CN103466702B - 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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- CN103466702B CN103466702B CN201310446740.3A CN201310446740A CN103466702B CN 103466702 B CN103466702 B CN 103466702B CN 201310446740 A CN201310446740 A CN 201310446740A CN 103466702 B CN103466702 B CN 103466702B
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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 without Template preparation porous bismuth-containing nano material.
Background technology
Bismuth based material 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 due to its special physico-chemical property.Along with the fast development of nanotechnology, multifunctional nano material is used widely in every field with the character of its uniqueness.Bismuth based nano-material studies interest widely because the physico-chemical property of its uniqueness has caused people in the application in the fields such as semi-conductor, catalysis and biological medicine, and its application and development prospect is very wide.And the bismuth-containing nano material of porous, have that specific surface area is large, surface penetration ability and a feature such as lower thermal expansivity and good specific refractory power.Simultaneously because vesicular structure has tightly packed and interlaced network structure and larger interior surface area, show the quick mobility of current carrier and good photocatalytic activity, inner hollow structure easily causes scattering of light, add the absorption of high light, add the quantity of light induced electron and photohole, and due to bismuth oxide its own face with positive charge, can effectively and anionic pollutant produce electrostatic interaction, reach the effect of Adsorption of Heavy Metals pollutent.Therefore in the fields such as Industrial Catalysis (as photocatalysis to degrade organic matter), environmental improvement (as heavy metal adsorption process), there is important potential using value containing porous bismuth-containing nano material.
Bismuth oxide crystal inside also exists a large amount of Lacking oxygen, crystal formation can change at different temperatures, especially under nanoscale, there is special catalytic performance, make it all obtain in the Industrial Catalysis such as photocatalytic degradation of dye, nitric oxide gas sensor, heavy metal ion adsorbed and wastewater treatment and environmental improvement and study widely.Chinese patent CN101748484B describes 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 report a kind of method of synthesizing porous flower-shaped bismuth oxide material, but the bismuth oxide size that these methods synthesize comparatively large (being respectively 10 μm and 5 μm), pore size distribution is uneven, and do not belong to nano material, not there is the special performance of nano-scale.The method more than reported cannot be prepared and is porous and the bismuth oxide material of Nano grade, can not play the property of porous nanometer material.Therefore the synthesis containing porous bismuth-containing nano material has suitable meaning, has important potential using value in the field 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 the preparation method providing a kind of porous bismuth oxide nano material.The method can obtain the porous bismuth oxide nano material homogeneous compared with bigger serface, pattern, and preparation method is simple and easy, can be by force handling.
The inventive method realizes as follows:
Be dissolved in polyol solvent by Bismuth trinitrate, tensio-active agent and oxygen source presoma, be placed in autoclave in 150 DEG C of reaction 3 ~ 12h, products therefrom removes residual solvent and tensio-active agent through centrifuge washing, namely obtains 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 is with deionized water by abundant for product ultrasonic disperse, then through centrifugal (10000rpm) 10min, removes supernatant liquid.Centrifuge washing repeats 5 times.
Described drying process is cooled after dry 24h in 60 DEG C of baking ovens by product again.
Adopt the porous bismuth oxide nano material that the method obtains, specific surface area reaches 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 hinders Bi
3+further cluster, bismuth oxide nucleus just grows with less unit form.When the nuclei growth of numerous junior unit, after forming a complete structure, tensio-active agent can be removed through deionized water wash.Now, the tensio-active agent space stayed that comes off just defines vesicular bismuth oxide nano material.Preparation method of the present invention is simple and easy, and equipment is simple, and synthesis temperature is low; Low in raw material price, without the need to the template of costliness; Reproducible.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of embodiment 1 products therefrom bismuth oxide.
Fig. 2 is scanning electron microscope (SEM) photo of embodiment 1 products therefrom bismuth oxide.
Fig. 3 is transmission electron microscope (TEM) photo of embodiment 1 products therefrom bismuth oxide.
Fig. 4 is scanning electron microscope (SEM) and transmission electron microscope (TEM) photo of embodiment 2 products therefrom bismuth oxide.
Fig. 5 is scanning electron microscope (SEM) and transmission electron microscope (TEM) photo of embodiment 3 products therefrom bismuth oxide.
Fig. 6 is scanning electron microscope (SEM) and transmission electron microscope (TEM) photo of embodiment 4 products therefrom bismuth oxide.
Fig. 7 is absorption/desorption isotherm and the pore distribution curve of embodiment 4 products therefrom bismuth oxide.
Embodiment
Be described further the present invention below in conjunction with embodiment and accompanying drawing, 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, comprises the steps:
Get 1mmol Bismuth trinitrate, 0.50g polyvinylpyrrolidone (PVP), 4mmol urea is dissolved in 75mL ethylene glycol (EG) solution; Again reaction soln is placed in the 150mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 3h; Remove residual solvent and tensio-active agent through centrifuge washing, by product in 60 DEG C of dry 24h, cooled sample is porous bismuth oxide nano material.The specific surface area of this sample is 9.2m
2/ g.
Fig. 1 is the sample XRD figure spectrum adopting Bruker axs D8 type X-ray diffraction analysis instrument to obtain.As can be seen from collection of illustrative plates, 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 made up of very little Bismuth oxide particles.
Fig. 2 adopts the viewed sample SEM of Hitachi S4800 type scanning electronic microscope to scheme.As can be seen from the figure, synthesized sample is the ball shaped nano bismuth oxide that diameter is about 150nm, and pattern is homogeneous, and distribution of sizes is narrower.
