CN102336431B - SnO2 flowerlike structure nano material and hydrothermal preparation method for the same - Google Patents
SnO2 flowerlike structure nano material and hydrothermal preparation method for the same Download PDFInfo
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- CN102336431B CN102336431B CN201110177297.5A CN201110177297A CN102336431B CN 102336431 B CN102336431 B CN 102336431B CN 201110177297 A CN201110177297 A CN 201110177297A CN 102336431 B CN102336431 B CN 102336431B
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Abstract
The invention discloses a SnO2 flowerlike structure nano material and a hydrothermal preparation method for the same. The method comprises the following steps of: respectively dissolving SnCl4.5H2O and NaOH in deionized water; stirring the SnCl4 solution at 4-25 DEG C, and dropping the NaOH in the SnCl4 solution to get a precursor solution, wherein in the precursor solution, concentration of tin ions is 0.1 mol/L-0.3 mol/L, concentration of hydroxy radical is 0.9 mol/L-3.3 mol/L, and molar concentration ratio of the hydroxy radical ions to the tin ions is 9-11:1; transferring the precursor solution into a reaction kettle so as to be sealed, and preserving heat for 8-12 hours at 190-200 DEG C, wherein the degree of filling of the reaction kettle is 70%; cooling to room temperature after reaction, repeatedly washing and filtering the reacted product with the deionized water and the absolute ethyl alcohol, until obtaining the filtrate with pH value of 7, drying the filtered product at 60 DEG C, and obtaining the flowerlike structure SnO2 nano material. The product is in the shape of three-dimensional flowerlike nano line clusters, specifically, a flower bud is composed of monocrystalline SnO2 nano lines arranged along the radial direction from the same center of sphere, diameter of the nano line is 90-400 nm, length of the nano line is 950-1200 nm, and draw ratio of the nano line is 3.00-10.56.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to a kind of SnO
2flower-like structure nano material and hydrothermal preparing process thereof.
Background technology
SnO
2be a kind of typical N-shaped direct band gap broad stopband oxide semiconductor material, it has advantages of the following aspects: under (1) room temperature, have broad-band gap (E
g=3.6eV) and high exciton bind energy (130meV); (2) low cost; (3) preparation method and product morphological structure are various.These features make SnO above
2in semiconducter device and field of functional materials, there is its unique advantage and broad application potential, especially SnO
2low-dimension nano material has shown wide application prospect at aspects such as the negative material of catalyzer, lithium ion battery, absorption of electromagnetic wave, solar cell, sensor, opto-electronic devices.Meanwhile, the controlled flower-like nanostructure SnO of length-to-diameter ratio
2the multifunctionality of height, makes it in the manufacture of nano electron device, have immeasurable application prospect.
In recent years, about low-dimensional SnO
2the preparation of nano material and application have obtained research widely.L. people (Ling-Yan Jiang, Xing-Long Wu, Yu-Guo Guo, the et al. SnO such as Y. Jiang
2-Based hierarchical nanomicrostructure:facile synthesis and their applications in gas sensors and lithium-ion batteries [J]. J. Phys. Chem. C, 2009,113:14213-14219) at 500 ℃, prepared flower-shaped SnO
2nanostructure, reaction source material contains multiple organic composition, as: oxalic acid, alcohol etc.The SnO preparing under this paper high temperature
2the petal that bud consists of multi beam nano wire forms.D. people (Dong-Feng Zhang, Ling-Dong Sun, Gang Xu, the et al. Size-controllable one-dimensinal SnO such as F. Zhang
2nanocrystals:synthesis, growth mechanism, and gas sensing property [J]. Phys. Chem. Chem. Phys., 2006,8:4874-4880) adopt microemulsion assisting alcohol-hydrothermal method to prepare SnO
2nano wire, although prepared SnO
2nano wire length-to-diameter ratio has larger variable range, but temperature of reaction still higher (being 240 ℃), and preparation process is more complicated also.Chinese patent (application number: 200910153400.5) proposed a kind of floriform appearance by hydrothermal synthesis SnO
2the method of nano structural material, the material of this patent is by SnO
2laminar flower-shaped cluster.In current achievement in research, also there is no to find the SnO being formed by the common centre of sphere and the monocrystal nanowire arranged along radial direction
2the relevant report of flower-like structure nano material.
