CN103739007B - The porous SnO 2 nanostructure that template synthesis size is controlled - Google Patents
The porous SnO 2 nanostructure that template synthesis size is controlled Download PDFInfo
- Publication number
- CN103739007B CN103739007B CN201310739625.5A CN201310739625A CN103739007B CN 103739007 B CN103739007 B CN 103739007B CN 201310739625 A CN201310739625 A CN 201310739625A CN 103739007 B CN103739007 B CN 103739007B
- Authority
- CN
- China
- Prior art keywords
- size
- template
- polystyrene sphere
- nanostructure
- vinylbenzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The porous SnO 2 nanostructure that template synthesis size is controlled, comprise the following steps: (1) is by vinylbenzene and deionized water mixing, supersound process 15-25min, heating in water bath is to 65-75 DEG C, add the potassium persulfate solution of supersound process afterwards, stirred at ambient temperature 7-13h, obtains polystyrene sphere suspension liquid; (2) adopt vertical sedimentation legal system for polystyrene sphere template; (3) by SnCl
44H
2o joins in ethanol solution, and cool to room temperature after stirring also leaves standstill, and obtains precursor sol solution; (4) precursor sol dropwise is added drop-wise in polystyrene sphere template, then dries, be gradually warming up to 480-530 DEG C after oven dry and keep 2-4h, then naturally cooling.The present invention is by realizing the regulation and control to photocatalysis performance to the control of vinylbenzene bead size, the porous SnO 2 nanostructure prepared is stablized, and size is controlled, and photocatalysis performance is stablized, and can repeated multiple timesly use.
Description
Technical field
The invention discloses the porous SnO 2 nanostructure utilizing template synthesis size controlled, and realize efficient photocatalysis performance, belong to technical field prepared by nano material and photocatalyst.
Background technology
Tindioxide is a kind of important catalytic material, and it is insoluble in bronsted lowry acids and bases bronsted lowry, is a kind of amphoteric substance, not only can be used as the carrier of catalyzer, can also as the active ingredient of catalyzer and cocatalyst.Utilizing tindioxide as in photocatalyst for degrading organic pollutant at present, normally as other wide semiconductor material as TiO
2, Fe
2o
3, the photocatalyst such as ZnO modified component.Due to tindioxide self, as wide band gap magnitude and dipole transition are prohibited, it is made to be difficult to singlely become a kind of photocatalyst efficiently, so almost have no report for pure tindioxide as the research of photocatalyst and catalytic performance at present.Before making the present invention, how many preparation methods of stannic oxide nanometer vesicular structure also exists problem, and most important is exactly effective control how to porous size, utilizes these vesicular structures not have especially to realize efficient photocatalytic degradation.
Summary of the invention
The object of this invention is to provide the porous SnO 2 nanostructure that a kind of template synthesis size is controlled, the present invention realizes the control to porous SnO 2 nanostructure size by the control of p-poly-phenyl ethene small ball mould board size, and the control of template size only can need realize by controlling polystyrene concentrations, technique is simple, easy handling, large-scale industrial production can be realized, and the porous nanometer structure uniform and ordered prepared, Stability Analysis of Structures, present good photocatalysis performance, also effectively can realize the regulation and control to photocatalysis performance, photocatalyst can repeated multiple timesly use, realize tindioxide one-component high efficiency photocatalysis and to its Effective Regulation.
