CN102671669A - Visible light-responsive oxide photocatalyst with structure containing lithium, tungsten and bronze and preparation method - Google Patents
Visible light-responsive oxide photocatalyst with structure containing lithium, tungsten and bronze and preparation method Download PDFInfo
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- CN102671669A CN102671669A CN2012101375871A CN201210137587A CN102671669A CN 102671669 A CN102671669 A CN 102671669A CN 2012101375871 A CN2012101375871 A CN 2012101375871A CN 201210137587 A CN201210137587 A CN 201210137587A CN 102671669 A CN102671669 A CN 102671669A
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Abstract
The invention discloses a visible light-responsive oxide photocatalyst with a structure containing lithium, tungsten and bronze and a preparation method. The chemical composition formula of the oxide photocatalyst with the structure containing lithium, tungsten and bronze is as follows: Ba5LiFe0.5(NbxTa<1-x >)9.5O30 (x is more than or equal to 0 and less than or equal to 1). According to the preparation method, 1) chemical raw materials BaCO3, Li2CO3, Fe2O3, Nb2O5, and Ta2O5 with the analytic purity of 99.9 percent are weighed and prepared according to the chemical formula Ba5LiFe0.5(NbxTa<1-x >)9.5O30, wherein x is more than or equal to 0 and less than or equal to 1; 2) the raw materials prepared in Step (1) are mixed and placed into a ball mill, zirconia balls and absolute ethanol are added, the raw materials are ball-milled for 2-8 hours, mixed, pulverized, taken out, dried and screened by a 200-mesh sieve; and 3) the powder prepared in Step (2) is pre-burned at 1175-1275 DEG C, the temperature is kept for 6-8 hours, the powder is naturally cooled to the room temperature and then crushed by the ball mill or in other crushing methods so that the diameter of particles is reduced to 2mum. The preparation method is simple, the cost is low, and the prepared photocatalyst has excellent catalytic performance and has the effects of decomposition of hazardous chemical substances and organic biomass and also sterilization under visible light irradiation.
Description
Technical field
The present invention relates to a kind of visible light-responded lithium tungsten bronze structure oxidation photocatalyst and preparation method of containing, belong to inorganic field of photocatalytic material.
Background technology
Environmental pollution is the problem that countries in the world are extremely paid close attention to, and has caused drinking water source, the industry water source quality of people's lives constantly to descend, and causes atmosphere pollution constantly to aggravate, and causes the continuous destruction of ecological environment, and human existence is constituted a serious threat.In order to address these problems, people control through the whole bag of tricks and curb environmental pollution.
From phase late 1970s, people proposed to utilize in the photochemical catalyst decomposition water with atmosphere in organic matters such as agricultural chemicals and odorant, and application examples such as self-cleaning that scribble the surface of solids of photochemical catalyst.At present; The photochemical catalyst that uses is mainly titanium dioxide, utilized titanium dioxide in the water with atmosphere in organic matters such as agricultural chemicals and odorant decompose, yet the band gap of titanium dioxide is 3.2eV; Only under than the short ultraviolet irradiation of 400nm, just can show activity; Can only almost can not utilize visible light indoor or the local work of uviol lamp is arranged, this has limited the use of titanium dioxide optical catalyst greatly.
Consider the practicality of photochemical catalyst in decomposing harmful substances, utilizing sunshine is indispensable as light source.Irradiation is maximum near sunshine medium wavelength visible light intensity 500nm on the face of land; Wavelength is that the energy of the visible region of 400nm-750nm approximately is 43% of a sunshine gross energy; So in order to utilize solar spectrum efficiently, searching has the attention that visible light-responded photochemical catalyst has caused people.At present report to have visible light-responded photochemical catalyst kind still very limited, be very necessary so research and develop the new visible light-responded high efficiency photocatalyst that has.
Summary of the invention
The purpose of this invention is to provide a kind of have visible light-responded contain lithium tungsten bronze structure oxidation photocatalyst with and preparation method thereof.
Provided by the invention a kind ofly have the visible light-responded chemical constitution formula that contains lithium tungsten bronze structure oxidation photocatalyst and be: Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30, 0≤x≤1 wherein.
