CN103611526A - Preparation method for bismuth tungstate microsphere with core-shell structure - Google Patents
Preparation method for bismuth tungstate microsphere with core-shell structure Download PDFInfo
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- CN103611526A CN103611526A CN201310065652.9A CN201310065652A CN103611526A CN 103611526 A CN103611526 A CN 103611526A CN 201310065652 A CN201310065652 A CN 201310065652A CN 103611526 A CN103611526 A CN 103611526A
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Abstract
The invention discloses a preparation method for bismuth tungstate microsphere powder with a homogeneous core-shell structure. Bismuth nitrate, sodium tungstate and polyvinylpyrrolidone are dissolved in ethanediol weighing 30-50 times of bismuth nitrate. Inorganic base is added and the pH value of the solution is adjusted to 12.5-13. The above mixture is reacted in an airtight reactor for 10-20h at the temperature of 140-180 DEG C and bismuth tungstate with a core-shell structure is obtained. The preparation method is advantaged by low reaction temperature, simple and controllable technology and environmental protection, the prepared product has advantages of uniform morphology, narrow size distribution and large specific surface area.
Description
Technical field
The present invention relates to a kind of synthetic method of homogeneous core/shell structure bismuth tungstate microballoon, belong to inorganic material and functional material fabricating technology field.
Background technology
Environmental pollution and energy shortage are the ultimate challenges that the mankind face at present, and the hydrogen energy source of utilizing photocatalysis technology to administer environmental problem and preparation environmental protection is one of current most active research field, and finding high efficiency and stable catalyst is top priority.Early stage research mainly concentrates on titanium dioxide, and it has, and catalytic activity is high, good stability, the advantage such as nontoxic and cheap and get most of the attention.Yet its energy gap is 3.2 eV, corresponding maximum absorption wavelength is 390 nm, and meaning can only be by ultraviolet excitation.In arriving the solar energy on ground, the energy shortage 5% of this wave band, and the shared ratio of visible light part is 45%, the catalyst that therefore exploitation, design have high visible light catalytic activity becomes one of current study hotspot of photocatalysis field.
Bismuth tungstate is the simplest compound in bismuth oxide-based layered perovskite family, and its energy gap is 2.75 eV, and it possesses good physics and chemical property, as ferroelectric, piezoelectricity and catalysis etc.Because it has absorption at visible region, and have thermally-stabilised, the advantage such as photocatalysis is stable, and cost is relatively low and cheap.Thereby, Bi
2wO
6it is a kind of very potential visible-light response type semiconductor catalyst material.Early the bismuth tungstate of bibliographical information adopts high temperature solid-state method, the preparations such as coprecipitation and sol-gel process more.Wherein, particle prepared by solid phase method is larger, and pattern is uncontrollable, and specific area is little, and catalytic activity is relatively lower; Coprecipitation and sol-gel process all need high-temperature calcination just can obtain crystallinity bismuth tungstate in preparation process, and pyroprocess can directly cause crystal grain to be reunited and particle diameter skewness, thereby cause bismuth tungstate photocatalytic activity low.Result of study shows, the character of catalysis material and its size, pattern, structure and specific area have very large relation, but its controlled high-quality synthetic be still a difficult point.
Summary of the invention
The object of this invention is to provide that a kind of reaction temperature is low, repeatability is high, technique is simple and the synthetic method of eco-friendly homogeneous nucleocapsid structure bismuth tungstate microballoon.
Implementation procedure of the present invention is as follows:
A preparation method for nucleocapsid structure bismuth tungstate microballoon, comprises the following steps:
(1) bismuth nitrate, sodium tungstate and polyvinylpyrrolidone are dissolved in the ethylene glycol of 30～50 times of bismuth nitrate weight, wherein the mol ratio of bismuth nitrate and sodium tungstate is 2:1, and the addition of polyvinylpyrrolidone is 1.5～3 times of bismuth nitrate weight;
(2) add inorganic base regulator solution pH value 12.5～13;
(3) in closed reactor, at 140～180 ℃, react 10～20 hours;
(4) reaction temperature is down to separating solids after room temperature, and washing is dry.
In step (1), the molecular weight of polyvinylpyrrolidone is Mr ≈ 8000～24000, is preferably 10000.
In step (2), described inorganic base is NaOH or potassium hydroxide.