The object of the invention is to be achieved through the following technical solutions, the porous SnO 2 nanostructure that template synthesis size is controlled, comprises the following steps:
(1) preparation of polystyrene sphere suspension liquid: by vinylbenzene and deionized water mixing, supersound process 15-25min, ultrasonic frequency is 200KHz, vinylbenzene after supersound process and deionized water mixing solutions heating in water bath are to 65-75 DEG C, backward be cooled to room temperature vinylbenzene and deionized water mixing solutions in add the potassium persulfate solution of supersound process, ultrasonic frequency is 200KHz frequency, stirred at ambient temperature 7-13h, stirring velocity is 280-330r/min, obtains polystyrene sphere suspension liquid; Vinylbenzene described in every milliliter of corresponding 0.0086-0.0214g of described deionized water, described potassium persulfate solution concentration is 12g/L, and the volume ratio of described vinylbenzene and potassium persulfate solution is 5:1;
(2) adopt vertical sedimentation legal system for polystyrene sphere template: to be that dichromic acid and the vitriol oil mixing solutions of 1:1 soaks 20-26h by substrate base volume ratio, two panels substrate base after immersion sticks together, the two panels substrate base fit together vertically is put into described polystyrene sphere suspension liquid, due to wicking action, substrate base inside can be full of suspension liquid, the substrate base being full of suspension liquid, in 48-52 DEG C of oven dry, obtains the polystyrene sphere template of different size;
(3) preparation of precursor sol solution: by SnCl
44H
2o joins in ethanol solution, at 75-85 DEG C, stir 9-12h, and then cool to room temperature also leaves standstill 22-26h, obtains precursor sol solution; SnCl described in every mmole
44H
2the corresponding 1.8ml dehydrated alcohol of O;
(4) described precursor sol dropwise is added drop-wise in the described polystyrene sphere template of different size size, then oven for drying is used, polystyrene sphere template after oven dry is gradually warming up to 480-530 DEG C and keeps 2-4h, heating-up time 4-6h, remove the organic bead of polystyrene, then naturally cool to room temperature, obtain the porous SnO 2 nanostructure of different pore size.
Further, dripping of precursor sol solution described in step (4) counts as 1-3 drips.
Further, described in step (2), substrate base is glass, silicon single crystal, quartz or metal substrate.
Compared with prior art, the present invention has following beneficial effect:
First, the present invention is by the control of p-poly-phenyl ethylene concentration, the size of effective control polystyrene sphere, the vinylbenzene bead utilizing these sizes controlled goes out the controlled porous SnO 2 nanostructure of size as Template preparation, the more important thing is that the tin dioxide nanostructure of these porous has shown good photocatalysis performance, and its photocatalysis performance of the vesicular structure of different size is also different, namely can by realizing the regulation and control to photocatalysis performance to the control of vinylbenzene bead size:
The second, polystyrene sphere substrate used in the present invention can be silicon single crystal, quartz or other metals etc.;
3rd, the porous SnO 2 nanostructure sample photocatalysis performance of the different pore size size that the present invention obtains differs widely, but compared with the tindioxide powder of non-porous structure, all presents good catalytic performance.Along with the reduction in aperture, photocatalysis performance strengthens gradually.The porous SnO 2 photocatalyst that this invention is prepared has good secondary recovery recycling performance.The porous SnO 2 nanostructure that the present invention prepares is stablized, and size is controlled, and photocatalysis performance is stablized, and can repeated multiple timesly use.
Accompanying drawing explanation
Fig. 1 is the SEM figure of different size polystyrene (PS) the bead template that the present invention obtains;
Fig. 2 is the SEM figure of the different pore size sized silica tin that the present invention obtains;
Fig. 3 is the photocatalysis effect figure of the different size tindioxide vesicular structure that the present invention obtains; C in ordinate zou
0represent pollutent starting point concentration, C representative Pollutant levels sometime; Powers representative has the powder of good catalytic;
The secondary recovery of Fig. 4 to be aperture that the present invention obtains be 250nm tindioxide vesicular structure utilizes degraded figure again, in figure, first represents aperture is the first time catalysis of 250nm tindioxide vesicular structure, and retry represents the secondary recovery utilization that aperture is 250nm tindioxide vesicular structure.
