CN103754837A - Method for preparation of bismuth-containing nano-hollow ball by using porous bismuth oxide as template - Google Patents
Method for preparation of bismuth-containing nano-hollow ball by using porous bismuth oxide as template Download PDFInfo
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Abstract
The invention relates to a method for preparation of a bismuth-containing nano-hollow ball by using porous bismuth oxide as a template. The method includes: adding porous bismuth oxide and a precursor into deionized water to undergo reaction under hydrothermal conditions, subjecting the product to centrifugation washing to remove the residual solute, and finally carrying out drying and cooling, thus obtaining the bismuth-containing nano-hollow ball. Specifically, the dosage of the porous bismuth oxide is 0.05-0.5mmol, the dosage of the precursor is 0.15-2mmol, and the dosage of the deionized water is 5-30mL. The method provided by the invention has the advantages that: (1) great change of the shell material appearance and performance, as well as a loose and porous shell structure can be avoided; (2) the bismuth-containing nano-hollow material with uniform appearance and controllable size can be synthesized (with the size decided by the size of the porous bismuth oxide template); and (3) a hydrothermal synthesis process is employed, no surfactant or template needs to be added, the process is simple, the production cost is lowered, and large-scale production of the product can be realized.
Description
Technical field
The invention belongs to chemical, functional materials, hollow nano-material technical field, be specifically related to a kind of porous bismuth oxide that utilizes and prepare the method for bismuth-containing nano-hollow ball for template.
Background technology
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 fire-retardant material, high refractive index glass, nuclear engineering glass manufacture and nuclear reactor fuels.The features such as nano-hollow ball has that density is low, specific surface area is large, good stability, surperficial penetrating power and lower thermal expansivity and good specific refractory power.Simultaneously because hollow structure has tightly packed and interlaced network structure and larger interior surface area, show rapid flow and the good photocatalytic activity of current carrier, inner hollow structure easily causes scattering of light, add the absorption of high light, increased the quantity of light induced electron and photohole.Therefore bismuth-containing nano-hollow ball has huge development prospect in the fields such as photochemical catalysis, environmental improvement.
Up to the present, the preparation method of bibliographical information bismuth-containing nano-hollow ball mainly adopts template, comprises dura mater plate method, soft template method and sacrifice section mould plate method.Hard template method refers to the template of maintaining specific shape with covalent linkage, certain inorganic metal precursor is introduced in dura mater plate hole road, then through roasting, in nano pore, generate oxide crystal, after removing dura mater plate, prepare corresponding mesoporous material, ideally resulting materials can keep the duct pattern of original template.(the Crystal Growth & Design such as Shang, 2009,9:991-996) reported a kind of method of preparing bismuth tungstate nanometer ball take carbon as hard template, the five water SODIUMNITRATE that are 2:1 by mol ratio and sodium wolframate are dissolved in the ethylene glycol that contains carbon ball and reflux, and wherein take colloidal carbon as template and through 450 ℃ of high-temperature calcinations, obtain the bismuth tungstate nanocages of diameter as 300nm left and right.Hard template method needs high-temperature calcination to remove template conventionally.
Soft template method is the template to be formed by materials such as organic surface active agent, polymer, virus, bacterium, bubbles, these materials can be self-assembled into ordered structure under certain condition, as micella or reverse micelle, emulsion or microemulsion, vesica etc., target substance or its precursor are at the template surface nucleating growth of these ordered structure compositions.As (Chinese patent ZL200910243644.2) such as (Dalton Trans, 2010,39:3426-3432) such as Dai and Dai Hongxing reported respectively the method for the hot legal system of tensio-active agent secondary solvent for bismuth tungstate hollow ball and pucherite hollow ball of utilizing.The former is dissolved in ethanol, acetic acid, deionized water by the sodium wolframate aqueous solution, five water Bismuth trinitrates and polyvinylpyrrolidone (PVP) is the mixing solutions that ratio is made in 1:1:3, and under solvent thermal condition, reaction can obtain the bismuth tungstate hollow ball that diameter is 1 μ m.The latter is dissolved in five water Bismuth trinitrates, ammonium meta-vanadate, PVP and urea in salpeter solution, and by solvent thermal reaction and 550 ℃ of high-temperature calcinations, obtaining diameter is 3～6 μ m, the pucherite hollow ball that aperture is 100～200nm.Wherein PVP has vital role as soft template for synthetic hollow ball.(the Journal of Molecular Catalysis such as Ma Zhanying, 2010,24:549-555) using bubble as soft template, provide a kind of take five water Bismuth trinitrates and ammonium meta-vanadate as raw material complexing gel calcination method the method for synthetic pucherite hollow ball, adopt 500 ℃ of high-temperature calcinations to make ammonium nitrate and citric acid produce gas, thereby this gas serves as soft template to be encapsulated in and in pucherite, to have formed hollow structure, but unbalanced due to aggregate convergent force on each position and content resistibility, has caused the inhomogeneity of wall thickness of tiny balloon even.
