CN103979505B - A kind of preparation method of minority layer bismuth selenide nanometer sheet - Google Patents

A kind of preparation method of minority layer bismuth selenide nanometer sheet Download PDF

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CN103979505B
CN103979505B CN201410208150.1A CN201410208150A CN103979505B CN 103979505 B CN103979505 B CN 103979505B CN 201410208150 A CN201410208150 A CN 201410208150A CN 103979505 B CN103979505 B CN 103979505B
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nanometer sheet
preparation
minority layer
bismuth selenide
powder
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CN103979505A (en
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翁建
孙莉萍
林智钦
彭健
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Xiamen University
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Xiamen University
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Abstract

A preparation method for minority layer bismuth selenide nanometer sheet, relates to bismuth selenide body material.Selenium powder, bismuth oxide, polyvinylpyrrolidone, ethylene glycol and ethylenediamine tetraacetic acid (EDTA) are loaded in reactor and carry out hydrothermal synthesis reaction, the mixed solution obtained is centrifugal, removes supernatant liquor, then uses ultrapure water and absolute ethanol washing respectively, obtains Bi after drying 2se 3powder; By the Bi obtained 2se 3powder joins N-Methyl pyrrolidone solvent or is dissolved with in the acetum of chitosan, after ultrasonic, obtains minority layer Bi 2se 3the dispersion liquid of nanometer sheet, leave standstill again, the part of getting its upper strata 2/3rds is put into low-speed centrifugal in whizzer, collect the upper liquid of centrifugal gained, again the upper liquid of gained is put into whizzer high speed centrifugal, remove supernatant fraction, the lower floor material NMP of gained or acetum are heavily disperseed, finally obtain the minority layer bismuth selenide nanometer sheet be dispersed in solution.Preparation method is easy, quick.