Embodiment
The porous SnO 2 nanostructure that template synthesis size is controlled, comprises the following steps:
(1) preparation of polystyrene sphere suspension liquid: by vinylbenzene and deionized water mixing, supersound process 15-25min, ultrasonic frequency is 200KHz, vinylbenzene after supersound process and deionized water mixing solutions heating in water bath are to 65-75 DEG C, backward be cooled to room temperature vinylbenzene and deionized water mixing solutions in add the potassium persulfate solution of supersound process, ultrasonic frequency is 200KHz frequency, stirred at ambient temperature 7-13h, stirring velocity is 280-330r/min, obtains polystyrene sphere suspension liquid; Vinylbenzene described in every milliliter of corresponding 0.0086-0.0214g of described deionized water, described potassium persulfate solution concentration is 12g/L, and the volume ratio of described vinylbenzene and potassium persulfate solution is 5:1;
(2) adopt vertical sedimentation legal system for polystyrene sphere template: to be the dichromic acid of 1:1 and concentration by substrate base volume ratio be 98% vitriol oil mixing solutions soak 20-26h, two panels substrate base after immersion sticks together, the two panels substrate base fit together vertically is put into described polystyrene sphere suspension liquid, due to wicking action, substrate base inside can be full of suspension liquid, the substrate base being full of suspension liquid, in 48-52 DEG C of oven dry, obtains the polystyrene sphere template of different size;
(3) preparation of precursor sol solution: by SnCl
44H
2o joins in ethanol solution, at 75-85 DEG C, stir 9-12h, and then cool to room temperature also leaves standstill 22-26h, obtains precursor sol solution; SnCl described in every mmole
44H
2the corresponding 1.8ml dehydrated alcohol of O;
(4) described precursor sol dropwise is added drop-wise in the described polystyrene sphere template of different size size, then oven for drying is used, polystyrene sphere template after oven dry is gradually warming up to 480-530 DEG C and keeps 2-4h, heating-up time 4-6h, remove the organic bead of polystyrene, then naturally cool to room temperature, obtain the porous SnO 2 nanostructure of different pore size.
In step (4), dripping of precursor sol solution counts as 1-3 drips.
In step (2), substrate base is glass, silicon single crystal, quartz or metal substrate.
Embodiment 1
The preparation of different size porous SnO 2 nanostructure:
Quality is respectively 0.6,0.9,1.2 and the vinylbenzene of 1.5g join in the beaker that 70ml deionized water is housed, sonic oscillation 20min, heating in water bath to 70 DEG C, the potassium persulfate solution of a small amount of ultrasonic mistake is added to it, keep rotor to stir 10h under 300r/min, polystyrene sphere suspension liquid can be obtained.The two panels glass substrate soaking 24h process with dichromic acid and vitriol oil mixing solutions is sticked together, that it is vertically fixed with clip adds in the beaker of polystyrene suspension liquid, due to wicking action, glass substrate inside can be full of suspension liquid, dries and obtain the PS microsphere template of different size at 50 DEG C.By the SnCl of 50mmol
44H
2o joins in 90ml ethanol solution, and water-bath 80 DEG C keeps 10h, is cooled to room temperature and ageing 24h, obtains precursor sol solution.Sol solution is dropwise added drop-wise to (1 to 3) in the polystyrene sphere template of different size size, then oven for drying is used, utilize resistance furnace that the glass template of having dried is warming up to 500 DEG C (temperature-rise period continues 4-6h), keep 2-4h, then naturally cooling, can obtain the porous SnO 2 nanostructure of different pore size.
The test of porous SnO 2 nanostructure photocatalysis performance:
The methyl orange solution 300ml getting 20M is contained in watch-glass, and adds the porous SnO of 50mg
2nano material, at room temperature leaves standstill 10min, to make solid-liquid two-phase reach adsorption equilibrium, then through centrifugation, gets supernatant liquid and tests its concentration and as the initial concentration of photo-catalytic degradation of methyl-orange.Illumination is carried out under sample being placed in the ultraviolet xenon lamp of 250W.Every 60min, sampling 5ml, with centrifuge, and then testing with visible spectrophotometer the photoabsorption that methyl orange solution wavelength is 462nm place, for avoiding repeatedly extracting the impact on test result, all being refunded by the solution after test at every turn.Finally the sample collection participated in after light-catalyzed reaction is come, with water ion water repetitive scrubbing, dry at 120 DEG C, under identical catalytic condition, test its quadric catalysis performance.
