CN104492419A - Visible light responding photocatalyst LiBi3B3O11 and preparation method thereof - Google Patents
Visible light responding photocatalyst LiBi3B3O11 and preparation method thereof Download PDFInfo
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- CN104492419A CN104492419A CN201410825540.3A CN201410825540A CN104492419A CN 104492419 A CN104492419 A CN 104492419A CN 201410825540 A CN201410825540 A CN 201410825540A CN 104492419 A CN104492419 A CN 104492419A
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Abstract
The invention discloses a wide-band high-efficiency visible light responding photocatalyst LiBi3B3O11 and a preparation method thereof. The chemical composition formula of the photocatalyst is LiBi3B3O11. The invention further discloses a preparation method of the photocatalyst. The photocatalyst has the advantages of wide spectral response range, high light conversion efficiency, good stability and the like, and has the effects of decomposing harmful chemical substances and organic biomass and sterilizing under visible light radiation; and the preparation method is simple, low in synthesizing temperature and low in cost, and is suitable for industrial production and application.
Description
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Li Bi
3b
4o
11and preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with socioeconomic development, people more and more pay close attention to for the energy and ecological environment, solve energy shortage and problem of environmental pollution be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.
From phase late 1970s, there has been proposed and to utilize in photochemical catalyst decomposition water and the organic matter such as agricultural chemicals in air and odorant, and scribble the application example such as self-cleaning of the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after absorbing the photon higher than its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO
2), titanium dioxide has been utilized to decompose organic matters such as the agricultural chemicals in water and in air and odorants, but the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just activity can be shown, can only at indoor or the local work having uviol lamp, almost can not utilize visible ray, this limits the use of titanium dioxide optical catalyst greatly.
Consider the practicality of photochemical catalyst in decomposing harmful substances, utilize sunshine to be indispensable as light source.Irradiate maximum to sunshine medium wavelength intensity of visible ray near 500nm on earth's surface, wavelength is the energy of the visible region of 400nm ~ 750nm is approximately 43% of sunshine gross energy, so in order to efficient utilization, the R and D of bismuth series photocatalyst have achieved a series of great achievement, and bismuthous compound is as BiVO
4, Bi
2moO
6, Bi
2mo
2o
9, Bi
2mo
3o
12and Bi
2wO
4be in the news and there is good absorption under visible light.A series of niobium (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.Such as, niobate photocatalyst Pb
3nb
4o
13, BiNbO
4and Bi
2mNbO
7(M=Al, Ga, In, Y, rare earth element and Fe) etc. with niobium potassium compound oxide photocatalyst as KNbO
3, KNb
3o
8, K
4nb
6o
17and K
6nb
10.6o
30deng all, there is good photocatalysis performance, but its intrinsic photocatalytic effect is very weak or do not have activity in visible-range.
Although photocatalysis research has carried out the several years, the current exploration to visible light-responded photochemical catalyst is the summary of experience drawn by great many of experiments with exploitation major part, in theory also cannot from the structure of compound, composition, the physicochemical properties such as molecular weight are predicted its photocatalysis performance, therefore at present report to have visible light-responded photochemical catalyst kind still very limited, and it is low to there is light conversion efficiency, synthesis difficulty, poor stability and the problem such as spectral response range is narrow, research and develop that new preparation method is simple and to have the visible light-responded high efficiency photocatalyst of wideband be that this area scientific and technical personnel thirst for solving always but are difficult to the difficult problem that succeeds all the time, which greatly limits extensive use and the development of photochemical catalyst.We are to consisting of LiBi
3b
4o
11, LiBiB
2o
5, LiBi
2b
3o
8sample carried out Photocatalytic Performance Study.Found that LiBi
3b
4o
11band gap is 2.67eV, has excellent visible light-responded photocatalysis performance; LiBiB
2o
5with LiBi
2b
3o
8band gap width is greater than 3.2eV, can only show activity under ultraviolet irradiation.
Summary of the invention
The object of this invention is to provide and a kind of there is visible light-responded photocatalyst Li Bi
3b
4o
11and preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst that the present invention relates to is: LiBi
3b
4o
11.
Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material Li
2cO
3, Bi
2o
3and H
3bO
3starting powder press LiBi
3b
4o
11composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 650 ~ 700 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiBi
3b
4o
11powder.
Advantage of the present invention: photocatalyst Li Bi
3b
4o
11visible light response range wide, the high and good stability of light conversion efficiency, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under visible light illumination; Preparation method is simple in addition, synthesis temperature is low, and cost is low, is applicable to industrial production and application.
Detailed description of the invention
To be specifically described the present invention below:
1, in order to obtain the composite oxides used in the present invention, first use solid-phase synthesis to prepare powder, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.
2, in order to effectively utilize light, the size of the photochemical catalyst in the present invention is preferably in micron level, or even nano particle, and specific area is larger.With oxide powder prepared by solid-phase synthesis, its particle is comparatively large and surface area is less, but can pulverize means by ball mill makes particle diameter diminish.
3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Photocatalyst Li Bi
3b
4o
11addition be 1g/L; Light source uses the xenon lamp of 300W, the vessel that reactive tank uses pyrex to make, and obtains the light that wavelength is greater than 420nm, then irradiate photochemical catalyst by wave filter; Catalysis time is set as 60 minutes.
