CN102951682A - Preparation method of cellular spherical bismuth vanadate microcrystalline - Google Patents

Abstract

The invention relates to a preparation method of cellular spherical bismuth vanadate microcrystalline; Bi(NO3)3.5H2O is dissolved in HNO3 to obtain solution A; NH4VO3 is dissolved into distilled water to obtain solution B; the solution A and the solution B are mixed uniformly; then the pH value of the mixed solution is regulated to 3 to 9 through NaOH solution to obtain solution C; sodium lignosulphonate solution D is prepared, and the solution C and the solution D are mixed uniformly to obtain solution E; the solution E is arranged in a microwave water heating reaction kettle, reaction is carried out through a temperature pressure double-control microwave water heating reactor; after the reaction, the solution E is naturally cooled to room temperature; and a product is centrifugally collected, washed by deionized water and anhydrous ethanol, and is finally vacuumized and dried to obtain the bright yellow cellular spherical bismuth vanadate microcrystalline. According to the preparation method of the cellular spherical bismuth vanadate microcrystalline, the simple microwave water heating method preparation process is adopted, the reaction cycle is short, the energy consumption is low, the reaction is completed in a liquid phase at one time, and no post treatment is needed. BiVO4 particles which are prepared are of cellular spherical structures, the surface area is larger, and the method can be used in the catalysis field.

Description

A kind of preparation method of how empty spherical pucherite crystallite

Technical field

The invention belongs to the preparation method of pucherite, be specifically related to a kind of preparation method-microwave-hydrothermal method of how empty spherical pucherite crystallite.

Background technology

In the last few years, environmental pollution and energy dilemma had brought serious threat for human existence, and photocatalysis technology has obtained to pay close attention to widely as a kind of new technique.The photocatalyst that is most widely used at present such as titanium dioxide (TiO ₂) etc., be the wide band gap semiconducter catalyzer, only have corresponding in ultraviolet light range.Sunlight medium ultraviolet light is less than 5%, and that visible light accounts for is nearly 43%, and therefore developing the corresponding high-activity photocatalyst of visible light is to improve the trend that solar energy utilization ratio is the photocatalysis technology development.

Pucherite also has simultaneously photocatalytic, pastes the characteristics such as elasticity, acousto-optic transformant, particle conductive as a kind of lead-free inorganic yellow dyestuff, has been applied to the research of degradation of contaminant, photodissociation aquatic products oxygen and photoelectrochemistry water of decomposition at present.

The method for preparing at present pucherite mainly contain chemical precipitation method [Gao Shanmin, Qiao Qingan, Zhao Peipei, Tao Furong, Zhangjiang is worn beautiful jade, the golden cypress mark. the precipitator method prepare the nanometer BiVO4[J of different-shape and structure]. Chinese Journal of Inorganic Chemistry, 2007; 23 (7): 1153-1158], low-temperature solid-phase method [Shenmue loud, high-pitched sound, Hou Xiaohu, Na Ren figure is refined, Li Jinmei, Zhao Zhihong. combustion method prepares nanometer bismuth vanadate powder and performance [J]. non-ferrous metal (Smelting Part), 2011 (6): 45-49.], hydrothermal method [Yang T, Xia D, Chen G, ChenY.Influence of thesurfactant and temperature on the morphology and physico-chemical properties ofhydrothermally synthesized composite oxide BiVO ₄[J] .Materials Chemistry andPhysics.2009; 114 (1): 69-72.], microemulsion method [Chung C-Y, Lu C-H.Reverse-microemulsion preparation of visible-light-driven nano-sized BiVO4[J] .Journal ofAlloys and Compounds.2010; 502 (1): L1-L5.].Yet the pucherite size heterogeneity of these methods preparation perhaps needs reaction times of growing and larger for environmental pollution.Therefore seek a kind of ease of Use, environmental friendliness and reaction times, short method seemed rather important.

Although microwave-hydrothermal method prepare pucherite the someone study, synthetic how empty spherical product reports that but the porous spherical pucherite has larger specific surface area, more is conducive to improve photocatalysis efficiency.

Summary of the invention

The objective of the invention is to propose the method for the how empty spherical pucherite crystallite of a kind of microwave-hydrothermal method preparation.This preparation method reaction time is short, temperature of reaction is low, and environmental friendliness is with low cost, and simple to operate, good reproducibility.

For achieving the above object, technical scheme of the present invention is as follows:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 2-5mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.005-0.05mol/L;

With NH ₄VO ₃Be dissolved in 40-80 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.005-0.05mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stir 30-120min at magnetic stirring apparatus, then regulating pH with NaOH solution is that 3-9 gets solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.003-0.009mol/L is designated as D, with solution C and solution D by 100:(0.5-2) volume ratio mix to get solution E;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 50%-80%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 120-180 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.5-2.2Mpa, reaction 40min-80min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 50-80 ℃ of lower vacuum-drying at last.

