CN101885471A - Hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure - Google Patents
Hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure Download PDFInfo
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- CN101885471A CN101885471A CN 201010236510 CN201010236510A CN101885471A CN 101885471 A CN101885471 A CN 101885471A CN 201010236510 CN201010236510 CN 201010236510 CN 201010236510 A CN201010236510 A CN 201010236510A CN 101885471 A CN101885471 A CN 101885471A
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- tin oxide
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- doped tin
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Abstract
The invention provides a hydrothermal synthesis method of zinc-doped tin oxide with a hollow cubic structure, comprising the following steps: dropwise adding a mixed aqueous solution of SnCl4 and Zn(NO3)2 to a NaOH aqueous solution with a certain concentration, wherein, the volume ratio of the mixed aqueous solution of SnCl4 and Zn(NO3)2 to the NaOH aqueous solution is 1:3-1:15, the concentration of SnCl4 is 0.1094-0.1144mol/L, the concentration of Zn(NO3)2.6H2O is 0.0106-0.0156mol/L, and the concentration of NaOH is 1.875mol/L; evenly stirring and transferring the mixed solution to a hydrothermal reaction kettle so that the filling degree reaches 80%; carrying out isothermal reaction at the temperature of 180-190 DEG C for 25 hours; and finally centrifuging, washing and drying the obtained reaction product to obtain the zinc-doped tin oxide. The hydrothermal synthesis method has simple process and easy operation; and the synthesized zinc-doped tin oxide particles have controllable size and high purity, and the obtained product has excellent electrical property.
Description
Technical field
The present invention relates to a kind of oxide semiconductor nano-powder chemical synthesis process, be specifically related to have the hydrothermal synthesis method of the zinc-doped tin oxide of cube hollow-core construction.
Background technology
Tin oxide (SnO
2) crystal mainly contain the four directions and two kinds of structures of rhombic form.Tetragonal structure is a rutile-type tin oxide, it is a kind of important broad-band gap n type semiconductor, energy gap is 3.65eV, can be used for aspects such as solar cell, transparent conductor, catalyst and air-sensitive sensing, is causing concern widely aspect scientific research and the commercial Application.The drawbacks limit of stannic oxide materials self its application and development, the carrier concentration of intrinsic tin oxide is low, resistivity is higher, influences its service efficiency aspect optics and electric property.Studies show that to have the SnO of nanostructured
2Behind the doping vario-property, it is luminous, air-sensitive, electricity and catalytic performance can be significantly improved, meanwhile, and SnO
2Self shape characteristic has significant effects to its performance, and the result shows to have pyramid surface nano-structure and hollow-core construction ball SnO
2Demonstrate good optical and electric property.
Tin oxide (SnO with nano hollow structure
2) powder adopts solvent thermal process synthetic usually, usually need to introduce organic solvent and surfactant in the building-up process, acting in conjunction by organic solvent and surfactant, form hollow-core construction, its synthesis technique complexity, not easy to operate, synthetic product need be removed introducing solvent and surfactant through washing or heat treatment, but the heat treatment meeting of later stage introducing destroys the hollow-core construction of synthetic product.Adopt Zn
2+Doping vario-property has the SnO of nanostructured
2, band structure is changed, thereby the state at interface is changed, and synthetic product has excellent photoelectric properties.Yet Zn
2+The hollow cubic structure of doped stannum oxide and method thereof are not seen relevant report as yet.
Hydrothermal synthesis reaction is (can produce certain pressure) in hydrothermal reaction kettle, as reaction medium, by heating produces high pressure to reaction system, carries out a kind of effective ways of the synthetic and preparation of material with the aqueous solution.This method can make some very slow thermodynamical reaction realization responses under hydrothermal condition of reaction rate at normal temperatures and pressures rapid, and synthetic nano material purity height, crystal structure and grow, controlled amount, and impurity and the fault of construction that can avoid subsequent techniques such as high-temperature calcination and ball milling to introduce.
List of references
[1] Shi Er fear, summer Changtai, Wang Buguo, Journal of Inorganic Materials, 11 (1996) 193-206.
[2]P.Feng，X.Bu，G.D.Stucky.Nature?388(1997)735-741.
[3]N.Chen，W.Zhang，W.Yu，Y.Qian，Mater.Lett.55(2002)230-233.
