CN110316756A - A kind of Sb2S3The synthetic method of nanometer rods - Google Patents
A kind of Sb2S3The synthetic method of nanometer rods Download PDFInfo
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- CN110316756A CN110316756A CN201910611431.4A CN201910611431A CN110316756A CN 110316756 A CN110316756 A CN 110316756A CN 201910611431 A CN201910611431 A CN 201910611431A CN 110316756 A CN110316756 A CN 110316756A
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- nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/008—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of Sb2S3The synthetic method of nanometer rods, comprising the following steps: a, high purity sulphur and oleyl amine are added in reaction flask, vacuumized, is heated while stirring；B, when temperature reaches 60 DEG C, nitrogen three times is replaced；C, when temperature reaches 90 DEG C, nitrogen valve is opened, vacuum pump is turned off；Until stopping reaction after sulphur all dissolves；D, by SbCl3It is added in reaction flask, octadecylene and oleyl amine is then added, vacuumizes, heats while stirring；E, when temperature reaches 60 DEG C, nitrogen three times is replaced；F, when temperature reaches 100 DEG C, nitrogen valve is opened, vacuum pump is turned off, when being warming up to 200 DEG C, inject sulphur source, reaction 5 ~ stop heating after twenty minutes, up to nanometer rods after centrifugation.The present invention provides a kind of methods of hot injection method synthesis antimony trisulfide, substantially reduce the reaction time, and do not need annealing and directly reach crystalline state, process is simpler.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, relate in particular to a kind of Sb2S3The synthetic method of nanometer rods.
Background technique
Antimony trisulfide (Sb2S3) it is a kind of binary direct band gap compound, since its band gap covers the range of solar spectrum,
It is a kind of ideal photovoltaic material.As a kind of important V-VI compounds of group, antimony trisulfide is because of its good photovoltaic property, high fever
Electrical power, spectral response and suitable valence band location, cause the special attention of people, band gap 1.5 ~ 2.2 eV it
Between, the various fields such as solar battery and solid state battery are widely used to, television camera, thermoelectricity system such as with photoconductive target
Cool equipment, electronics and optoelectronic device etc..Solar energy conversion and visible light responsible photocatalytic are studies have shown that the property of antimony trisulfide is main
Depending on its crystal structure, size and shape.Therefore, the controllable antimony trisulfide (Sb of synthesis size and shape2S3) material is applied to
It is of great significance.
It is existing to prepare antimony trisulfide (Sb2S3) method of nano material mainly has hydro-thermal method, sputtering method, chemical baths, spin coating
Method, although above-mentioned preparation method efficiently, is widely used, in the presence of time-consuming, preparation process is cumbersome, post annealed is needed to tie it completely
The problems such as brilliant, S in annealing process missing.As prepared Sb at present2S3Hydro-thermal method method and step mainly have: (1) precursor solution
Preparation；(2) presoma is moved in Teflon inner liner stainless steel autoclave；(3) FTO glass is put into autoclave；It (4) will be high
Pressure kettle is put into vacuum-tight reacting furnace, sets the reaction temperature time；(5) after stopping reaction, room is cooled to reaction kettle
Temperature；(6) FTO glass is taken out, nitrogen atmosphere glove box is moved to and is made annealing treatment.Hydro-thermal method synthesizes antimony sulfide nano material anti-
Ying Qianxu configures precursor solution, carries out that presoma is moved to Teflon inner liner stainless steel autoclave after the stirring of long period
In, 10-12 hour is reacted under high temperature and pressure atmosphere, is cooled down 1-3 hours, the time used in preparation process is longer, cost compared with
Height, and need the later period to be made annealing treatment to reach crystallization effect.In annealing process, there is also the missings of S, and the later period is needed to carry out
The supplement of S.
Summary of the invention
It is an object of the invention to provide a kind of Sb2S3The synthetic method of nanometer rods, when solving the reaction of existing preparation method
Between long, complex procedures, there are problems that S missing.