" core " and " shell " of the nucleocapsid structure bismuth tungstate microballoon that the present invention prepares is bismuth tungstate component.Compared with prior art, the method of the synthetic homogeneous nucleocapsid structure bismuth tungstate microballoon of solvent-thermal method of the present invention has that reaction temperature is low, technique is simple and controlled, environmental friendliness, synthetic product pattern homogeneous, narrow size distribution, specific area is large, the existing shortcomings such as crystal grain in bismuth tungstate method is easily reunited, and pattern is uncontrollable, specific area is little of preparing have been overcome.
Accompanying drawing explanation
Fig. 1 adds the XRD collection of illustrative plates (a is 2.0g, and b is 2.5g, and c is 3.0g) that different weight northylen pyrrolidones obtain homogeneous nucleocapsid structure bismuth tungstate microballoon;
Fig. 2 adds the field emission scanning electron microscope photo (a is 2.0g, and b is 2.5g, and c is 3.0g) that different weight northylen pyrrolidones obtain homogeneous nucleocapsid structure bismuth tungstate microballoon;
Fig. 3 adds the isothermal nitrogen adsorption desorption curve map that different weight northylen pyrrolidones (a is 2.0g, and b is 2.5g, and c is 3.0g) obtain homogeneous core/shell structure bismuth tungstate microballoon;
Fig. 4 is to be the field emission scanning electron microscope photo of the bismuth tungstate product that obtains for 6 hours in the reaction time;
Fig. 5 is to be the field emission scanning electron microscope photo of the bismuth tungstate product that obtains for 10 hours in the reaction time;
Fig. 6 is that (a is blank sample for the bismuth tungstate prepared of embodiment 1 to 3 and conventional solid-state method and the photocatalytic activity evaluation map of P25 rhodamine B degradation under radiation of visible light, b is P25, c is bismuth tungstate prepared by conventional solid-state method, and d, e, f are respectively and add the bismuth tungstate that 2.0g, 2.5g, 3.0g polyvinylpyrrolidone obtain).
The specific embodiment
Embodiment 1
Taking 2.5mmol five water bismuth nitrates, 1.25mmol tungstate dihydrate acid sodium and 2.0 g polyvinylpyrrolidones (Mr ≈ 10000) joins in 40mL ethylene glycol; Stirring at room mixes raw material, then add NaOH to control precursor liquid pH value 12.5 ~ 13, obtain the precursor liquid of solvent thermal reaction, it is in 50mL teflon-lined reactor that precursor liquid is moved into volume, then reactor is put into baking oven, stops reaction after being incubated 20 hours at 160 ℃ of temperature, question response temperature is down to after room temperature, take out the sediment in reactor, centrifugation is also respectively washed sediment three times with deionized water and absolute ethyl alcohol, and at 60 ℃, freeze-day with constant temperature is 8 hours.
As shown in Figure 1a, the bismuth tungstate degree of crystallinity preparing is good, is quadrature phase bismuth tungstate structure.As shown in Figure 2 a, product is nucleocapsid structure, the medicine ball that shell is comprised of granule, and shell is comprised of nanometer sheet unit.Fig. 3 a is the isothermal nitrogen adsorption desorption curve map of homogeneous core/shell structure bismuth tungstate microballoon.
Similar to Example 1, different is that polyvinylpyrrolidone is 2.5 g, and XRD, SEM and absorption result are as shown in Fig. 1 b, 2b and 3b.
Embodiment 3
Similar to Example 1, different is that polyvinylpyrrolidone is 3.0 g, and XRD, SEM and absorption result, as shown in Fig. 1 c, 2c and 3c, can find out that the amount along with polyvinylpyrrolidone increases, and pore size distribution is narrower, and specific area is also larger.
Embodiment 4
Similar with embodiment 1-3, different is to use the polyvinylpyrrolidone that molecular weight is 24000, all obtains similar nucleocapsid structure bismuth tungstate.
Similar with embodiment 1-3, the consumption of solvent ethylene glycol that different is is 60mL, arrives equally similar nucleocapsid structure bismuth tungstate.
Similar with embodiment 1-3, different is to regulate pH value with potassium hydroxide, obtains similar nucleocapsid structure bismuth tungstate.
Similar with embodiment 1-3, different is that reaction temperature is at 180 ℃, to react 10 hours, obtains similar nucleocapsid structure bismuth tungstate.