[4]H.Q.Chiang，J.F.Wager，R.L.Hoffman，J.Jeong，D.A.Keszler，Appl.Phys.Lett.86(2005)013503
[5]Q.R.Zhao，Y.Gao，X.Bai，C.Z.Wu，Yi?Xie，Eur.J.Inorg.Chem.2006，1643-1648
[6]B.Li，G.Rong，Y.Xie，L.Huang，and?C.Feng，Inorg.Chem.45(2006)6404
Summary of the invention
Technical problem to be solved by this invention provides a kind of hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure, and this method technology is simple, easy to operate, synthetic product purity height, and the product electric property that obtains is good.
In order to solve the technical problem that the present invention proposes, technical scheme of the present invention is:
The hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure may further comprise the steps:
(1) preparation SnCl
4(Zn (NO
3)
2Mixed aqueous solution;
(2) preparation amount of substance concentration is the NaOH aqueous solution of 2-2.5mol/L;
(3) SnCl that step (1) is obtained
4(Zn (NO
3)
2Mixed solution be added drop-wise in the NaOH aqueous solution of step (2) SnCl
4And Zn (NO
3)
2Mixed aqueous solution and the volume ratio of the NaOH aqueous solution be 1: 3-1: 15, make SnCl
4Amount of substance concentration is 0.1094～0.1144mol/L, (Zn (NO
3)
26H
2The amount of substance concentration of O is 0.0106～0.0156mol/L, and the amount of substance concentration of NaOH is 1.875mol/L, stirs, and obtains predecessor;
(4) predecessor with step (3) is transferred in the hydrothermal reaction kettle, and making its compactedness is 80%, 180 ℃～190 ℃ isothermal reactions at least 25 hours, obtains the hydro-thermal reaction product;
(5) treat hydrothermal reaction kettle cooling after, the hydro-thermal reaction product is centrifugal, and washing is drying to obtain zinc-doped tin oxide with hollow cubic structure.
Explore by experiment and draw in conjunction with document analysis, compactedness is 80% o'clock, and the suitable pressure of this research system crystal growth and higher productive rate can be provided, and obtains hollow cubic structure.
Press such scheme, the described drop rate of step (3) is 2ml～3ml/min.
Press such scheme, the described washing step of step (5) is: use deionized water and absolute ethanol washing product successively.
Press such scheme, the described drying steps of step (5) is: the powder after will cleaning is at 80 ℃～90 ℃ dry 10h.
The present invention has following beneficial effect:
1, the raw materials used cost of the hydrothermal synthesis method of this zinc-doped tin oxide with hollow cubic structure is low, technology is easy, avoided subsequent techniques such as high-temperature calcination and ball milling to introduce impurity and fault of construction, easy to operate, synthetic zinc-doped tin oxide granular size is controlled, the product purity height.
2, the synthetic zinc-doped tin oxide of this method is a hollow cubic structure, and sub-cell is a nanocone, and this structure has bigger surface area, and can reduce nano material to a certain extent and reunite, and helps bringing into play the advantage of nano material; Synthetic product has good electric property through test.
Description of drawings
Fig. 1 is the XRD figure at embodiment 1 gained zinc-doped tin oxide hollow cubic structure end.
Fig. 2, Fig. 3 are the SEM figure of embodiment 1 gained zinc-doped tin oxide hollow cubic structure powder.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with example, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The method of the synthetic zinc-doped tin oxide hollow cubic structure of hydro-thermal, it comprises the steps:
(1) configuration SnCl
45H
2O and (Zn (NO
3)
26H
2The mixed aqueous solution of O;
(2) configuration amount of substance concentration is the NaOH aqueous solution of 2.5mol/L;
(3) SnCl that step (1) is obtained
4(Zn (NO
3)
2Mixed aqueous solution be added drop-wise in the NaOH aqueous solution of step (2) SnCl
4(Zn (NO
3)
2Mixed solution and the volume ratio of the NaOH aqueous solution be 1: 3, make SnCl
4Amount of substance concentration is 0.1094mol/L, (Zn (NO
3)
26H
2The amount of substance concentration of O is 0.0156mol/L, and the amount of substance concentration of NaOH is 1.875mol/L, and drop rate is 2ml～3ml/min, stirs, and obtains predecessor;
(4) predecessor with step (3) is transferred in the hydrothermal reaction kettle, and making its compactedness is 80%, 180 ℃ of isothermal reaction 25h at least, obtains the hydro-thermal reaction product;
(5) treat hydrothermal reaction kettle cooling after, the hydro-thermal reaction product is centrifugal, wash successively through deionized water and absolute ethyl alcohol, 80 ℃ of dry 10h promptly get zinc-doped tin oxide with hollow cubic structure.
