CN103754837B - Utilize porous bismuth oxide for the method for Template preparation bismuth-containing nano-hollow ball - Google Patents
Utilize porous bismuth oxide for the method for Template preparation bismuth-containing nano-hollow ball Download PDFInfo
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Abstract
The present invention relates to a kind of porous bismuth oxide that utilizes for the method for Template preparation bismuth-containing nano-hollow ball, add porous bismuth oxide and presoma in deionized water, under hydrothermal conditions after reaction, products therefrom removes residual solute through centrifuge washing, bismuth-containing nano-hollow ball can be obtained after last Drying and cooling, 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.Beneficial outcomes of the present invention is: (1) avoids the pattern of shell material and the generation of the performance larger change of generation and loose porous shell structure situation; (2) the bismuth-containing nano-hollow material (size is determined by porous bismuth oxide template size) that pattern is homogeneous, size is controlled can be synthesized; (3) adopt water heat transfer technique, without the need to adding tensio-active agent and template, technique is simple, reduces production cost, can realize the large-scale production of product.
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 for the method for Template preparation bismuth-containing nano-hollow ball.
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 fire-retardant material, high refractive index glass, nuclear engineering glass manufacture and nuclear reactor fuels due to its special physico-chemical property.Nano-hollow ball has that density is low, specific surface area is large, good stability, surface penetration ability and the feature such as 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 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.Therefore bismuth-containing nano-hollow ball has huge development prospect in the field 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 sacrificial template.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 in nano pore, oxide crystal is generated through roasting, prepare corresponding mesoporous material after removing dura mater plate, ideally resulting materials can keep the duct pattern of original template.(the CrystalGrowth & Design such as Shang, 2009,9:991-996) reporting a kind of take carbon as the method that hard template prepares bismuth tungstate nanometer ball, be reflux mol ratio during the five water SODIUMNITRATE of 2:1 and sodium wolframate are dissolved in containing carbon ball ethylene glycol, be wherein template with colloidal carbon and obtain through 450 DEG C of high-temperature calcinations the bismuth tungstate nanocages that diameter is about 300nm.Hard template method needs high-temperature calcination to remove template usually.
Soft template method is with the template 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., the template surface nucleating growth that target substance or its precursor form in these ordered structures.As (DaltonTrans, 2010,39:3426-3432) and the Dai Hongxing etc. (Chinese patent ZL200910243644.2) such as Dai report the method utilizing the hot legal system of tensio-active agent secondary solvent for bismuth tungstate hollow ball and pucherite hollow ball respectively.It is the mixing solutions that ratio is made that the sodium wolframate aqueous solution, five water Bismuth trinitrates and polyvinylpyrrolidone (PVP) are dissolved in ethanol, acetic acid, deionized water in 1:1:3 by the former, and under solvent thermal condition, reaction can obtain the bismuth tungstate hollow ball that diameter is 1 μm.Five water Bismuth trinitrates, ammonium meta-vanadate, PVP and urea are dissolved in salpeter solution by the latter, and obtaining diameter by solvent thermal reaction and 550 DEG C of high-temperature calcinations is 3 ~ 6 μm, and aperture is the pucherite hollow ball of 100 ~ 200nm.Wherein PVP has vital role as soft template for synthesis hollow ball.(the Journal of Molecular Catalysis such as Ma Zhanying, 2010,24:549-555) then as soft template using bubble, a kind of method being raw material complex coacervation calcination method synthesis pucherite hollow ball with five water Bismuth trinitrates and ammonium meta-vanadate is provided, 500 DEG C of high-temperature calcinations are adopted to make ammonium nitrate and citric acid produce gas, this gas serves as soft template and to be encapsulated in pucherite thus to define hollow structure, but due to aggregate convergent force and content resistibility unbalanced on each position, the inhomogeneity of wall thickness that result in tiny balloon is even.
Up to now, there is no that document and patent report cross with porous bismuth oxide is sacrificial Template preparation bismuth-containing nano-hollow ball, and does not have a kind of technical scheme can realize by the different bismuth-containing nano-hollow ball of a kind of Template preparation.
