CN101612574A - Compound oxide photocatalyst Bi 12MO 19Preparation method and application thereof - Google Patents

Abstract

The invention discloses a kind of compound oxide photocatalyst Bi ₁₂MO ₁₉Preparation method and application thereof.Press Bi ₁₂MO ₁₉Chemical formula, wherein the M element be among Ni, Zn and the Cu one or both; Choose Bi (NO ₃) ₃5H ₂O, NiO, ZnO and CuO are standby; Be made into the bismuth nitrate solution of 0.01-0.1mol/L with deionized water, one or both forms with pressed powder among NiO, ZnO and the CuO joined in the bismuth nitrate solution fully mix, obtain suspension; Above-mentioned suspension moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is that 70%-80% adds deionized water by the compactedness of hydro-thermal reaction, at 120-180 ℃ of insulation 12-24h down.To be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 1-5 time, place 60-80 ℃ the dry 4-8h of thermostatic drying chamber.Prepared compound oxide photocatalyst Bi ₁₂MO ₁₉As photocatalyst applications, the specific activity conventional solid-state method height of photochemical catalyst, and good stability.

Description

Compound oxide photocatalyst Bi 12MO 19Preparation method and application thereof

Technical field

The present invention relates to a kind of visible light responded composite oxide photocatalyst Bi ₁₂MO ₁₉The preparation method and the application thereof of (wherein the M element is Ni, Zn, one or both among the Cu).

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.

Photocatalysis technology degraded environmental contaminants are expected to make full use of solar energy, and it has that energy consumption is low, reaction condition is gentle, easy and simple to handle, can reduce outstanding advantage such as secondary pollution, come into one's own day by day.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.

Therefore, develop the hot issue that the catalyst that has the high light catalytic activity under a kind of novel visible light has again become photocatalysis field.And in decades recently, 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 and 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 photocatalysis performance preferably.At present, the R and D of bismuth series photocatalyst 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.

The preparation of niobium (tantalum) the hydrochlorate photochemical catalyst of report at present mainly is to adopt traditional solid-phase synthesis; by under higher temperature for a long time sintering reaction obtain to expect product; but because of raw material difficulty mix; reaction temperature is higher; reaction is difficult for carrying out fully, so the powder granule of preparing is bigger, and skewness and; usually be mixed with dephasign, this makes the activity of the photochemical catalyst that solid phase method is synthetic reduce.The particle size of hydrothermal synthesis method preparation is little, and the purity height, and crystal grain is grown, contained defective is few, crystal structure is relatively near ideal crystal, and its physical property also relatively approaches theoretical value, can also control the pattern of product by regulating hydrothermal reaction condition.

Summary of the invention

The purpose of this invention is to provide a kind of visible light responded composite oxide photocatalyst Bi that has ₁₂MO ₁₉The preparation method and the application thereof of (wherein the M element is one or both among Ni, Zn and the Cu), this method has low, the easy and simple to handle characteristics of synthesis temperature.

Has visible light responded composite oxide photocatalyst Bi ₁₂MO ₁₉The preparation method of (wherein M element be among Ni, Zn and the Cu one or both) is characterized in that, carries out according to the following steps:

1) presses Bi ₁₂MO ₁₉Chemical formula, wherein the M element be among Ni, Zn and the Cu one or both; Choose Bi (NO ₃) ₃5H ₂O, NiO, ZnO and CuO are standby; Be made into the bismuth nitrate solution of 0.01-0.1mol/L with deionized water, one or both forms with pressed powder among NiO, ZnO and the CuO joined in the bismuth nitrate solution fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is that 70%-80% adds deionized water by the compactedness of hydro-thermal reaction, puts into thermostatic drying chamber after covering tight kettle cover, at 120-180 ℃ of insulation 12-24h down.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 1-5 time, place 60-80 ℃ the dry 4-8h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂MO ₁₉Powder.

The visible light responded composite oxide photocatalyst Bi of method for preparing ₁₂MO ₁₉The application of (wherein M element be among Ni, Zn and the Cu one or both) is characterized in that it is as photocatalyst applications.

The specific embodiment

To be specifically described the present invention below:

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 120min.

Embodiment

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

Embodiment 1:

1) presses Bi ₁₂NiO ₁₉Chemical formula is chosen Bi (NO ₃) ₃5H ₂O and NiO are standby; Be made into the bismuth nitrate solution of 0.01mol/L with deionized water, NiO joined in the bismuth nitrate solution with the form of pressed powder fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is 70% to add deionized water by the compactedness of hydro-thermal reaction, does not add hydrochloric acid, under the pH of nature value, puts into thermostatic drying chamber after covering tight kettle cover, is incubated 24h down at 120 ℃.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 5 times, place 80 ℃ the dry 4h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂NiO ₁₉Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 99% to the methyl orange clearance.