The concentration of described NaOH solution is 2-10mol/L.

Useful effect:

1) the present invention adopts simple microwave-hydrothermal method preparation technology, and reaction time is short, and energy consumption is low, and reaction is once finished in liquid phase, does not need post-processed.

2) BiVO that makes of this method ₄Particle is how empty ball-like structure, and surface-area is larger, can be used for catalytic field.

Description of drawings

Fig. 1 is the spherical pucherite crystallite of the many skies D/max2000PCX-x ray diffractometer x of science analysis chart of embodiment 1 preparation;

Fig. 2 is the spherical pucherite crystallite of the many skies electron scanning micrograph of embodiment 1 preparation.

Embodiment

Embodiment 1:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 2mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.005mol/L;

With NH ₄VO ₃Be dissolved in 40 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.005mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stirs 30min at magnetic stirring apparatus, then with the NaOH solution of 2mol/L regulate pH be 3 solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.003mol/L is designated as D, and solution C and solution D are mixed to get solution E by the volume ratio of 100:0.5;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 50%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 120 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.5Mpa, reaction 40min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 50 ℃ of lower vacuum-dryings at last.

BiVO with gained ₄Particle finds that with Rigaku D/max2000PCX-x ray diffractometer x analytic sample product is monoclinic phase BiVO ₄Scheelite-type structure (JCPDS 14-0688) is seen Fig. 1.This sample is observed with the JSM-6700F type scanning electronic microscope that Japanese firm produces, as can be seen from Figure 2 made BiVO ₄That diameter is spherical at many skies of 2-3 μ m.

Embodiment 2:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 3mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.015mol/L;

With NH ₄VO ₃Be dissolved in 50 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.015mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stirs 60min at magnetic stirring apparatus, then with the NaOH solution of 5mol/L regulate pH be 5 solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.005mol/L is designated as D, and solution C and solution D are mixed to get solution E by the volume ratio of 100:1;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 60%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 140 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 1.1Mpa, reaction 60min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 60 ℃ of lower vacuum-dryings at last.

Embodiment 3:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 4mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.03mol/L;

With NH ₄VO ₃Be dissolved in 70 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.03mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stirs 90min at magnetic stirring apparatus, then with the NaOH solution of 7mol/L regulate pH be 7 solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.007mol/L is designated as D, and solution C and solution D are mixed to get solution E by the volume ratio of 100:1.5;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 70%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 160 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 1.7Mpa, reaction 70min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 60 ℃ of lower vacuum-dryings at last.

Embodiment 4:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 5mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.05mol/L;

With NH ₄VO ₃Be dissolved in 80 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.05mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stirs 120min at magnetic stirring apparatus, then with the NaOH solution of 10mol/L regulate pH be 9 solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.009mol/L is designated as D, and solution C and solution D are mixed to get solution E by the volume ratio of 100:2;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 80%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 180 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 2.2Mpa, reaction 80min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 80 ℃ of lower vacuum-dryings at last.

Claims (2)

1. the preparation method of empty spherical pucherite crystallite more than a kind is characterized in that:

1) with Bi (NO ₃) ₃5H ₂O is dissolved in the HNO of 2-5mol/L ₃In the solution, be mixed with the solution A that the Bi ionic concn is 0.005-0.05mol/L;

With NH ₄VO ₃Be dissolved in 40-80 ℃ the distilled water preparation NH ₄VO ₃Concentration is the solution B of 0.005-0.05mol/L;

2) solution A and the solution B volume ratio by 1:1 is mixed, stir 30-120min at magnetic stirring apparatus, then regulating pH with NaOH solution is that 3-9 gets solution C;

3) the lignosulfonic acid ammonia solution of preparation 0.003-0.009mol/L is designated as D, with solution C and solution D by 100:(0.5-2) volume ratio mix to get solution E;

4) solution E is placed microwave hydrothermal reaction kettle, compactedness is 50%-80%, then sealed reactor, put it in the MDS-8 type warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 120-180 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.5-2.2Mpa, reaction 40min-80min, reaction naturally cools to room temperature after finishing;

5) open hydrothermal reaction kettle, the centrifugal collection of product process, and with behind deionized water wash 3-5 time, use again absolute ethanol washing 1-2 time, obtain the how empty spherical pucherite crystallite of glassy yellow 50-80 ℃ of lower vacuum-drying at last.

2. the preparation method of according to claim 1 how empty spherical pucherite crystallite, it is characterized in that: the concentration of described NaOH solution is 2-10mol/L.

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