CN102962056A - Method for producing spherical ZnWO4 photocatalysis materials - Google Patents

Abstract

The invention relates to a method for producing spherical ZnWO4 photocatalysis materials. According to the method, a Na2WO4 solution A and a ZnSO4 solution B are prepared; the solution A is slowly dripped into the solution B and the pH value is adjusted to 4-4.5 to obtained a solution C; the solution C is added into a microwave photochemistry reaction instrument, heating reaction is carried out by taking a mercury lamp as the ultrasonic light source and the microwave energy and the ultrasonic energy as the energy source and naturally cooling to the room temperature after the reaction is finished, and the reaction instrument is taken out; and the reaction instrument is opened, and then the product is cleaned by using deionized water and anhydrous alcohol and dried to obtain the spherical ZnWO4 photocatalysis material. According to the method, the production process of the spherical ZnWO4 photocatalysis material is finished in liquid phase in one time without the consequent crystallization heat treatment, so that the defects that the shape is changed, the sample reacts with the atmosphere, and the like are avoided, the technological equipment is simple, and the product has high purity and is controllable in shape; and the rhodamine B degradation rate within 60min by adopting the spherical ZnWO4 prepared according to the method is up to 95-98 percent.

Description

A kind of flower ball-shaped ZnWO 4The preparation method of catalysis material

Technical field

The present invention relates to a kind of ZnWO of preparation ₄The preparation method of catalysis material, particularly a kind of employing ultraviolet assisted microwave synthesis reaction method prepares flower ball-shaped ZnWO ₄The method of catalysis material.

Background technology

ZnWO ₄Belong to monoclinic system, cation Zn ²⁺And W ⁶⁺All with the oxygen atom hexa-coordinate, orderly six sides are tightly packed for Zn and W atomic building oxygen octahedra.The oxonium ion of half is furnished with two W ⁶⁺, second half oxonium ion cooperates two Zn ²⁺[Zhang Liwu, Zhu Yongfa. tungsten hydrochlorate composite oxides novel visible photocatalysis research [J]. the Chinese material progress, 2010,29(1): 45-53.].ZnWO ₄Powder has Photoluminescence and photocatalytic, can be used for the organic pollution in the empty G﹠W is effectively degraded as photochemical catalyst.

The ZnWO that has reported ₄The preparation method of nano-powder be mainly hydro-thermal method [Wu Ju. the nanostructured [D] of the synthetic tungstate material of hydro-thermal method. Jiangsu: Southern Yangtze University, 2008,6.], the people such as Wang Lingling adopt hydro-thermal method, take PEG as template, prepare bar-shaped and tire-like ZnWO ₄[WANG Ling-Ling.Hydrothermal Synthesis and Photoluminescent Properties of Zinc TungstateNanostructures.Journal of Shanghai second polytechnic university[J], 2009,26 (2): 99-104.], the people such as Song Chunxu are by hydro-thermal method, with ZnSO ₄And Na ₂WO ₄For raw material has been prepared bar-shaped ZnWO ₄Nanocrystalline [SONG Xu-Chun, YANG E, ZHENG Yi-Fan, et al.Effects ofPrepration Conditions on the MorpHology and PHotoluminescence of ZnWO ₄Nanocrystals[J] .Wuli Huaxue Xuebao, 2007,23 (7): 1123-1126.].Hydro-thermal method is simple to operate, and technique is adjustable flexibly, product pattern homogeneous, and good dispersion, but its deficiency just is that the reaction time is long.

Summary of the invention

The object of the present invention is to provide a kind of employing ultraviolet assisted microwave synthesis reaction method, in acid system, need not to add template, and short flower ball-shaped ZnWO of reaction time ₄The preparation method of catalysis material.

For achieving the above object, the technical solution used in the present invention is:

1) compound concentration is the Na of 0.1mol/L ~ 0.4mol/L respectively ₂WO ₄Solution A and ZnSO ₄Solution B;

2) according to A:B=(0.5 ~ 2): 1 volume ratio slowly is added drop-wise to solution A in the solution B, with the NaOH solution of 0.1 ~ 0.2mol/L or the HNO of 0.1 ~ 0.2mol/L ₃Solution is regulated pH=4 ~ 4.5, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 400 ~ 700W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 140 ~ 190 ℃ with microwave energy and uv energy, reaction time is 30min ~ 60min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then obtain flower ball-shaped ZnWO 70 ~ 100 ℃ of dryings ₄Catalysis material.

The described dry electric drying oven with forced convection that adopts.

Useful effect:

The present invention prepares flower ball-shaped ZnWO ₄Catalysis material, preparation process is once finished in liquid phase, does not need the crystallization and thermal treatment in later stage, avoided the defectives such as pattern change and sample and atmosphere reaction, and process equipment is simple, and products therefrom purity is high, and pattern is controlled.Flower ball-shaped ZnWO according to the present invention's preparation ₄Can in 60min, reach 95 ~ 98% by the degradation rate to rhodamine B.

