CN108840367A - A method of regulation bismuth tungstate self assembly micron spherical macrospore - Google Patents

A method of regulation bismuth tungstate self assembly micron spherical macrospore Download PDF

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CN108840367A
CN108840367A CN201810628751.6A CN201810628751A CN108840367A CN 108840367 A CN108840367 A CN 108840367A CN 201810628751 A CN201810628751 A CN 201810628751A CN 108840367 A CN108840367 A CN 108840367A
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bismuth
tungstate
self assembly
regulation
solution
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徐刚
江婉
陈同舟
皇甫统帅
韩高荣
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a kind of methods of regulation bismuth tungstate self assembly micron spherical macrospore, including：Bismuth nitrate solution is added in sodium tungstate solution, and carries out hydro-thermal reaction, controls the molar ratio of bismuth nitrate and sodium tungstate, the molar ratio control of the bismuth nitrate and sodium tungstate is 1.5~3:1.This method is realized by the molar ratio of control bismuth nitrate and sodium tungstate to Bi2WO6The pore structure of self assembly micron ball is regulated and controled.

Description

A method of regulation bismuth tungstate self assembly micron spherical macrospore
Technical field
The present invention relates to inorganic material to synthesize field, and in particular to a kind of regulation bismuth tungstate self assembly micron spherical macrospore Method.
Background technique
Currently, a large amount of water environment pollution, seriously restricts the sustainable development in China, and it is strong to influence national body Health is the social concern urgently to be resolved concerning national economy.According to statistics, 70% water pollution is caused by organic pollution , the degradation removing of organic pollutant is the key that administer water pollution.Conductor photocatalysis degradation is to remove organic pollution One of most effectual way has the advantages that at low cost, high-efficient and without secondary pollution.
However due to TiO2Photochemical catalyst greater band gap (Rutile Type 3.0eV, Anatase 3.2eV), only to wave Long shorter ultraviolet region (λ<387nm) there is response, this part luminous energy only accounts for the 4% of solar energy, and produced when excitation Light induced electron and hole-recombination rate it is higher, reduce photo-quantum efficiency.On the other hand, it is seen that light region accounts for the 43% of sunlight. This makes TiO2Practical research process does not have biggish breakthrough for a long time.
Tungstate nano material is in scintillation material, optical fiber, photoluminescence material, microwave applications, humidity sensor, magnetic Property device, catalyst and corrosion inhibiter etc. have a good application prospect, and become the hot spot studied in recent years.From 1999 Kudo etc. reports bismuth tungstate Bi for the first time2WO6After there is photocatalytic activity under visible optical radiation of the wavelength greater than 420nm, Bi2WO6It, can by excited by visible light and under visible light catalytic activity with higher because of its relatively narrow forbidden bandwidth (about 2.7eV) To cause more and more concerns as a kind of novel catalysis material, as recent study is found visible light-responded Lower Bi2WO6Can effectively be degraded the harmful substances such as chloroform and acetaldehyde, and can effective degradation of dye waste water.Therefore, Bi2WO6Light The research of catalysis material will open up a new way for photocatalysis removal and degradable organic pollutant.
Since the efficiency of photocatalysis removal and degradable organic pollutant is largely dependent upon the specific surface of catalysis material The Pore Characteristics such as long-pending and hole appearance, it has been investigated how to Bi2WO6The pore structure of catalysis material is regulated and controled, in the depollution of environment There to be very important practical value in terms of new energy development.It is had disclosed in the prior art using bismuth source and the progress of tungsten source Hydro-thermal reaction prepares bismuth tungstate (Bi2WO6) self assembly micron ball, but the conclusion that existing theory provides is by adjusting bismuth source With the feed ratio in tungsten source, Bi can only be changed2WO6Size, and its pore structure can not be regulated and controled.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of regulation bismuth tungstate self assembly micron ball knot The method of structure is realized by controlling the molar ratio of bismuth nitrate and sodium tungstate to bismuth tungstate (Bi2WO6) self assembly micron ball hole knot Structure is regulated and controled.
Technical solution provided by the present invention is：
A method of regulation bismuth tungstate self assembly micron spherical macrospore, including：Bismuth nitrate solution is added to sodium tungstate In solution, and hydro-thermal reaction is carried out, controls the molar ratio of bismuth nitrate and sodium tungstate, the molar ratio control of the bismuth nitrate and sodium tungstate System is 1.5~3:1.