Up to now, there is no document and patent report and cross take porous bismuth oxide and prepare bismuth-containing nano-hollow ball as sacrificing section mould plate, and do not have a kind of technical scheme can realize by a kind of template to prepare different bismuth-containing nano-hollow balls.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned prior art, to propose a kind of porous bismuth oxide that utilizes to prepare the method for bismuth-containing nano-hollow ball for template, the method cost is low, process is simple and easy, and can obtain a series of have hollow structure, pattern homogeneous, the controlled bismuth based nano-materials of size.
The present invention solves the problems of the technologies described above adopted technical scheme: utilize porous bismuth oxide to prepare the method for bismuth-containing nano-hollow ball for template, it is characterized in that adding porous bismuth oxide and presoma in deionized water, after reacting under hydrothermal condition, products therefrom is removed residual solute through centrifuge washing, after last Drying and cooling, can obtain bismuth-containing nano-hollow ball, the consumption of wherein said porous bismuth oxide is 0.05～0.5mmol, the consumption of presoma is 0.15～2mmol, and the consumption of deionized water is 5～30mL.
Press such scheme, be also added with reductive agent in deionized water, the consumption of reductive agent is 2～12mmol.
Press such scheme, the preparation method of described porous bismuth oxide is: in the ethylene glycol solvent of 75mL, add 1.05mmol five water Bismuth trinitrates, the polyvinylpyrrolidone of 0.50g and the urea of 4mmol, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, under the hydrothermal condition of 150 ℃, react after 3h, through centrifuge washing, remove residual solute, solvent and polyvinylpyrrolidone, by product in 60 ℃ of dry 24h, after cooling, obtain porous bismuth oxide nano material, mean diameter is 180nm.
Press such scheme, described presoma is any one in ammonium meta-vanadate, thioacetamide and sodium wolframate.
Press such scheme, when presoma is tellurium oxide, reductive agent used is sodium borohydride; When presoma is Sodium Selenite, reductive agent used is xitix.
Press such scheme, described hydrothermal condition is that reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 6～15h.
Press such scheme, described centrifuge washing be with deionized water by abundant product ultrasonic dispersion, then under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times.
Press such scheme, described bismuth-containing nano-hollow ball is any one in Tellurobismuthite, bismuth selenide, pucherite, bismuth sulfide and bismuth tungstate, and its mean diameter is at 165～205nm.
The mechanism that the present invention prepares bismuth-containing nano-hollow ball is: porous bismuth oxide when synthetic bismuth-containing nano-hollow ball as sacrifice section mould plate, precursor molecule is dispersed in uniformly in whole system and by Intermolecular Forces and is adsorbed on porous bismuth oxide nanometer ball surface, bismuth oxide local dissolution is participated in reaction, in reaction system, the rate of diffusion of bismuth ion is larger than the rate of diffusion that participates in the presoma ion reacting, caused reaction interface to produce scattered vacancy, along with the carrying out of reaction, thereby these scattered vacancies reach supersaturation shrinks porous bismuth oxide generation dot matrix, the bismuth oxide molecular diffusion of nanometer ball inside is filled vacancy to interface, and be dissolved as bismuth ion and presoma ionic reaction, thereby vacancy forms hollow ball structure from interface to interior shifting.
