CN104069850A

CN104069850A - Photocatalyst LiTi2V3O12 in response to visible light and preparation method thereof

Info

Publication number: CN104069850A
Application number: CN201410207757.8A
Authority: CN
Inventors: 唐莹; 方亮; 李洁
Original assignee: Guilin University of Technology
Current assignee: Guilin University of Technology
Priority date: 2014-05-17
Filing date: 2014-05-17
Publication date: 2014-10-01

Abstract

The invention discloses a photocatalyst LiTi2V3O12 in response to visible light and a preparation method thereof. The chemical formula of the photocatalyst is LiTi2V3O12. The preparation method comprises the following steps: (1) weighing and preparing the following chemical raw materials according to the chemical formula LiTi2V3O12: 99.9% analytically pure Li2CO3, 99.9% analytically pure TiO2 and 99.9% analytically pure V2O5; (2) mixing the raw materials prepared in the step (1), putting the raw materials in a ball milling tank, adding zirconia balls and distilled water, ball-milling the raw materials for 8 hours, mixing and levigating the raw materials, taking out and drying the powder and sieving the powder with a 200-mesh sieve; and (3) presintering the powder uniformly mixed in the step (2) at 580-600 DEG C, preserving heat for 6 hours, naturally cooling the powder to the room temperature and then reducing the diameters of the granules below 2mu m by means of grinding with a ball mill, thus obtaining the powder LiTi2V3O12. The preparation method is simple and is low in cost. The prepared photocatalyst has excellent catalytic performance, has the function of decomposing harmful chemical substances under irradiation of visible light, has good stability and has a good application prospect.

Description

Visible light-responded photocatalyst Li Ti 2v 3o 12and preparation method thereof

Technical field

The present invention relates to a kind of visible light-responded photocatalyst Li Ti ₂v ₃o ₁₂and 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 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.The principle of light-catalyzed reaction is that photochemical catalyst is after the photon having absorbed higher than its band-gap energy, hole and electronics are generated, these holes and electronics carry out respectively oxidation reaction and reduction reaction, reach the object of decomposing harmful chemical, organic-biological matter and sterilization.Photochemical catalyst has many kinds, and wherein most representative is titanium dioxide (TiO ₂), 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 be indoor or have a 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 for efficient utilization, the R and D of bismuth series photocatalyst have obtained a series of great achievements, and bismuthous compound is as BiVO ₄, Bi ₂moO ₆, Bi ₂mo ₂o ₉, Bi ₂mo ₃o ₁₂and Bi ₂wO ₄be reported in and under visible ray, there is good absorption.A series of niobiums (tantalum) hydrochlorate photochemical catalyst is because the photocatalytic activity having compared with high is widely studied.For example, niobate photocatalyst Pb ₃nb ₄o ₁₃, BiNbO ₄and Bi ₂mNbO ₇(M=Al, Ga, In, Y, rare earth element and Fe) etc. with niobium potassium compound oxide photocatalyst as KNbO ₃, KNb ₃o ₈, K ₄nb ₆o ₁₇and K ₆nb _10.6o ₃₀deng all thering is good 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, still exist that light conversion efficiency is low, poor stability and the problem such as spectral response range is narrow, be very necessary so research and develop the new visible light-responded high efficiency photocatalyst that has.We are to synthetic noval chemical compound LiTi in research ₂v ₃o ₁₂carry out Photocatalytic Performance Study, found that LiTi ₂v ₃o ₁₂band gap be 2.0eV, there is excellent visible light-responded photocatalysis performance.

Summary of the invention

The object of this invention is to provide a kind of visible light-responded photocatalyst Li Ti that has ₂v ₃o ₁₂and preparation method thereof.

The chemical composition general formula with visible light-responded photochemical catalyst the present invention relates to is: LiTi ₂v ₃o ₁₂.

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

(1) by 99.9% analytically pure chemical raw material Li ₂cO ₃, TiO ₂with and V ₂o ₅, by LiTi ₂v ₃o ₁₂chemical formula weigh batching.

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

(3) powder step (2) being mixed is 580 ~ 600 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, average diameter of particles diminished, and lower than 2 μ m, obtains LiTi ₂v ₃o ₁₂powder.

Of the present invention beneficial effect: the spectral response range of the photochemical catalyst that the present invention obtains is wide that the high and good stability of light conversion efficiency has the effect of decomposing harmful chemical, organic-biological matter and sterilization under radiation of visible light; Preparation method is simple in addition, synthesis temperature is low, and cost is low, is applicable to industrial production and application.

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 ball mill pulverizing means.

3, photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L; Photocatalyst Li Ti 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 60 minutes.

Embodiment 1:

(3) powder step (2) being mixed is 580 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, average diameter of particles diminished, and lower than 2 μ m, obtains LiTi 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 98.7% in 60 minutes.

Embodiment 2:

(3) powder step (2) being mixed is 590 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, average diameter of particles diminished, and lower than 2 μ m, obtains LiTi 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 99.5% in 60 minutes.

Embodiment 3:

(3) powder step (2) being mixed is 600 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then by ball mill pulverizing means, average diameter of particles diminished, and lower than 2 μ m, obtains LiTi ₂v ₃o ₁₂powder.

Prepared photochemical catalyst, is greater than at wavelength under the radiation of visible light of 420nm, and 60min reaches 98.4% to methyl orange clearance.

The present invention is never limited to above embodiment.Bound, the interval value of each temperature 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 or quartz sand etc., and photochemical catalyst can be carried on matrix surface with the form of film.

Claims

1. a visible light-responded photochemical catalyst, is characterized in that the chemical constitution formula of described photochemical catalyst is: LiTi ₂v ₃o ₁₂;

Preparation method's concrete steps of described photochemical catalyst are:

(1) by 99.9% analytically pure chemical raw material Li ₂cO ₃, TiO ₂with and V ₂o ₅, by LiTi ₂v ₃o ₁₂chemical formula weigh batching;

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

(3) powder step (2) being mixed is 580 ~ 600 DEG C of pre-burnings, and is incubated 6 hours, naturally cools to room temperature, then makes average diameter of particles lower than 2 μ m by ball mill pulverizing means, obtains LiTi ₂v ₃o ₁₂powder.