Description

A kind of preparation method of minority layer bismuth selenide nanometer sheet
Technical field
The present invention relates to bismuth selenide body material, especially relate to a kind of preparation method of minority layer bismuth selenide nanometer sheet.
Background technology
Topological insulator is a class body phase insulation, but surface shows a kind of novel quantum material of Special Metal state, and it is starting one research boom at Condensed Matter Physics, chemical field and Material Field.Its this character is mainly due to its spin and caused (Nature, 2010, the 464:194-198 of being coupled of Time-reversal symmetry; NatureChemistry, 2011,3:845-849).Wherein, bismuth selenide (Bi 2se 3) the topological insulator character that represents allows it become a kind of material (Nature, 2009,460:1101-1105) with applications well prospect.At present, minority layer or individual layer Bi is prepared 2se 3nanometer sheet mainly relies on mode from bottom to top, carries out synthesizing (Journal ofthe American Chemical Society, 2012,134:6132-6135 from atom or molecular scale by chemical reaction; Journal of the American Chemical Society, 2012,134:2872-2875).In top-down building-up process, from monocrystalline block sample, obtain individual layer or minority layer Bi by the method for mechanically peel or chemical stripping 2se 3nanometer sheet (ACS Nano, 2011,5:2657-2663; Journal of theAmerican Chemical Society, 2012,134:20294-20297).Wherein, in synthetic technology from bottom to top, as molecular beam epitaxy needs to utilize accurate plant and instrument to synthesize, apparatus expensive, consumes large, is not suitable for carrying out large batch of production; The individual layer obtained from bottom to top or minority layer Bi 2se 3in the mode of nanometer sheet, carry out the mode peeled off as utilized lithium ion intercalation, relatively loaded down with trivial details, need to carry out polystep reaction, washing, removal of impurities etc.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of minority layer bismuth selenide nanometer sheet.
The present invention includes following steps:
1) carry out hydrothermal synthesis reaction by selenium powder, bismuth oxide, polyvinylpyrrolidone, ethylene glycol and ethylenediamine tetraacetic acid (EDTA) loading reactor, the mixed solution obtained is centrifugal, removes supernatant liquor, then uses ultrapure water and absolute ethanol washing respectively, obtains Bi after drying 2se 3powder;
2) by step 1) Bi that obtains 2se 3powder joins N-Methyl pyrrolidone solvent (NMP) or is dissolved with in the acetum (CS-HAc) of chitosan, after ultrasonic, obtains minority layer Bi 2se 3the dispersion liquid of nanometer sheet, leave standstill again, the part of getting its upper strata 2/3rds is put into low-speed centrifugal in whizzer, collect the upper liquid of centrifugal gained, again the upper liquid of gained is put into whizzer high speed centrifugal, remove supernatant fraction, the lower floor material NMP of gained or acetum are heavily disperseed, finally obtain the minority layer bismuth selenide nanometer sheet be dispersed in solution.
In step 1) in, the proportioning of described selenium powder, bismuth oxide, polyvinylpyrrolidone, ethylene glycol and ethylenediamine tetraacetic acid (EDTA) can be 3mmol: 1mmol: 0.9g: 36mL: 4mmol; The temperature of described hydrothermal synthesis reaction can be 180 ~ 200 DEG C, and the time of hydrothermal synthesis reaction can be 20h; The number of times of described washing can be 2 times; The condition of described drying can be 60 DEG C of dry 96h in vacuum drying oven.
In step 2) in, described Bi 2se 3the proportioning of powder and N-Methyl pyrrolidone solvent (NMP) can be 50 ~ 100mg: 50mL; Described Bi 2se 3powder can be 50 ~ 100mg: 50mL with the proportioning of the acetum (CS-HAc) being dissolved with chitosan; Described ultrasonic power can be 250W, and the ultrasonic time can be 0.5 ~ 50h; The described standing time can be 2 ~ 240h; The speed of described low-speed centrifugal can be 400 ~ 2000r/min, and the time of low-speed centrifugal can be 30min; Described ultracentrifugal speed can be 5000 ~ 20000r/min, and the ultracentrifugal time can be 20min.