Summary of the invention
The defect or the deficiency that for above-mentioned prior art, exist, the object of the invention is to, and a kind of SnO is provided
2flower-like structure nano material and preparation method thereof, the present invention adopts hydrothermal method, by controlling [the OH in reaction system
-]/[Sn
4+], [Sn
4+], the factor such as temperature of reaction, reaction times, system pressure obtained a kind of flower-like structure SnO
2nano material.
In order to realize above-mentioned task, the present invention adopts following technical solution:
A kind of SnO
2flower-like structure nano material, is characterized in that, this material is three-dimensional flower-shaped nano line cluster, the monocrystalline SnO that its bud is arranged along radial direction by the common centre of sphere
2nano wire forms, and described nanowire diameter is 90 ~ 400nm, and nanowire length is 950 ~ 1200nm, and nano wire length-to-diameter ratio is 3.00 ~ 10.56.
Above-mentioned SnO
2the preparation method of flower-like structure nano material, is characterized in that, specifically comprises the steps:
(1) by SnCl
45H
2o and NaOH are dissolved in respectively deionized water; By SnCl
4solution stirs under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into SnCl
4in solution, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1; Or
By SnCl
45H
2o and tensio-active agent are dissolved in deionized water and obtain mixing solutions, and described tensio-active agent is polyacrylamide, ratio [PAM]/[Sn of polyacrylamide and the volumetric molar concentration of tin ion in this mixing solutions
4+] be less than 0.0003%; Described mixing solutions is stirred under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into mixing solutions, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1;
(2) precursor solution of step (1) is transferred in reactor and sealed, the compactedness of reactor is 70%, at 190 ℃ ~ 200 ℃, is incubated 8 ~ 12h;
(3) reaction is down to room temperature after finishing, and will react products therefrom with deionized water and dehydrated alcohol repetitive scrubbing and filter, until filtrate pH=7 is dried the product after filtering at 60 ℃, obtains flower-like structure SnO
2nano material.
The present invention has following two outstanding advantages:
(1) in water-heat process without any organic solvent, technique is simple, productive rate is high, and with low cost, is applicable to batch production;
(2) prepared flower-like structure SnO
2the form homogeneous of nano line cluster, length-to-diameter ratio L
dbe easy to control.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD, the X-ray Diffraction) collection of illustrative plates that embodiment 1-3 obtains product;
Fig. 2 is the transmission electron microscope (TEM that embodiment 1 obtains product, Transmission Electron Microscopy) photo, wherein Fig. 2 (a) is that TEM photo, Fig. 2 (b) are selected area electron diffraction (SAED, Selected-area Electron Diffraction) photo, Fig. 2 (c) are high resolution transmission electron microscopy (HRTEM, High-resolution Transmission Electron Microscopy) photo.
Fig. 3 (a) is the scanning electronic microscope (FEESEM that embodiment 2 obtains product, Field Emission Environment Scanning Electron Microscope) photo, Fig. 3 (b) is high magnification FEESEM photo, and Fig. 3 (c) is the SAED photo that embodiment 2 obtains product.
Fig. 4 (a) is the TEM photo that embodiment 3 obtains product, and Fig. 4 (b) is the SAED photo that embodiment 3 obtains product.
Below in conjunction with the drawings and specific embodiments, the present invention is further explained to explanation.
Embodiment
The invention discloses a kind of SnO
2flower-like structure nano material, this material is three-dimensional flower-shaped nano line cluster, the monocrystalline SnO that its bud is arranged along radial direction by the common centre of sphere
2nano wire forms, and nanowire diameter is 90 ~ 400nm, and nanowire length is 950 ~ 1200nm, and nano wire length-to-diameter ratio is 3.00 ~ 10.56.