Using sodium tungstate and bismuth nitrate as reaction mass in the present invention, Bi is realized by the molar ratio in the control source Bi and the source W2WO6 The pore structure artificial regulatory of self assembly micron ball.Sodium tungstate is strong base-weak acid salt, and bismuth nitrate is strong acid weak base salt, mixed solution Show certain faintly acid, OH-Ion is more.In more OH-Under ionization, nucleation point quantity increases, and is conducive to forming core simultaneously And obtain the lesser nanometer sheet of size.To reduce system surfaces energy, nanometer sheet carries out self assembly, ultimately forms Bi2WO6Micron ball. When W content is relatively more, W concentration is relatively large, and the introducing of Bi makes synthesized Bi for quickly in connection2WO6Nanometer sheet It is closer to form compact micron spherical structure；When W content is relatively fewer, W concentration is relatively small, the introducing of Bi Synthesized Bi2WO6Nanometer sheet distance is farther out to form in conjunction with more loose micron spherical structure.
Preferably, the control of the molar ratio of the bismuth nitrate and sodium tungstate is 2.5~3:1.
0.10~0.40mol/L of molar concentration of heretofore described sodium tungstate solution.Preferably, the sodium tungstate is molten The volume of liquid is 18-22ml.
0.15~1.20mol/L of molar concentration of heretofore described bismuth nitrate solution.Preferably, the bismuth nitrate is molten The volume of liquid is 18-22ml.
The reaction temperature of heretofore described hydro-thermal reaction is 170~190 DEG C, and the reaction time is 5~7h.Preferably, The reaction temperature is 175~185 DEG C.
Heretofore described bismuth nitrate solution is added in sodium tungstate solution by way of dropwise addition, and the rate of addition is 1~2 drop/sec.
The molar ratio of heretofore described bismuth nitrate and sodium tungstate is controlled 2.5~3:1, mole of the sodium tungstate solution 0.30~0.40mol/L of concentration, 0.75~1.2mol/L of molar concentration of the bismuth nitrate solution.
Compared with the existing technology, the beneficial effects of the present invention are embodied in：
(1) present invention process process is simple, easily controllable, and non-environmental-pollution is at low cost, is easy to large-scale production.
(2) it is realized by the molar ratio of control bismuth nitrate and sodium tungstate to Bi in the present invention2WO6The hole of self assembly micron ball Structure is regulated and controled, and the size of micron ball is between 2~4 μm, and micron ball quality is stablized, purity is high, powder granule good dispersion.
Detailed description of the invention
Fig. 1 is Bi prepared by Examples 1 to 42WO6The X-ray diffractogram of self assembly micron ball；
Fig. 2 is Bi prepared by embodiment 12WO6The SEM photograph of self assembly micron ball；
Fig. 3 is Bi prepared by embodiment 22WO6The SEM photograph of self assembly micron ball；
Fig. 4 is Bi prepared by embodiment 32WO6The SEM photograph of self assembly micron ball；
Fig. 5 is Bi prepared by embodiment 42WO6The SEM photograph of self assembly micron ball；
Fig. 6 is the X-ray diffractogram of micron ball powder prepared by comparative example 1；
Fig. 7 is the SEM photograph of micron ball powder prepared by comparative example 1.
Specific embodiment
Below with reference to specific embodiment, present invention will be explained in further detail.
Embodiment 1
1) 2mmol tungstate dihydrate acid sodium is dissolved in 20ml deionized water, so that the molar concentration of tungstate dihydrate acid sodium solution 0.10mol/L。
2) five water bismuth nitrate of 3mmol is dissolved in 20ml deionized water, so that the molar concentration of five water bismuth nitrate solutions Five water bismuth nitrate solutions are added drop-wise in sodium tungstate solution by 0.15mol/L with 1~2 drop/sec of speed, after stirring 30min, 6 hours are kept the temperature at 180 DEG C to be heat-treated.Then, be down to room temperature, take out reaction product, filtering, successively with spirit of vinegar, go from Sub- water cleans, and dries at a temperature of 60 DEG C, obtains Bi2WO6Self assembly micron ball powder.
Synthesized Bi2WO6The X-ray diffractogram of self assembly micron ball, as shown in Figure 1, product is Bi2WO6Self assembly is micro- Rice ball illustrates that product is the Bi of pure phase without other impurity peaks2WO6。
Scanning electron microscope SEM photograph is as shown in Fig. 2, Bi obtained2WO6Self assembly micron ball nano-scale between 2~ 4μm。
Embodiment 2
1) 4mmol tungstate dihydrate acid sodium is dissolved in 20ml deionized water, so that the molar concentration of tungstate dihydrate acid sodium solution 0.20mol/L。