The purpose of the present invention is what is be achieved through the following technical solutions: a kind of Sb2S3The synthetic method of nanometer rods, including with
Lower step:
A, high purity sulphur and oleyl amine are added sequentially in reaction flask, open vacuum pump and vacuumize, then heats while stirring；
B, it when temperature reaches 60 DEG C, opens nitrogen valve and is filled with nitrogen into reaction flask, vacuumize again later, so replace three
The secondary subsequent temperature of continuing rising of nitrogen；
C, when temperature reaches 90 DEG C, being evacuated to liquid surface does not have bubble, then opens nitrogen valve, turns off vacuum pump；
Until stop agitating and heating after the high purity sulphur in reaction flask all dissolves, sulphur source is prepared after cooling, it is spare；
D, by SbCl3It is added in reaction flask, octadecylene and oleyl amine is then added, open vacuum pump and vacuumize, then while stirring
Heating；
E, it when temperature reaches 60 DEG C ~ 80 DEG C, opens nitrogen valve and is filled with nitrogen into reaction flask, vacuumize again later, so
Replace the subsequent temperature of continuing rising of nitrogen three times；
F, when temperature reaches 90 DEG C ~ 100 DEG C, nitrogen valve is opened, vacuum pump is turned off, when being continuously heating to 200 DEG C ~ 300 DEG C,
Be rapidly injected previously prepared sulphur source, then react 5 ~ stop agitating and heating after twenty minutes, when temperature is cooled to 90 DEG C or less,
Turn off nitrogen valve, obtains reaction solution, reaction solution is after being centrifuged up to Sb2S3Nanometer rods.
In step a, the amount ratio of the high purity sulphur and oleyl amine is 0.16g: 3 ~ 5mL.
In step a, the high purity sulphur is the elemental sulfur of purity >=99.99%.
In step d, the SbCl3: octadecylene: g: 3 ~ 4mL: 4 ~ 5 mL of oleyl amine=0.0456.
In step d, the SbCl3Purity >=99.9%.
In step f, centrifugal condition is to be centrifuged 1 ~ 5 minute with 5000 ~ 8000 revs/min of revolving speed.
The present invention provides a kind of methods of hot injection method synthesis antimony trisulfide, shorten existing hydro-thermal method and prepare antimony trisulfide
The time of nanometer rods, and do not need annealing and directly reach crystalline state, process is simpler.
The present invention first reacts antimony chloride and oleyl amine, octadecylene to certain temperature, then that the sulphur source prepared in advance is fast
Speed, which is injected into reaction flask, is reacted, and reaction can be completed in 10 minutes, and speed is fast, can be obtained most through simple rotary process
Product afterwards.And existing hydro-thermal method, precursor solution needs are ready-to-use, the General reactions time is 10 ~ 12 hours, and
To product be not exclusively crystalline phase.
The present invention is using the method for heat injection, and early period, the sulphur source of configuration can be stored for a long time, will not make to late phase reaction
At influence.The configuration process of precursor solution is not needed, the time of preparation nanometer rods is directly shortened, and does not need the later period and moves back
Fire can directly obtain crystalline phase.And Sb is prepared with sputtering method2S3When, for the missing of S than more serious, researcher can pass through solid sulfur
Thermal evaporation, annealing when be coated with the presoma of sulfur-bearing to supplement S, method of the invention not will cause the missing of S, and consersion unit
Only need to be similar to the device of three-necked bottle, without expensive sputtering equipment and reaction kettle etc., equipment input cost is low, process letter
Just, good product quality.
Detailed description of the invention
Fig. 1 is the electron microscope that nanometer rods are made in the embodiment of the present invention 1.
Fig. 2 is the flow chart of preparation method of the present invention.
Specific embodiment
Below with specific embodiment the present invention is described in detail.
Embodiment 1
As shown in Fig. 2, preparation process of the invention is as follows:
(1) preparation of sulphur source
The high purity sulphur (s, 99.99%) for weighing 0.16g is placed in three-neck flask, and the oleyl amine (C of 5mL is added18H37N, content 80-
90%).It on the device that three-neck flask access is put up rapidly, opens vacuum pump and vacuumizes, open heating mantle and heated and stirred
Mix (magnetic agitation), etc. reaction temperatures when reaching 60 DEG C, open nitrogen valve and be filled with nitrogen into three-neck flask, then take out again true
Sky so replaces the subsequent temperature of continuing rising of nitrogen three times.When temperature reaches 90 DEG C, and when being evacuated to liquid surface and there is no bubble,
Nitrogen valve is opened, vacuum pump is turned off.Until the sulphur in three-neck flask all dissolves, stop reaction.50 DEG C are cooled to temperature
When, three-neck flask is removed, the sulphur source prepared is contained spare in bottle.
