CN103466702A - Method for preparing porous bismuth oxide nano-material without template - Google Patents
Method for preparing porous bismuth oxide nano-material without template Download PDFInfo
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- CN103466702A CN103466702A CN2013104467403A CN201310446740A CN103466702A CN 103466702 A CN103466702 A CN 103466702A CN 2013104467403 A CN2013104467403 A CN 2013104467403A CN 201310446740 A CN201310446740 A CN 201310446740A CN 103466702 A CN103466702 A CN 103466702A
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Abstract
The invention relates to a method for preparing a porous bismuth oxide nano-material without a template. The method comprises the following steps of dissolving bismuth nitrate, a surfactant and an oxygen source precursor in a polyhydric alcohol solvent, putting the mixed solution into a high-pressure reactor for a reaction at a temperature of 150 DEG C for 3-12h to obtain a product, carrying out centrifugal washing to remove the residual solvent and surfactant, and carrying out drying to obtain the porous bismuth oxide nano-material having a large specific surface area. The method has the advantages of simple equipment, low synthesis temperature, low raw material price, no expensive template and good repeatability. The porous bismuth oxide nano-material obtained by the method has the advantages of uniform pore structure and large specific surface area.
Description
Technical field
The invention belongs to field of functional materials, relate to a kind of method for preparing porous bismuth-containing nano material without template.
Background technology
The bismuth based material is because its special physico-chemical property is widely used in each fields such as electron ceramic material, electrolyte, photoelectric material, sensor, microelectronic element, high temperature superconducting materia, catalyzer, ferroelectric material, simultaneously also for fields such as chemical reagent, bismuth salt, fire-retardant material, high refractive index glass, nuclear engineering glass manufacture and nuclear reactor fuels.Along with the fast development of nanotechnology, the multifunctional nano material character unique with it is used widely in every field.The bismuth based nano-material is because its unique physico-chemical property application in fields such as semi-conductor, catalysis and biological medicines has caused that people study interest widely, and its application and development prospect is very wide.And the bismuth-containing nano material of porous has large, the surperficial penetrating power of specific surface area and lower thermal expansivity and the good characteristics such as specific refractory power.Simultaneously because vesicular structure has tightly packed and interlaced network structure and larger interior surface area, show the rapid flow of current carrier and photocatalytic activity preferably, inner hollow structure easily causes scattering of light, add the absorption of high light, increased the quantity of light induced electron and photohole, and due to bismuth oxide self surface with positive charge, can be effectively and anionic pollutant produce electrostatic interaction, reach the effect of Adsorption of Heavy Metals pollutent.Therefore there is important potential using value containing porous bismuth-containing nano material in the fields such as Industrial Catalysis (as photocatalysis to degrade organic matter), environmental improvement (processing as heavy metal adsorption).
Bismuth oxide crystal inside exists a large amount of oxygen rooms, under differing temps, crystal formation can change, especially there is special catalytic performance under nanoscale, make it aspect Industrial Catalysis such as photocatalytic degradation of dye, nitric oxide gas sensor, heavy metal ion adsorbed and wastewater treatment and environmental improvement, all obtain research widely.Chinese patent CN101748484B has introduced a kind of method of synthesis of nano bismuth oxide single-crystal chips, and the bismuth oxide that the method synthesizes only has the sheet structure of one dimension, does not have vesicular structure, and specific surface area is less.Chinese patent CN101565204B and Chinese Journal of Inorganic Chemistry (Vol.26, No.10,1880-1884) all reported a kind of method of synthesizing porous flower-shaped bismuth oxide material, but the bismuth oxide size that these methods synthesize is large (being respectively 10 μ m and 5 μ m), the pore size distribution inequality, and do not belong to nano material, do not there is the special performance of nano-scale.Can't prepare by the method for above report is the bismuth oxide material of porous and Nano grade, can not bring into play the property of porous nanometer material.Therefore there is suitable meaning containing porous bismuth-containing nano material synthetic, there is important potential using value in the fields such as Industrial Catalysis, environmental improvement.
Summary of the invention
For the deficiencies in the prior art, technical problem to be solved by this invention is to provide a kind of preparation method of porous bismuth oxide nano material.The method can obtain than the porous bismuth oxide nano material of bigger serface, pattern homogeneous, and the preparation method is simple and easy,, can be handling strong.