Embodiment 2:

1) presses Bi ₁₂ZnO ₁₉Chemical formula is chosen Bi (NO ₃) ₃5H ₂O and ZnO are standby; Be made into the bismuth nitrate solution of 0.1mol/L with deionized water, ZnO joined in the bismuth nitrate solution with the form of pressed powder fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is 70% to add deionized water by the compactedness of hydro-thermal reaction, is 4 with the salt acid for adjusting pH value, puts into thermostatic drying chamber after covering tight kettle cover, is incubated 18h down at 150 ℃.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 3 times, place 70 ℃ the dry 6h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂ZnO ₁₉Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 98.4% to the methyl orange clearance.

Embodiment 3:

1) presses Bi ₁₂CuO ₁₉Chemical formula is chosen Bi (NO ₃) ₃5H ₂O and CuO are standby; Be made into the bismuth nitrate solution of 0.05mol/L with deionized water, CuO joined in the bismuth nitrate solution with the form of pressed powder fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is 70% to add deionized water by the compactedness of hydro-thermal reaction, and regulating pH value with ammoniacal liquor is 9, puts into thermostatic drying chamber after covering tight kettle cover, is incubated 12h down at 180 ℃.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 2 times, place 60 ℃ the dry 8h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂CuO ₁₉Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 97.5% to the methyl orange clearance.

Embodiment 4:

1) presses Bi ₁₂Ni _0.9Zn _0.1O ₁₉Chemical formula is chosen Bi (NO ₃) ₃5H ₂O, NiO and ZnO, standby; Be made into the bismuth nitrate solution of 0.08mol/L with deionized water, NiO, ZnO joined in the bismuth nitrate solution with the form of pressed powder fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is 70% to add deionized water by the compactedness of hydro-thermal reaction, does not add hydrochloric acid, under the pH of nature value, puts into thermostatic drying chamber after covering tight kettle cover, is incubated 20h down at 140 ℃.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 1 time, place 80 ℃ the dry 4h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂Ni _0.9Zn _0.1O ₁₉Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 99% to the methyl orange clearance.

Embodiment 5:

1) presses Bi ₁₂Zn _0.6Cu _0.4O ₁₉Chemical formula is chosen Bi (NO ₃) ₃5H ₂O, CuO and ZnO, standby; Be made into the bismuth nitrate solution of 0.02mol/L with deionized water, CuO, ZnO joined in the bismuth nitrate solution with the form of pressed powder fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is 70% to add deionized water by the compactedness of hydro-thermal reaction, is 4 with the salt acid for adjusting pH value, puts into thermostatic drying chamber after covering tight kettle cover, is incubated 16h down at 170 ℃.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 5 times, place 80 ℃ the dry 4h of thermostatic drying chamber, can obtain compound oxide photocatalyst Bi ₁₂Zn _0.6Cu _0.4O ₁₉Powder.

Prepared photochemical catalyst, under the radiation of visible light of wavelength greater than 420nm, 120min reaches 98% to the methyl orange clearance.

The bound of each raw material of the present invention, interval value, and bound, the interval value of technological parameter (as temperature, time, pH value 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 (2)

1. compound oxide photocatalyst Bi ₁₂MO ₁₉The preparation method, it is characterized in that concrete steps are:

1) presses Bi ₁₂MO ₁₉Chemical formula, wherein the M element be among Ni, Zn and the Cu one or both; Choose Bi (NO ₃) ₃5H ₂O, NiO, ZnO and CuO are standby; Be made into the bismuth nitrate solution of 0.01-0.1mol/L with deionized water, one or both forms with pressed powder among NiO, ZnO and the CuO joined in the bismuth nitrate solution fully mix, obtain suspension;

2) above-mentioned suspension is moved into being lined with in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is that 70%-80% adds deionized water by the compactedness of hydro-thermal reaction, puts into thermostatic drying chamber after covering tight kettle cover, at 120-180 ℃ of insulation 12-24h down.

3) to be cooled to room temperature, take out reacted product, behind deionized water, each centrifuge washing of absolute ethyl alcohol 1-5 time, place 60-80 ℃ the dry 4-8h of thermostatic drying chamber, can obtain bismuth-system compound oxide photocatalyst Bi ₁₂MO ₁₉Powder.

2. compound oxide photocatalyst Bi as claimed in claim 1 ₁₂MO ₁₉Application, it is characterized in that described compound oxide photocatalyst Bi ₁₂MO ₁₉As photocatalyst applications, wherein the M element be among Ni, Zn and the Cu one or both.