CN102962053B - Visible light responsive bismuth-containing garnet structure oxide photocatalyst BiLi2Ca2V3O12 and preparation method thereof - Google Patents

Abstract

The invention discloses a visible light responsive bismuth-containing garnet structure oxide photocatalyst BiLi2Ca2V3O12 and a preparation method thereof. A chemical composition type of the visible light responsive bismuth-containing garnet structure oxide photocatalyst is BiLi2Ca2V3O12. The preparation method comprises the following steps of: weighing and batching 99.9% analytic pure chemical feedstock Bi2O3, Li2CO3, CaCO3 and V2O3 according to the BiLi2Ca2V3O12 formulae; (2) mixing the prepared raw material in the step (1), placing the mixture in a ball mill tank, adding a zirconia ball and absolute ethyl alcohol, performing ball milling for 2-8 hours, mixing and grinding, taking out the raw material so as to dry, and causing the raw material to pass a 200-mesh screen; and (3) preburning the fine material in the step (2) at 650-700 DEG C, carrying out heat preservation for 6-8 hours, naturally cooling to the room temperature, then decreasing the particle diameter through smash instruments such as a ball grinder so as to achieve 2 mu m, thereby obtaining bismuth-containing garnet structure light catalyzer BiLi2Ca2V3O12 powder. The preparation method provided by the invention has the advantages that the preparation method is simple, the cost is low, the preparative photocatalyst has a good catalytical property, and the photocatalyst has the decomposition harmfulness chemical substances, organic biomass and germicidal action under the visible light irradiation.

Description

Visible light-responded bismuth-containing garnet structure oxidation photocatalyst BiLi 2ca 2v 3o 12and preparation method thereof

Technical field

The present invention relates to a kind of visible light-responded bismuth-containing garnet structure oxidation photocatalyst BiLi ₂ca ₂v ₃o ₁₂and preparation method thereof, 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, cause drinking water source, the industry water source quality of people's lives constantly to decline, cause atmosphere pollution constantly to aggravate, cause the continuous destruction of ecological environment, existence to the mankind constitutes a serious threat, in order to address these problems, people are by the whole bag of tricks control and curb environmental pollution.

From phase late 1970s, people proposed to utilize in photochemical catalyst decomposition water and atmosphere in the organic matter such as agricultural chemicals and odorant, and scribble the application example such as self-cleaning of the surface of solids of photochemical catalyst; At present, the photochemical catalyst using is mainly titanium dioxide, utilize titanium dioxide to decompose the organic matter such as agricultural chemicals and odorant in water and in atmosphere, but the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just can show activity, can only, indoor or have the local work of uviol lamp, almost can not utilize visible ray, 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, irradiate near sunshine medium wavelength visible light intensity maximum 500nm to earth's surface, wavelength is that the energy of the visible region of 400nm-750nm is approximately 43% of sunshine gross energy, so in order to utilize efficiently solar spectrum, searching has visible light-responded photochemical catalyst and has caused people's attention, the R and D of bismuth series photocatalyst have obtained a series of great achievements, bismuthous compound, as BiVO ₄and Bi ₂wO ₄be reported in and under visible ray, there is good absorption, and pentavalent bismuth equally also causes application widely.

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, we are to bismuth-containing garnet structure oxide BiLi ₂ca ₂v ₃o ₁₂carry out Photocatalytic Performance Study, found that this compounds has excellent visible light-responded photocatalysis performance.

Summary of the invention

The object of this invention is to provide a kind of visible light-responded bismuth-containing garnet structure photochemical catalyst BiLi that has ₂ca ₂v ₃o ₁₂with and preparation method thereof.

The constitutional chemistry formula with visible light-responded bismuth-containing garnet structure oxidation photocatalyst the present invention relates to is: BiLi ₂ca ₂v ₃o ₁₂.

Above-mentioned visible light-responded bismuth-containing garnet structure photochemical catalyst BiLi ₂ca ₂v ₃o ₁₂preparation method's concrete steps be:

(1) by 99.9% analytically pure chemical raw material Bi ₂o ₃, Li ₂cO ₃, CaCO ₃and V ₂o ₃press BiLi ₂ca ₂v ₃o ₁₂chemical formula weigh batching;

(2) raw material step (1) being prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 2 ~ 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;

(3) by step (2) gained powder 650 ~ 700 DEG C of pre-burnings, and be incubated 6 ~ 8 hours, naturally cool to room temperature, then by ball mill ball milling, particle diameter is diminished, reach 2 μ m, can obtain bismuth-containing garnet structure photochemical catalyst BiLi ₂ca ₂v ₃o ₁₂powder.

Preparation method of the present invention is simple, cost is low, and the photochemical catalyst of preparation has good catalytic performance, has the effect of decomposing harmful chemical, organic-biological matter and sterilization under radiation of visible light.

