CN104307506A - Visible-light response photocatalyst CaNb4V2O16 and preparation method thereof - Google Patents
Visible-light response photocatalyst CaNb4V2O16 and preparation method thereof Download PDFInfo
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- CN104307506A CN104307506A CN201410548170.3A CN201410548170A CN104307506A CN 104307506 A CN104307506 A CN 104307506A CN 201410548170 A CN201410548170 A CN 201410548170A CN 104307506 A CN104307506 A CN 104307506A
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Abstract
The invention discloses a visible-light response photocatalyst CaNb4V2O16 and a preparation method thereof. A chemical composition formula of the photocatalyst is CaNb4V2O16. The invention further discloses a preparation method of the visible-light response photocatalyst CaNb4V2O16. The photocatalyst obtained by adopting the invention has the advantages of wide spectrum response range, high light conversion efficiency, good stability and the like; the visible-light response photocatalyst CaNb4V2O16 has functions of decomposing harmful chemical substances and organic biomasses, and sterilizing under the visible light illumination; and in addition, the preparation method is simple, is low in synthesis temperature and low in cost, and is suitable for industrialized production and application.
Description
Technical field
The present invention relates to a kind of visible light-responded photochemical catalyst CaNb
4v
2o
16and 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, but at present report to have visible light-responded photochemical catalyst kind still very limited, still also exist that light conversion efficiency is low, poor stability and the problem such as spectral response range is narrow, so it is very necessary for researching and developing the new visible light-responded high efficiency photocatalyst that has.We are to consisting of CaNb
4v
2o
16, BaNb
4v
2o
16, PbNb
4v
2o
16, SrNb
4v
2o
16compound carried out Photocatalytic Performance Study, found that CaNb
4v
2o
16band gap be 2.74 eV, have excellent visible light-responded photocatalysis performance, the band gap width of other sample is all greater than 3.2eV, just can only can 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 photochemical catalyst CaNb
4v
2o
16and preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst that the present invention relates to is: CaNb
4v
2o
16.
Preparation method's concrete steps of above-mentioned visible light-responded photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material CaCO
3, Nb
2o
5and V
2o
5starting powder press CaNb
4v
2o
16composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and distilled water, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 800 ~ 850 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 CaNb
4v
2o
16powder.
The spectral response range of the photochemical catalyst that the present invention obtains is 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; Photochemical catalyst CaNb
4v
2o
16addition 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 CaCO
3, Nb
2o
5and V
2o
5starting powder press CaNb
4v
2o
16composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and distilled water, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 800 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 CaNb
4v
2o
16powder.
Prepared photochemical catalyst, under being greater than the radiation of visible light of 420nm, reaches 97.2% to methyl orange clearance in 60 minutes at wavelength.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material CaCO
3, Nb
2o
5and V
2o
5starting powder press CaNb
4v
2o
16composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and distilled water, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 820 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 CaNb
4v
2o
16powder.
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 3:
(1) by 99.9% analytically pure chemical raw material CaCO
3, Nb
2o
5and V
2o
5starting powder press CaNb
4v
2o
16composition weigh batching.
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and distilled water, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.
(3) powder step (2) mixed 850 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 CaNb
4v
2o
16powder.
Prepared photochemical catalyst, be greater than the radiation of visible light of 420nm at wavelength under, 60min reaches 97.7% 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 CaNb
4v
2o
16;
Preparation method's concrete steps of described photochemical catalyst are:
(1) by 99.9% analytically pure chemical raw material CaCO
3, Nb
2o
5and V
2o
5starting powder press CaNb
4v
2o
16composition weigh batching;
(2) raw material mixing step (1) prepared, put into ball grinder, add zirconia ball and distilled water, ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;
(3) powder step (2) mixed 800 ~ 850 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 CaNb
4v
2o
16powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410548170.3A CN104307506B (en) | 2014-10-16 | 2014-10-16 | Visible light-responded photocatalyst CaNb4v2o16and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410548170.3A CN104307506B (en) | 2014-10-16 | 2014-10-16 | Visible light-responded photocatalyst CaNb4v2o16and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104307506A true CN104307506A (en) | 2015-01-28 |
| CN104307506B CN104307506B (en) | 2016-08-10 |
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ID=52362898
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| CN201410548170.3A Active CN104307506B (en) | 2014-10-16 | 2014-10-16 | Visible light-responded photocatalyst CaNb4v2o16and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772135A (en) * | 2015-04-08 | 2015-07-15 | 三峡大学 | Wide-frequency high-efficiency visible light response photocatalyst CaNb2V2O11 and method for preparing wide-frequency high-efficiency visible light response photocatalyst |
Citations (5)
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| JP2004275946A (en) * | 2003-03-18 | 2004-10-07 | National Institute For Materials Science | Perovskite type multicomponent oxide visible light responsive photocatalyst, hydrogen manufacturing method using the same and harmful chemical substance decomposing method |
| JP2007021354A (en) * | 2005-07-15 | 2007-02-01 | Nikon Corp | Photo-catalyst and its manufacturing method |
| CN101612560A (en) * | 2009-07-19 | 2009-12-30 | 桂林理工大学 | Compound oxide photocatalyst Bi 4M 2O 11Preparation method and application thereof |
| CN103191714A (en) * | 2013-04-16 | 2013-07-10 | 桂林理工大学 | Layered composite oxide photocatalyst Sr2KM3O10 and preparation method thereof |
| US20140231241A1 (en) * | 2011-10-25 | 2014-08-21 | University Court Of The University Of St Andrews | Method for effecting a photocatalytic or photoelectrocatalytic reaction |
-
2014
- 2014-10-16 CN CN201410548170.3A patent/CN104307506B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004275946A (en) * | 2003-03-18 | 2004-10-07 | National Institute For Materials Science | Perovskite type multicomponent oxide visible light responsive photocatalyst, hydrogen manufacturing method using the same and harmful chemical substance decomposing method |
| JP2007021354A (en) * | 2005-07-15 | 2007-02-01 | Nikon Corp | Photo-catalyst and its manufacturing method |
| CN101612560A (en) * | 2009-07-19 | 2009-12-30 | 桂林理工大学 | Compound oxide photocatalyst Bi 4M 2O 11Preparation method and application thereof |
| US20140231241A1 (en) * | 2011-10-25 | 2014-08-21 | University Court Of The University Of St Andrews | Method for effecting a photocatalytic or photoelectrocatalytic reaction |
| CN103191714A (en) * | 2013-04-16 | 2013-07-10 | 桂林理工大学 | Layered composite oxide photocatalyst Sr2KM3O10 and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772135A (en) * | 2015-04-08 | 2015-07-15 | 三峡大学 | Wide-frequency high-efficiency visible light response photocatalyst CaNb2V2O11 and method for preparing wide-frequency high-efficiency visible light response photocatalyst |
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| CN104307506B (en) | 2016-08-10 |
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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 |