CN101584985A - Ca-Bi-O series visible-light photocatalysis material and preparation method thereof - Google Patents
Ca-Bi-O series visible-light photocatalysis material and preparation method thereof Download PDFInfo
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- CN101584985A CN101584985A CNA2009100162626A CN200910016262A CN101584985A CN 101584985 A CN101584985 A CN 101584985A CN A2009100162626 A CNA2009100162626 A CN A2009100162626A CN 200910016262 A CN200910016262 A CN 200910016262A CN 101584985 A CN101584985 A CN 101584985A
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Abstract
The present invention relates to the preparation method of Ca-Bi-O series visible-light photocatalysis material, belong to technical field of inorganic nanometer material.The preparation method comprises that chemical solution method prepares predecessor and 450～800 ℃ of following annealing 10～15 hours.The present invention utilizes chemical solution method by uniform prepared in reaction Ca-Bi-O series visible-light photocatalysis material, overcome the high defective of prior art reaction temperature, and can obtain photo-catalysis function material single-phase or Heterogeneous Composite respectively by the control annealing temperature.The inventive method is simple to operate, easy control of reaction, good reproducibility; Gained Heterogeneous Composite photo-catalysis function material has the photocatalytic activity of obvious raising.
Description
Technical field
The present invention relates to Ca-Bi-O is photo-catalysis function material and preparation method thereof, belongs to field of inorganic nano-material preparation.
Background technology
The conductor photocatalysis oxidation technology is a kind of novel water technology that utilizes the luminous energy degradation of contaminant, it is simple that it has technology, with low cost, the organic matter of stable, the difficult for biological degradation of degrading texture under the normal temperature and pressure, advantage such as pollution-free has been subjected to the common concern of Chinese scholars.Garey TiO in 1976
2Photochemical catalyst has removed the chlorine in the Polychlorinated biphenyls (Bull.Environ.Contam.Toxical., 1976,16,697.), Frank photochemical catalytic oxidation CN in 1977
-Be OCN
-(J.Phys.Chem., 1977,81,1484.) have started the beginning that the photoactivation agent is disposed of sewage.The core of photocatalysis technology research is to seek the catalysis material of function admirable.At present, study TiO the most widely
2Absorption to light only limits to ultra-violet (UV) band (Eg=3.2eV), has limited the utilization to solar energy, therefore, seek novel, the visible light photocatalysis functional material has become a new research focus efficiently.
As a kind of novel photo-catalysis function material, Bi in the bismuth system oxide
3+Have three-dimensional active lone pair electrons and depart from its ligand symmetrical centre, the asymmetrical coordination environment that causes will make and contain Bi
3+Oxide produce a series of interesting physical property, especially photocatalysis characteristics.Research is in recent years found, the multicomponent composite oxide of a series of bismuth-containings is because of the diversity of its crystal structure and electronic structure, might possess band structure that responding to visible light excites and high photo-generated carrier mobility simultaneously, be used as potential high efficiency photocatalysis functional material and obtained extensive studies.2004, Zou Zhigang reported a kind of bismuth series photocatalyst CaBi
2O
4(Angew.Chem.Int.Ed., 2004,43,4463.), this catalyst under visible light (λ 〉=420nm) can the efficient degradation methylene blue etc. organic pollution, but adopt high temperature solid phase synthesis can only obtain high-temperature stable phase compound, can not get to have the more low temperature metastable phase bismuth oxygen compound of highlight catalytic active.Because the problem that the photocatalysis technology another one receives much attention is the compound of photo-generated carrier (hole and electronics), Heterogeneous Composite can improve the separation of charge rate of semiconductor light-catalyst effectively, thereby improve or improve the photocatalytic activity of semiconductor structure, aspect practical application, have the meaning of particular importance.
Summary of the invention
At present present Research, the invention provides a kind of chemical solution method that utilizes by uniform prepared in reaction series Ca-Bi-O series visible-light photocatalysis material, to overcome the high defective of prior art reaction temperature.
The series compound that the Ca-Bi-O series visible-light photocatalysis material is made up of by different proportion Ca, Bi, three kinds of elements of O has following general formula: Ca
xBi
yO
z., x=1-5 in the formula, y=2-14, z=4-26.
