CN104437461B - Visible light-responded photocatalyst Li3bi5o9and preparation method thereof - Google Patents
Visible light-responded photocatalyst Li3bi5o9and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the visible light responsive photocatalyst Li of a kind of high-efficient wide-frequency3Bi5O9And preparation method thereof.The chemical constitution formula of this photochemical catalyst is Li3Bi5O9.The invention also discloses the preparation method of above-mentioned material.The photochemical catalyst that the present invention obtains has the advantages such as spectral response range width, light conversion efficiency height and good stability.There is decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method is simple, synthesis temperature is low, low cost, is suitable for industrial production and application.
Description
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Li3Bi5O9And preparation method thereof, belong to inorganic field of photocatalytic material.
Background technology
Along with socioeconomic development, people increasingly 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 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 be photochemical catalyst after absorbing higher than the photon of its band-gap energy, generate hole and electronics, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach to decompose harmful chemical, organic-biological matter and the purpose of sterilization.Photochemical catalyst has many kinds, and the most most representative is titanium dioxide (TiO2), utilize titanium dioxide that the organic matters such as the agricultural chemicals in water and in air and odorant are decomposed, but the band gap of titanium dioxide is 3.2eV, under the ultraviolet irradiation shorter than 400nm, only just can show activity, can only be at indoor or the local work having uviol lamp, being little to utilize visible ray, this greatly limits the use of titanium dioxide optical catalyst.
In view of photochemical catalyst practicality in decomposing harmful substances, it is indispensable for utilizing sunlight as light source.Irradiate the sunshine medium wavelength maximum intensity of visible ray near 500nm to earth's surface, wavelength is that the energy of the visible region of 400nm ~ 750nm is about the 43% of sunshine gross energy, so in order to utilize efficiently, the R and D of bismuth series photocatalyst have been achieved for a series of great achievement, bismuthous compound such as BiVO4、Bi2MoO6、Bi2Mo2O9、Bi2Mo3O12And Bi2WO4It is in the news and there is good absorption under visible light.A series of niobiums (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.Such as, niobate photocatalyst Pb3Nb4O13、BiNbO4And Bi2MNbO7(M=Al, Ga, In, Y, rare earth element and Fe) etc. and niobium potassium compound oxide photocatalyst such as KNbO3、KNb3O8、K4Nb6O17And K6Nb10.6O30Deng all having preferable photocatalysis performance, but in visible-range, its intrinsic photocatalytic effect is the most weak or does not has activity.
Although photocatalysis research has been carried out the several years, major part of exploring and develop to visible light-responded photochemical catalyst is the summary of experience drawn by great many of experiments at present, the most also cannot be from the crystal structure of compound, composition, its photocatalysis performance is predicted in the physicochemical properties such as molecular weight, therefore at present report to have visible light-responded photochemical catalyst kind the most 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 succeeded all the time, which greatly limits extensively application and the development of photochemical catalyst.We are to consisting of Li3Bi5O9、Li3Ga5O9、Li3Al5O9And Li3Fe5O9Sample carried out Photocatalytic Performance Study.Found that Li3Bi5O9Band gap is 2.49eV, has the visible light-responded photocatalysis performance of excellence；Li3Ga5O9Band gap is 3.49eV, just shows activity under ultraviolet irradiation；Li3Al5O9And Li3Fe5O9For insulator, under ultraviolet irradiation, the most do not show activity.
Summary of the invention
It is an object of the invention to provide and a kind of there is visible light-responded photocatalyst Li3Bi5O9And preparation method thereof.
The chemical constitution formula with visible light-responded photochemical catalyst that the present invention relates to is: Li3Bi5O9。
The preparation method of above-mentioned visible light-responded photochemical catalyst concretely comprises the following steps:
(1) by 99.9% analytically pure chemical raw material Li2CO3And Bi2O3Starting powder press Li3Bi5O9Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) powder step (2) mixed is 700 ~ 750 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 diminish, less than 2 μm, i.e. obtains Li3Bi5O9Powder.
Advantages of the present invention: Li3Bi5O9The visible light-responded wide frequency range of photochemical catalyst, light conversion efficiency height and good stability, there is decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method is simple, synthesis temperature is low, low cost, is suitable for industrial production and application.
Detailed description of the invention
Present invention will be described in detail below:
1, in order to obtain the composite oxides used in the present invention, prepare powder first by solid-phase synthesis, i.e. various oxides or the carbonate as raw material is mixed according to target constitutional chemistry metering ratio, then synthesize in air atmosphere at ambient pressure.
2 in order to effectively utilize light, the size of the photochemical catalyst in the present invention preferably in micron level, even nano particle, and specific surface area is bigger.The oxide powder prepared with solid-phase synthesis, its particle is relatively big and surface area is less, but can be by ball mill pulverizing means and make particle diameter diminish.
3, the photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L；Photocatalyst Li3Bi5O9Addition be 1g/L；Light source uses the xenon lamp of 300W, and reactive tank uses the vessel that pyrex is made, and obtains the wavelength light more than 420nm by wave filter, then irradiates photochemical catalyst；Catalysis time is set as 60 minutes.
Embodiment 1:
(1) by 99.9% analytically pure chemical raw material Li2CO3And Bi2O3Starting powder press Li3Bi5O9Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) powder step (2) mixed is 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 diminish, less than 2 μm, i.e. obtains Li3Bi5O9Powder.
Prepared photochemical catalyst, under the wavelength radiation of visible light more than 420nm, reaches 97.9% to methyl orange clearance in 60 minutes.
Embodiment 2:
(1) by 99.9% analytically pure chemical raw material Li2CO3And Bi2O3Starting powder press Li3Bi5O9Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) powder step (2) mixed is 720 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 diminish, less than 2 μm, i.e. obtains Li3Bi5O9Powder.
Prepared photochemical catalyst, under the wavelength radiation of visible light more than 420nm, reaches 98.9% to methyl orange clearance in 60 minutes.
Embodiment 3:
(1) by 99.9% analytically pure chemical raw material Li2CO3And Bi2O3Starting powder press Li3Bi5O9Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves.
(3) powder step (2) mixed is 750 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 diminish, less than 2 μm, i.e. obtains Li3Bi5O9Powder.
Prepared photochemical catalyst, under the wavelength radiation of visible light more than 420nm, 60min reaches 97.4% to methyl orange clearance.
The present invention is never limited to above example.The bound of each temperature, interval value can realize the present invention, embodiment numerous to list herein.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass, pottery, activated 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, it is characterised in that the chemical constitution formula of described photochemical catalyst is Li3Bi5O9；
The preparation method of described photochemical catalyst concretely comprises the following steps:
(1) by 99.9% analytically pure chemical raw material Li2CO3And Bi2O3Starting powder press Li3Bi5O9Composition weigh dispensing；
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and absolute ethyl alcohol, ball milling 8 hours, be mixed and finely ground, take out and dry, cross 200 mesh sieves；
(3) powder step (2) mixed is 700 ~ 750 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 be less than 2 μm, i.e. obtains Li3Bi5O9Powder.
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