Above-mentioned SnO
2the preparation method of flower-like structure nano material specifically comprises the steps:
(1) by SnCl
45H
2o and NaOH are dissolved in respectively deionized water; By SnCl
4solution stirs under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into SnCl
4in solution, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1; Or
By SnCl
45H
2o and tensio-active agent are dissolved in deionized water and obtain mixing solutions, and described tensio-active agent is polyacrylamide, ratio [PAM]/[Sn of polyacrylamide and the volumetric molar concentration of tin ion in this mixing solutions
4+] be less than 0.0003%; Described mixing solutions is stirred under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into mixing solutions, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1;
(2) precursor solution of step (1) is transferred in reactor and sealed, the compactedness of reactor is 70%, at 190 ℃ ~ 200 ℃, is incubated 8 ~ 12h;
(3) reaction is down to room temperature after finishing, and will react products therefrom with deionized water and dehydrated alcohol repetitive scrubbing and filter, until filtrate pH=7 is dried the product after filtering at 60 ℃, obtains flower-like structure SnO
2nano material.
embodiment 1
Take 2.8331g purity and be 99% SnCl
45H
2o is placed in beaker A, the NaOH that takes purity and be 96%3.0000g is placed in beaker B, and with 20ml deionized water dissolving, form clear solution respectively, beaker A is carried out to the cooling bath of 4 ℃ and stirs, in whipping process, the sodium hydroxide solution in beaker B is splashed into beaker A, use successively the deionized water wash beaker B of 20ml, 10ml and 10ml, and each washings is splashed in beaker A and obtains precursor solution.Now, tin ion concentration [Sn in precursor solution
4+]=0.1mol/L, hydroxide ion concentration [OH
-]=0.9mol/L, [OH
-]/[Sn
4+]=9:1.With graduated cylinder, measure successively the precursor solution of two 35ml, and two precursor solutions that measure are transferred to respectively to two volumes be that 50ml has in teflon-lined autoclave and sealing, at 190 ℃, react 8 hours, treat two reactor cool to room temperature, by reaction deionized water and dehydrated alcohol repetitive scrubbing for products therefrom, be filtered to the PH=7 of filtrate, then at 60 ℃, be dried, finally product carried out to XRD, TEM and SEM sign.
embodiment 2
Take 2.8331g purity and be 99% SnCl
45H
2the polyacrylamide (PAM) that O and 0.0276g purity are 85% is placed in beaker A jointly, take 3.6667g purity and be 96% NaOH and be placed in beaker B, and with 20ml deionized water dissolving, form clear solution respectively, beaker A is carried out to the cooling bath of 4 ℃ and stirs, in whipping process, the sodium hydroxide solution in beaker B is splashed in the mixing solutions of beaker A, use successively the deionized water wash beaker B of 20ml, 10ml and 10ml, and each washings is splashed in beaker A and obtains precursor solution.Now, tin ion concentration [Sn in precursor solution
4+]=0.1mol/L, hydroxide ion concentration [OH
-]=1.1mol/L, the ratio PAM of polyacrylamide and the volumetric molar concentration of tin ion]/[Sn
4+]=0.0001%, the ratio [OH of hydroxide ion and the volumetric molar concentration of tin ion
-]/[Sn
4+]=11:1.With graduated cylinder, measure successively the precursor solution of two 35ml, and two precursor solutions that measure are transferred to respectively to two volumes be that 50ml has in teflon-lined autoclave and sealing, at 200 ℃, react 12 hours, treat two reactor cool to room temperature, by reaction deionized water and dehydrated alcohol repetitive scrubbing for products therefrom, be filtered to the PH=7 of filtrate, then at 60 ℃, be dried, finally product carried out to XRD, TEM and SEM sign.