Summary of the invention
Technical problem to be solved by this invention proposes a kind of porous bismuth oxide that utilizes for the method for Template preparation bismuth-containing nano-hollow ball for above-mentioned prior art, the method cost is low, process is simple and easy, and can obtain a series of there is hollow structure, pattern is homogeneous, size is controlled bismuth based nano-material.
The present invention solves the problems of the technologies described above adopted technical scheme: utilize porous bismuth oxide for the method for Template preparation bismuth-containing nano-hollow ball, it is characterized in that adding porous bismuth oxide and presoma in deionized water, under hydrothermal conditions after reaction, products therefrom removes residual solute through centrifuge washing, bismuth-containing nano-hollow ball can be obtained after last Drying and cooling, 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.
By such scheme, be also added with reductive agent in deionized water, the consumption of reductive agent is 2 ~ 12mmol.
By such scheme, the preparation method of described porous bismuth oxide is: in the ethylene glycol solvent of 75mL, add 1.05mmol five water Bismuth trinitrate, the polyvinylpyrrolidone of 0.50g and the urea of 4mmol, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, react 3h under the hydrothermal condition of 150 DEG C after, residual solute, solvent and polyvinylpyrrolidone is removed through centrifuge washing, by product in 60 DEG C of dry 24h, namely obtain porous bismuth oxide nano material after cooling, mean diameter is 180nm.
By such scheme, described presoma is any one in ammonium meta-vanadate, thioacetamide and sodium wolframate.
By such scheme, reductive agent used when presoma is tellurium oxide is sodium borohydride; Reductive agent used when presoma is Sodium Selenite is xitix.
By such scheme, described hydrothermal condition is the stainless steel autoclave that reaction soln is placed in that liner is tetrafluoroethylene, at 150 DEG C of temperature, react 6 ~ 15h.
By such scheme, described centrifuge washing is with deionized water by abundant for product ultrasonic disperse, then through centrifugal 10min under 10000rpm condition, removes supernatant liquid, repeats 5 times.
By 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 synthesize bismuth-containing nano-hollow ball time as sacrificial template, precursor molecule to be dispersed in uniformly in whole system and to be adsorbed on porous bismuth oxide nanometer ball surface by Intermolecular Forces, bismuth oxide local dissolution participates in reaction, in reaction system, the rate of diffusion of bismuth ion is larger than the rate of diffusion of the presoma ion participating in reaction, result in reaction interface and produce scattered vacancy, along with the carrying out of reaction, these scattered vacancies reach supersaturation thus make porous bismuth oxide generation lattice contraction, the bismuth oxide molecular diffusion of nanometer ball inside fills vacancy to interface, and be dissolved as bismuth ion and presoma ionic reaction, vacancy then internally shifts from interface thus forms hollow ball structure.
Beneficial outcomes of the present invention is:
(1) preparation method of the present invention's employing is by a multiple bismuth-containing nano-hollow material of Template preparation, is a blanket method;
(2) the present invention prepares the template of hollow ball employing is exactly reactant, does not need to remove template through techniques such as calcining or dissolution with solvents, avoids the pattern of shell material and the generation of the performance larger change of generation and loose porous shell structure situation;
(3) the present invention can synthesize the bismuth-containing nano-hollow material (size is determined by porous bismuth oxide template size) that pattern is homogeneous, size is controlled, avoids the shortcomings such as the even or size distribution of the obtained hollow nano-sphere inhomogeneity of wall thickness of some method is wider;
(4) the present invention adopts water heat transfer technique, and without the need to 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 Tellurobismuthite;
Fig. 4 is the TEM collection of illustrative plates of embodiment 3 products therefrom Tellurobismuthite;
Fig. 5 is the XRD figure spectrum of embodiment 5 products therefrom bismuth selenide;
Fig. 6 is the TEM collection of illustrative plates of embodiment 5 products therefrom bismuth selenide;
Fig. 7 is the XRD figure spectrum of embodiment 7 products therefrom pucherite;
Fig. 8 is the TEM collection of illustrative plates of embodiment 7 products therefrom pucherite;
Fig. 9 is the XRD figure spectrum of embodiment 8 products therefrom bismuth sulfide;
Figure 10 is the TEM collection of illustrative plates of embodiment 8 products therefrom bismuth sulfide;
Figure 11 is the XRD figure spectrum of embodiment 10 products therefrom bismuth tungstate;
Figure 12 is the TEM collection of illustrative plates of embodiment 10 products therefrom bismuth tungstate.