The zinc-doped tin oxide powder that present embodiment is obtained carries out XRD test (see figure 1), and can be got by Fig. 1: only there is the corresponding diffraction maximum of tin oxide in the XRD diffraction maximum, the diffraction maximum of ZnO do not occur, and the crystalline phase that shows synthetic product is SnO
2, and Zn
2+Entered the tin oxide lattice by mixing; Because the crystal particle scale of synthetic product is little, caused diffraction maximum existence broadening to a certain degree simultaneously.
Synthetic product carries out the SEM test, and (see Fig. 2, Fig. 3), can be got by Fig. 2 and Fig. 3: the zinc-doped tin oxide powder is a hollow cubic structure, and the composition sub-cell is a nanocone, and the cross section scale of nanocone is 10～15nm, and the direction of growth is [001].
With the negative material of synthetic product as lithium ion battery, be assembled into lithium ion battery, carry out a volt-ampere charge-discharge test.The result shows that synthetic product has demonstrated the excellent properties of negative material, good cyclical stability and higher capacitance, and present less attenuation rate, after discharging and recharging for 50 times, its capacitance is 544mAh/g (compares with the negative material of traditional carbon class, had greatly and improved).Therefore, synthetic product has demonstrated good electrochemical.
Embodiment 2:
The method of the synthetic zinc-doped tin oxide hollow cubic structure of hydro-thermal, it comprises the steps:
(1) configuration SnCl
45H
2O and (Zn (NO
3)
2Mixed aqueous solution;
(2) configuration amount of substance concentration is the NaOH aqueous solution of 2.25mol/L;
(3) step (1) is obtained SnCl
4(Zn (NO
3)
2Mixed solution be added drop-wise in the NaOH aqueous solution of step (2) SnCl
4(Zn (NO
3)
2Mixed solution and the volume ratio of the NaOH aqueous solution be 1: 5, drop rate is 2ml～3ml/min, makes SnCl
4Amount of substance concentration is 0.1118mol/L, (Zn (NO
3)
26H
2The amount of substance concentration of O is 0.013lmol/L, and the amount of substance concentration of NaOH is 1.875mol/L, stirs, and obtains predecessor;
(4) predecessor with step (3) is transferred in the hydrothermal reaction kettle, and making its compactedness is 80%, 180 ℃ of isothermal reaction 25h at least, obtains the hydro-thermal reaction product;
(5) treat hydrothermal reaction kettle cooling after, the hydro-thermal reaction product is centrifugal, wash successively through deionized water and absolute ethyl alcohol, 80 ℃ of dry 10h promptly get zinc-doped tin oxide with hollow cubic structure.
The zinc-doped tin oxide powder that present embodiment obtains carries out the XRD test and can get: obtaining the product crystalline phase is tin oxide; Carrying out the SEM test can get: its structure is a hollow cubic structure, and sub-cell is for (cross section scale is 10～15nm) nanocone.
Embodiment 3:
The method of the synthetic zinc-doped tin oxide hollow cubic structure of hydro-thermal, it comprises the steps:
(1) configuration SnCl
4(Zn (NO
3)
2Mixed aqueous solution;
(2) configuration amount of substance concentration is the NaOH aqueous solution of 2mol/L;
(3) SnCl that step (1) is obtained
4(Zn (NO
3)
2Mixed aqueous solution be added drop-wise in the NaOH aqueous solution of step (2) SnCl
4(Zn (NO
3)
2Mixed solution and the volume ratio of the NaOH aqueous solution be 1: 15, drop rate is 2ml～3ml/min, makes SnCl
4Amount of substance concentration is 0.1144mol/L, (Zn (NO
3)
26H
2The amount of substance concentration of O is 0.0106, and the amount of substance concentration of NaOH is 1.875mol/L, stirs, and obtains predecessor;
(4) predecessor with step (3) is transferred in the hydrothermal reaction kettle, and making its compactedness is 80%, 190 ℃ of isothermal reaction 25h at least, obtains the hydro-thermal reaction product;
(5) treat hydrothermal reaction kettle cooling after, the hydro-thermal reaction product is centrifugal, wash successively through deionized water and absolute ethyl alcohol, 90 ℃ of dry 10h promptly get zinc-doped tin oxide with hollow cubic structure.
