
CN103058285A (en) * 2012-12-04 2013-04-24 内蒙古工业大学 Two-step solid-phase synthesis method of pure-phase LaNiMnO6 powder
CN106390996A (en) * 2016-09-27 2017-02-15 中北大学 Preparation method and synergetic photocatalysis effect of composite oxide La0.7Sr0.3MnO3-delta/TiO2
CN107200378A (en) * 2017-06-23 2017-09-26 华南师范大学 A kind of simple method for preparing of the mix powder of efficient degradation tetracycline
CN107376964A (en) * 2017-07-21 2017-11-24 湘潭大学 A kind of composite photo-catalyst using adulterated with Ca and Ti ore as carrier prepares and its application

Non-Patent Citations (3)

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YUQIAO GUO ET AL.: ""Tunable exchange bias effect in Sr-doped double perovskite La2NiMnO6"", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 *
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