The inventive method realizes as follows:
Bismuth trinitrate, tensio-active agent and oxygen source presoma are dissolved in polyol solvent, are placed in autoclave in 150 ℃ of reaction 3～12h, products therefrom is removed residual solvent and tensio-active agent through centrifuge washing, obtains the porous bismuth oxide nano material after drying;
Described tensio-active agent is polyvinylpyrrolidone (PVP), cetyl trimethylammonium bromide (CTAB), polyoxyethylene glycol (PEG);
Described oxygen source presoma is urea, sodium hydroxide or a hydration ammonia.
Described polyol solvent is glycol ether (DEG), ethylene glycol (EG) or triethylene glycol (TEG).
Described Bismuth trinitrate consumption is 0.25～1mmol, and dosage of surfactant is 0.10～0.50g, and oxygen presoma consumption is 1～4mmol, and solvent load is 25～75mL.
Described centrifuge washing be with deionized water by the abundant ultrasonic dispersion of product, then pass through centrifugal (10000rpm) 10min, remove supernatant liquid.Centrifuge washing repeats 5 times.
Described drying process is that product is cooling again after dry 24h in 60 ℃ of baking ovens.
The porous bismuth oxide nano material that adopts the method to obtain, specific surface area has reached 9.2～21.0m
2/ g.
Tensio-active agent plays an important role in formation porous bismuth oxide nano material in the method.Add Bi
3+after, there is the structure of a large amount of similar glue bunch in solution, now surfactant molecule is adsorbed on glue bunch surface.Because the existence of tensio-active agent has hindered Bi
3+further cluster, the bismuth oxide nucleus is just grown with less unit form.When the nuclei growth of numerous junior units, after forming a complete structure, through deionized water wash, can remove tensio-active agent.Now, the tensio-active agent space stayed that comes off has just formed the vesicular bismuth oxide nano material.Preparation method of the present invention is simple and easy, and equipment is simple, and synthesis temperature is low; Cost of material is cheap, without expensive template; Reproducible.
The accompanying drawing explanation
The X-ray diffraction that Fig. 1 is embodiment 1 products therefrom bismuth oxide (XRD) collection of illustrative plates.
The scanning electron microscope that Fig. 2 is embodiment 1 products therefrom bismuth oxide (SEM) photo.
The transmission electron microscope that Fig. 3 is embodiment 1 products therefrom bismuth oxide (TEM) photo.
The scanning electron microscope that Fig. 4 is embodiment 2 products therefrom bismuth oxides (SEM) and transmission electron microscope (TEM) photo.
The scanning electron microscope that Fig. 5 is embodiment 3 products therefrom bismuth oxides (SEM) and transmission electron microscope (TEM) photo.
The scanning electron microscope that Fig. 6 is embodiment 4 products therefrom bismuth oxides (SEM) and transmission electron microscope (TEM) photo.
Absorption/desorption isotherm and pore distribution curve that Fig. 7 is embodiment 4 products therefrom bismuth oxides.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described further, the scope of protection of present invention is not limited to the scope of embodiment statement:
The preparation method of embodiment 1 porous bismuth oxide nano material, comprise the steps:
Get 1mmol Bismuth trinitrate, 0.50g polyvinylpyrrolidone (PVP), 4mmol urea and be dissolved in 75mL ethylene glycol (EG) solution; Again reaction soln is placed in to the 150mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 3h; Remove residual solvent and tensio-active agent through centrifuge washing, by product, in 60 ℃ of dry 24h, cooled sample is the porous bismuth oxide nano material.The specific surface area of this sample is 9.2m
2/ g.
Fig. 1 adopts the resulting sample XRD figure spectrum of Bruker axs D8 type X-ray diffraction analysis instrument.From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with bismuth oxide standard diagram (JCPDS76-2478), illustrates that products obtained therefrom is highly purified bismuth oxide.Collection of illustrative plates has obvious broadening phenomenon, and interpret sample is comprised of very little bismuth oxide particle.
Fig. 2 adopts the viewed sample SEM figure of Hitachi S4800 type scanning electronic microscope.As can be seen from the figure, the sample of synthesized is the ball shaped nano bismuth oxide that diameter is about 150nm, and the pattern homogeneous, and distribution of sizes is narrower.
Fig. 3 adopts the viewed sample TEM figure of Philips Tecnai G2 type transmission electron microscope.As can be seen from the figure, the spherical bismuth oxide nano material of synthesized is not solid, but the porous material formed by many small-particles, and the small particle size homogeneous, even aperture distribution.