2) five water bismuth nitrate of 8mmol is dissolved in 20ml deionized water, so that the molar concentration of five water bismuth nitrate solutions Five water bismuth nitrate solutions are added drop-wise in sodium tungstate solution by 0.40mol/L with 1~2 drop/sec of speed, after stirring 30min, 6 hours are kept the temperature at 180 DEG C to be heat-treated.Then, be down to room temperature, take out reaction product, filtering, successively with spirit of vinegar, go from Sub- water cleans, and dries at a temperature of 60 DEG C, obtains Bi2WO6Self assembly micron ball nano-powder.
Synthesized Bi2WO6The X-ray diffractogram of self assembly micron ball, as shown in Figure 1, product is Bi2WO6Self assembly is micro- Rice ball illustrates that product is the Bi of pure phase without other impurity peaks2WO6。
Scanning electron microscope SEM photograph is as shown in figure 3, Bi obtained2WO6Self assembly micron ball nano-scale between 2~ 4μm。
Embodiment 3
1) 6mmol tungstate dihydrate acid sodium is dissolved in 20ml deionized water, so that the molar concentration of tungstate dihydrate acid sodium solution 0.30mol/L。
2) five water bismuth nitrate of 15mmol is dissolved in 20ml deionized water, so that the molar concentration of five water bismuth nitrate solutions Five water bismuth nitrate solutions are added drop-wise in sodium tungstate solution by 0.75mol/L with 1~2 drop/sec of speed, after stirring 30min, 6 hours are kept the temperature at 180 DEG C to be heat-treated.Then, be down to room temperature, take out reaction product, filtering, successively with spirit of vinegar, go from Sub- water cleans, and dries at a temperature of 60 DEG C, obtains Bi2WO6Self assembly micron ball powder.
Synthesized Bi2WO6The X-ray diffractogram of self assembly micron ball, as shown in Figure 1, product is Bi2WO6Self assembly is micro- Rice ball illustrates that product is the Bi of pure phase without other impurity peaks2WO6。
Scanning electron microscope SEM photograph is as shown in figure 4, Bi obtained2WO6Self assembly micron ball nano-scale between 2~ 4μm。
Embodiment 4
1) 8mmol tungstate dihydrate acid sodium is dissolved in 20ml deionized water, so that the molar concentration of tungstate dihydrate acid sodium solution 0.40mol/L。
2) five water bismuth nitrate of 24mmol is dissolved in 20ml deionized water, so that the molar concentration of five water bismuth nitrate solutions Five water bismuth nitrate solutions are added drop-wise in sodium tungstate solution by 1.20mol/L with 1~2 drop/sec of speed, after stirring 30min, 6 hours are kept the temperature at 180 DEG C to be heat-treated.Then, be down to room temperature, take out reaction product, filtering, successively with spirit of vinegar, go from Sub- water cleans, and dries at a temperature of 60 DEG C, obtains Bi2WO6Self assembly micron ball powder.
Synthesized Bi2WO6The X-ray diffractogram of self assembly micron ball, as shown in Figure 1, product is Bi2WO6Self assembly is micro- Rice ball illustrates that product is the Bi of pure phase without other impurity peaks2WO6。
Scanning electron microscope SEM photograph is as shown in figure 5, Bi obtained2WO6Self assembly micron ball nano-scale between 2~ 4μm。
Performance test：Pore structure test
To Bi obtained by Examples 1 to 42WO6Self assembly micron ball carries out N2 adsorption desorption test.As shown in table 1, it lists Bi obtained by Examples 1 to 42WO6The pore structure of self assembly micron ball changes.
Table 1：Pore structure variation in Examples 1 to 4
By data in table it is concluded that：Molar ratio by adjusting bismuth nitrate and sodium tungstate can realize Bi2WO6From group Fill the pore structure regulation of micron ball.When W content is relatively more (such as 1.5:1), W concentration is relatively large, and the introducing of Bi will be fast Speed is in connection to make synthesized Bi2WO6Nanometer sheet is closer to form compact micron spherical structure；Work as W content When relatively fewer (such as 2.5:1 and 3:1), W concentration is relatively small, Bi synthesized by the introducing of Bi2WO6Nanometer sheet distance is farther out To be formed in conjunction with more loose micron spherical structure.
Comparative example 1
1) 2mmol tungstate dihydrate acid sodium is dissolved in 20ml deionized water, so that the molar concentration of tungstate dihydrate acid sodium solution 0.10mol/L。
2) five water bismuth nitrate of 2mmol is dissolved in 20ml deionized water, so that the molar concentration of five water bismuth nitrate solutions Five water bismuth nitrate solutions are added drop-wise in sodium tungstate solution by 0.10mol/L with 1~2 drop/sec of speed, after stirring 30min, 6 hours are kept the temperature at 180 DEG C to be heat-treated.Then, be down to room temperature, take out reaction product, filtering, successively with spirit of vinegar, go from Sub- water cleans, and dries at a temperature of 60 DEG C, obtains product powder.
The X-ray diffractogram of synthesized product, as shown in fig. 6, there is WO3Impurity peaks occur, and illustrate that product is Bi2WO6With WO3Mixture.
Scanning electron microscope SEM photograph is as shown in fig. 7, Bi obtained2WO6And WO3Mixture pattern is finer and close ball Body.