embodiment 3
Take 8.4993g purity and be 99% SnCl
45H
2the polyacrylamide (PAM) that O and 0.0276g purity are 85% is placed in beaker A jointly, take 11.0001g purity and be 96% NaOH and be placed in beaker B, and with 20ml deionized water dissolving, form clear solution respectively, beaker A is carried out to the cooling bath of 25 ℃ and stirs, in whipping process, the sodium hydroxide solution in beaker B is splashed in the mixing solutions of beaker A, use successively the deionized water wash beaker B of 20ml, 10ml and 10ml, and each washings is splashed in beaker A and obtains precursor solution.Now, tin ion concentration [Sn in precursor solution
4+]=0.3mol/L, hydroxide ion concentration [OH
-]=3.3mol/L, ratio [PAM]/[Sn of polyacrylamide and the volumetric molar concentration of tin ion
4+]=0.0003%, the ratio [OH of hydroxide ion and the volumetric molar concentration of tin ion
-]/[Sn
4+]=11:1.With graduated cylinder, measure successively the precursor solution of two 35ml, and two precursor solutions that measure are transferred to respectively to two volumes be that 50ml has in teflon-lined autoclave and sealing, at 200 ℃, react 12 hours, treat two reactor cool to room temperature, by reaction deionized water and dehydrated alcohol repetitive scrubbing for products therefrom, be filtered to the PH=7 of filtrate, then at 60 ℃, be dried, finally product carried out to XRD, TEM and SEM sign.
[0017]fig. 1 is X-ray diffraction (XRD, the X-ray Diffraction) collection of illustrative plates of embodiment 1-3 product, and as can be seen from the figure, embodiment 1-3 products therefrom is the SnO of tetragonal system rutile structure
2;
Fig. 2 is the transmission electron microscope (TEM of embodiment 1 product, Transmission Electron Microscopy) photo, wherein Fig. 2 (a) is that TEM photo, Fig. 2 (b) are selected area electron diffraction (SAED, Selected-area Electron Diffraction) photo, Fig. 2 (c) are high resolution transmission electron microscopy (HRTEM, High-resolution Transmission Electron Microscopy) photo, as can be seen from the figure prepared SnO
2for flower-like structure, the monocrystalline that single nano-wire is rutile structure, and along [001] direction oriented growth.
Fig. 3 (a) is the scanning electronic microscope (FEESEM of embodiment 2 products, Field Emission Environment Scanning Electron Microscope) photo, Fig. 3 (b) is high magnification FEESEM photo, as can be seen from the figure prepared sample is flower-like nanometer line a small bundle of straw, etc. for silkworms to spin cocoons on of form homogeneous, the bud of flower-like structure is to form by the common centre of sphere and along the nano wire that radial direction is arranged, the mean length of nano wire is about 950nm, mean diameter is about 90nm, and length-to-diameter ratio is about 10.56; Fig. 3 (c) is the SAED photo of embodiment 2 products, and the nano wire that as can be seen from the figure forms flower-like structure is monocrystalline, and single nano-wire is along the growth of [001] direction.
Fig. 4 (a) is the TEM photo of embodiment 3 products, and Fig. 4 (b) is the SAED photo of embodiment 3 products.
As seen from Figure 4, embodiment 3 products have three-dimensional flower-shaped structure, and specifically, bud is by the common centre of sphere and the monocrystalline SnO that arranges along radial direction
2nano wire forms, and the mean length of nano wire is about 750nm, and mean diameter is about 75nm, and length-to-diameter ratio is about 10.
Can find out, adopt tensio-active agent and SnCl
45H
2after O mixes, the solution of preparation is as reaction raw materials, than independent employing SnCl
45H
2solution prepared by O will be grown as the length of the prepared nano wire of reaction raw materials, and diameter is short.