The above-mentioned visible light-responded preparation method who contains lithium tungsten bronze structure oxidation photocatalyst carries out according to the following steps:
1) with 99.9% analytically pure chemical raw material BaCO
3, Li
2CO
3, Fe
2O
3, Nb
2O
5And Ta
2O
5, press Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30Chemical formula weigh batching, wherein 0≤x≤1;
2) step (1) confected materials is mixed, puts into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 2-8 hour, mixes levigately, take out oven dry, 200 mesh sieves;
3) with step (2) gained powder 1175-1275 ℃ of pre-burning, and the insulation 6-8 hour, naturally cool to room temperature, through pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain containing lithium tungsten bronze structure oxidation photocatalyst Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30(0≤x≤1) powder.
Preparation method of the present invention is simple, cost is low, and the photochemical catalyst of preparation has excellent catalytic performance, under radiation of visible light, has the effect of decomposing harmful chemical, organic-biological matter and sterilization.
The specific embodiment
To specify the present invention below:
1, in order to obtain employed composite oxides among the present invention, at first use solid-phase synthesis to prepare powder, promptly mix various oxides or carbonate according to target composition stoichiometric proportion as raw material, synthetic in air atmosphere under normal pressure again.
2, in order effectively to utilize light, the size of the photochemical catalyst among the present invention is preferably in micron level, or even nano particle, and specific area is bigger.With the oxide powder of solid-phase synthesis preparation, its particle is big and surface area is less, but can particle diameter diminished through pulverizing means such as ball mills.
3, as the simulation organic pollution, its concentration is 20mg/L with methyl orange in photocatalysis experiment of the present invention; The addition that contains lithium tungsten bronze structure oxidation photocatalyst is 1g/L; Light source uses the xenon lamp of 300W, and the vessel that reactive tank uses pyrex to process obtain the light of wavelength greater than 420nm long wavelength, irradiates light catalyst then through wave filter; The catalysis time set is 120min.
Embodiment 1:
1) with 99.9% analytically pure chemical raw material BaCO
3, Li
2CO
3, Fe
2O
3And Ta
2O
5, press Ba
5LiFe
0.5Ta
9.5O
30The chemical formula weigh batching.
2) chemical raw material that step (1) is prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 2 hours mixes levigately, takes out oven dry, 200 mesh sieves.
3) with step (2) gained powder 1275 ℃ of pre-burnings, and be incubated 8 hours, naturally cool to room temperature, through pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain containing lithium tungsten bronze structure oxidation photocatalyst Ba
5LiFe
0.5Ta
9.5O
30Powder.
Prepared photochemical catalyst under the radiation of visible light of wavelength greater than 420nm, reached 99% to the methyl orange clearance in 120 minutes.
Embodiment 2:
1) with 99.9% analytically pure chemical raw material BaCO
3, Li
2CO
3, Fe
2O
3, Nb
2O
5And Ta
2O
5, press Ba
5LiFe
0.5Nb
4.75Ta
4.75O
30The chemical formula weigh batching.
2) chemical raw material that step (1) is prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 4 hours mixes levigately, takes out oven dry, 200 mesh sieves.
3) with step (2) gained powder 1225 ℃ of pre-burnings, and be incubated 7 hours, naturally cool to room temperature, through pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain containing lithium tungsten bronze structure oxidation photocatalyst Ba
5LiFe
0.5Nb
4.75Ta
4.75O
30Powder.
Prepared photochemical catalyst under the radiation of visible light of wavelength greater than 420nm, reached 99.4% to the methyl orange clearance in 120 minutes.
Embodiment 3:
1) with 99.9% analytically pure chemical raw material BaCO
3, Li
2CO
3, Fe
2O
3And Nb
2O
5, press Ba
5LiFe
0.5Nb
9.5O
30The chemical formula weigh batching.
2) chemical raw material that step (1) is prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours mixes levigately, takes out oven dry, 200 mesh sieves.
3) with step (2) gained powder 1175 ℃ of pre-burnings, and be incubated 6 hours, naturally cool to room temperature, through pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain containing lithium tungsten bronze structure oxidation photocatalyst Ba
5LiFe
0.5Nb
9.5O
30Powder.