Description of drawings

Fig. 1 is the flower ball-shaped ZnWO of the embodiment of the invention 1 preparation ₄Catalysis material is with the JSM-5910LV type scanning electron microscope (SEM) photograph of Japanese JEOL company.

Specific embodiments:

Embodiment 1:

1) compound concentration is the Na of 0.1mol/L respectively ₂WO ₄Solution A and 0.1mol/L ZnSO ₄Solution B;

2) according to the A:B=1:1 volume ratio solution A slowly is added drop-wise in the solution B, with the NaOH solution of 0.2mol/L or the HNO of 0.15mol/L ₃Solution is regulated pH=4.2, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 700W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 160 ℃ with microwave energy and uv energy, reaction time is 60min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then in electric drying oven with forced convection, obtain flower ball-shaped ZnWO in 100 ℃ of dryings ₄Catalysis material.

Referring to accompanying drawing, with the flower ball-shaped ZnWO of the present invention's preparation ₄Catalysis material is found to be the ZnWO of pure phase with Rigaku D/max2000PC X-ray diffractometer analytic sample ₄As can be seen from Figure 1, product be size at the ZnWO4 of 3 ~ 4 μ m left and right sides flower ball-shapeds, and, flower ball-shaped ZnWO ₄All be by ZnWO ₄Nanometer rods assembles.

Embodiment 2:

1) compound concentration is the Na of 0.2mol/L respectively ₂WO ₄Solution A and 0.2mol/L ZnSO ₄Solution B;

2) according to the A:B=0.5:1 volume ratio solution A slowly is added drop-wise in the solution B, with the NaOH solution of 0.1mol/L or the HNO of 0.2mol/L ₃Solution is regulated pH=4.3, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 600W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 140 ℃ with microwave energy and uv energy, reaction time is 40min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then in electric drying oven with forced convection, obtain flower ball-shaped ZnWO in 90 ℃ of dryings ₄Catalysis material.

Embodiment 3:

1) compound concentration is the Na of 0.2mol/L respectively ₂WO ₄Solution A and 0.4mol/L ZnSO ₄Solution B;

2) according to the A:B=0.5:1 volume ratio solution A slowly is added drop-wise in the solution B, with the NaOH solution of 0.15mol/L or the HNO of 0.13mol/L ₃Solution is regulated pH=4.5, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 500W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 180 ℃ with microwave energy and uv energy, reaction time is 30min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then in electric drying oven with forced convection, obtain flower ball-shaped ZnWO in 70 ℃ of dryings ₄Catalysis material.

Embodiment 4:

1) compound concentration is the Na of 0.4mol/L respectively ₂WO ₄Solution A and 0.2mol/L ZnSO ₄Solution B;

2) according to the A:B=2:1 volume ratio solution A slowly is added drop-wise in the solution B, with the NaOH solution of 0.19mol/L or the HNO of 0.1mol/L ₃Solution is regulated pH=4.0, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 400W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 190 ℃ with microwave energy and uv energy, reaction time is 50min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then in electric drying oven with forced convection, obtain flower ball-shaped ZnWO in 80 ℃ of dryings ₄Catalysis material.

The flower ball-shaped ZnWO that makes according to preparation method of the present invention ₄Purity is high, pattern homogeneous, and preparation flower ball-shaped ZnWO ₄Do not need the crystallization and thermal treatment in later stage, thereby avoided the defectives such as reunion, grain coarsening, pattern change and the sample that in heat treatment process, may cause and atmosphere reaction.

Claims (2)

1. flower ball-shaped ZnWO ₄The preparation method of catalysis material is characterized in that may further comprise the steps:

1) compound concentration is the Na of 0.1mol/L ~ 0.4mol/L respectively ₂WO ₄Solution A and ZnSO ₄Solution B;

2) according to A:B=(0.5 ~ 2): 1 volume ratio slowly is added drop-wise to solution A in the solution B, with the NaOH solution of 0.1 ~ 0.2mol/L or the HNO of 0.1 ~ 0.2mol/L ₃Solution is regulated pH=4 ~ 4.5, stirs, and obtains solution C;

3) solution C is added in the microwave light chemical reaction instrument, the setting microwave power is 400 ~ 700W, the employing mercury lamp is ultraviolet source, ultraviolet power is 300W, and simultaneously as energy source, selecting reaction temperature is 140 ~ 190 ℃ with microwave energy and uv energy, reaction time is 30min ~ 60min, question response naturally cools to room temperature after finishing, and takes out the reaction instrument;

4) open the reaction instrument, adopt deionized water and absolute ethyl alcohol wash products, then obtain flower ball-shaped ZnWO 70 ~ 100 ℃ of dryings ₄Catalysis material.

2. flower ball-shaped ZnWO according to claim 1 ₄The preparation method of catalysis material is characterized in that: the described dry electric drying oven with forced convection that adopts.

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