Bead as seen from Figure 1: different concentration of styrene can prepare the PS(polystyrene of different size size), PS bead is evenly distributed, by hexagonal close packed array.In addition, the size of PS the small ball's diameter, can also by changing KPS(Potassium Persulphate except can by regulating cinnamic concentration to realize) concentration, magneton rotating speed etc. in whipping process control.
As seen from Figure 2: the aperture of the porous SnO 2 nanostructure prepared is directly corresponding with the diameter of PS bead, present a kind of cavernous structure of solid, marshalling, surface is without covering, specific surface area is large, large with extraneous contact area, the fields such as photochemical catalysis, gas sensing and lithium ion battery can be widely used in.
As seen from Figure 3: the sample photocatalysis performance of different pore size size differs widely, but compared with the tindioxide powder of non-porous structure, all present good catalytic performance.Along with the reduction in aperture, photocatalysis performance strengthens gradually.
As can be seen from Figure 4: the porous SnO 2 photocatalyst that the present invention prepares has good secondary recovery recycling performance.
The present invention is by the control of p-poly-phenyl ethylene concentration, the size of effective control polystyrene sphere, the vinylbenzene bead utilizing these sizes controlled goes out the controlled porous SnO 2 nanostructure of size as Template preparation, the more important thing is that the tin dioxide nanostructure of these porous has shown good photocatalysis performance, and its photocatalysis performance of the vesicular structure of different size is also different, namely can by realizing the regulation and control to photocatalysis performance to the control of vinylbenzene bead size.
The present invention utilizes polystyrene to go out the controlled porous SnO 2 nanostructure of size as Template preparation, and realizes efficient photocatalysis performance.Porous SnO 2 nanostructure prepared by the present invention has that specific surface area is large, and size is controlled, and photocatalysis effect is obvious, can the feature such as Reusability, has great using value in photocatalysis field.In addition, the porous SnO 2 nanostructure that the present invention prepares also can be used on the practical application area such as gas sensor, lithium ion battery, solar cell.
Claims (2)
1. the method for the porous SnO 2 nanostructure that template synthesis size is controlled, is characterized in that, comprise the following steps:
(1) preparation of polystyrene sphere suspension liquid: quality is respectively 0.6,0.9,1.2 and the vinylbenzene of 1.5g mix with 0.07L deionized water respectively, supersound process 20min, ultrasonic frequency is 200KHz, vinylbenzene after supersound process and deionized water mixing solutions heating in water bath to 70 DEG C, backward be cooled to room temperature vinylbenzene and deionized water mixing solutions in add the potassium persulfate solution of supersound process, ultrasonic frequency is 200KHz frequency, stirred at ambient temperature 10h, stirring velocity is 300r/min, obtains polystyrene sphere suspension liquid; Described potassium persulfate solution concentration is 12g/L, and the volume ratio of described vinylbenzene and potassium persulfate solution is 5:1;
(2) adopt vertical sedimentation legal system for polystyrene sphere template: to be that dichromic acid and the vitriol oil mixing solutions of 1:1 soaks 20-26h by substrate base volume ratio, two panels substrate base after immersion sticks together, the two panels substrate base fit together vertically is put into described polystyrene sphere suspension liquid, due to wicking action, substrate base inside can be full of suspension liquid, the substrate base being full of suspension liquid, in 50 DEG C of oven dry, obtains the polystyrene sphere template of different size;
(3) preparation of precursor sol solution: by 50mmolSnCl
44H
2o joins in 0.09L ethanol solution, at 80 DEG C, stir 10h, and then cool to room temperature also leaves standstill 24h, obtains precursor sol solution;
(4) described precursor sol dropwise being dripped 1-3 drips in the described polystyrene sphere template of different size size, then oven for drying is used, polystyrene sphere template after oven dry is gradually warming up to 500 DEG C and keeps 2-4h, heating-up time 4-6h, remove the organic bead of polystyrene, then naturally cool to room temperature, obtain the porous SnO 2 nanostructure of different pore size.