Prepared photochemical catalyst under the radiation of visible light of wavelength greater than 420nm, reached 99.2% to the methyl orange clearance in 120 minutes.
The present invention never is limited to above embodiment.Have element such as Sr with Ba analog structure and chemical property, Ca, Pb etc. also can make the photochemical catalyst with analogous crystalline structure of the present invention and performance.Bound, the interval value of each technological parameter (like temperature, time etc.) can both realize the present invention, do not enumerate embodiment one by one at this.
The made photocatalyst powder of above inventive embodiments can be carried on the multiple matrix surface.Matrix can be glass, pottery, active carbon, quartz sand etc., and photochemical catalyst can be carried on matrix surface with the form of film.
Claims (1)
1. application that contains lithium tungsten bronze structure oxide as visible light-responded photochemical catalyst is characterized in that the said chemical constitution formula that contains lithium tungsten bronze structure oxide is: Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30, 0≤x≤1 wherein;
The said preparation method's step that contains lithium tungsten bronze structure oxide is:
1) with 99.9% analytically pure chemical raw material BaCO
3, Li
2CO
3, Fe
2O
3, Nb
2O
5And Ta
2O
5, press Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30Chemical formula weigh batching, wherein 0≤x≤1;
2) step (1) confected materials is mixed, puts into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 2-8 hour, mixes levigately, take out oven dry, 200 mesh sieves;
3) with step (2) gained powder 1175-1275 ℃ of pre-burning, and the insulation 6-8 hour, naturally cool to room temperature, through ball mill pulverizing means particle diameter is diminished then, reach 2 μ m, can obtain containing lithium tungsten bronze structure oxide Ba
5LiFe
0.5(Nb
xTa
1-x)
9.5O
30(0≤x≤1) powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210137587 CN102671669B (en) | 2012-05-03 | 2012-05-03 | Visible light-responsive oxide photocatalyst with structure containing lithium, tungsten and bronze and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210137587 CN102671669B (en) | 2012-05-03 | 2012-05-03 | Visible light-responsive oxide photocatalyst with structure containing lithium, tungsten and bronze and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102671669A true CN102671669A (en) | 2012-09-19 |
| CN102671669B CN102671669B (en) | 2013-09-18 |
Family
ID=46804609
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210137587 Expired - Fee Related CN102671669B (en) | 2012-05-03 | 2012-05-03 | Visible light-responsive oxide photocatalyst with structure containing lithium, tungsten and bronze and preparation method |
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Citations (4)
| 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 |
| JP2007326738A (en) * | 2006-06-07 | 2007-12-20 | Asahi Kasei Chemicals Corp | Method for producing oxide having bronze structure |
| CN101559371A (en) * | 2009-05-08 | 2009-10-21 | 武汉理工大学 | Molybdenum-containing semi-conductor photocatalysis material responding to visible light, preparation method and application thereof |
| CN101773823A (en) * | 2010-01-02 | 2010-07-14 | 桂林理工大学 | Visible light responded composite oxide photocatalyst BaLi2Nb2-xTaxO9 and preparation method thereof |
-
2012
- 2012-05-03 CN CN 201210137587 patent/CN102671669B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| JP2007326738A (en) * | 2006-06-07 | 2007-12-20 | Asahi Kasei Chemicals Corp | Method for producing oxide having bronze structure |
| CN101559371A (en) * | 2009-05-08 | 2009-10-21 | 武汉理工大学 | Molybdenum-containing semi-conductor photocatalysis material responding to visible light, preparation method and application thereof |
| CN101773823A (en) * | 2010-01-02 | 2010-07-14 | 桂林理工大学 | Visible light responded composite oxide photocatalyst BaLi2Nb2-xTaxO9 and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHAO YANG ET AL.: ""Dielectric properties and high-temperature dielectric relaxation of tungsten-bronze structure ceramics Ba2GdFeNbTa3O15"", 《JOURNAL OF MATERIALS SCIENCE:MATERIALS IN ELECTRONICS》 * |
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| CN102671669B (en) | 2013-09-18 |
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