The preparation method of Ca-Bi-O series visible-light photocatalysis material of the present invention, step is as follows:
(1) preparation predecessor
Take by weighing 0.24-0.48g Ca (NO
3)
2With 0.97-1.94g Bi (NO
3)
3Be dissolved in the 50mL ethylene glycol, dripping 0-1mL concentration is the poly of 12%wt, stirs 4-5 minute under the room temperature, and transferring pH with concentrated ammonia liquor is 8-10, stirs 20-24 hour under the room temperature; Products therefrom is at room temperature used the 50-100mL absolute ethanol washing, centrifugation then, with solid product 70 ℃ of temperature dryings 24 hours, predecessor.
The concentration of preferred concentrated ammonia liquor is 25-28%wt.
(2) annealing
Get the predecessor of step (1) preparation,, be chilled to room temperature naturally, annealed 10-15 hour down, be chilled to room temperature naturally, promptly for 450～800 ℃ in 300 ℃ of following preliminary treatment 1-10 hours.
Preferably, ground 10-30 minute earlier before predecessor begins to anneal in the above-mentioned steps (2).
Reaction described in the inventive method all is to carry out in the reactor of accurate temperature controlling is arranged, so that accurately control reaction temperature.
To be 600 ℃ be single thing product mutually during with 800 ℃ to annealing temperature in the above-mentioned steps (2), and what all the other annealing temperatures obtained is Heterogeneous Composite phase product.
The product granularity diameter of the inventive method preparation is 10-90nm.
The thing of the product of the inventive method preparation adopts Bruker D8X-x ray diffractometer x with Cu-K alpha ray (wavelength X=1.54178 mutually by X-ray diffraction spectra (XRD) test
) for diffraction light sources product is made X light diffracting analysis.The UV, visible light diffuse reflection of product (UV-Vis diffuse reflectance) spectrum is measured with the U-1901UV-Vis spectrophotometer.Specifically referring to Fig. 1-3.
Characteristics of the present invention and excellent results are as follows:
1, at first adopt the coordination method in conjunction with coprecipitation (belonging to chemical solution method) preparation predecessor, to improve the uniformity of material, the multicomponent weak solution is the mixing of molecular level, atom level, and therefore the material that is synthesized has the homogeneity of height on composition and pattern.Can select for use poly as chelating agent in preparation during predecessor, prevent to precipitate inhomogeneous, improve calcining heat.
2, can obtain photo-catalysis function material single thing phase or Heterogeneous Composite respectively by the control annealing temperature, wherein, the Heterogeneous Composite structure can improve the separation of charge rate and the photocatalytic activity of semiconductor light-catalyst effectively.
3, the present invention is reasonable in design, and is simple to operate, easy control of reaction, good reproducibility.
The present invention makes metal ion reach the homogeneous reaction of molecular level, atom level by chemical solution method, can obtain photo-catalysis function material single thing phase or Heterogeneous Composite respectively by the control annealing temperature, the photocatalysis performance test result shows that Heterogeneous Composite can improve the separation of charge rate and the photocatalytic activity of semiconductor light-catalyst effectively, is a kind of new efficient visible light photo-catalysis function material.
Description of drawings
Fig. 1 is respectively the 450-800 ℃ of X-ray diffraction spectra (XRD) of annealing gained Ca-Bi-O series visible-light photocatalysis material down.The molecular formula on each line in the XRD figure is seen in the different phase compositions that different annealing temperature obtains.
Fig. 2 is respectively the UV, visible light diffuse reflection spectrum (DRS) of gained catalysis material under the different annealing temperature.Curve is at the 430nm place among the figure, and each curve representation temperature is followed successively by from top to bottom: 550,800,700,750,650,600,450,500 ℃.
Fig. 3 is respectively the MB aqueous solution under radiation of visible light (15mg/L) t:0 in time of gained catalysis material under the different annealing temperature, 1,2,3,4,5,6,7 and the UV-Visible spectrum change of 8h.(a)-(h) is 450,500,550,600,650,700,750,800 ℃ of annealing temperatures successively among the figure.Wherein,
0,1,2,3,4,5h (a) at the 665nm place, each curve representative time is respectively from top to bottom:.
0,1,2,3,4,5,6h (b) at the 665nm place, each curve representative time is respectively from top to bottom:.