Embodiment 1:
(1) by 99.9% analytically pure chemical raw material Li
2cO
3, Bi
2o
3and H
3bO
3starting powder press LiBi
3b
4o
11composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 650 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiBi
3b
4o
11powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 97.9% to methyl orange clearance in 60 minutes at wavelength.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material Li
2cO
3, Bi
2o
3and H
3bO
3starting powder press LiBi
3b
4o
11composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 680 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiBi
3b
4o
11powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 98.9% to methyl orange clearance in 60 minutes at wavelength.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material Li
2cO
3, Bi
2o
3and H
3bO
3starting powder press LiBi
3b
4o
11composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 700 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and average diameter of particles is diminished, lower than 2 μm, namely obtain LiBi
3b
4o
11powder.
Prepared photochemical catalyst, be greater than the radiation of visible light of 420nm at wavelength under, 60min reaches 97.9% to methyl orange clearance.
The present invention is never limited to above embodiment.Bound, the interval value of each temperature can realize the present invention, do not enumerate embodiment at this.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, active carbon or quartz sand etc., and photochemical catalyst can be carried on matrix surface in the form of a film.
Claims (1)
1. a visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described photochemical catalyst is LiBi
3b
4o
11;
Preparation method's concrete steps of described photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material Li
2cO
3, Bi
2o
3and H
3bO
3starting powder press LiBi
3b
4o
11composition weigh batching;
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;
(3) powder step (2) mixed 650 ~ 700 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, is then pulverized by ball mill and makes average diameter of particles lower than 2 μm, namely obtain LiBi
3b
4o
11powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825540.3A CN104492419B (en) | 2014-12-28 | 2014-12-28 | Visible light-responded photocatalyst Li Bi3b4o11and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825540.3A CN104492419B (en) | 2014-12-28 | 2014-12-28 | Visible light-responded photocatalyst Li Bi3b4o11and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104492419A true CN104492419A (en) | 2015-04-08 |
| CN104492419B CN104492419B (en) | 2016-08-17 |
Family
ID=52933921
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|---|---|---|---|
| CN201410825540.3A Active CN104492419B (en) | 2014-12-28 | 2014-12-28 | Visible light-responded photocatalyst Li Bi3b4o11and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166490A (en) * | 2016-07-24 | 2016-11-30 | 桂林理工大学 | Visible light-responded photocatalyst Li Fe3si2o9and preparation method thereof |
| CN110605112A (en) * | 2019-05-10 | 2019-12-24 | 盐城工学院 | Lithium oxide photocatalytic material and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| CN101856611A (en) * | 2010-06-10 | 2010-10-13 | 南开大学 | Novel high-activity indium borate photo-catalyst |
| CN101879443A (en) * | 2010-07-07 | 2010-11-10 | 南开大学 | Novel high-efficiency strontium borate-like photocatalyst |
| CN102600828A (en) * | 2012-02-08 | 2012-07-25 | 桂林理工大学 | Visible light responded composite oxide photocatalyst LiBiTiO4 and its preparation method |
| CN103641231A (en) * | 2013-12-09 | 2014-03-19 | 浙江工业大学 | Application of cupric borate as visible light catalyst for degrading dye wastewater |
-
2014
- 2014-12-28 CN CN201410825540.3A patent/CN104492419B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101856611A (en) * | 2010-06-10 | 2010-10-13 | 南开大学 | Novel high-activity indium borate photo-catalyst |
| CN101879443A (en) * | 2010-07-07 | 2010-11-10 | 南开大学 | Novel high-efficiency strontium borate-like photocatalyst |
| CN102600828A (en) * | 2012-02-08 | 2012-07-25 | 桂林理工大学 | Visible light responded composite oxide photocatalyst LiBiTiO4 and its preparation method |
| CN103641231A (en) * | 2013-12-09 | 2014-03-19 | 浙江工业大学 | Application of cupric borate as visible light catalyst for degrading dye wastewater |
Non-Patent Citations (1)
| Title |
|---|
| JIKAI LIU, ET AL.: "Visible-light-responsive copper(Ⅱ) borate photocatalysts with intrinsic midgap states for water splitting", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106166490A (en) * | 2016-07-24 | 2016-11-30 | 桂林理工大学 | Visible light-responded photocatalyst Li Fe3si2o9and preparation method thereof |
| CN110605112A (en) * | 2019-05-10 | 2019-12-24 | 盐城工学院 | Lithium oxide photocatalytic material and preparation method thereof |
| CN110605112B (en) * | 2019-05-10 | 2022-07-19 | 盐城工学院 | Lithium oxide photocatalytic material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104492419B (en) | 2016-08-17 |
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Effective date of registration: 20201209 Address after: No.25-1, Gangcheng Road, dongyinggang Economic Development Zone, Hekou District, Dongying City, Shandong Province Patentee after: Shandong Xingqiang Chemical Industry Technology Research Institute Co.,Ltd. Address before: Room 502, building 1, No. 40, xiayuangang East Street, Tianhe District, Guangzhou City, Guangdong Province Patentee before: Guangzhou Boyi Intellectual Property Operation Co.,Ltd. Effective date of registration: 20201209 Address after: Room 502, building 1, No. 40, xiayuangang East Street, Tianhe District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Boyi Intellectual Property Operation Co.,Ltd. Address before: 541004 the Guangxi Zhuang Autonomous Region Guilin Construction Road No. 12 Patentee before: GUILIN University OF TECHNOLOGY |