The zinc-doped tin oxide powder that present embodiment obtains carries out the XRD test and can get: obtaining the product crystalline phase is tin oxide; Carrying out the SEM test can get: its structure is a hollow cubic structure, and sub-cell is for (cross section scale is 10～15nm) nanocone.
Claims (4)
1. the hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure, it is characterized in that: it may further comprise the steps:
(1) preparation SnCl
4(Zn (NO
3)
2Mixed aqueous solution;
(2) preparation amount of substance concentration is the NaOH aqueous solution of 2-2.5mol/L;
(3) SnCl that step (1) is obtained
4(Zn (NO
3)
2Mixed solution be added drop-wise in the NaOH aqueous solution of step (2) SnCl
4And Zn (NO
3)
2Mixed aqueous solution and the volume ratio of the NaOH aqueous solution be 1: 3-1: 15, make SnCl
4Amount of substance concentration is 0.1094～0.1144mol/L, (Zn (NO
3)
26H
2The amount of substance concentration of O is 0.0106～0.0156mol/L, and the amount of substance concentration of NaOH is 1.875mol/L, stirs, and obtains predecessor;
(4) predecessor with step (3) is transferred in the hydrothermal reaction kettle, and making its compactedness is 80%, 180 ℃～190 ℃ isothermal reactions at least 25 hours, obtains the hydro-thermal reaction product;
(5) treat hydrothermal reaction kettle cooling after, the hydro-thermal reaction product is centrifugal, and washing is drying to obtain zinc-doped tin oxide with hollow cubic structure.
2. the hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure according to claim 1, it is characterized in that: the described drop rate of step (3) is 2ml～3ml/min.
3. the hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure according to claim 1, the described washing step of step (5) is: use deionized water and absolute ethanol washing product successively.
4. the hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure according to claim 1, the described drying steps of step (5) is: the powder after will cleaning is at 80 ℃～90 ℃ dry 10h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483351A (en) * | 2014-11-27 | 2015-04-01 | 武汉工程大学 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
| CN106512978A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Method for preparing visible-light response photocatalyst by utilizing nano Zn2SnO4 |
| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
| CN110697777A (en) * | 2019-10-09 | 2020-01-17 | 西北工业大学 | Preparation method of tin molybdenum disulfide with hollow structure |
| US20220169525A1 (en) * | 2019-01-31 | 2022-06-02 | University Of Houston System | Doped tin oxide particles and doped tin oxide shells for core-shell particles |
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2010
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| CN101251508A (en) * | 2008-04-01 | 2008-08-27 | 重庆大学 | Method for manufacturing gas sensor for testing hydrogen |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104483351A (en) * | 2014-11-27 | 2015-04-01 | 武汉工程大学 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
| CN104483351B (en) * | 2014-11-27 | 2017-05-03 | 武汉工程大学 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
| CN106512978A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Method for preparing visible-light response photocatalyst by utilizing nano Zn2SnO4 |
| CN106512978B (en) * | 2016-11-29 | 2018-12-25 | 洛阳理工学院 | Utilize nanometer Zn2SnO4The method for preparing visible light responsive photocatalyst |
| CN108288693A (en) * | 2017-12-22 | 2018-07-17 | 天津师范大学 | A kind of anode material of lithium-ion battery zinc-tin bimetallic sulfide and the preparation method and application thereof |
| CN108288693B (en) * | 2017-12-22 | 2020-07-10 | 天津师范大学 | Zinc-tin bimetallic sulfide as negative electrode material of sodium-ion battery and preparation method and application thereof |
| US20220169525A1 (en) * | 2019-01-31 | 2022-06-02 | University Of Houston System | Doped tin oxide particles and doped tin oxide shells for core-shell particles |
| CN110697777A (en) * | 2019-10-09 | 2020-01-17 | 西北工业大学 | Preparation method of tin molybdenum disulfide with hollow structure |
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