1,2,3,4,5,0,6,7,8h (c) at the 665nm place, each curve representative time is respectively from top to bottom:.
2,0,1,3,4,5h (d) at the 620nm place, each curve representative time is respectively from top to bottom:.
2,0,1,3,4,5h (e) at the 620nm place, each curve representative time is respectively from top to bottom:.
3,4,5,2,1,6,7,0,8h (f) at the 665nm place, each curve representative time is respectively from top to bottom:.
1,2,3,4,5,0,6,7,8h (g) at the 665nm place, each curve representative time is respectively from top to bottom:.
0,1,2,3,4,5,6,7,8h (h) at the 665nm place, each curve representative time is respectively from top to bottom:.
The specific embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:Ca-Bi-O visible light photocatalysis preparation of nanomaterials, step is as follows:
(1) preparation predecessor
Take by weighing 0.24g Ca (NO
3)
2With 0.97g Bi (NO
3)
3Be dissolved in the 50mL ethylene glycol, drip the 1mL poly, stirred 5 minutes under the room temperature, transfer pH=9, stirred 24 hours under the room temperature with concentrated ammonia liquor; Will be under the products therefrom room temperature with the washing of 100mL ethanol, centrifugation and 70 ℃ of dryings 24 hours then, predecessor.
(2) annealing
Get the predecessor of 0.4g step (1) preparation, 300 ℃ of following preliminary treatment 8 hours are chilled to room temperature naturally; Ground 20 minutes, and annealed 10 hours down for 450～800 ℃, be chilled to room temperature naturally, promptly getting Ca-Bi-O is the photo-catalysis function material.
Reaction described in step (1) and (2) is that reactor is placed in the baking oven of energy accurate temperature controlling.
The thing of product adopts Bruker D8X-x ray diffractometer x with Cu-K alpha ray (wavelength X=1.54178 mutually by X-ray diffraction spectra (XRD) test
) for diffraction light sources product is made X light diffracting analysis.The UV, visible light diffuse reflection of product (UV-Vis diffuse reflectance) spectrum is measured with the U-1901UV-Vis spectrophotometer.The result is as follows:
The Ca-Bi-O that Fig. 1 is respectively annealing preparation under 450,500,550,600,650,700,750,800 ℃ of temperature is the X-ray diffraction spectra (XRD) of photo-catalysis function material.Wherein, when calcining heat was 600 ℃ or 800 ℃, product was respectively by single thing phase CaBi
2O
4(JCPDS card No.48-0216) and Ca
3Bi
8O
15(JCPDS card No.49-0021) forms.The gap of calcining heat is decided to be 50 ℃, clearly to understand the crystalline phase conversion process.When calcining heat was 450 ℃, 500 ℃ and 550 ℃, product was CaBi
2O
4And portion C aBi
4O
7The compound of (JCPDS card No.41-0309), semi-quantitative analysis is found, along with temperature rising CaBi
2O
4Amount become many gradually, CaBi in the time of 600 ℃
4O
7The phase complete obiteration.In the process that calcining heat continues to raise, Ca is arranged respectively
5Bi
14O
26(JCPDS card No.48-0215), Ca
4Bi
6O
13(JCPDS card No.42-1439) and Ca
3Bi
8O
15(JCPDS card No.49-0021) component produces, and then changes Ca into along with temperature is increased to 800 ℃ of end products
3Bi
8O
15Single phase.
Fig. 2 is respectively the UV, visible light diffuse reflection spectrum (DRS) of different annealing temperature gained sample, and the novel C a-Bi-O that is synthesized as can be seen from the DRS spectrum is that the photo-catalysis function material all has absorption in various degree in the visible region of λ＞400nm.
Fig. 3 is respectively the visible light photocatalytic degradation process of different annealing temperature gained sample to the methylene blue waste water solution, the photocatalytic activity of gained material is followed successively by S450＞S650＞S500＞S750＞S550＞S700＞S600＞S800 in proper order, wherein 600 ℃ with the 800 ℃ of following single thing that obtains of annealing CaBi mutually
2O
4And Ca
3Bi
8O
15Degradation efficiency is relatively low, and Heterogeneous Composite can improve the separation of charge rate and the photocatalytic activity of semiconductor light-catalyst effectively.