The present invention adopts simple, fast mode to prepare minority layer Bi 2se 3nanometer sheet, provides a kind of method utilizing liquid phase to peel off to prepare minority layer Bi 2se 3nanometer sheet.The method utilizes two kinds of different solution, under ultrasonic effect, by Bi 2se 3body material is peeled off, thus obtains the minority layer Bi be dispersed in a large number in solution 2se 3nanometer sheet, can by Bi 2se 3for this research field more widely.Minority layer bismuth selenide nanometer sheet prepared by the present invention all has good dispersiveness in N-Methyl pyrrolidone solvent and chitosan aqueous solution, and has specific absorbent properties in visible region.Material prepared by the method can carry out the application of wider scope, as biosensor, and laser apparatus manufacture etc.
Accompanying drawing explanation
Fig. 1 is Bi prepared by the embodiment of the present invention 1 2se 3body material X-ray diffraction (XRD) spectrogram.
Fig. 2 is the embodiment of the present invention 1 prepared Bi in NMP 2se 3x-ray diffraction (XRD) spectrogram of nanometer sheet.
Fig. 3 is the embodiment of the present invention 1 prepared Bi in NMP 2se 3transmission electron microscope (TEM) figure of nanometer sheet.
Fig. 4 is the embodiment of the present invention 1 prepared Bi in NMP 2se 3atomic force microscope (AFM) figure of nanometer sheet.
Fig. 5 is the embodiment of the present invention 1 prepared Bi in NMP 2se 3the height map that nanometer sheet is corresponding with Fig. 4.
Fig. 6 is the embodiment of the present invention 1 prepared Bi in NMP 2se 3raman (Raman) figure of nanometer sheet.
Fig. 7 is the embodiment of the present invention 1 Bi prepared by NMP 2se 3nanometer sheet ultraviolet-visible light (UV-Vis) figure.
Fig. 8 is the embodiment of the present invention 2 prepared Bi in CS-HAc 2se 3x-ray diffraction (XRD) spectrogram of nanometer sheet.
Fig. 9 is the embodiment of the present invention 2 prepared Bi in CS-HAc 2se 3transmission electron microscope (TEM) figure of nanometer sheet.
Figure 10 is the embodiment of the present invention 2 prepared Bi in CS-HAc 2se 3atomic force microscope (AFM) figure of nanometer sheet.
Figure 11 is the embodiment of the present invention 2 prepared Bi in NMP 2se 3the height map that nanometer sheet is corresponding with Figure 10.
Figure 12 is the embodiment of the present invention 2 prepared Bi in CS-HAc 2se 3raman (Raman) figure of nanometer sheet.
Figure 13 is the embodiment of the present invention 2 prepared Bi in CS-HAc 2se 3nanometer sheet ultraviolet-visible light (UV-Vis) figure.
Embodiment
After now specific embodiments of the invention being discussed in.
Embodiment 1
Bi 2se 3the preparation of body material: take the dissolving of 0.9g polyvinylpyrrolidone with electronic balance and be to be equipped with in the beaker of 36mL ethylene glycol, get 1mmol bismuth oxide, 3mmol selenium powder and 4mmol ethylenediamine tetraacetic acid (EDTA) in addition respectively and join in above-mentioned solution, abundant stirring and evenly mixing.Mixed solution is poured in autoclave and seals, be then positioned over homogeneous reactor and be warmed up to 200 DEG C, and at 200 DEG C of reaction 20h, make it react completely.The mixed solution obtained, by high speed centrifugation process, is removed supernatant liquor, is respectively washed 2 times with ultrapure water and dehydrated alcohol respectively, finally 60 DEG C of dry 96h in vacuum drying oven.
NMP is utilized to prepare minority layer bismuth selenide nanometer sheet: to synthesize Bi 2se 3powder is raw material, by 50mg, grinds thin Bi 2se 3powder joins in 50mL NMP, is then ultrasonic 30h in the ultrasonic apparatus of 250W in electric power by this mixed system.Gained dispersion liquid is left standstill 48h, obtain upper strata dispersion liquid 2/3rds part and by its low-speed centrifugal 30min in the whizzer of 1000 rpms, collect centrifugal after upper liquid and by its centrifugal 20min of whizzer high speed at 10000 rpms, removing supernatant liquor, obtain the centrifugal thing of lower floor, the lower floor material NMP of gained is disperseed, finally obtains being dispersed in minority layer Bi in NMP 2se 3nanometer sheet.
Few layer Bi 2se 3the detection of nanometer sheet: to Bi 2se 3body material carries out XRD detection.To few layer of Bi 2se 3nanometer sheet carries out the detections such as XRD, TEM, AFM, Raman, UV-Vis.
Fig. 1 is the Bi of synthesis in embodiment 1 2se 3the contrast of the collection of illustrative plates that the detection that body material carries out XRD obtains and standard card, proves that the powder synthesized is Bi 2se 3crystal.