Useful result of the present invention is:
(1) preparation method that the present invention adopts can prepare multiple bismuth-containing nano-hollow material by a template, is a blanket method;
(2) to prepare the template that hollow ball adopts be exactly reactant in the present invention, do not need to remove template through calcining or the technique such as dissolution with solvents, avoided the pattern of shell material and performance that the generation of larger variation and loose porous shell structure situation occurs;
(3) the present invention can synthesize pattern homogeneous, the controlled bismuth-containing nano-hollow material (size is determined by porous bismuth oxide template size) of size, the shortcoming such as the even or size distribution of the hollow nano-sphere inhomogeneity of wall thickness of having avoided some method to make is wider;
(4) the present invention adopts hydrothermal method synthesis technique, and without adding tensio-active agent and template, technique is simple, effectively reduces production cost, can realize the large-scale production of product.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 porous bismuth oxide template;
Fig. 2 is the TEM collection of illustrative plates of embodiment 1 porous bismuth oxide template;
Fig. 3 is the XRD figure spectrum of embodiment 3 products therefrom Tellurobismuthites;
Fig. 4 is the TEM collection of illustrative plates of embodiment 3 products therefrom Tellurobismuthites;
Fig. 5 is the XRD figure spectrum of embodiment 5 products therefrom bismuth selenides;
Fig. 6 is the TEM collection of illustrative plates of embodiment 5 products therefrom bismuth selenides;
Fig. 7 is the XRD figure spectrum of embodiment 7 products therefrom pucherites;
Fig. 8 is the TEM collection of illustrative plates of embodiment 7 products therefrom pucherites;
Fig. 9 is the XRD figure spectrum of embodiment 8 products therefrom bismuth sulfides;
Figure 10 is the TEM collection of illustrative plates of embodiment 8 products therefrom bismuth sulfides;
Figure 11 is the XRD figure spectrum of embodiment 10 products therefrom bismuth tungstates;
Figure 12 is the TEM collection of illustrative plates of embodiment 10 products therefrom bismuth tungstates.
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 template, comprises the steps:
In ethylene glycol (EG) solvent of 75mL, add the polyvinylpyrrolidone (PVP) of 1.05mmol five water Bismuth trinitrates, 0.50g and the urea of 4mmol, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, under the hydrothermal condition of 150 ℃, react after 3h, through centrifuge washing, remove residual solute, solvent and PVP, by product in 60 ℃ of dry 24h, after cooling, obtain porous bismuth oxide (Bi2O3) nano material, mean diameter is 180nm.
Fig. 1 is the XRD figure spectrum that adopts the porous bismuth oxide template that obtains of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).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, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified bismuth oxide.
Fig. 2 is the TEM figure that adopts the viewed porous bismuth oxide template of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the bismuth oxide of synthesized is the porous spherical structure being assembled into by small-particle, and porous bismuth oxide size homogeneous, and mean diameter is 180nm, even aperture distribution.
The preparation method of embodiment 2 Tellurobismuthite hollow ball nano materials, comprises the steps:
Get 0.05mmol embodiment 1 gained porous bismuth oxide, 0.15mmol tellurium oxide and 2mmol sodium borohydride in 5mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 12h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, can obtain Tellurobismuthite (Bi2Te3) nano-hollow ball after cooling, its mean diameter is 196nm.
The preparation method of embodiment 3 Tellurobismuthite hollow ball nano materials, comprises the steps:
Get 0.15mmol embodiment 1 gained porous bismuth oxide, 0.4mmol tellurium oxide and 5.29mmol sodium borohydride in 10mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 8h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, can obtain Tellurobismuthite (Bi2Te3) nano-hollow ball after cooling, its mean diameter is 201nm.
Fig. 3 is the XRD figure spectrum that adopts embodiment 3 samples that obtain of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with standard diagram JCPDS15-0863, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified Tellurobismuthite.
Fig. 4 is the TEM figure that adopts viewed embodiment 3 samples of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the nano material that the Tellurobismuthite sample of synthesized is hollow ball structure, and big or small homogeneous, its mean diameter is 201nm.
The preparation method of embodiment 4 bismuth selenide hollow ball nano materials, comprises the steps:
Get 0.5mmol embodiment 1 gained porous bismuth oxide, 1.2mmol Sodium Selenite and 11.4mmol xitix (AA) in 30mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 6h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, coolingly can obtain bismuth selenide (Bi2Se3) nano-hollow ball, its mean diameter is 172nm.