Embodiment 2:
Preparation process is with embodiment 1, and difference is: the used calcium salt of step (1) is Ca (NO
3)
2, bismuth salt is BiCl
3
Embodiment 3:
Preparation process is with embodiment 1, and difference is: the used calcium salt of step (1) is CaCl
2, bismuth salt is: Bi (NO
3)
3
Embodiment 4:
Preparation process is with example 1, and difference is: step (1) is got 0.48g Ca (NO
3)
2With 0.97g Bi (NO
3)
3Be dissolved in the 50mL ethylene glycol.
Embodiment 5:
Preparation process is with embodiment 1, and difference is: step (1) is got 0.24g Ca (NO
3)
2With 1.94g Bi (NO
3)
3Be dissolved in the 50mL ethylene glycol.
Embodiment 6:
Preparation process is with embodiment 1, and difference is: in the preparation predecessor process, do not drip poly.
Embodiment 7:
Preparation process is with embodiment 1, and difference is: in step (1) the preparation predecessor process, transfer its pH=8 with concentrated ammonia liquor.
Embodiment 8:
Preparation process is with embodiment 1, and difference is: in step (1) the preparation predecessor process, transfer its pH=10 with concentrated ammonia liquor.
Embodiment 9:
Preparation process is with embodiment 1, and difference is: in step (1) the preparation predecessor process, use the 50mL water washing under the products therefrom room temperature.
Embodiment 10:
Preparation process is with embodiment 1, and difference is: in step (2) annealing operation, and 300 ℃ of following preliminary treatment 1 hour.
Embodiment 11:
Preparation process is with embodiment 1, and difference is: in step (2) annealing operation, 300 ℃ of following preliminary treatment are after 10 hours, without grinding promptly annealing at high temperature.
Embodiment 12:
Preparation process is with executing example 1, and difference is: in step (2) annealing operation, grind after 30 minutes, annealed 15 hours down at 450～800 ℃.
Claims (2)
1, a kind of preparation method of Ca-Bi-O series visible-light photocatalysis material, step is as follows:
(1) preparation predecessor
Take by weighing 0.24～0.48g Ca (NO
3)
2With 0.97～1.94g Bi (NO
3)
3Be dissolved in the 50mL ethylene glycol, dripping 0～1mL concentration is the poly of 12%wt, stirs 4-5 minute under the room temperature, and transferring pH with concentrated ammonia liquor is 8～10, stirs under the room temperature 20～24 hours; Products therefrom is at room temperature used 50～100mL absolute ethanol washing, centrifugation then, with solid product 70 ℃ of temperature dryings 20～24 hours, predecessor;
(2) annealing
Get the predecessor of step (1) preparation,, be chilled to room temperature naturally, annealed 10～15 hours down, be chilled to room temperature naturally, promptly for 450～800 ℃ in 300 ℃ of following preliminary treatment 1-10 hours.
2, the preparation method of Ca-Bi-O series visible-light photocatalysis material as claimed in claim 1 is characterized in that, grinds 10-30 minute earlier before predecessor begins to anneal in the described step (2).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607174A (en) * | 2014-12-31 | 2015-05-13 | 中国石油天然气股份有限公司 | Calcium-doped beta-Bi2O3 photocatalyst as well as preparation method and application thereof |
| CN107866214A (en) * | 2017-11-17 | 2018-04-03 | 中国矿业大学 | A kind of chemical solution method prepares Ca3Bi8O15The method of film |
| CN111545189A (en) * | 2020-04-17 | 2020-08-18 | 中国地质大学（北京） | Visible light activity CaBi synthesized by hydrothermal technology2O4Photocatalyst and preparation method thereof |
-
2009
- 2009-06-23 CN CN2009100162626A patent/CN101584985B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607174A (en) * | 2014-12-31 | 2015-05-13 | 中国石油天然气股份有限公司 | Calcium-doped beta-Bi2O3 photocatalyst as well as preparation method and application thereof |
| CN107866214A (en) * | 2017-11-17 | 2018-04-03 | 中国矿业大学 | A kind of chemical solution method prepares Ca3Bi8O15The method of film |
| CN111545189A (en) * | 2020-04-17 | 2020-08-18 | 中国地质大学（北京） | Visible light activity CaBi synthesized by hydrothermal technology2O4Photocatalyst and preparation method thereof |
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