CN103316656A - Visible-light-responded photocatalyst Ba4ZnTi11O27 and preparation method thereof - Google Patents

Abstract

The invention discloses a visible-light-responded titanate photocatalyst Ba4ZnTi11O27 and a preparation method thereof. The chemical composition formula of the titanate photocatalyst is Ba4ZnTi11O27. The invention further discloses the preparation method of the photocatalyst. According to the photocatalyst and the preparation method thereof, the preparation method is simple and is low in cost, and the prepared photocatalyst has excellent catalysis performance, plays a role in decomposing harmful chemical substances under the irradiation of visible light and is good in stability, thereby having good application prospects.

Description

Visible light-responded photocatalyst Ba 4ZnTi 11O 27And preparation method thereof

Technical field

The present invention relates to a kind of visible light-responded photocatalyst Ba ₄ZnTi ₁₁O ₂₇And 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 and be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.

From phase late 1970s, people proposed to utilize in the photochemical catalyst decomposition water and atmosphere in agricultural chemicals and the 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 respectively oxidation reaction and reduction reaction, reach the purpose of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO ₂), utilized titanium dioxide in the water and the agricultural chemicals in the atmosphere and the organic matters such as odorant decompose, yet the band gap of titanium dioxide is 3.2eV, only under the ultraviolet irradiation shorter than 400nm, just can show activity, can only be indoor or the local work of uviol lamp arranged, almost can not utilize visible light, 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 earth's surface, wavelength is that the energy of the visible region of 400nm ~ 750nm approximately is 43% of sunshine gross energy, so for efficient utilization, the R and D of bismuth series photocatalyst have obtained a series of great achievements, bismuthous compound such as BiVO ₄, Bi ₂MoO ₆, Bi ₂Mo ₂O ₉, Bi ₂Mo ₃O ₁₂And Bi ₂WO ₄Be reported in and have good absorption under the visible light.A series of niobiums (tantalum) hydrochlorate photochemical catalyst is widely studied owing to having higher photocatalytic activity.For example, niobate photocatalyst Pb ₃Nb ₄O ₁₃, BiNbO ₄And Bi ₂MNbO ₇(M=Al, Ga, In, Y, rare earth element or Fe) etc. and niobium potassium compound oxide photocatalyst such as KNbO ₃, KNb ₃O ₈, K ₄Nb ₆O ₁₇And K ₆Nb _10.6O ₃₀Deng all having preferably photocatalysis performance.

Although photocatalysis research has been carried out the several years, but at present report to have visible light-responded photochemical catalyst kind still very limited, exist still that light conversion efficiency is low, the problem such as poor stability and spectrum respective range are narrow, be very necessary so research and develop the new visible light-responded high efficiency photocatalyst that has.Existing document [Huanfu Zhou, Xiuli Chen, Liang Fang, Changzheng Hu, Preparation and Characterization of a New Microwave Dielectric Ceramic Ba ₄ZnTi ₁₁O ₂₇J. American Ceramic Society. 2010,93 (6): 1537-1539] and [Xiuli Chen, Huanfu Zhou, Liang Fang, Laijun Liu, Changda Li, Ruli Guo, Hong Wang. Low-temperature sintering and compatibility with silver electrode of Ba ₄MgTi ₁₁O ₂₇Microwave dielectric ceramic, Materials Research Bulletin, 2010,45 (10): 1509-1512 ]Reported titanate ceramics Ba ₄ZnTi ₁₁O ₂₇And Ba ₄MgTi ₁₁O ₂₇Preparation and microwave dielectric property, but have not yet to see the research report of relevant this compounds photocatalysis performance, we are to Ba ₄ZnTi ₁₁O ₂₇And Ba ₄MgTi ₁₁O ₂₇Carry out Photocatalytic Performance Study, found that Ba ₄ZnTi ₁₁O ₂₇Have excellent visible light-responded photocatalysis performance, but Ba ₄MgTi ₁₁O ₂₇But do not have visible light-responded photocatalysis performance.

Summary of the invention

The purpose of this invention is to provide a kind of visible light-responded photocatalyst Ba that has ₄MgTi ₁₁O ₂₇And preparation method thereof.

The chemical constitution formula with visible light-responded titanate photochemical catalyst that the present invention relates to is: Ba ₄ZnTi ₁₁O ₂₇

Preparation method's concrete steps of above-mentioned visible light-responded titanate photochemical catalyst are:

(1) with 99.9% analytically pure chemical raw material BaCO ₃, ZnO and TiO ₂, press Ba ₄ZnTi ₁₁O ₂₇The chemical formula weigh batching.

(2) raw material that step (1) 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) powder that step (2) is mixed is 1040 ~ 1080 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by pulverizing means such as ball mills particle diameter diminished, and is lower than 2 μ m, namely obtains titanate Ba ₄ZnTi ₁₁O ₂₇Powder.

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.

The specific embodiment

The below will be specifically described the present invention:

1, in order to obtain employed composite oxides among the present invention, at first use solid-phase synthesis to prepare powder, namely various oxides or carbonate as raw material are measured than mixing according to the target constitutional chemistry, 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 larger.With the oxide powder of solid-phase synthesis preparation, its particle is large 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 titanate photocatalyst Ba ₄ZnTi ₁₁O ₂₇Addition be 1g/L; Light source uses the xenon lamp of 300W, and the vessel that reactive tank uses pyrex to make obtain wavelength greater than 420nm long wavelength's light by wave filter, then shine photochemical catalyst; Catalysis time is set as 120 minutes.

Embodiment 1:

(1) with 99.9% analytically pure chemical raw material BaCO ₃, ZnO and TiO ₂, press Ba ₄ZnTi ₁₁O ₂₇The chemical formula weigh batching.

(2) raw material that step (1) 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) powder that step (2) is mixed is 1040 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means particle diameter diminished, and is lower than 2 μ m, namely obtains titanate Ba ₄ZnTi ₁₁O ₂₇Powder.

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

Embodiment 2:

(1) with 99.9% analytically pure chemical raw material BaCO ₃, ZnO and TiO ₂, press Ba ₄ZnTi ₁₁O ₂₇The chemical formula weigh batching.

(2) raw material that step (1) 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) powder that step (2) is mixed is 1060 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means particle diameter diminished, and is lower than 2 μ m, namely obtains titanate Ba ₄ZnTi ₁₁O ₂₇Powder.

Prepared photochemical catalyst under the radiation of visible light of wavelength greater than 420nm, reached 98.2% to the methyl orange clearance in 120 minutes.

Embodiment 3:

(1) with 99.9% analytically pure chemical raw material BaCO ₃, ZnO and TiO ₂, press Ba ₄ZnTi ₁₁O ₂₇The chemical formula weigh batching.

(2) raw material that step (1) 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) powder that step (2) is mixed is 1080 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means particle diameter diminished, and is lower than 2 μ m, namely obtains titanate Ba ₄ZnTi ₁₁O ₂₇Powder.

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

The present invention never is limited to above embodiment.The bound of each temperature, interval value can both realize the present invention, do not enumerate one by one embodiment 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 or quartz sand etc., and photochemical catalyst can be carried on matrix surface with the form of film.

Claims (1)

1. a titanate is characterized in that the chemical constitution formula of described titanate is: Ba as the application of visible light-responded photochemical catalyst ₄ZnTi ₁₁O ₂₇

Preparation method's concrete steps of described titanate are:

(1) with 99.9% analytically pure chemical raw material BaCO ₃, ZnO and TiO ₂, press Ba ₄ZnTi ₁₁O ₂₇The chemical formula weigh batching;

(2) raw material that step (1) 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) powder that step (2) is mixed is 1040 ~ 1080 ℃ of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means particle diameter diminished, and is lower than 2 μ m, namely obtains titanate Ba ₄ZnTi ₁₁O ₂₇Powder.