(2) Sb2S3Preparation
Weigh 0.0456g antimony trichloride (SbCl3, 99.9%) and it is placed in three-neck flask, the octadecylene (C of 2mL is added18H36, content
> 90.0 %) and 3 mL oleyl amine (C18H37N, content 80-90%).On the device that three-neck flask access is put up rapidly, open
Vacuum pump vacuumizes, and opens heating mantle and carries out heating and stirring (magnetic agitation), etc. reaction temperatures when reaching 60 DEG C, beat
It opens nitrogen valve and is filled with nitrogen into three-neck flask, then vacuumize again, so replace the subsequent temperature of continuing rising of nitrogen three times.Work as temperature
When reaching 90 DEG C, nitrogen valve is opened, vacuum pump is turned off.Continue to heat up, extracts 0.7mL with medical syringe at this time and prepare in advance
Good sulphur source, etc. reaction temperatures when reaching 200 DEG C, be rapidly injected sulphur source, maintain temperature and timing stops heating after five minutes, go
Fall reaction set, when temperature is cooled to 90 DEG C or less, turns off nitrogen valve.Reactant in three-neck flask is moved into centrifuge tube, with
6000 revs/min of revolving speed is centrifuged 3 minutes.Final product is repeatedly collected after centrifugation.Sb2S3The yield of nanometer rods is 0.03g,
For electron microscope as shown in Figure 1, as seen from Figure 1, the length of nanometer rods is about 500nm-700nm, diameter is about 120-
130nm。
Embodiment 2
(1) preparation of sulphur source
The high purity sulphur (s, 99.99%) for weighing 0.16g is placed in three-neck flask, and the oleyl amine (C of 5mL is added18H37N, content 80-
90%).It on the device that three-neck flask access is put up rapidly, opens vacuum pump and vacuumizes, open heating mantle and heated and stirred
Mix (magnetic agitation), etc. reaction temperatures when reaching 60 DEG C, open nitrogen valve and be filled with nitrogen into three-neck flask, then take out again true
Sky so replaces the subsequent temperature of continuing rising of nitrogen three times.When temperature reaches 90 DEG C, and when being evacuated to liquid surface and there is no bubble,
Nitrogen valve is opened, vacuum pump is turned off.Until the sulphur in three-neck flask all dissolves, stop reaction.50 DEG C are cooled to temperature
When, three-neck flask is removed, the sulphur source prepared is contained spare in bottle.
(2) Sb2S3Preparation
Weigh 0.456g antimony trichloride (SbCl3, 99.9%) and it is placed in three-neck flask, the octadecylene (C of 3mL is added18H36, content >
90.0 %) and 4 mL oleyl amine (C18H37N, content 80-90%).On the device that three-neck flask access is put up rapidly, open
Vacuum pump vacuumizes, and opens heating mantle and carries out heating and stirring (magnetic agitation), etc. reaction temperatures when reaching 80 DEG C, beat
It opens nitrogen valve and is filled with nitrogen into three-neck flask, then vacuumize again, so replace the subsequent temperature of continuing rising of nitrogen three times.Work as temperature
When reaching 100 DEG C, nitrogen valve is opened, vacuum pump is turned off.Continue to heat up, extracts 0.7mL with medical syringe at this time and make in advance
The sulphur source got ready, etc. reaction temperatures when reaching 200 DEG C, be rapidly injected sulphur source, maintain temperature and timing stops heating after ten minutes,
Remove reaction set, when temperature is cooled to 90 DEG C or less, turns off nitrogen valve.Reactant in three-neck flask is moved into centrifuge tube,
It is centrifuged 3 minutes with 6000 revs/min of revolving speed.Final product is repeatedly collected after centrifugation.Sb2S3The yield of nanometer rods is 0.025g.
Embodiment 3
(1) preparation of sulphur source
The high purity sulphur (s, 99.99%) for weighing 0.16g is placed in three-neck flask, and the oleyl amine (C of 5mL is added18H37N, content 80-
90%).It on the device that three-neck flask access is put up rapidly, opens vacuum pump and vacuumizes, open heating mantle and heated and stirred
Mix (magnetic agitation), etc. reaction temperatures when reaching 60 DEG C, open nitrogen valve and be filled with nitrogen into three-neck flask, then take out again true
Sky so replaces the subsequent temperature of continuing rising of nitrogen three times.When temperature reaches 90 DEG C, and when being evacuated to liquid surface and there is no bubble,
Nitrogen valve is opened, vacuum pump is turned off.Until the sulphur in three-neck flask all dissolves, stop reaction.50 DEG C are cooled to temperature
When, three-neck flask is removed, the sulphur source prepared is contained spare in bottle.
(2) Sb2S3Preparation
Weigh 0.456g antimony trichloride (SbCl3, 99.9%) and it is placed in three-neck flask, the octadecylene (C of 4 mL is added18H36, content
> 90.0 %) and 5 mL oleyl amine (C18H37N, content 80-90%).On the device that three-neck flask access is put up rapidly, open
Vacuum pump vacuumizes, and opens heating mantle and carries out heating and stirring (magnetic agitation), etc. reaction temperatures when reaching 80 DEG C, beat
It opens nitrogen valve and is filled with nitrogen into three-neck flask, then vacuumize again, so replace the subsequent temperature of continuing rising of nitrogen three times.Work as temperature
When reaching 100 DEG C, nitrogen valve is opened, vacuum pump is turned off.Continue to heat up, extracts 0.7mL with medical syringe at this time and make in advance
The sulphur source got ready, etc. reaction temperatures when reaching 200 DEG C, be rapidly injected sulphur source, maintain temperature and timing stops heating after twenty minutes,
Remove reaction set, when temperature is cooled to 90 DEG C or less, turns off nitrogen valve.Reactant in three-neck flask is moved into centrifuge tube,
It is centrifuged 3 minutes with 6000 revs/min of revolving speed.Final product is repeatedly collected after centrifugation.Sb2S3The yield of nanometer rods is 0.032g.