Fig. 3 adopts the viewed sample TEM of Philips Tecnai G2 type transmission electron microscope to scheme.As can be seen from the figure, synthesized spherical alumina bismuth nano material is not solid, but the porous material be made up of many small-particles, and small particle size is homogeneous, even aperture distribution.
The preparation method of embodiment 2 porous bismuth oxide nano material, comprises the steps:
Get 0.25mmol Bismuth trinitrate, 0.10g polyvinylpyrrolidone (PVP), 1mmol sodium hydroxide is dissolved in 25mL glycol ether (DEG) solution; Again reaction soln is placed in the 50mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 12h; Remove residual solvent and tensio-active agent through centrifuge washing, by product in 60 DEG C of dry 24h, cooled sample is porous bismuth oxide nano material.The specific surface area of this sample is 13.2m
2/ g.
Fig. 4 adopts Hitachi S4800 type scanning electronic microscope viewed sample SEM figure and the viewed sample TEM of Philips Tecnai G2 type transmission electron microscope to scheme.As can be seen from the figure, synthesized sample is the ball shaped nano bismuth oxide that diameter is about 180nm, and pattern is homogeneous, and distribution of sizes is narrower.Spherical alumina bismuth nano material is not solid, but the porous material be made up of many small-particles, and small particle size is homogeneous, even aperture distribution.
The preparation method of embodiment 3 porous bismuth oxide nano material, comprises the steps:
Get 0.5mmol Bismuth trinitrate, 0.25g polyoxyethylene glycol (PEG), 1.5mmol sodium hydroxide is dissolved in 50mL triethylene glycol (TEG) solution; Again reaction soln is placed in the 50mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 3h; Remove residual solvent and tensio-active agent through centrifuge washing, by product in 60 DEG C of dry 24h, cooled sample is porous bismuth oxide nano material.The specific surface area of this sample is 18.7m
2/ g.
Fig. 5 adopts Hitachi S4800 type scanning electronic microscope viewed sample SEM figure and the viewed sample TEM of Philips Tecnai G2 type transmission electron microscope to scheme.As can be seen from the figure, synthesized sample is the ball shaped nano bismuth oxide that diameter is about 160nm, and pattern is homogeneous, and distribution of sizes is narrower.Spherical alumina bismuth nano material is not solid, but the porous material be made up of many small-particles, and small particle size is homogeneous, even aperture distribution.
The preparation method of embodiment 4 porous bismuth oxide nano material, comprises the steps:
Get 0.8mmol Bismuth trinitrate, 0.36g cetyl trimethylammonium bromide (CTAB), 2.5mmol mono-hydration ammonia is dissolved in 65mL ethylene glycol (EG) solution; Again reaction soln is placed in the 100mL stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 8h; Remove residual solvent and tensio-active agent through centrifuge washing, by product in 60 DEG C of dry 24h, cooled sample is porous bismuth oxide nano material.The specific surface area of this sample is 21.0m
2/ g.
Fig. 6 adopts Hitachi S4800 type scanning electronic microscope viewed sample SEM figure and the viewed sample TEM of Philips Tecnai G2 type transmission electron microscope to scheme.As can be seen from the figure, synthesized sample is the ball shaped nano bismuth oxide that diameter is about 120nm, and pattern is homogeneous, and distribution of sizes is narrower.Spherical alumina bismuth nano material is not solid, but the porous material be made up of many small-particles, and small particle size is homogeneous, even aperture distribution.
Fig. 7 is absorption/desorption isotherm and the pore distribution curve of the product adopting Micromeritics ASAP2020 type specific surface area analysis instrument to obtain, according to N
2absorption calculates, 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 (5)
1. prepare a method for porous bismuth oxide nano material, it is characterized in that, Bismuth trinitrate, tensio-active agent and oxygen source presoma are dissolved in polyol solvent, are placed in autoclave in 150
oc reacts 3 ~ 12 h, and products therefrom removes residual solvent and tensio-active agent through centrifuge washing, namely obtains 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 source presoma consumption is 1 ~ 4 mmol, and polyvalent alcohol consumption is 25 ~ 75 mL.
4. method according to claim 1, is characterized in that, described centrifuge washing is with deionized water by product ultrasonic disperse, then through centrifugal 10 min of 10000 rpm, removes supernatant liquid.
5. method according to claim 1, is characterized in that, described drying process is in 60 by product
ocool again after dry 24 h in C baking oven.
6.method according to claim 1, is characterized in that, the porous bismuth oxide nano material of acquisition, specific surface area reaches 9.2 ~ 21.0 m
2/ g.
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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 |
| 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 |
| CN109399726B (en) * | 2018-11-15 | 2020-10-16 | 沈阳理工大学 | Preparation method of iron lanthanum oxide molecular sieve type purification 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 |
| CN111097384B (en) * | 2019-12-16 | 2022-02-22 | 合肥学院 | C-Bi2O3-CuO-ZnO adsorption material and preparation method and application thereof |
| CN112516991B (en) * | 2020-12-24 | 2023-01-20 | 新乡学院 | Preparation method of bismuth oxide photocatalyst with two-dimensional structure |
| 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 |
| CN114291844A (en) * | 2021-12-29 | 2022-04-08 | 山东大学 | Preparation method of bismuth oxide coated YSZ powder |
| CN115944732B (en) * | 2023-03-14 | 2023-05-23 | 成都中医药大学 | Bismuth-based porous nanomaterial and preparation method and application thereof |
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