Claims (7)

1. a kind of method of regulation bismuth tungstate self assembly micron spherical macrospore, including：It is molten that bismuth nitrate solution is added to sodium tungstate In liquid, and carry out hydro-thermal reaction, which is characterized in that the molar ratio of control bismuth nitrate and sodium tungstate, the bismuth nitrate and sodium tungstate Molar ratio control 1.5~3:1.
2. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the nitre The molar ratio of sour bismuth and sodium tungstate is controlled 2.5~3:1.
3. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the tungsten 0.10~0.4mol/L of molar concentration of acid sodium solution.
4. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the nitre 0.15~1.2mol/L of molar concentration of sour bismuth solution.
5. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the water The reaction temperature of thermal response is 170~190 DEG C, and the reaction time is 5~7h.
6. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the nitre Sour bismuth solution is added in sodium tungstate solution by way of dropwise addition, and the rate of addition is 1~2 drop/sec.
7. the method for regulation bismuth tungstate self assembly micron spherical macrospore according to claim 1, which is characterized in that the nitre The molar ratio of sour bismuth and sodium tungstate is controlled 2.5~3:1,0.30~0.4mol/L of molar concentration of the sodium tungstate solution, institute State 0.75~1.20mol/L of molar concentration of bismuth nitrate solution.
CN201810628751.6A 2018-06-19 2018-06-19 A method of regulation bismuth tungstate self assembly micron spherical macrospore Pending CN108840367A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112044470A (en) * 2020-08-28 2020-12-08 南京大学环境规划设计研究院集团股份公司 Photocatalyst-loaded fluorocarbon fiber film for sewage station and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698739A (en) * 2012-06-15 2012-10-03 南开大学 Preparation method of sunlight-responding mesoporous Bi2WO6 microspheres
CN105753054A (en) * 2016-02-05 2016-07-13 陕西师范大学 Microspheric three-dimensional grading micro-nano structure bismuth tungstate photocatalytic material and preparation method thereof
CN107376899A (en) * 2017-07-19 2017-11-24 河南师范大学 The method that one step hydro thermal method synthesizes different-shape bismuth tungstate two dimension catalysis material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102698739A (en) * 2012-06-15 2012-10-03 南开大学 Preparation method of sunlight-responding mesoporous Bi2WO6 microspheres
CN105753054A (en) * 2016-02-05 2016-07-13 陕西师范大学 Microspheric three-dimensional grading micro-nano structure bismuth tungstate photocatalytic material and preparation method thereof
CN107376899A (en) * 2017-07-19 2017-11-24 河南师范大学 The method that one step hydro thermal method synthesizes different-shape bismuth tungstate two dimension catalysis material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112044470A (en) * 2020-08-28 2020-12-08 南京大学环境规划设计研究院集团股份公司 Photocatalyst-loaded fluorocarbon fiber film for sewage station and preparation method thereof
CN112044470B (en) * 2020-08-28 2021-06-18 南京大学环境规划设计研究院集团股份公司 Photocatalyst-loaded fluorocarbon fiber film for sewage station and preparation method thereof

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Application publication date: 20181120