2. the method for the porous SnO 2 nanostructure that template synthesis size according to claim 1 is controlled, is characterized in that, described in step (2), substrate base is glass, silicon single crystal, quartz or metal substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310739625.5A CN103739007B (en) | 2013-12-30 | 2013-12-30 | The porous SnO 2 nanostructure that template synthesis size is controlled |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310739625.5A CN103739007B (en) | 2013-12-30 | 2013-12-30 | The porous SnO 2 nanostructure that template synthesis size is controlled |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103739007A CN103739007A (en) | 2014-04-23 |
| CN103739007B true CN103739007B (en) | 2016-01-20 |
Family
ID=50496101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310739625.5A Expired - Fee Related CN103739007B (en) | 2013-12-30 | 2013-12-30 | The porous SnO 2 nanostructure that template synthesis size is controlled |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103739007B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277039B (en) * | 2016-07-21 | 2018-01-12 | 徐州工程学院 | A kind of cellular SnO2Semiconductor light-catalyst and preparation method thereof |
| CN106629822B (en) * | 2016-10-28 | 2018-02-23 | 长春理工大学 | A kind of unordered porous oxidation tin material and preparation method thereof |
| CN110078385A (en) * | 2019-04-09 | 2019-08-02 | 西安交通大学 | A kind of template fast-growth 3DOM WO3Method |
| CN113774418B (en) * | 2021-09-23 | 2022-12-27 | 常州工程职业技术学院 | Preparation of three-dimensional conductive framework and application of three-dimensional conductive framework in iron oxide photo-anode |
| CN113979469A (en) * | 2021-11-22 | 2022-01-28 | 合肥融捷能源材料有限公司 | SnO (stannic oxide)2Preparation method of porous carbon hollow composite microspheres |
| CN115092957B (en) * | 2022-05-16 | 2023-08-18 | 中南大学 | Method for cooperatively disposing arsenic alkali slag leaching slag by adopting pyrometallurgy of antimony concentrate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487108A (en) * | 2003-07-28 | 2004-04-07 | �Ϻ���ͨ��ѧ | Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process |
| CN101857381A (en) * | 2010-05-31 | 2010-10-13 | 河南大学 | Preparation method of polystyrene microsphere template and method for preparing zinc oxide thin film |
| CN102153133A (en) * | 2011-03-17 | 2011-08-17 | 扬州大学 | Method for preparing controllable ordered porous tin dioxide nano structures |
| CN102199003A (en) * | 2010-03-23 | 2011-09-28 | 中国科学院合肥物质科学研究院 | Porous membrane with two-dimensional ordered arrangement, and preparation method thereof |
| CN102380428A (en) * | 2011-09-26 | 2012-03-21 | 复旦大学 | Solvent packaging method for polymer micro fluidic chips based on hydrogel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8518561B2 (en) * | 2009-07-03 | 2013-08-27 | National Tsing Hua University | Antireflection structures with an exceptional low refractive index and devices containing the same |
-
2013
- 2013-12-30 CN CN201310739625.5A patent/CN103739007B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487108A (en) * | 2003-07-28 | 2004-04-07 | �Ϻ���ͨ��ѧ | Ordered 2D and 3D nano structure metal material comprising hollow metal spheres and its prepn process |
| CN102199003A (en) * | 2010-03-23 | 2011-09-28 | 中国科学院合肥物质科学研究院 | Porous membrane with two-dimensional ordered arrangement, and preparation method thereof |
| CN101857381A (en) * | 2010-05-31 | 2010-10-13 | 河南大学 | Preparation method of polystyrene microsphere template and method for preparing zinc oxide thin film |
| CN102153133A (en) * | 2011-03-17 | 2011-08-17 | 扬州大学 | Method for preparing controllable ordered porous tin dioxide nano structures |