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 template, comprises the steps:
1.05mmol five water Bismuth trinitrate, the polyvinylpyrrolidone (PVP) of 0.50g and the urea of 4mmol is added in ethylene glycol (EG) solvent of 75mL, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, react 3h under the hydrothermal condition of 150 DEG C after, residual solute, solvent and PVP is removed through centrifuge washing, by product in 60 DEG C of dry 24h, namely obtain porous bismuth oxide (Bi2O3) nano material after cooling, mean diameter is 180nm.
Fig. 1 is the XRD figure spectrum of the porous bismuth oxide template adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) 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, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed porous bismuth oxide template.As can be seen from the figure, synthesized bismuth oxide is the porous spherical structure be assembled into by small-particle, and porous bismuth oxide size is homogeneous, and mean diameter is 180nm, even aperture distribution.
The preparation method of embodiment 2 Tellurobismuthite hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 12h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C 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 material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 8h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, can obtain Tellurobismuthite (Bi2Te3) nano-hollow ball after cooling, its mean diameter is 201nm.
Fig. 3 is the XRD figure spectrum of embodiment 3 sample adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to obtain.As can be seen from collection of illustrative plates, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed embodiment 3 sample.As can be seen from the figure, synthesized Tellurobismuthite sample is the nano material of hollow ball structure, and size is homogeneous, and its mean diameter is 201nm.
The preparation method of embodiment 4 bismuth selenide hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 6h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, cooling can obtain bismuth selenide (Bi2Se3) nano-hollow ball, and its mean diameter is 172nm.
The preparation method of embodiment 5 bismuth selenide hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 12h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, cooling can obtain bismuth selenide (Bi2Se3) nano-hollow ball, and its mean diameter is 167nm.
Fig. 5 is the XRD figure spectrum of embodiment 5 sample adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to obtain.As can be seen from collection of illustrative plates, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed embodiment 5 sample.As can be seen from the figure, synthesized bismuth selenide sample is the nano material of hollow ball structure, and size is homogeneous, and its mean diameter is 167nm.
The preparation method of embodiment 6 pucherite hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 9h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C 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 material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 12h; Products therefrom removes residual solute through centrifuge washing, and described centrifuge washing is with deionized water by abundant for product ultrasonic disperse, then through centrifugal 10min under 10000rpm condition, remove supernatant liquid, repeat 5 times, then in 60 DEG C 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 of embodiment 7 sample adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to obtain.As can be seen from collection of illustrative plates, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed embodiment 7 sample.As can be seen from the figure, synthesized pucherite sample is the nano material of hollow ball structure, and size is homogeneous, and its mean diameter is 169nm.
The preparation method of embodiment 8 bismuth sulfide hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 15h; Products therefrom removes residual solute through centrifuge washing, and described centrifuge washing is with deionized water by abundant for product ultrasonic disperse, then through centrifugal 10min under 10000rpm condition, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, cooling can obtain bismuth sulfide (Bi
2s
3) nano-hollow ball, its mean diameter is 203nm.
Fig. 9 is the XRD figure spectrum of embodiment 8 sample adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to obtain.As can be seen from collection of illustrative plates, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed embodiment 8 sample.As can be seen from the figure, synthesized bismuth sulfide sample is the nano material of hollow ball structure, and size is homogeneous, and its mean diameter is 203nm.
The preparation method of embodiment 9 bismuth sulfide hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 9h; Products therefrom removes residual solute through centrifuge washing, described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, cooling can obtain bismuth sulfide (Bi2S3) nano-hollow ball, and its mean diameter is 192nm.