Claims (6)
1. a kind of Sb2S3The synthetic method of nanometer rods, characterized in that the following steps are included:
A, high purity sulphur and oleyl amine are added sequentially in reaction flask, open vacuum pump and vacuumize, then heats while stirring；
B, it when temperature reaches 60 DEG C, opens nitrogen valve and is filled with nitrogen into reaction flask, vacuumize again later, so replace three
The secondary subsequent temperature of continuing rising of nitrogen；
C, when temperature reaches 90 DEG C, being evacuated to liquid surface does not have bubble, then opens nitrogen valve, turns off vacuum pump；
Until stop agitating and heating after the high purity sulphur in reaction flask all dissolves, sulphur source is prepared after cooling, it is spare；
D, by SbCl3It is added in reaction flask, octadecylene and oleyl amine is then added, open vacuum pump and vacuumize, then add while stirring
Heat；
E, it when temperature reaches 60 ~ 80 DEG C, opens nitrogen valve and is filled with nitrogen into reaction flask, vacuumize, so set again later
Change the subsequent temperature of continuing rising of nitrogen three times；
F, when temperature reaches 90 ~ 100 DEG C, nitrogen valve is opened, turns off vacuum pump, when being continuously heating to 200 ~ 300 DEG C, quickly
Inject previously prepared sulphur source, then react 5 ~ stop agitating and heating after twenty minutes, when temperature is cooled to 90 DEG C or less, turn off
Nitrogen valve obtains reaction solution, and reaction solution is after being centrifuged up to Sb2S3Nanometer rods.
2. Sb according to claim 12S3The synthetic method of nanometer rods, characterized in that in step a, the high purity sulphur and oil
The amount ratio of amine is 0.16g: 3 ~ 5mL.
3. Sb according to claim 12S3The synthetic method of nanometer rods, characterized in that in step a, the high purity sulphur is pure
The elemental sulfur of degree >=99.99%.
4. Sb according to claim 12S3The synthetic method of nanometer rods, characterized in that in step d, the SbCl3: 18
Alkene: g: 3 ~ 4mL: 4 ~ 5 mL of oleyl amine=0.0456.
5. Sb according to claim 12S3The synthetic method of nanometer rods, characterized in that in step d, the SbCl3It is pure
Degree >=99.9%.
6. Sb according to claim 12S3The synthetic method of nanometer rods, characterized in that in step f, centrifugal condition be with
5000 ~ 8000 revs/min of revolving speed is centrifuged 1 ~ 5 minute.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110844936A (en) * | 2019-12-10 | 2020-02-28 | 中国科学院合肥物质科学研究院 | Preparation method of antimony trisulfide nanorod array and solar cell based on antimony trisulfide nanorod array |
| CN112079383A (en) * | 2020-09-24 | 2020-12-15 | 昆明理工大学 | Method for preparing antimony sulfide powder through flash heat treatment |
| CN112342623A (en) * | 2020-10-20 | 2021-02-09 | 山东大学 | Nano-rod-shaped antimony trisulfide electromagnetic wave absorption material, absorber, preparation method and application |
| CN113651359A (en) * | 2021-03-31 | 2021-11-16 | 江苏大学 | Preparation method and application of antimony sulfide nanorod |
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Cited By (4)
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| CN110844936A (en) * | 2019-12-10 | 2020-02-28 | 中国科学院合肥物质科学研究院 | Preparation method of antimony trisulfide nanorod array and solar cell based on antimony trisulfide nanorod array |
| CN112079383A (en) * | 2020-09-24 | 2020-12-15 | 昆明理工大学 | Method for preparing antimony sulfide powder through flash heat treatment |
| CN112342623A (en) * | 2020-10-20 | 2021-02-09 | 山东大学 | Nano-rod-shaped antimony trisulfide electromagnetic wave absorption material, absorber, preparation method and application |
| CN113651359A (en) * | 2021-03-31 | 2021-11-16 | 江苏大学 | Preparation method and application of antimony sulfide nanorod |
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Application publication date: 20191011 |