The preparation method of embodiment 5 bismuth selenide hollow ball nano materials, comprises the steps:
Get 0.1mmol embodiment 1 gained porous bismuth oxide, 0.25mmol Sodium Selenite and 2.27mmol xitix (AA) in 10mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 12h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, coolingly can obtain bismuth selenide (Bi2Se3) nano-hollow ball, its mean diameter is 167nm.
Fig. 5 is the XRD figure spectrum that adopts embodiment 5 samples that obtain of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with standard diagram JCPDS33-0214, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified bismuth selenide.
Fig. 6 is the TEM figure that adopts viewed embodiment 5 samples of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the nano material that the bismuth selenide sample of synthesized is hollow ball structure, and big or small homogeneous, its mean diameter is 167nm.
The preparation method of embodiment 6 pucherite hollow ball nano materials, comprises the steps:
Get 0.3mmol embodiment 1 gained porous bismuth oxide and 0.4mmol ammonium meta-vanadate in 20mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 9h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, Drying and cooling can obtain pucherite (BiVO4) nano-hollow ball, and its mean diameter is 165nm.
The preparation method of embodiment 7 pucherite hollow ball nano materials, comprises the steps:
Get 0.4mmol embodiment 1 gained porous bismuth oxide and 0.5mmol ammonium meta-vanadate in 30mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 12h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing be with deionized water by abundant product ultrasonic dispersion, then under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then, in 60 ℃ of dry 24h, Drying and cooling can obtain pucherite (BiVO
4) nano-hollow ball, its mean diameter is 169nm.
Fig. 7 is the XRD figure spectrum that adopts embodiment 7 samples that obtain of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with standard diagram JCPDS75-1866, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified pucherite.
Fig. 8 is the TEM figure that adopts viewed embodiment 7 samples of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the nano material that the pucherite sample of synthesized is hollow ball structure, and big or small homogeneous, its mean diameter is 169nm.
The preparation method of embodiment 8 bismuth sulfide hollow ball nano materials, comprises the steps:
Get 0.05mmol embodiment 1 gained porous bismuth oxide and 0.4mmol thioacetamide (TAA) in 5mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 15h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing be with deionized water by abundant product ultrasonic dispersion, then under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, coolingly can obtain bismuth sulfide (Bi
2s
3) nano-hollow ball, its mean diameter is 203nm.
Fig. 9 is the XRD figure spectrum that adopts embodiment 8 samples that obtain of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with standard diagram JCPDS89-8964, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified bismuth sulfide.
Figure 10 is the TEM figure that adopts viewed embodiment 8 samples of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the nano material that the bismuth sulfide sample of synthesized is hollow ball structure, and big or small homogeneous, its mean diameter is 203nm.
The preparation method of embodiment 9 bismuth sulfide hollow ball nano materials, comprises the steps:
Get 0.2mmol embodiment 1 gained porous bismuth oxide and 2mmol thioacetamide (TAA) in 15mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 9h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition again, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, coolingly can obtain bismuth sulfide (Bi2S3) nano-hollow ball, its mean diameter is 192nm.
The preparation method of embodiment 10 bismuth tungstate hollow ball nano materials, comprises the steps:
Get 0.3mmol embodiment 1 gained porous bismuth oxide and 0.3mmol sodium wolframate in 30mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 8h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing be with deionized water by abundant product ultrasonic dispersion, then under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 ℃ of dry 24h, coolingly can obtain sodium wolframate (Bi
2wO
6) nano-hollow ball, its mean diameter is 186nm.
Figure 11 is the XRD figure spectrum that adopts embodiment 10 samples that obtain of Bruker axs D8 type X-ray diffraction analysis instrument (XRD).From collection of illustrative plates, can find out, the main peak of collection of illustrative plates is consistent with standard diagram JCPDS39-256, and does not have other impurity peaks to occur, illustrates that products obtained therefrom is highly purified sodium wolframate.
Figure 12 is the TEM figure that adopts viewed embodiment 10 samples of Philips Tecnai G2 type transmission electron microscope (TEM).As can be seen from the figure, the nano material that the sodium wolframate sample of synthesized is hollow ball structure, and big or small homogeneous, its mean diameter is 186nm.
