CN102616844A - Pompon bismuthous sulfide and preparation method thereof - Google Patents
Pompon bismuthous sulfide and preparation method thereof Download PDFInfo
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- CN102616844A CN102616844A CN2012100994978A CN201210099497A CN102616844A CN 102616844 A CN102616844 A CN 102616844A CN 2012100994978 A CN2012100994978 A CN 2012100994978A CN 201210099497 A CN201210099497 A CN 201210099497A CN 102616844 A CN102616844 A CN 102616844A
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Abstract
The invention discloses pompon bismuthous sulfide and a preparation method thereof. The preparation method is characterized in that bismuth nitrate serves as a bismuth source, thiourea or thioacetamide serves as a sulfur source, and hydrothermal/solvothermal reaction is preformed on the bismuth source and the sulfur source under the action of carboxylated polyphenylvinylene surfactant. Prepared bismuth sulfide pompon has an orthorhombic system structure, and cell parameters of crystals in the directions of coordinate axes X, Y and Z are respectively 11.149nm, 11.304nm and 3.981nm; and nanoribbon sliver-shaped pompon formed by the crystals of the bismuthous sulfide is subjected to agglomeration to generate bismuthous sulfide pompon, the size of the bismuthous sulfide pompon is 2 plus/minus 0.3 mu m, the length of the single nanoribbon sliver-shaped pompon is 0.3 plus/minus 0.1 mu m, the width of the pompon sliver is 300 plus/minus 10 nm, and the thickness of the pompon sliver is 100 plus/minus 10 nm. Compared with bismuth sulfide materials prepared by the convention method, the bismuth sulfide material prepared by the method disclosed by the invention has larger specific surface area and is good in crystallization and uniform in size, thus having better application prospect in the fields of catalysis and sensing.
Description
Technical field
The invention belongs to bismuth sulfide preparation method technical field, be specifically related to bobbles shape bismuth trisulfide and the method that adopts solvent thermal/Hydrothermal Preparation bobbles shape bismuth trisulfide.
Background technology
Bi
2S
3Be a kind of direct narrow bandgap semiconductor material, its energy gap is 1.3eV, is widely used in sensitive cell material, photorectifier material, transmitter and catalytic field.In recent years through adopting solvent thermal/hydrothermal method, microwave method and template to prepare particulate state, bar-shaped, hedgehog and flower-shaped bismuth sulfide.For example; " Chinese Journal of Inorganic Chemistry " (2008; Vol.24No.4; 547～552) reported that people such as the Zhang Qi of University Of Xiangtan use different surface active agents such as polyoxyethylene octyl phenyl ether+TX10, TX10, polyoxyethylene octyl phenyl ether, with circumfluence method synthetic bismuth sulfide nano floral material, can see from given sem photograph; This is to assemble bunchy by bar-shaped bismuth sulfide to form flower-shaped bismuth sulfide nano floral material, and it has bigger surface-area than particulate state and bar-shaped bismuth sulfide material; But adopt this method owing to receive the restriction of employed tensio-active agent, be difficult to obtain the more bismuth sulfide material of high surface area.So far do not see as yet about having bigger specific surface area; Advantages of good crystallization, size are even, in catalysis with sensory field has the bobbles shape bismuth sulfide material of better application prospect and adopt solvent thermal/hydrothermal method to synthesize the preparing method's of the uniform bobbles shape of size bismuth sulfide material public reported through carboxylated polyparaphenylene's acetylene (PPV).
Summary of the invention
The objective of the invention is to propose a kind of bobbles shape bismuth sulfide material and preparation method thereof, to overcome the above-mentioned deficiency of prior art.
The preparation method of bobbles shape bismuth sulfide material of the present invention is characterized in that: earlier Bismuth trinitrate is dissolved in N (DMF) or the water, is mixed with the solution of 0.01～2mol/L; Carboxylated polyparaphenylene's acetylene (PPV) is dissolved into the solution that is mixed with 0.001～2mol/L in methyl alcohol or the water; Above-mentioned two kinds of solution that configure are mixed stirring by 1: 0.01～1: 10 volume ratio obtain mixed solution; Again the sulphur source is dissolved into and is mixed with the solution that concentration is 0.01～2mol/L in methyl alcohol or ethanol or the water, in the mixed solution that obtains above joining, after stirring; 80～200 ℃ of thermostatically heating 4～24 hours; After being cooled to room temperature, obtain black solid with 1000～8000 rev/mins rotating speed spinnings, it is transparent to adopt liquid after deionized water and ethanol repetitive scrubbing black solid to the spinning to be achromaticity and clarification more respectively; And then the solid that obtains at last with ethanol extracting spinning; The solid that at last the ethanol extracting is obtained places vacuum drying oven, 50～100 ℃ of oven dry, promptly obtains bobbles shape bismuth sulfide material; Said sulphur source is thiocarbamide or thioacetamide.
The bobbles shape bismuth sulfide material that adopts method for preparing of the present invention to obtain; Xln for bismuth trisulfide; The unit cell parameters a=11.149nm that it is characterized in that this crystalline X-direction; Y direction unit cell parameters b=11.304nm, Z-direction unit cell parameters c=3.981nm belongs to rhombic system; By the reunite big small scale of the bismuth trisulfide bobbles that forms of the nano belt strip of sheet fine hair that xln constituted of this bismuth trisulfide is 2 ± 0.3 μ m; Long 0.3 ± 0.1 μ m of single nano belt strip of sheet fine hair, the wide 300 ± 10nm of fine hair silver, the thick 100 ± 10nm of silver.
It is the bismuth source that preparation method of the present invention has taked with the Bismuth trinitrate, is the sulphur source with thiocarbamide or thioacetamide, under carboxylated polyparaphenylene's acetylene influence of surfactant, has obtained the bismuth sulfide bobbles of rhombic system structure through the hydrothermal/solvent reaction for preparation.Adopt the inventive method preparation bobbles shape bismuth sulfide material since its nano belt strip of sheet fine hair edge atom with respect to the atom that is on the plane; Have higher activity and selectivity; Therefore the bismuth sulfide material than existing method preparation has bigger specific surface area; Advantages of good crystallization, size are even, have the better application prospect in catalysis and sensory field.
Description of drawings
Fig. 1 is the X-ray diffractogram of bismuth sulfide material.
Bismuth sulfide material sem photograph when Fig. 2 is 120 ℃ for temperature of reaction under the 20kvX20000.
Bismuth sulfide material sem photograph when Fig. 3 is 160 ℃ for temperature of reaction under the 20kvX10000.
Embodiment
Below the inventive method is done further to specify through specific embodiment.
Embodiment 1:
At first, Bismuth trinitrate is dissolved in DMF, is mixed with the solution of 0.2mol/L; And carboxylated PPV is dissolved in methyl alcohol or the water, be mixed with the solution of 0.2mol/L; Above-mentioned two kinds of solution that configure are mixed by 3: 1 volume ratios, stir 30min under the room temperature and obtain mixed solution; Thioacetamide is dissolved in the methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi: S=3: 2, in the mixed solution that obtains above joining, after stirring under the room temperature, place water heating kettle, 120 ℃ of thermostatically heating 12 hours; Water heating kettle is taken out, be cooled to after the room temperature solid that under 5000 rev/mins rotating speed spinning obtains black, it is transparent that the liquid after adopting deionized water and ethanol repetitive scrubbing extremely centrifugal more respectively is achromaticity and clarification; The solid that again spinning is gone out is used the ethanol extracting, and the solid that at last the ethanol extracting is obtained places vacuum drying oven 60 ℃ of oven dry, promptly obtains product bobbles shape bismuth sulfide material.
Resulting product is identified its crystalline phase with X-ray diffraction, characterize its pattern with ESEM.
Accompanying drawing 1 is the X-ray diffractogram of the product bobbles shape bismuth sulfide material for preparing in the present embodiment.X-ray diffractogram by this bismuth sulfide material can find out that the diffraction peak peak shape is sharp-pointed, and each diffraction peak intensity is high, shows that the crystallization of product sample is better, and crystal growth is complete; By standard card comparative analysis product is the bismuth sulfide of rhombic system structure, the unit cell parameters a=11.149nm of crystalline X-direction, the unit cell parameters b=11.304nm of Y direction, the unit cell parameters c=3.981nm of Z-direction.
Bismuth sulfide material sem photograph when Fig. 2 is 120 ℃ for temperature of reaction under the 20kvX20000; Bismuth sulfide material sem photograph when Fig. 3 is 160 ℃ for temperature of reaction under the 20kvX10000.Can observe product bismuth sulfide crystalline pattern and the size for preparing in the present embodiment by sem photograph accompanying drawing 2 and accompanying drawing 3; Proved the bismuth trisulfide bobbles that nano belt strip of sheet fine hair that the bismuth sulfide bobbles that obtains in the present embodiment constitutes for the xln by bismuth trisulfide is reunited and formed, the big small scale of this bismuth trisulfide bobbles is 2 ± 0.3 μ m; Single fine hair by being scattered can be observed, long 0.3 ± 0.1 μ m of single nano belt strip of sheet fine hair, the wide 300 ± 10nm of fine hair silver, the thick 100 ± 10nm of silver.Because this nano belt strip of sheet fine hair edge atom is with respect to the atom that is on the plane; Have higher activity and selectivity; Therefore the bismuth sulfide material for preparing than existing method has bigger specific surface area, and advantages of good crystallization, size are even, have the better application prospect in catalysis and sensory field.
Embodiment 2:
At first, with Bi (NO
3)
35H
2O is dissolved in DMF, is mixed with the solution of 2mol/L; And carboxylated PPV is dissolved in methyl alcohol or the water, be mixed with the solution of 0.001mol/L; Above-mentioned two kinds of solution that configure are mixed by 1: 10 volume ratio, stir 30min under the room temperature and obtain mixed solution; Again thiocarbamide is dissolved in the methyl alcohol, is mixed with the solution of 0.01mol/L, according to mol ratio Bi: S=3: 2, in the mixed solution that obtains above joining, after stirring under the room temperature, place water heating kettle, 80 ℃ of thermostatically heating 24 hours; Water heating kettle is taken out, be cooled to room temperature after, spinning obtains the solid of black under 8000 rev/mins rotating speed, it is transparent that the liquid after adopting deionized water and ethanol repetitive scrubbing extremely centrifugal more respectively is achromaticity and clarification, the solid that spinning goes out; The solid that again spinning is gone out is used the ethanol extracting, and the solid that at last the ethanol extracting is obtained places vacuum drying oven 50 ℃ of oven dry, promptly obtains product bobbles shape bismuth sulfide material.
Resulting product is identified its crystalline phase with X-ray diffraction, characterize its pattern with ESEM.Identical among its operation and resulting result and the embodiment 1.
Embodiment 3:
At first, with Bi (NO
3)
35H
2O is dissolved in DMF, is mixed with the solution of 0.01mol/L; And carboxylated PPV is dissolved in methyl alcohol or the water, be mixed with the solution of 2mol/L; Above-mentioned two kinds of solution that configure are mixed by 1: 0.01 volume ratio, stir 30min under the room temperature and obtain mixed solution; Thiocarbamide is dissolved in the methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi: S=3: 2, in the mixed solution that obtains above joining, after stirring under the room temperature, place water heating kettle, 160 ℃ of thermostatically heating 8 hours; Water heating kettle is taken out, be cooled to after the room temperature solid that under 3000 rev/mins rotating speed spinning obtains black, it is transparent that the liquid after adopting the washing of deionized water and ethanol alternate repetition extremely centrifugal more respectively is achromaticity and clarification, the solid that spinning goes out; The solid that again spinning is gone out is used the ethanol extracting, and the solid that at last the ethanol extracting is obtained places vacuum drying oven 80 ℃ of oven dry, promptly obtains product bobbles shape bismuth sulfide material.
Resulting product is identified its crystalline phase with X-ray diffraction, characterize its pattern with ESEM.Identical among its operation and resulting result and the embodiment 1.
Embodiment 4:
At first, with Bi (NO
3)
35H
2O is dissolved in DMF, is mixed with the solution of 1mol/L; And carboxylated PPV is dissolved in methyl alcohol or the water, be mixed with the solution of 0.8mol/L; Above-mentioned two kinds of solution that configure are mixed by 1: 5 volume ratio, stir 30min under the room temperature and obtain mixed solution; Thiocarbamide is dissolved in the methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi: S=3: 2, in the mixed solution that obtains above joining, after stirring under the room temperature, place water heating kettle, 200 ℃ of thermostatically heating 4 hours; Water heating kettle is taken out, be cooled to after the room temperature solid that under 1000 rev/mins rotating speed spinning obtains black, it is transparent that the liquid after adopting the washing of deionized water and ethanol alternate repetition extremely centrifugal more respectively is achromaticity and clarification, the solid that spinning goes out; The solid that again spinning is gone out is used the ethanol extracting, and the solid that at last the ethanol extracting is obtained places vacuum drying oven 100 ℃ of oven dry, promptly obtains product bobbles shape bismuth sulfide material.
Resulting product is identified its crystalline phase with X-ray diffraction, characterize its pattern with ESEM.Identical among its operation and resulting result and the embodiment 1.
Through resulting product among above-mentioned each embodiment being used X-ray diffraction identify its crystalline phase respectively, characterize its pattern above, analyze gained basically identical as a result with ESEM.Fig. 1 representes is the X-ray diffractogram that adopts the product bismuth sulfide material that method of the present invention prepares.Can be found out that by accompanying drawing 1 the diffraction peak peak shape is sharp-pointed, each diffraction peak intensity is high, shows that the product crystallization of adopting the inventive method to prepare is better, and crystal growth is complete; By standard card comparative analysis product is the bismuth sulfide of rhombic system structure, the unit cell parameters a=11.149nm of crystalline X-direction, the unit cell parameters b=11.304nm of Y direction, the unit cell parameters c=3.981nm of Z-direction.
Accompanying drawing 2 and accompanying drawing 3 shown respectively when temperature of reaction is 120 ℃ resulting bismuth sulfide material under 20kvX20000 sem photograph and when temperature of reaction is 160 ℃ the sem photograph of resulting bismuth sulfide material under 20kvX10000.Sem photograph by accompanying drawing 2 and accompanying drawing 3 can be observed product bismuth sulfide crystalline pattern and the size that adopts the inventive method to prepare; But the big small scale of the bismuth trisulfide bobbles that the bismuth sulfide bobbles for preparing in knowledge capital invention the foregoing description forms for being reunited by the nano belt strip of sheet that xln constituted of bismuth trisulfide is 2 ± 0.3 μ m; Long 0.3 ± 0.1 μ m of single nano belt strip of sheet fine hair, the wide 300 ± 10nm of fine hair silver, the thick 100 ± 10nm of silver.
Result and check and analysis explanation thereof by the foregoing description: because the present invention has adopted novel face active: the PPV that agent is carboxylated, thus conveniently, simply prepared bismuth sulfide material with big specific surface area.Because its nano belt strip of sheet fine hair edge atom is with respect to the atom that is on the plane; Have higher activity and selectivity; Therefore the bismuth sulfide material for preparing than existing method has bigger specific surface area, and advantages of good crystallization, size are even, have the better application prospect in catalysis and sensory field.
Claims (2)
1. the preparation method of a bobbles shape bismuth sulfide material is characterized in that: earlier Bismuth trinitrate is dissolved in N or the water, is mixed with the solution of 0.01～2mol/L; Carboxylated polyparaphenylene's acetylene is dissolved into the solution that is mixed with 0.001～2mol/L in methyl alcohol or the water; Above-mentioned two kinds of solution that configure are mixed stirring by 1: 0.01～1: 10 volume ratio obtain mixed solution; Again the sulphur source is dissolved into and is mixed with the solution that concentration is 0.01～2mol/L in methyl alcohol or ethanol or the water, in the mixed solution that obtains above joining, after stirring; 80～200 ℃ of thermostatically heating 4～24 hours; After being cooled to room temperature, obtain black solid with 1000～8000 rev/mins rotating speed spinnings, it is transparent to adopt liquid after deionized water and ethanol repetitive scrubbing black solid to the spinning to be achromaticity and clarification more respectively; And then the solid that obtains at last with ethanol extracting spinning; The solid that at last the ethanol extracting is obtained places vacuum drying oven, 50～100 ℃ of oven dry, promptly obtains bobbles shape bismuth sulfide material; Said sulphur source is thiocarbamide or thioacetamide.
2. the spherical bismuth sulfide material of thorn of the said method of claim 1 preparation; Be the xln of bismuth trisulfide, it is characterized in that the unit cell parameters a=11.149nm of this crystalline X-direction, Y direction unit cell parameters b=11.304nm; Z-direction unit cell parameters c=3.981nm belongs to rhombic system; By the reunite big small scale of the bismuth trisulfide bobbles that forms of the nano belt strip of sheet fine hair that xln constituted of this bismuth trisulfide is 2 ± 0.3 μ m; Long 0.3 ± 0.1 μ m of single nano belt strip of sheet fine hair, the wide 300 ± 10nm of fine hair silver, the thick 100 ± 10nm of silver.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626228A (en) * | 2013-12-02 | 2014-03-12 | 陕西师范大学 | Flaky Bi2S3 powder preparation method |
| CN104894646A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Method for improving conductivity of bismuth sulfide polycrystal |
| CN104894647A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Low-thermal conductivity bismuth sulfide polycrystalline thermoelectric material and preparation method thereof |
| CN106299357A (en) * | 2016-10-14 | 2017-01-04 | 成都理工大学 | There is bismuth sulfide electrode material and the application thereof of specific morphology structure |
| CN108355673A (en) * | 2018-01-22 | 2018-08-03 | 西北师范大学 | A kind of preparation method of loess particulate load bismuth sulfide composite photo-catalyst |
| CN112299481A (en) * | 2020-08-31 | 2021-02-02 | 武汉工程大学 | Bi2S3Preparation method of (1) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311385A (en) * | 2008-04-15 | 2008-11-26 | 中国建筑材料科学研究总院 | Method for preparing bismuth sulfide whiskers and the bismuth sulfide whiskers |
| CN101549887A (en) * | 2009-03-20 | 2009-10-07 | 清华大学 | A method to synthesize the nano structure of bismuth trisulfide |
-
2012
- 2012-04-06 CN CN201210099497.8A patent/CN102616844B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311385A (en) * | 2008-04-15 | 2008-11-26 | 中国建筑材料科学研究总院 | Method for preparing bismuth sulfide whiskers and the bismuth sulfide whiskers |
| CN101549887A (en) * | 2009-03-20 | 2009-10-07 | 清华大学 | A method to synthesize the nano structure of bismuth trisulfide |
Non-Patent Citations (5)
| Title |
|---|
| HONGYANG ZHOU ET AL.: "Acetylacetone-Directed Controllable Synthesis of Bi2S3 Nanostructures with Tunable Morphology", 《CRYSTAL GROWTH & DESIGN》 * |
| XIAODONG ZHOU ET AL.: "Facile synthesis and electrochemical application of surface-modified Bi2S3 urchin-like nano-spheres at room temperature", 《MATERIALS LETTER》 * |
| 代艳竹: "硫化铋纳米材料的制备及其光学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 张琪等: "表面活性剂控制合成不同形貌的纳米硫化铋", 《无机化学学报》 * |
| 李华华等: "一种含羧基的PPV衍生物的制备与表征", 《化工新型材料》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626228A (en) * | 2013-12-02 | 2014-03-12 | 陕西师范大学 | Flaky Bi2S3 powder preparation method |
| CN104894646A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Method for improving conductivity of bismuth sulfide polycrystal |
| CN104894647A (en) * | 2015-04-01 | 2015-09-09 | 中国科学院上海高等研究院 | Low-thermal conductivity bismuth sulfide polycrystalline thermoelectric material and preparation method thereof |
| CN104894646B (en) * | 2015-04-01 | 2017-07-11 | 中国科学院上海高等研究院 | A kind of method for improving bismuth-sulfide polycrystalline electrical conductivity |
| CN104894647B (en) * | 2015-04-01 | 2017-11-10 | 中国科学院上海高等研究院 | A kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof |
| CN106299357A (en) * | 2016-10-14 | 2017-01-04 | 成都理工大学 | There is bismuth sulfide electrode material and the application thereof of specific morphology structure |
| CN108355673A (en) * | 2018-01-22 | 2018-08-03 | 西北师范大学 | A kind of preparation method of loess particulate load bismuth sulfide composite photo-catalyst |
| CN112299481A (en) * | 2020-08-31 | 2021-02-02 | 武汉工程大学 | Bi2S3Preparation method of (1) |
| CN112299481B (en) * | 2020-08-31 | 2023-06-16 | 武汉工程大学 | Bi (Bi) 2 S 3 Is prepared by the preparation method of (2) |
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