Similar with embodiment 1-3, different is that reaction temperature is at 140 ℃, to react 20 hours, obtains similar nucleocapsid structure bismuth tungstate.
Embodiment 5
Similar with the synthetic method of embodiment 1, different is that the reaction time is 6 hours, and the bismuth tungstate ESEM obtaining as shown in Figure 4, is larger-size medicine ball and irregular bulk, non-nucleocapsid structure.
But when the reaction time extends to 10 hours, obtain bismuth tungstate ESEM as shown in Figure 5, bismuth tungstate product pattern is all nucleocapsid structure, therefore, reaction time has material impact to product pattern, and it is necessary that the reaction time be greater than 10 hours to form bismuth tungstate nucleocapsid structure.
Embodiment 6
Bismuth tungstate prepared by the bismuth tungstate that employing embodiment 1 to 3 prepares and conventional solid-state method and the photocatalytic activity evaluation of P25 rhodamine B degradation under radiation of visible light, the results are shown in Figure 6.
Step 1: take 50mg sample dispersion to 50mL, 1 * 10
-5in the rhodamine solution of M;
Step 2: stir in the dark 1 hour to guarantee to arrive adsorption/desorption balance;
Step 3: open photocatalysis instrument (350W xenon lamp, 420nm optical filter), start illumination;
Step 4: get at regular intervals 3mL solution, measure supernatant concentration after centrifugal removal photochemical catalyst.
The bismuth tungstate that the bismuth tungstate photocatalytic activity that can find out nucleocapsid structure is prepared higher than P25 type titanium dioxide and conventional solid-state method, in addition, the photocatalytic activity of the bismuth tungstate of nucleocapsid structure is directly proportional to specific area.
Claims (3)
1. a preparation method for nucleocapsid structure bismuth tungstate microballoon, is characterized in that, comprises the following steps:
(1) bismuth nitrate, sodium tungstate and polyvinylpyrrolidone are dissolved in the ethylene glycol of 30～50 times of bismuth nitrate weight, wherein the mol ratio of bismuth nitrate and sodium tungstate is 2:1, and the addition of polyvinylpyrrolidone is 1.5～3 times of bismuth nitrate weight;
(2) add inorganic base regulator solution pH value 12.5～13;
(3) in closed reactor, at 140～180 ℃, react 10～20 hours;
(4) reaction temperature is down to separating solids after room temperature, and washing is dry.
2. the method for preparing homogeneous nucleocapsid structure bismuth tungstate microballoon according to claim 1, is characterized in that: in step (1), the molecular weight of polyvinylpyrrolidone is 8000～24000.
3. the method for preparing homogeneous nucleocapsid structure bismuth tungstate microballoon according to claim 1, is characterized in that: in step (2), described inorganic base is NaOH or potassium hydroxide.
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| CN104163746A (en) * | 2014-07-21 | 2014-11-26 | 西北大学 | Application and preparation method of nano metal composite oxide bismuth tungstate |
| CN107188234A (en) * | 2017-06-13 | 2017-09-22 | 浙江大学 | A kind of sheet Bi2WO6Preparation method |
| CN110711591A (en) * | 2019-07-12 | 2020-01-21 | 盐城工学院 | Preparation method and application of catalyst for photocatalytic degradation of VOCs (volatile organic compounds) |
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| EP2324913A1 (en) * | 2009-10-22 | 2011-05-25 | Basf Se | Photo catalyst with increased daylight activity |
| CN101757908A (en) * | 2009-12-29 | 2010-06-30 | 南开大学 | Method for preparing Bi2WO6 with high efficiency and visible light photocatalytic activity by adjusting pH |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163746A (en) * | 2014-07-21 | 2014-11-26 | 西北大学 | Application and preparation method of nano metal composite oxide bismuth tungstate |
| CN104163746B (en) * | 2014-07-21 | 2017-03-15 | 西北大学 | Application of nano-metal composite oxide bismuth tungstate and preparation method thereof |
| CN107188234A (en) * | 2017-06-13 | 2017-09-22 | 浙江大学 | A kind of sheet Bi2WO6Preparation method |
| CN110711591A (en) * | 2019-07-12 | 2020-01-21 | 盐城工学院 | Preparation method and application of catalyst for photocatalytic degradation of VOCs (volatile organic compounds) |
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Application publication date: 20140305 |