The preparation method of embodiment 10 bismuth tungstate hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 8h; Products therefrom removes residual solute through centrifuge washing, and described centrifuge washing is with deionized water by abundant for product ultrasonic disperse, then through centrifugal 10min under 10000rpm condition, remove supernatant liquid, repeat 5 times, then in 60 DEG C of dry 24h, cooling can obtain sodium wolframate (Bi
2wO
6) nano-hollow ball, its mean diameter is 186nm.
Figure 11 is the XRD figure spectrum of embodiment 10 sample adopting BrukeraxsD8 type X-ray diffraction analysis instrument (XRD) to obtain.As can be seen from collection of illustrative plates, 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 adopting PhilipsTecnaiG2 type transmission electron microscope (TEM) viewed embodiment 10 sample.As can be seen from the figure, synthesized sodium wolframate sample is the nano material of hollow ball structure, and size is homogeneous, and its mean diameter is 186nm.
The preparation method of embodiment 11 bismuth tungstate hollow ball nano material, 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 the stainless steel autoclave that liner is tetrafluoroethylene, at 150 DEG C of temperature, reacts 15h; Products therefrom removes residual solute through centrifuge washing, and described centrifuge washing is with deionized water by abundant for product ultrasonic disperse, then through centrifugal 10min under 10000rpm condition, then in 60 DEG C of dry 24h, cooling can obtain sodium wolframate (Bi
2wO
6) nano-hollow ball, its mean diameter is 195nm.
Claims (6)
1. utilize porous bismuth oxide for the method for Template preparation bismuth-containing nano-hollow ball, it is characterized in that adding porous bismuth oxide and presoma in deionized water, also reductive agent is added with in deionized water, the consumption of reductive agent is 2 ~ 12mmol, under hydrothermal conditions after reaction, products therefrom removes residual solute through centrifuge washing, bismuth-containing nano-hollow ball can be obtained after last Drying and cooling, 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; The preparation method of described porous bismuth oxide is: in the ethylene glycol solvent of 75mL, add 1.05mmol five water Bismuth trinitrate, the polyvinylpyrrolidone of 0.50g and the urea of 4mmol, gained reaction soln is placed in the stainless steel autoclave that liner is tetrafluoroethylene, react 3h under the hydrothermal condition of 150 DEG C after, residual solute, solvent and polyvinylpyrrolidone is removed through centrifuge washing, by product in 60 DEG C of dry 24h, namely obtain porous bismuth oxide nano material after cooling, mean diameter is 180nm.
2. the porous bismuth oxide that utilizes according to claim 1 is for the method for Template preparation bismuth-containing nano-hollow ball, it is characterized in that described presoma is any one in ammonium meta-vanadate, thioacetamide and sodium wolframate.
3. the porous bismuth oxide that utilizes according to claim 1 is for the method for Template preparation bismuth-containing nano-hollow ball, and reductive agent used when it is characterized in that presoma is tellurium oxide is sodium borohydride; Reductive agent used when presoma is Sodium Selenite is xitix.
4. the porous bismuth oxide that utilizes according to claim 1 is for the method for Template preparation bismuth-containing nano-hollow ball, it is characterized in that described hydrothermal condition is the stainless steel autoclave that reaction soln is placed in that liner is tetrafluoroethylene, at 150 DEG C of temperature, react 6 ~ 15h.
5. the porous bismuth oxide that utilizes according to claim 1 is for the method for Template preparation bismuth-containing nano-hollow ball, it is characterized in that described centrifuge washing is by abundant for product ultrasonic disperse with deionized water, again under 10000rpm condition through centrifugal 10min, remove supernatant liquid, repeat 5 times.
6. the porous bismuth oxide that utilizes according to claim 1 is for the method for Template preparation bismuth-containing nano-hollow ball, 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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| 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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| One-dimensional hierarchical Bi2WO6 hollow tubes with porous walls: synthesis and photocatalytic property;Shu-Juan Liu等;《CrystEngComm》;20130319;第15卷;第4124–4130页 * |
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