Fig. 2 is prepared Bi in embodiment 1 2se 3the XRD spectra of the dried sample of nanometer sheet dispersion liquid and the contrast of standard spectrogram, found the peak of [006] of enhancing, and the disappearance at some peaks, proves the Bi obtaining few layer 2se 3nanometer sheet.
Fig. 3 is minority layer Bi in embodiment 1 2se 3the TEM figure of nanometer sheet, minority layer Bi as we know from the figure 2se 3for two-dimensional sheet structure.
Fig. 4 is gained minority layer Bi in embodiment 1 2se 3nanometer sheet AFM schemes.
Fig. 5 is gained minority layer Bi in embodiment 1 2se 3nanometer sheet AFM schemes corresponding height map, can know the Bi of preparation 2se 3nanometer sheet is only layer 2-3.
Fig. 6 is embodiment 1 minority layer Bi 2se 3nanometer sheet and Bi 2se 3the Raman comparison diagram of body material, minority layer Bi in figure 2se 3nanometer sheet vibration modes contrast Bi2Se3 body material Raman spectrogram there occurs red shift, confirms the Bi of preparation further 2se 3nanometer sheet is minority layer.
Fig. 7 is minority layer Bi in embodiment 1 2se 3nanometer sheet and Bi 2se 3the UV-Vis comparison diagram of body material.Wherein the absorption peak of minority layer bismuth selenide nanometer sheet/NMP is 574nm.
Embodiment 2
Bi 2se 3the preparation of body material: take the dissolving of 0.9g polyvinylpyrrolidone with electronic balance and be to be equipped with in the beaker of 36ml ethylene glycol, get 1mmol bismuth oxide, 3mmol selenium powder and 4mmol ethylenediamine tetraacetic acid (EDTA) in addition respectively and join in above-mentioned solution, abundant stirring and evenly mixing.Mixed solution is poured in autoclave and seals, be then positioned over homogeneous reactor and be warmed up to 200 DEG C, and at 200 DEG C of reaction 20h, make it react completely.The mixed solution obtained, by high speed centrifugation process, is removed supernatant liquor, is respectively washed 2 times with ultrapure water and dehydrated alcohol respectively, finally 60 DEG C of dry 96h in vacuum drying oven.
Utilize CS-HAc minority layer bismuth selenide nanometer sheet: to synthesize Bi 2se 3powder is raw material, by 50mg, grinds thin Bi 2se 3it is in the aqueous acetic acid of 0.2mg every milliliter that powder joins 50mL chitosan concentration, is then ultrasonic 30h in the ultrasonic apparatus of 250W in electric power by this mixed system.Gained dispersion liquid is left standstill 48h, obtain upper strata dispersion liquid 2/3rds part and by its low-speed centrifugal 30min in the whizzer of 1000 rpms, collect centrifugal after upper liquid and by its centrifugal 20min of whizzer high speed at 10000 rpms, removing supernatant liquor, obtain the centrifugal thing of lower floor, lower floor's material acetum of gained is disperseed, finally obtains the minority layer Bi disperseing acetum 2se 3nanometer sheet.
Few layer Bi 2se 3the detection of nanometer sheet: to Bi 2se 3body material carries out XRD detection.To few layer of Bi 2se 3nanometer sheet carries out the detections such as XRD, TEM, AFM, Raman, UV-Vis.
Fig. 8 is prepared Bi in embodiment 2 2se 3the XRD spectra of the dried sample of nanometer sheet dispersion liquid and the contrast of standard spectrogram, found the peak of [006] of enhancing, and the disappearance at some peaks, proves the Bi obtaining few layer 2se 3nanometer sheet.
Fig. 9 is minority layer Bi in embodiment 2 2se 3the TEM figure of nanometer sheet, minority layer Bi as we know from the figure 2se 3for two-dimensional sheet structure.
Figure 10 is gained minority layer Bi in embodiment 2 2se 3nanometer sheet AFM schemes.
Figure 11 is gained minority layer Bi in embodiment 2 2se 3nanometer sheet AFM schemes corresponding height map, can know the Bi of preparation 2se 3nanometer sheet is only layer 2-3.
Figure 12 is minority layer Bi in embodiment 2 2se 3nanometer sheet and Bi 2se 3the Raman comparison diagram of body material, minority layer Bi in figure 2se 3nanometer sheet vibration modes contrast Bi 2se 3body material Raman spectrogram there occurs red shift, confirms the Bi of preparation further 2se 3nanometer sheet is minority layer.
Figure 13 is minority layer Bi in embodiment 2 2se 3nanometer sheet and Bi 2se 3the UV-Vis comparison diagram of body material.Wherein, the absorption peak of minority layer bismuth selenide nanometer sheet/CS-HAc is 552nm.

