CN102671668B

CN102671668B - Visible light-responsive oxide photocatalyst with structure containing iron, tungsten and bronze and preparation method

Info

Publication number: CN102671668B
Application number: CN 201210137564
Authority: CN
Inventors: 韦珍海; 方亮; 苏聪学
Original assignee: Guilin University of Technology
Current assignee: Suzhou Shihao Building Materials New Technology Engineering Co Ltd
Priority date: 2012-05-03
Filing date: 2012-05-03
Publication date: 2013-09-18
Anticipated expiration: 2032-05-03
Also published as: CN102671668A

Abstract

The invention discloses a visible light-responsive oxide photocatalyst with a structure containing iron, tungsten and bronze and a preparation method. The chemical composition formula of the oxide photocatalyst with the structure containing iron, tungsten and bronze is as follows: Ba5KFe0.5(NbxTa<1-x >)9.5O30 (x is more than or equal to 0 and less than or equal to 1). According to the preparationmethod, 1) chemical raw materials BaCO3, K2CO3, Fe2O3, Nb2O5, and Ta2O5 with the analytic purity of 99.9 percent are weighed and prepared according to the chemical formula Ba5KFe0.5(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, theraw 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 1250-1350 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

Visible light-responded iron content tungsten bronze structure oxidation photocatalyst and preparation method

Technical field

The present invention relates to a kind of visible light-responded iron content tungsten bronze structure oxidation photocatalyst and preparation method, 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.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 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 iron content tungsten bronze structure oxidation photocatalyst with and preparation method thereof.

A kind of chemical constitution formula with visible light-responded iron content dove bronze-structured oxides photochemical catalyst provided by the invention is: Ba ₅KFe _0.5(Nb _xTa _1-x) _9.5O ₃₀, 0≤x≤1 wherein.

The preparation method of above-mentioned visible light-responded iron content dove bronze-structured oxides photochemical catalyst carries out according to the following steps:

1) with 99.9% analytically pure chemical raw material BaCO ₃, K ₂CO ₃, Fe ₂O ₃, Nb ₂O ₅And Ta ₂O ₅, press Ba ₅KFe _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 1250-1350 ℃ of pre-burning, and the insulation 6-8 hour, naturally cool to room temperature, by pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain iron content dove bronze-structured oxides photocatalyst Ba ₅KFe _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, 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, namely 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 iron content 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 make obtain wavelength greater than 420nm long wavelength's light by wave filter, then the irradiates light catalyst; The catalysis time set is 120min.

Embodiment 1:

1) with 99.9% analytically pure chemical raw material BaCO ₃, K ₂CO ₃, Fe ₂O ₃And Ta ₂O ₅, press Ba ₅KFe _0.5Ta _9.5O ₃₀The chemical formula weigh batching.

2) chemical raw material that step (1) 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 1350 ℃ of pre-burnings, and be incubated 8 hours, naturally cool to room temperature, by pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain iron content tungsten bronze structure oxidation photocatalyst Ba ₅KFe _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, K ₂CO ₃, Fe ₂O ₃, Nb ₂O ₅And Ta ₂O ₅, press Ba ₅KFe _0.5Nb _4.75Ta _4.75O ₃₀The chemical formula weigh batching.

2) chemical raw material that step (1) 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 1300 ℃ of pre-burnings, and be incubated 7 hours, naturally cool to room temperature, by pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain iron content dove bronze-structured oxides photocatalyst Ba ₅KFe _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, K ₂CO ₃, Fe ₂O ₃And Nb ₂O ₅, press Ba ₅KFe _0.5Nb _9.5O ₃₀The chemical formula weigh batching.

2) chemical 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) with step (2) gained powder 1250 ℃ of pre-burnings, and be incubated 6 hours, naturally cool to room temperature, by pulverizing means such as ball mills particle diameter is diminished then, reach 2 μ m, can obtain iron content tungsten bronze structure oxidation photocatalyst Ba ₅KFe _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 analog structures such as Ba 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 (as 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. an iron content tungsten bronze structure oxide is characterized in that the chemical constitution formula of described iron content tungsten bronze structure oxide is: Ba as the application of visible light-responded photochemical catalyst ₅KFe _0.5(Nb _xTa _1-x) _9.5O ₃₀, 0≤x≤1 wherein;

Preparation method's step of described iron content tungsten bronze structure oxide is:

2) the 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) the gained powder is 1250-1350 ℃ of pre-burning, and insulation 6-8 hour, naturally cools to room temperature, by ball mill pulverizing means particle diameter diminished then, reaches 2 μ m, namely obtains iron content tungsten bronze structure oxide Ba ₅KFe _0.5(Nb _xTa _1-x) _9.5O ₃₀Powder.