Claims (1)
1. a SnO
2the preparation method of flower-like structure nano material, is characterized in that, specifically comprises the steps:
(1) by SnCl
45H
2o and NaOH are dissolved in respectively deionized water; By SnCl
4solution stirs under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into SnCl
4in solution, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1; Or
By SnCl
45H
2o and tensio-active agent are dissolved in deionized water and obtain mixing solutions, and described tensio-active agent is polyacrylamide, ratio [PAM]/[Sn of polyacrylamide and the volumetric molar concentration of tin ion in this mixing solutions
4+] be less than 0.0003%; Described mixing solutions is stirred under 4 ~ 25 ℃ of conditions, in whipping process, NaOH solution is splashed into mixing solutions, obtain tin ion [Sn
4+] concentration is 0.1mol/L ~ 0.3mol/L, hydroxide ion [OH
-] concentration is 0.9mol/L ~ 3.3mol/L, the ratio [OH of hydroxide ion and tin ion volumetric molar concentration
-]/[Sn
4+the precursor solution of]=9 ~ 11:1;
(2) precursor solution of step (1) is transferred in reactor and sealed, the compactedness of reactor is 70%, at 190 ℃ ~ 200 ℃, is incubated 8 ~ 12h;
(3) reaction is down to room temperature after finishing, and will react products therefrom with deionized water and dehydrated alcohol repetitive scrubbing and filter, until filtrate pH=7 is dried the product after filtering at 60 ℃, obtains flower-like structure SnO
2nano material;
Described flower-like structure SnO
2nano material is three-dimensional flower-shaped nano line cluster, the monocrystalline SnO that its bud is arranged along radial direction by the common centre of sphere
2nano wire forms, and described nanowire diameter is 90 ~ 400nm, and nanowire length is 950 ~ 1200nm, and nano wire length-to-diameter ratio is 3.00 ~ 10.56.
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| CN102213688B (en) * | 2011-04-11 | 2013-06-05 | 大连理工大学 | Method of electrochemically measuring permanganate index by virtue of stannic oxide nanometer electrode |
| CN103043710B (en) * | 2011-10-17 | 2015-09-16 | 中国科学院福建物质结构研究所 | A kind of at α-Fe 2o 3nanocrystal surface Heteroepitaxy nano SnO 2method |
| CN102942215A (en) * | 2012-09-10 | 2013-02-27 | 重庆大学 | Three-dimensional SnO2 nano flower-like material grown on titanium substrate and preparation method thereof |
| CN104803411B (en) * | 2015-05-12 | 2016-08-24 | 中国科学院新疆理化技术研究所 | A kind of preparation method of hypersensitive nitrogen dioxide sensing material |
| CN104865296B (en) * | 2015-06-02 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Method for controlling sensitivity of nitrogen dioxide through adjusting and controlling surface defect concentrations of stannic oxide |
| CN104974752B (en) * | 2015-08-07 | 2017-03-22 | 京东方科技集团股份有限公司 | White-light fluorescent material as well as preparation method and application thereof |
| CN105198004B (en) * | 2015-08-18 | 2017-03-29 | 西北大学 | A kind of Fe3O4‑SnO2Nano composite material and preparation method thereof |
| CN105600818B (en) * | 2016-01-12 | 2017-06-23 | 济南大学 | The method and products obtained therefrom of a kind of stannic oxide nanometer powder prepared rich in Lacking oxygen |
| CN106830057B (en) * | 2017-01-13 | 2018-01-12 | 西北大学 | A kind of stannous oxide material and preparation method thereof |
| CN111116232A (en) * | 2019-12-13 | 2020-05-08 | 苏州麦茂思传感技术有限公司 | Synthesis method of formaldehyde gas sensor sensitive material |
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| WO2005062785A2 (en) * | 2003-12-17 | 2005-07-14 | The University Of North Carolina At Chapel Hill | Solution-phase synthesis of metal oxide nanostructures |
| CN101941734A (en) * | 2010-10-08 | 2011-01-12 | 北京化工大学 | Tin oxide nanomaterial and preparation method thereof |
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| CN101941734A (en) * | 2010-10-08 | 2011-01-12 | 北京化工大学 | Tin oxide nanomaterial and preparation method thereof |
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