Claims (8)

1. a preparation method for minority layer bismuth selenide nanometer sheet, is characterized in that comprising the following steps:
1) carry out hydrothermal synthesis reaction by selenium powder, bismuth oxide, polyvinylpyrrolidone, ethylene glycol and ethylenediamine tetraacetic acid (EDTA) loading reactor, the mixed solution obtained is centrifugal, removes supernatant liquor, then uses ultrapure water and absolute ethanol washing respectively, obtains Bi after drying 2se 3powder; The proportioning of described selenium powder, bismuth oxide, polyvinylpyrrolidone, ethylene glycol and ethylenediamine tetraacetic acid (EDTA) is 3mmol: 1mmol: 0.9g: 36mL: 4mmol; The temperature of described hydrothermal synthesis reaction is 180 ~ 200 DEG C, and the time of hydrothermal synthesis reaction is 20h;
2) by step 1) Bi that obtains 2se 3powder joins N-Methyl pyrrolidone solvent or is dissolved with in the acetum of chitosan, after ultrasonic, obtains minority layer Bi 2se 3the dispersion liquid of nanometer sheet, leave standstill again, the part of getting its upper strata 2/3rds is put into low-speed centrifugal in whizzer, collect the upper liquid of centrifugal gained, again the upper liquid of gained is put into whizzer high speed centrifugal, remove supernatant fraction, lower floor's material N-Methyl pyrrolidone solvent of gained or acetum are heavily disperseed, finally obtain the minority layer bismuth selenide nanometer sheet be dispersed in solution.
2. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 1) in, the number of times of described washing is 2 times.
3. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 1) in, the condition of described drying is 60 DEG C of dry 96h in vacuum drying oven.
4. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 2) in, described Bi 2se 3the proportioning of powder and N-Methyl pyrrolidone solvent is 50 ~ 100mg: 50mL; Described Bi 2se 3powder is 50 ~ 100mg: 50mL with the proportioning of the acetum being dissolved with chitosan.
5. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 2) in, described ultrasonic power is 250W, and the ultrasonic time is 0.5 ~ 50h.
6. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 2) in, the described standing time is 2 ~ 240h.
7. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 2) in, the speed of described low-speed centrifugal is 400 ~ 2000r/min, and the time of low-speed centrifugal is 30min.
8. the preparation method of a kind of minority layer bismuth selenide nanometer sheet as claimed in claim 1, is characterized in that in step 2) in, described ultracentrifugal speed is 5000 ~ 20000r/min, and the ultracentrifugal time is 20min.
CN201410208150.1A 2014-05-16 2014-05-16 A kind of preparation method of minority layer bismuth selenide nanometer sheet Expired - Fee Related CN103979505B (en)

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CN104528663B (en) * 2014-12-18 2016-08-24 长春理工大学 A kind of preparation method of bismuth selenide micron film
CN109081315A (en) * 2017-06-13 2018-12-25 天津大学 A kind of preparation method of two-dimensional material telluride germanium
CN109943338B (en) * 2019-03-18 2021-12-28 中国计量大学 Preparation method of near-infrared luminescent rare earth doped indium selenide nanosheet
CN111229199A (en) * 2019-10-09 2020-06-05 武汉纺织大学 Method for preparing two-dimensional bismuth-based oxygen group compound nanosheet by liquid phase stripping method and application
CN110586930B (en) * 2019-10-22 2022-01-14 广东银纳科技有限公司 Preparation method of nano titanium material for corrosion prevention
CN110745790B (en) * 2019-11-25 2022-09-20 东北大学 Hydrothermal preparation method of bismuth selenide nano powder
CN111261737B (en) * 2020-01-21 2022-08-12 广东工业大学 SnSe/Bi 2 Se 3 Nanosheet heterojunction and preparation method thereof
CN113257933B (en) * 2021-05-26 2023-08-29 哈尔滨工业大学 Bismuth selenide/gallium nitride ultraviolet-infrared broadband detector and preparation method thereof
CN113817927B (en) * 2021-10-09 2022-09-02 中南大学 Method for efficiently preparing arsenic-alkene nanosheets

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CN101746738B (en) * 2009-09-29 2011-06-29 武汉理工大学 Preparing method of nano laminar thermoelectric Bi2Se3 compound
CN103046110B (en) * 2011-10-13 2016-04-06 国家纳米科学中心 One prepares monocrystalline Bi 2se 3the method of nanostructure
CN103288061B (en) * 2013-06-24 2014-10-01 福州大学 Bismuth selenide nanometer material, preparation method and applications thereof
CN103641079B (en) * 2013-10-21 2015-09-09 东南大学 A kind of preparation method of large-size ultrathin bismuth selenide nanosheet

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