The preparation method of embodiment 2 porous bismuth oxide nano materials, comprise the steps:
Get 0.25mmol Bismuth trinitrate, 0.10g polyvinylpyrrolidone (PVP), 1mmol sodium hydroxide and be dissolved in 25mL glycol ether (DEG) solution; Again reaction soln is placed in to the 50mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 12h; Remove residual solvent and tensio-active agent through centrifuge washing, by product, in 60 ℃ of dry 24h, cooled sample is the porous bismuth oxide nano material.The specific surface area of this sample is 13.2m
2/ g.
Fig. 4 adopts the viewed sample SEM figure of Hitachi S4800 type scanning electronic microscope and the viewed sample TEM figure of Philips Tecnai G2 type transmission electron microscope.As can be seen from the figure, the sample of synthesized is the ball shaped nano bismuth oxide that diameter is about 180nm, and the pattern homogeneous, and distribution of sizes is narrower.Spherical bismuth oxide nano material is not solid, but the porous material formed by many small-particles, and the small particle size homogeneous, even aperture distribution.
The preparation method of embodiment 3 porous bismuth oxide nano materials, comprise the steps:
Get 0.5mmol Bismuth trinitrate, 0.25g polyoxyethylene glycol (PEG), 1.5mmol sodium hydroxide and be dissolved in 50mL triethylene glycol (TEG) solution; Again reaction soln is placed in to the 50mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 3h; Remove residual solvent and tensio-active agent through centrifuge washing, by product, in 60 ℃ of dry 24h, cooled sample is the porous bismuth oxide nano material.The specific surface area of this sample is 18.7m
2/ g.
Fig. 5 adopts the viewed sample SEM figure of Hitachi S4800 type scanning electronic microscope and the viewed sample TEM figure of Philips Tecnai G2 type transmission electron microscope.As can be seen from the figure, the sample of synthesized is the ball shaped nano bismuth oxide that diameter is about 160nm, and the pattern homogeneous, and distribution of sizes is narrower.Spherical bismuth oxide nano material is not solid, but the porous material formed by many small-particles, and the small particle size homogeneous, even aperture distribution.
The preparation method of embodiment 4 porous bismuth oxide nano materials, comprise the steps:
Get 0.8mmol Bismuth trinitrate, 0.36g cetyl trimethylammonium bromide (CTAB), 2.5mmol mono-hydration ammonia and be dissolved in 65mL ethylene glycol (EG) solution; Again reaction soln is placed in to the 100mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 8h; Remove residual solvent and tensio-active agent through centrifuge washing, by product, in 60 ℃ of dry 24h, cooled sample is the porous bismuth oxide nano material.The specific surface area of this sample is 21.0m
2/ g.
Fig. 6 adopts the viewed sample SEM figure of Hitachi S4800 type scanning electronic microscope and the viewed sample TEM figure of Philips Tecnai G2 type transmission electron microscope.As can be seen from the figure, the sample of synthesized is the ball shaped nano bismuth oxide that diameter is about 120nm, and the pattern homogeneous, and distribution of sizes is narrower.Spherical bismuth oxide nano material is not solid, but the porous material formed by many small-particles, and the small particle size homogeneous, even aperture distribution.
Fig. 7 is absorption/desorption isotherm and the pore distribution curve that adopts the resulting product of Micromeritics ASAP2020 type specific surface area analysis instrument, according to N
2absorption is calculated, and the specific surface area of gained sample is 21.0m
2/ g, and be about 30nm according to the pore size that pore size distribution curve can obtain sample.
Claims (6)
1. a method for preparing the porous bismuth oxide nano material, is characterized in that, Bismuth trinitrate, tensio-active agent and oxygen source presoma are dissolved in polyol solvent, is placed in autoclave in 150
oc reacts 3 ~ 12 h, and products therefrom is removed residual solvent and tensio-active agent through centrifuge washing, obtains the porous bismuth oxide nano material after drying;
Described tensio-active agent is polyvinylpyrrolidone, cetyl trimethylammonium bromide or polyoxyethylene glycol;
Described oxygen source presoma is urea, sodium hydroxide or a hydration ammonia.
2. method according to claim 1, is characterized in that, described polyol solvent is glycol ether, ethylene glycol or triethylene glycol.
3. method according to claim 1, is characterized in that, described Bismuth trinitrate consumption is 0.25 ~ 1 mmol, and dosage of surfactant is 0.10 ~ 0.50 g, and oxygen presoma consumption is 1 ~ 4 mmol, and the polyvalent alcohol consumption is 25 ~ 75 mL.
4. method according to claim 1, is characterized in that, described centrifuge washing be with deionized water by the ultrasonic dispersion of product, then, through centrifugal 10 min of 10000 rpm, remove supernatant liquid.
5. method according to claim 1, is characterized in that, described drying process is in 60 by product
ocooling again after dry 24 h in the C baking oven.
6. method according to claim 1, is characterized in that, the porous bismuth oxide nano material of acquisition, and specific surface area reaches 9.2 ~ 21.0 m
2/ g.
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| CN107199030A (en) * | 2017-06-30 | 2017-09-26 | 常州豫春化工有限公司 | A kind of preparation method of cellular porous bismuth oxide |
| CN107416899A (en) * | 2017-04-05 | 2017-12-01 | 河南师范大学 | A kind of nano wire α Bi2O3The preparation method of dusty material |
| CN108704658A (en) * | 2018-06-04 | 2018-10-26 | 西南石油大学 | A kind of preparation method of bismuth oxide and nitrogen carbide nanosheet composite material |
| CN109205670A (en) * | 2018-10-19 | 2019-01-15 | 湖南柿竹园有色金属有限责任公司 | A kind of inorfil state bismuth compound and its application |
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| CN111097384A (en) * | 2019-12-16 | 2020-05-05 | 合肥学院 | C-Bi2O3-CuO-ZnO adsorption material and preparation method and application thereof |
| CN112516991A (en) * | 2020-12-24 | 2021-03-19 | 新乡学院 | Preparation method of bismuth oxide photocatalyst with two-dimensional structure |
| CN113713752A (en) * | 2021-08-20 | 2021-11-30 | 西安交通大学 | Micron flower-like bismuth oxide material, preparation method thereof and application thereof in radioactive anion adsorption |
| CN114291844A (en) * | 2021-12-29 | 2022-04-08 | 山东大学 | Preparation method of bismuth oxide coated YSZ powder |
| CN115944732A (en) * | 2023-03-14 | 2023-04-11 | 成都中医药大学 | Bismuth-based porous nano material and preparation method and application thereof |
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| CN107416899B (en) * | 2017-04-05 | 2019-01-22 | 河南师范大学 | A kind of nano wire α-Bi2O3The preparation method of dusty material |
| CN107416899A (en) * | 2017-04-05 | 2017-12-01 | 河南师范大学 | A kind of nano wire α Bi2O3The preparation method of dusty material |
| CN107199030A (en) * | 2017-06-30 | 2017-09-26 | 常州豫春化工有限公司 | A kind of preparation method of cellular porous bismuth oxide |
| CN108704658A (en) * | 2018-06-04 | 2018-10-26 | 西南石油大学 | A kind of preparation method of bismuth oxide and nitrogen carbide nanosheet composite material |
| CN109205670B (en) * | 2018-10-19 | 2021-02-26 | 湖南柿竹园有色金属有限责任公司 | Inorganic fibrous bismuth compound and application thereof |
| CN109205670A (en) * | 2018-10-19 | 2019-01-15 | 湖南柿竹园有色金属有限责任公司 | A kind of inorfil state bismuth compound and its application |
| CN109399726A (en) * | 2018-11-15 | 2019-03-01 | 沈阳理工大学 | A kind of preparation method of iron lanthanum-oxides molecular sieve type scavenging material |
| CN109745982A (en) * | 2019-01-08 | 2019-05-14 | 大连理工大学 | The preparation method and application of CeO 2 supporting copper oxide nano material |
| CN109745982B (en) * | 2019-01-08 | 2022-01-11 | 大连理工大学 | Preparation method and application of cerium dioxide loaded copper oxide nano material |
| CN111097384A (en) * | 2019-12-16 | 2020-05-05 | 合肥学院 | C-Bi2O3-CuO-ZnO adsorption material and preparation method and application thereof |
| CN112516991A (en) * | 2020-12-24 | 2021-03-19 | 新乡学院 | Preparation method of bismuth oxide photocatalyst with two-dimensional structure |
| CN112516991B (en) * | 2020-12-24 | 2023-01-20 | 新乡学院 | Preparation method of bismuth oxide photocatalyst with two-dimensional structure |
| CN113713752A (en) * | 2021-08-20 | 2021-11-30 | 西安交通大学 | Micron flower-like bismuth oxide material, preparation method thereof and application thereof in radioactive anion adsorption |
| CN113713752B (en) * | 2021-08-20 | 2023-06-02 | 西安交通大学 | Micron flower-like bismuth oxide material, preparation method thereof and application thereof in adsorbing radioactive anions |
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