CN101757909B - Visible light responding composite oxide photocatalyst Ba10W6-xMoxLi4O30 and preparation method - Google Patents

Abstract

The invention discloses a visible light responding composite oxide photocatalyst Ba10W6-xMoxLi4O30 and a preparation method. The method comprises the following steps: 1) weighing and batching 99.9% of the analytically pure chemical materials such as BaCO3, WO3, MoO3 and Li2CO3 according to the chemical formula Ba10W6-xMoxLi4O30, wherein x is not less than 0 and not more than 0.8; 2) mixing the batched materials, placing the materials into a ball milling pot, adding zirconia balls and absolute ethyl alcohol, carrying out ball milling for 12h, mixing and levigating the materials, taking out and drying the materials and sieving the materials with 200-mesh sieves; and 3) preburning the powder obtained in the step 2) at 900-1050 DEG C, preserving heat for 8-10h, naturally cooling the powder to the room temperature and then ensuring the diameter of the particles to be around 2mu m by using ball mills and other grinding methods, thus obtaining the composite oxide photocatalyst Ba10W6-xMoxLi4O30 powder. The method is simple and low in cost. The prepared photocatalyst has excellent catalytic performance and has the effect of decomposing harmful chemicals and organic biomass and the effect of sterilization under the irradiation of the visible light.

Description

Visible light responded composite oxide photocatalyst Ba＜sub〉10＜/sub〉W＜sub〉6-x＜/sub〉Mo＜sub〉x＜/sub〉Li＜sub〉4＜/sub〉O＜sub〉30＜/sub〉and the preparation method

Technical field

The present invention relates to a kind of visible light responded composite oxide photocatalyst Ba ₁₀W _6-xMo _xLi ₄O ₃₀And 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, 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 by the whole bag of tricks and curb environmental pollution.

From phase late 1970s, people proposed to utilize in the photochemical catalyst decomposition water and atmosphere in agricultural chemicals and organic matter such as odorant, and application examples such as self-cleaning that scribble the surface of solids of photochemical catalyst.The principle of light-catalyzed reaction is that photochemical catalyst is after having absorbed the photon that is higher than its band-gap energy, hole and electronics have been generated, these holes and electronics carry out oxidation reaction and reduction reaction respectively, reach the purpose of decomposing harmful chemical, organic-biological matter and sterilization.At present, the photochemical catalyst that uses is mainly titanium dioxide, utilized titanium dioxide in the water and the agricultural chemicals in the atmosphere and organic matters such as 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 near sunshine medium wavelength visible light intensity maximum 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.The R and D of photochemical catalyst have obtained a series of great achievements, and bismuthous compound is as BiVO ₄And Bi ₂WO ₄Be reported in and have good absorption under the visible light, and the pentavalent bismuth has equally also caused widely and used.

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 composite oxide photocatalyst with and preparation method thereof.

A kind of visible light responded composite oxide photocatalyst that has provided by the invention is characterized in that the chemical composition general formula of described compound oxide photocatalyst is: Ba ₁₀W _6-xMo _xLi ₄O ₃₀, 0≤x≤0.8 wherein.

The preparation method of above-mentioned visible light responded composite oxide photocatalyst, carry out according to the following steps:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _6-xMo _xLi ₄O ₃₀Chemical formula weigh batching, wherein 0≤x≤0.8;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 900-1050 ℃ of pre-burning, and the insulation 8-10h, naturally cool to room temperature, by pulverizing means such as ball mills particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _6-xMo _xLi ₄O ₃₀Powder.

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

The specific embodiment

To be specifically described 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 various oxides or carbonate as raw material are mixed according to target composition stoichiometric proportion, 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 be diminished by 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 of compound oxide photocatalyst is 1g/L; Light source uses the xenon lamp of 300W, and the vessel that reactive tank uses pyrex to make obtain the light of wavelength greater than 420nm long wavelength, irradiates light catalyst then by wave filter; The catalysis time set is 120mi n.

Embodiment

Serve as that the present invention is described in detail on the basis with concrete practical operation example below.

Embodiment 1:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃And Li ₂CO ₃, press Ba ₁₀W ₆Li ₄O ₃₀The chemical formula weigh batching;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 900 ℃ of pre-burnings, and the insulation 10h, naturally cool to room temperature, by ball mill pulverizing means particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W ₆Li ₄O ₃₀Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 98.6% to the methyl orange clearance.

Embodiment 2:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _5.8Mo _0.2Li ₄O ₃₀The chemical formula weigh batching;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 940 ℃ of pre-burnings, and the insulation 10h, naturally cool to room temperature, by ball mill pulverizing means particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _5.8Mo _0.2Li ₄O ₃₀Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 97.8% to the methyl orange clearance.

Embodiment 3:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _5.6Mo _0.4Li ₄O ₃₀The chemical formula weigh batching;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 980 ℃ of pre-burnings, and the insulation 9h, naturally cool to room temperature, by ball mill pulverizing means particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _5.6Mo _0.4Li ₄O ₃₀Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 98.3% to the methyl orange clearance.

Embodiment 4:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _5.4Mo _0.6Li ₄O ₃₀The chemical formula weigh batching;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 1020 ℃ of pre-burnings, and the insulation 9h, naturally cool to room temperature, by ball mill pulverizing means particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _5.4Mo _0.6Li ₄O ₃₀Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 97.2% to the methyl orange clearance.

Embodiment 5:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _5.2Mo _0.8Li ₄O ₃₀The chemical formula weigh batching;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 1050 ℃ of pre-burnings, and the insulation 8h, naturally cool to room temperature, by ball mill pulverizing means particle diameter is diminished then, reach about 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _5.2Mo _0.8Li ₄O ₃₀Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 96.8% to the methyl orange clearance.

The present invention never is limited to above embodiment.The bound of each raw material, interval value, and the bound of technological parameter (as temperature, time etc.), interval value 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 (2)

1. a visible light responded composite oxide photocatalyst is characterized in that the chemical composition general formula of described compound oxide photocatalyst is: Ba ₁₀W _6-xMo _xLi ₄O ₃₀, 0≤x≤0.8 wherein.

2. the preparation method of compound oxide photocatalyst according to claim 1 is characterized in that concrete steps are:

1) with 99.9% analytically pure chemical raw material BaCO ₃, WO ₃, MoO ₃And Li ₂CO ₃, press Ba ₁₀W _6-xMo _xLi ₄O ₃₀Chemical formula weigh batching, wherein 0≤x≤0.8;

2) confected materials is mixed, put into ball grinder, add zirconia ball and absolute ethyl alcohol, ball milling 12h mixes levigately, takes out oven dry, 200 mesh sieves;

3) with step (2) gained powder 900-1050 ℃ of pre-burning, and insulation 8-10h naturally cools to room temperature, pulverizes then particle diameter is diminished, and reaches 2 μ m, can obtain composite oxide photocatalyst Ba ₁₀W _6-xMo _xLi ₄O ₃₀Powder.