The preparation method of embodiment 11 bismuth tungstate hollow ball nano materials, comprises the steps:
Get 0.4mmol embodiment 1 gained porous bismuth oxide and 0.5mmol sodium wolframate in 30mL deionized water; Reaction soln is placed in to the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, reacts 15h; Products therefrom is removed residual solute through centrifuge washing, described centrifuge washing be with deionized water by abundant product ultrasonic dispersion, then under 10000rpm condition through centrifugal 10min, then in 60 ℃ of dry 24h, coolingly can obtain sodium wolframate (Bi
2wO
6) nano-hollow ball, its mean diameter is 195nm.
Claims (8)
1. utilize porous bismuth oxide to prepare the method for bismuth-containing nano-hollow ball for template, it is characterized in that adding porous bismuth oxide and presoma in deionized water, after reacting under hydrothermal condition, products therefrom is removed residual solute through centrifuge washing, after last Drying and cooling, can obtain bismuth-containing nano-hollow ball, the consumption of wherein said porous bismuth oxide is 0.05～0.5mmol, and the consumption of presoma is 0.15～2mmol, and the consumption of deionized water is 5～30mL.
2. the porous bismuth oxide that utilizes according to claim 1 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that being also added with reductive agent in deionized water, and the consumption of reductive agent is 2～12mmol.
3. the porous bismuth oxide that utilizes according to claim 1 and 2 is prepared the method for bismuth-containing nano-hollow ball for template, the preparation method who it is characterized in that described porous bismuth oxide is: in the ethylene glycol solvent of 75mL, add 1.05mmol five water Bismuth trinitrates, the polyvinylpyrrolidone of 0.50g and the urea of 4mmol, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, under the hydrothermal condition of 150 ℃, react after 3h, through centrifuge washing, remove residual solute, solvent and polyvinylpyrrolidone, by product in 60 ℃ of dry 24h, after cooling, obtain porous bismuth oxide nano material, mean diameter is 180nm.
4. the porous bismuth oxide that utilizes according to claim 1 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that described presoma is any one in ammonium meta-vanadate, thioacetamide and sodium wolframate.
5. the porous bismuth oxide that utilizes according to claim 2 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that reductive agent used when presoma is tellurium oxide is sodium borohydride; When presoma is Sodium Selenite, reductive agent used is xitix.
6. the porous bismuth oxide that utilizes according to claim 1 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that described hydrothermal condition is that reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, at 150 ℃ of temperature, react 6～15h.
7. the porous bismuth oxide that utilizes according to claim 1 and 2 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that described centrifuge washing is by abundant product ultrasonic dispersion with deionized water, the centrifugal 10min of process under 10000rpm condition, removes supernatant liquid again, repeats 5 times.
8. the porous bismuth oxide that utilizes according to claim 1 and 2 is prepared the method for bismuth-containing nano-hollow ball for template, it is characterized in that described bismuth-containing nano-hollow ball is any one in Tellurobismuthite, bismuth selenide, pucherite, bismuth sulfide and bismuth tungstate, its mean diameter is at 165～205nm.
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| CN104772134A (en) * | 2015-03-31 | 2015-07-15 | 浙江师范大学 | Method for massively preparing mesoporous BiVO4/Bi2O3 composite micro-rod p-n heterojunction photocatalyst |
| CN104772136A (en) * | 2015-04-15 | 2015-07-15 | 绍兴文理学院 | Pucherite as well as preparation method and application of pucherite |
| CN104817111A (en) * | 2015-04-21 | 2015-08-05 | 南京邮电大学 | Room-temperature water phase preparation method of bismuth sulfide nanospheres |
| CN105148949A (en) * | 2015-07-30 | 2015-12-16 | 中国石油大学(华东) | Bismuth oxyiodide-bismuth vanadium oxide heterojunction photocatalyst and preparation method thereof |
| CN105288625A (en) * | 2015-12-03 | 2016-02-03 | 哈尔滨工业大学 | Porous Bi2Se3 nano sponge material as well as preparation method and application thereof |
| CN107098388A (en) * | 2017-04-12 | 2017-08-29 | 新乡医学院 | A kind of preparation method of open-type bismuth oxide hollow ball |
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| CN109909511A (en) * | 2019-03-22 | 2019-06-21 | 中国工程物理研究院化工材料研究所 | A kind of preparation method and application of bismuthino hollow nano-material |
| CN114602515A (en) * | 2022-03-28 | 2022-06-10 | 王美珍 | Photocatalyst for removing heavy metal in sewage and preparation method and application thereof |
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