| CN102380428A (en) * | 2011-09-26 | 2012-03-21 | 复旦大学 | Solvent packaging method for polymer micro fluidic chips based on hydrogel |
Non-Patent Citations (3)
| Title |
|---|
| 三维有序大孔Sn02及Sn02／Si02材料的制备及结构特征;邬泉周等;《无机材料学报》;20040731;第19卷(第4期);第939-942页 * |
| 双基片垂直沉积法制备稳定的胶体晶体晶片;陈鑫等;《科学通报》;20050228;第50卷(第4期);第321-326页 * |
| 聚苯乙烯胶晶的组装;邬泉周;《广州化学》;20081231;第33卷(第4期);第26-30页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103739007A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103739007B (en) | The porous SnO 2 nanostructure that template synthesis size is controlled | |
| Zhao et al. | Facile preparation of a self-assembled artemia cyst shell–TiO2–MoS2 porous composite structure with highly efficient catalytic reduction of nitro compounds for wastewater treatment | |
| Zeng et al. | Preparation of interstitial carbon doped BiOI for enhanced performance in photocatalytic nitrogen fixation and methyl orange degradation | |
| Hou et al. | In situ synthesis of α–β phase heterojunction on Bi2O3 nanowires with exceptional visible-light photocatalytic performance | |
| CN103752313B (en) | Meso-porous carbon material of load Fe and its preparation method and application | |
| Chen et al. | Template-free synthesis of single-crystalline-like CeO2 hollow nanocubes | |
| CN101549895B (en) | Preparation method of carbon aerogel loaded titanium dioxide electrodes and application thereof | |
| Hong et al. | Oxide content optimized ZnS–ZnO heterostructures via facile thermal treatment process for enhanced photocatalytic hydrogen production | |
| CN105597777B (en) | A kind of ordered mesopore carbon loaded Cu-Mn bimetallic denitration catalysts and preparation method thereof | |
| CN103803643B (en) | Spherical titanium dioxide of a kind of monodisperse mesoporous hollow Nano and preparation method thereof | |
| CN104211040B (en) | The preparation method of high specific surface area porous carbon nano rod | |
| CN101804328B (en) | Titanate porous monolithic adsorbent using straws as template and preparation method thereof | |
| CN102424411A (en) | Preparation method for ordered mesoporous gamma-Al2O3 | |
| CN103611549B (en) | The preparation method of copper zinc tin sulfide/graphene oxide composite semiconductor photocatalyst | |
| Li et al. | Synthesis of hierarchical hollow MnO2 microspheres and potential application in abatement of VOCs | |
| CN103831093B (en) | A kind of Zinc oxide-base composite photocatalyst nano material and preparation method thereof | |
| CN102389788B (en) | Preparation method for porous titanium dioxide-carbon combined nano hollow microsphere | |
| CN105036250B (en) | A kind of preparation method and application of activated carbon fiber-loaded ordered mesopore carbon graphene composite material | |
| JPH06265534A (en) | Inorganic porous column | |
| CN103107024B (en) | A kind of nitrogenous mesoporous carbon/MnO 2composite material and preparation method thereof | |
| CN106938191B (en) | A kind of preparation method of nano composite adsorption material | |
| CN110668504A (en) | Mesoporous Fe3O4Granules and process for their preparation | |
| CN101734717A (en) | Method for preparing porous titanium dioxide based on light assistance | |
| CN103073017B (en) | Ordered mesopore silicon nano material with MCM-41 molecular sieve structure and preparation method | |
| CN106571240B (en) | A kind of preparation method and its usage of hollow silica/titanium dioxide microballoon sphere of original position carbon doped layer time structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20181230 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |