CN102616844B - Pompon bismuthous sulfide and preparation method thereof - Google Patents
Pompon bismuthous sulfide and preparation method thereof Download PDFInfo
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- CN102616844B CN102616844B CN201210099497.8A CN201210099497A CN102616844B CN 102616844 B CN102616844 B CN 102616844B CN 201210099497 A CN201210099497 A CN 201210099497A CN 102616844 B CN102616844 B CN 102616844B
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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 diameter 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 adopt solvent thermal/hydrothermal method to prepare the method for 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 photocell material, photorectifier material, sensor and catalytic field.In recent years by adopting solvent thermal/hydrothermal method, microwave method and template synthesis to go out 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 the people such as the Zhang Qi of University Of Xiangtan use Triton X-100+alkylphenol polyoxyethylene, alkylphenol polyoxyethylene, the tensio-active agent that Triton X-100 etc. are different, with the synthetic bismuth sulfide nano floral material of circumfluence method, from given scanning electron microscope (SEM) photograph, can see, this is by bar-shaped bismuth sulfide, to assemble bunchy to form flower-shaped bismuth sulfide nano floral material, it has larger surface-area than particulate state and bar-shaped bismuth sulfide material, but adopt the method owing to being subject to the restriction of used tensio-active agent, be difficult to obtain the more bismuth sulfide material of high surface area.It is not yet seen about thering is larger specific surface area, advantages of good crystallization, size uniform, have the bobbles shape bismuth sulfide material of better application prospect and adopt solvent thermal/hydrothermal method by carboxylated polyparaphenylene's acetylene (PPV), to synthesize preparation method's the open report of the bobbles shape bismuth sulfide material of size uniform at catalysis and sensory field.
Summary of the invention
The object 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: first Bismuth trinitrate is dissolved in dimethyl formamide (DMF) or water, is mixed with the solution A of 0.01～2mol/L, carboxylated polyparaphenylene's acetylene (PPV) is dissolved into the solution B that is mixed with 0.001～2mol/L in methyl alcohol or water, by above-mentioned two kinds of solution that prepare by solution A: solution B=1:0.01～10 volume ratio mix and blend obtains mixed solution, again sulphur source is dissolved into and in methyl alcohol or ethanol or water, is mixed with the solution that concentration is 0.01～2mol/L, join in mixed solution obtained above, after stirring, 80～200 ℃ of thermostatically heating 4～24 hours, be cooled to after room temperature, rotating speed centrifugation with 1000～8000 revs/min obtains black solid, adopt respectively again deionized water and ethanol repetitive scrubbing black solid to the liquid after centrifugation to be achromaticity and clarification transparent, and then the solid finally obtaining with ethanol extracting centrifugation, the solid finally ethanol extracting being obtained is placed in vacuum drying oven, 50～100 ℃ of oven dry, obtain bobbles shape bismuth sulfide material, described sulphur source is thiocarbamide or thioacetamide.
The bobbles shape bismuth sulfide material that adopts aforesaid method of the present invention to prepare, for the xln of bismuth trisulfide, it is characterized in that the unit cell parameters a=11.149nm of the X-direction of this crystal, Y direction unit cell parameters b=11.304nm, Z-direction unit cell parameters c=3.981nm, belongs to rhombic system; The reunite diameter of the bismuth trisulfide bobbles that forms of the nano belt strip of sheet fine hair consisting of the xln 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.
Preparation method of the present invention has taked take Bismuth trinitrate as bismuth source, take thiocarbamide or thioacetamide as sulphur source, has prepared the bismuth sulfide bobbles of rhombic system structure under the effect of carboxylated polyparaphenylene's Acetylene gauge surface-active agent by hydrothermal/solvent thermal response.Bobbles shape bismuth sulfide material prepared by employing the inventive method is because its nano belt strip of sheet fine hair edge atom is with respect to the atom in plane, there is higher activity and selectivity, therefore the bismuth sulfide material of preparing than existing method has larger specific surface area, advantages of good crystallization, size uniform, have better application prospect in catalysis and sensory field.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of bismuth sulfide material.
Fig. 2 is temperature of reaction bismuth sulfide material scanning electron microscope (SEM) photograph under 20kvX20000 while being 120 ℃.
Fig. 3 is temperature of reaction bismuth sulfide material scanning electron microscope (SEM) photograph under 20kvX10000 while being 160 ℃.
Embodiment
By specific embodiment, the inventive method is described in further detail below.
Embodiment 1:
First, Bismuth trinitrate is dissolved in to DMF, is mixed with the solution of 0.2mol/L; And carboxylated PPV is dissolved in methyl alcohol or water, be mixed with the solution of 0.2mol/L; Above-mentioned two kinds of solution that prepare are mixed by 3:1 volume ratio, under room temperature, stir 30min and obtain mixed solution; Thioacetamide is dissolved in methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi:S=3:2, join in mixed solution obtained above, after stirring under room temperature, be placed in water heating kettle, 120 ℃ of thermostatically heating 12 hours; Water heating kettle is taken out, be cooled to after room temperature centrifugation under the rotating speed of 5000 revs/min and obtain the solid of black, then it is transparent to adopt respectively deionized water and ethanol repetitive scrubbing to the liquid after centrifugal to be achromaticity and clarification; The solid again centrifugation being gone out ethanol extracting, the solid finally ethanol extracting being obtained is placed in vacuum drying oven 60 ℃ of oven dry, obtains product bobbles shape bismuth sulfide material.
Resulting product is identified to its crystalline phase with X-ray diffraction, by scanning electron microscope, characterize its pattern.
The X-ray diffractogram that accompanying drawing 1 is the product bobbles shape bismuth sulfide material for preparing in the present embodiment.X-ray diffractogram by this bismuth sulfide material can find out, 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, be the bismuth sulfide of rhombic system structure, the unit cell parameters a=11.149nm of the X-direction of crystal, the unit cell parameters b=11.304nm of Y direction, the unit cell parameters c=3.981nm of Z-direction.
Fig. 2 is temperature of reaction bismuth sulfide material scanning electron microscope (SEM) photograph under 20kvX20000 while being 120 ℃; Fig. 3 is temperature of reaction bismuth sulfide material scanning electron microscope (SEM) photograph under 20kvX10000 while being 160 ℃.By scanning electron microscope (SEM) photograph accompanying drawing 2 and accompanying drawing 3, can observe pattern and the size of the product bismuth sulfide crystal preparing in the present embodiment, proved the bismuth trisulfide bobbles that nano belt strip of sheet fine hair that the bismuth sulfide bobbles that obtains in the present embodiment forms for the xln by bismuth trisulfide is reunited and formed, the diameter of this bismuth trisulfide bobbles is 2 ± 0.3 μ m; By the single fine hair 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 in plane, there is higher activity and selectivity, therefore the bismuth sulfide material of preparing than existing method has larger specific surface area, and advantages of good crystallization, size uniform, have better application prospect in catalysis and sensory field.
Embodiment 2:
First, by 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 water, be mixed with the solution of 0.001mol/L; Above-mentioned two kinds of solution that prepare are mixed by 1:10 volume ratio, under room temperature, stir 30min and obtain mixed solution; Again thiocarbamide is dissolved in methyl alcohol, is mixed with the solution of 0.01mol/L, according to mol ratio Bi:S=3:2, join in mixed solution obtained above, after stirring under room temperature, be placed in water heating kettle, 80 ℃ of thermostatically heating 24 hours; Water heating kettle is taken out, be cooled to after room temperature, under the rotating speed of 8000 revs/min, centrifugation obtains the solid of black, then it is transparent to adopt respectively deionized water and ethanol repetitive scrubbing to the liquid after centrifugal to be achromaticity and clarification, the solid that centrifugation goes out; The solid again centrifugation being gone out ethanol extracting, the solid finally ethanol extracting being obtained is placed in vacuum drying oven 50 ℃ of oven dry, obtains product bobbles shape bismuth sulfide material.
Resulting product is identified to its crystalline phase with X-ray diffraction, by scanning electron microscope, characterize its pattern.Identical with embodiment 1 of its operation and resulting result.
Embodiment 3:
First, by 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 water, be mixed with the solution of 2mol/L; Above-mentioned two kinds of solution that prepare are mixed by 1:0.01 volume ratio, under room temperature, stir 30min and obtain mixed solution; Thiocarbamide is dissolved in methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi:S=3:2, join in mixed solution obtained above, after stirring under room temperature, be placed in water heating kettle, 160 ℃ of thermostatically heating 8 hours; Water heating kettle is taken out, be cooled to after room temperature centrifugation under the rotating speed of 3000 revs/min and obtain the solid of black, then it is transparent to adopt respectively deionized water and the washing of ethanol alternate repetition to the liquid after centrifugal to be achromaticity and clarification, the solid that centrifugation goes out; The solid again centrifugation being gone out ethanol extracting, the solid finally ethanol extracting being obtained is placed in vacuum drying oven 80 ℃ of oven dry, obtains product bobbles shape bismuth sulfide material.
Resulting product is identified to its crystalline phase with X-ray diffraction, by scanning electron microscope, characterize its pattern.Identical with embodiment 1 of its operation and resulting result.
Embodiment 4:
First, by 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 water, be mixed with the solution of 0.8mol/L; Above-mentioned two kinds of solution that prepare are mixed by 1:5 volume ratio, under room temperature, stir 30min and obtain mixed solution; Thiocarbamide is dissolved in methyl alcohol, is mixed with the solution of 0.2mol/L, according to mol ratio Bi:S=3:2, join in mixed solution obtained above, after stirring under room temperature, be placed in water heating kettle, 200 ℃ of thermostatically heating 4 hours; Water heating kettle is taken out, be cooled to after room temperature centrifugation under the rotating speed of 1000 revs/min and obtain the solid of black, then it is transparent to adopt respectively deionized water and the washing of ethanol alternate repetition to the liquid after centrifugal to be achromaticity and clarification, the solid that centrifugation goes out; The solid again centrifugation being gone out ethanol extracting, the solid finally ethanol extracting being obtained is placed in vacuum drying oven 100 ℃ of oven dry, obtains product bobbles shape bismuth sulfide material.
Resulting product is identified to its crystalline phase with X-ray diffraction, by scanning electron microscope, characterize its pattern.Identical with embodiment 1 of its operation and resulting result.
By using respectively X-ray diffraction to identify its crystalline phase to resulting product in the various embodiments described above, by scanning electron microscope, characterize its pattern above, analyze acquired results basically identical.Fig. 1 represents is the X-ray diffractogram that adopts the product bismuth sulfide material that method of the present invention prepares.By accompanying drawing 1, can be found out, diffraction peak peak shape is sharp-pointed, and each diffraction peak intensity is high, shows that the product crystallization that adopts the inventive method to prepare is better, and crystal growth is complete; By standard card comparative analysis product, be the bismuth sulfide of rhombic system structure, the unit cell parameters a=11.149nm of the X-direction of crystal, 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 have shown respectively scanning electron microscope (SEM) photograph under 20kvX20000 of when temperature of reaction is 120 ℃ resulting bismuth sulfide material and the scanning electron microscope (SEM) photograph of resulting bismuth sulfide material under 20kvX10000 when temperature of reaction is 160 ℃.By the scanning electron microscope (SEM) photograph of accompanying drawing 2 and accompanying drawing 3, can observe pattern and the size that adopts the product bismuth sulfide crystal that the inventive method prepares, the diameter of the bismuth trisulfide bobbles that the nano belt strip of sheet reunion that the bismuth sulfide bobbles preparing in known the above embodiment of the present invention forms for the xln by bismuth trisulfide forms 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 detection analytic explanation thereof by above-described embodiment: because the present invention has adopted novel face active: the PPV that agent is carboxylated, thus conveniently, simply prepared the bismuth sulfide material with large specific surface area.Because its nano belt strip of sheet fine hair edge atom is with respect to the atom in plane, there is higher activity and selectivity, therefore the bismuth sulfide material of preparing than existing method has larger specific surface area, and advantages of good crystallization, size uniform, have better application prospect in catalysis and sensory field.
Claims (2)
1. a preparation method for bobbles shape bismuth sulfide material, is characterized in that: first Bismuth trinitrate is dissolved in dimethyl formamide or water, is mixed with the solution A of 0.01～2mol/L, carboxylated polyparaphenylene's acetylene is dissolved into the solution B that is mixed with 0.001～2mol/L in methyl alcohol or water, by above-mentioned two kinds of solution that prepare by solution A: solution B=1:0.01～10 volume ratio mix and blend obtains mixed solution, again sulphur source is dissolved into and in methyl alcohol or ethanol or water, is mixed with the solution that concentration is 0.01～2mol/L, join in mixed solution obtained above, after stirring, 80～200 ℃ of thermostatically heating 4～24 hours, be cooled to after room temperature, rotating speed centrifugation with 1000～8000 revs/min obtains black solid, adopt respectively again deionized water and ethanol repetitive scrubbing black solid to the liquid after centrifugation to be achromaticity and clarification transparent, and then the solid finally obtaining with ethanol extracting centrifugation, the solid finally ethanol extracting being obtained is placed in vacuum drying oven, 50～100 ℃ of oven dry, obtain bobbles shape bismuth sulfide material, described sulphur source is thiocarbamide or thioacetamide.
2. the bobbles shape bismuth sulfide material that described in claim 1 prepared by method, for the xln of bismuth trisulfide, it is characterized in that the unit cell parameters a=11.149nm of the X-direction of this crystal, Y direction unit cell parameters b=11.304nm, Z-direction unit cell parameters c=3.981nm, belongs to rhombic system; The reunite diameter of the bismuth trisulfide bobbles that forms of the nano belt strip of sheet fine hair consisting of the xln 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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| CN103626228B (en) * | 2013-12-02 | 2015-06-10 | 陕西师范大学 | Flaky Bi2S3 powder preparation method |
| 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 |
| CN106299357B (en) * | 2016-10-14 | 2019-06-18 | 成都理工大学 | With the bismuth sulfide electrode material of specific morphology structure and its application |
| 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 |
| 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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