Detailed description of the invention

To be specifically described the present invention below:

1, the composite oxides in order to obtain using in the present invention, first use solid-phase synthesis to prepare powder, various oxides or carbonate as raw material measured than mixing according to target constitutional chemistry, more synthetic in air atmosphere under normal pressure.

2, in order effectively to 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; The oxide powder of preparing with solid-phase synthesis, its particle is compared with large and surface area is less, but can particle diameter be diminished by pulverizing means such as ball mills.

3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Bismuth-containing garnet structure light is urged agent BiLi ₂ca ₂v ₃o ₁₂addition be 1g/L; Light source uses the xenon lamp of 300W, and the vessel that reactive tank uses pyrex to make, obtain by wave filter the light that wavelength is greater than 420nm long wavelength, then light irradiation catalyst; Catalysis time is set as 120 minutes.

Embodiment 1:

(1) by 99.9% analytically pure chemical raw material Bi ₂o ₃, Li ₂cO ₃, CaCO ₃and V ₂o ₃press BiLi ₂ca ₂v ₃o ₁₂chemical formula weigh batching.

(2) raw material step (1) being prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 2 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.

(3) by step (2) gained powder 650 DEG C of pre-burnings, and be incubated 8 hours, naturally cool to room temperature, then by ball mill ball milling, particle diameter is diminished, reach 2 μ m, can obtain bismuth-containing garnet structure photochemical catalyst BiLi ₂ca ₂v ₃o ₁₂powder.

Prepared photochemical catalyst, is greater than at wavelength under the radiation of visible light of 420nm, methyl orange clearance is reached to 99% in 120 minutes.

Embodiment 2:

(1) by 99.9% analytically pure chemical raw material Bi ₂o ₃, Li ₂cO ₃, CaCO ₃and V ₂o ₃press BiLi ₂ca ₂v ₃o ₁₂chemical formula weigh batching.

(2) raw material step (1) being prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 4 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.

(3) by step (2) gained powder 670 DEG C of pre-burnings, and be incubated 7 hours, naturally cool to room temperature, then by ball mill ball milling, particle diameter is diminished, reach 2 μ m, can obtain bismuth-containing garnet structure photochemical catalyst BiLi ₂ca ₂v ₃o ₁₂powder.

Prepared photochemical catalyst, is greater than at wavelength under the radiation of visible light of 420nm, methyl orange clearance is reached to 99.4% in 120 minutes.

Embodiment 3:

(1) by 99.9% analytically pure chemical raw material Bi ₂o ₃, Li ₂cO ₃, CaCO ₃and V ₂o ₃press BiLi ₂ca ₂v ₃o ₁₂chemical formula weigh batching;

(2) raw material step (1) being prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves.

(3) by step (2) gained powder 700 DEG C of pre-burnings, and be incubated 6 hours, naturally cool to room temperature, then by ball mill ball milling, particle diameter is diminished, reach 2 μ m, can obtain bismuth-containing garnet structure photochemical catalyst BiLi ₂ca ₂v ₃o ₁₂powder.

Prepared photochemical catalyst, is greater than at wavelength under the radiation of visible light of 420nm, methyl orange clearance is reached to 99.2% in 120 minutes.

The present invention is never limited to above embodiment.Have with the element of the analog structures such as Bi and chemical property and also can make and the photochemical catalyst of analogous crystalline structure of the present invention and performance as La, Eu, Y, Ce, Gd, Tb, Dy, Ho, Tm, Yb and Lu etc.Bound, the interval value of each technological parameter (as temperature, time etc.) 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, quartz sand etc., and photochemical catalyst can be carried on matrix surface with the form of film.

Claims (1)

1. bismuth-containing garnet structure oxide, as an application for visible light-responded photochemical catalyst, is characterized in that the constitutional chemistry formula of described bismuth-containing garnet structure oxide is: BiLi ₂ca ₂v ₃o ₁₂;

Preparation method's concrete steps of described bismuth-containing garnet structure oxide are:

(1) by 99.9% analytically pure chemical raw material Bi ₂o ₃, Li ₂cO ₃, CaCO ₃and V ₂o ₃press BiLi ₂ca ₂v ₃o ₁₂chemical formula weigh batching;

(2) raw material step (1) being prepared mixes, and puts into ball grinder, adds zirconia ball and absolute ethyl alcohol, and ball milling 2 ~ 8 hours, is mixed and finely ground, and takes out and dries, and crosses 200 mesh sieves;

(3) by step (2) gained powder 650 ~ 700 DEG C of pre-burnings, and be incubated 6 ~ 8 hours, naturally cool to room temperature, then by ball mill ball milling, particle diameter is diminished, reach 2 μ m, can obtain bismuth-containing garnet structure oxide BiLi ₂ca ₂v ₃o ₁₂powder.