CN105293570A - Method for preparing mesoporous tin antimony oxide material through ultrasonic wave assistant supercritical carbon dioxide method - Google Patents

Method for preparing mesoporous tin antimony oxide material through ultrasonic wave assistant supercritical carbon dioxide method Download PDF

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Publication number
CN105293570A
CN105293570A CN201510667707.2A CN201510667707A CN105293570A CN 105293570 A CN105293570 A CN 105293570A CN 201510667707 A CN201510667707 A CN 201510667707A CN 105293570 A CN105293570 A CN 105293570A
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pressure
ultrasonic wave
supercritical
carbon dioxide
sbcl
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CN105293570B (en
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何丹农
冉伟
张春明
王艳丽
徐少洪
陈超
金彩虹
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Yufengnanuo Technology (Shanghai) Co., Ltd
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Shanghai Na Xu Industrial Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides a method for utilizing ultrasonic wave assistant supercritical carbon dioxide for preparing mesoporous tin antimony oxide powder. According to the method, a certain amount of SnC14.5H2O, a certain amount of SbC13, ammonia water and surfactant are weighed accurately according to the formula, added into a certain amount of distilled water, stirred to be dissolved fully, and prepared into a solution; the solution is placed into a supercritical reaction kettle, a carbon dioxide steel cylinder is opened, and carbon dioxide gas is cooled into liquid through a refrigerator, is pressurized through a high-pressure pump and then enters the reaction kettle; an ultrasonic device is started, certain pressure and temperature are controlled, and the pressure is kept for a certain period of time; a pressure relief opening is opened to enable the pressure in the supercritical reaction kettle to fall to normal pressure to obtain precursor powder; the collected powder is calcinated at the temperature of 500 DEG C-800 DEG C, so that the mesoporous tin antimony oxide powder is obtained. Toxic organic solvent is not used in the preparation process, and therefore pollution to environment is avoided; the prepared tin antimony oxide powder has large specific surface area and has excellent heat insulating, conducting and static resisting performance, the process is simple, and cost is low.

Description

Ultrasonic wave added supercritical carbon dioxide process prepares the method for mesoporous tin oxide antimony material
Technical field
The invention belongs to functional materials preparation field, be specifically related to a kind of method utilizing ultrasonic wave added supercritical co to prepare mesoporous tin oxide antimony powder body.
Technical background
Stannic oxide nano powder has very high specific surface area and excellent electroconductibility, be widely used in the aspects such as electrical contact material, sheet resistance, transparency electrode and gas sensor and there is excellent conductivity and optical property, be widely used in the fields such as flat-panel monitor, solar cell, electrochromism function film, infrared remote sensing.Tin antimony oxide nano-powder is widely used in the aspects such as coating, chemical fibre, polymeric membrane, papermaking, packaging and material of construction as antistatic material, larger superiority is demonstrated compared with other antistatic materials (as graphite, tensio-active agent, metal powder), main manifestations is have good electroconductibility and light-coloured transparent, good weathering resistance and stability and particle nanometer, multifunctionality etc., at present, the method preparing tin antimony oxide nano-powder mainly contains chemical coprecipitation, sol-gel method, hydrothermal method etc.
Mesoporous material refers to the polyporous materials of aperture between 2-50nm.Mesoporous material has the features such as high specific surface area, regular pore passage structure, narrow pore size distribution, pore size continuously adjustabe, the function of material can be improved further, mesoporous tin oxide antimony powder body material due to the structure of its uniqueness will heat insulation, the field such as antistatic plays larger effect.
Supercutical fluid is the fluid that temperature and pressure are all in more than stagnation point, it has liquid property and gas property concurrently, its density is close with liquid, viscosity and velocity of diffusion and gas close, never can be dissolved into dissolving to a certain degree to the solvability of material, this makes supercritical fluid technology have great operability.Ultrasonic technique, because it is simple to operate, be easy to control, efficiency advantages of higher, is widely used in the preparation of aided nano material, and has achieved good effect.The preparation of ultrasonic assistant nano material can refinement nanoparticle, promotes nanoparticle transformation of crystal, improves some property of nano material.The technology utilizing ultrasonic wave added supercritical co to prepare nano particle is introduced in the preparation of mesoporous tin oxide antimony material by the present invention, use two component tensio-active agent both to control granular size simultaneously, the structure of control punch again, possesses skills and the novelty applied and creativeness.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of method that ultrasonic wave added supercritical carbon dioxide fluid prepares mesoporous tin oxide antimony material.
A method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co, it is characterized in that, concrete steps are as follows:
(1) stannic chloride pentahydrate SnCl is accurately taken according to formula 4.5H 2o, butter of antimony SbCl 3, ammoniacal liquor and two component tensio-active agent, added in distilled water, stir and make it fully dissolve and be prepared into solution; Wherein, in two component tensio-active agent, the mass ratio of polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer: BYK180 is 1:1, SnCl 4.5H 2o:SbCl 3mass ratio be 10:0.3-1, two component tensio-active agent: (SnCl 4.5H 2o+SbCl 3) mass ratio be 0.5-3:100;
(2) inserted in supercritical reaction still by the mixing solutions of above-mentioned steps (1), open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Open Vltrasonic device, control certain pressure and temperature, and pressurize certain hour;
(3) open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, obtain presoma powder;
(4) by collect powder at 500-800 DEG C of temperature lower calcination, be mesoporous tin oxide antimony powder of the present invention end.
Described ammoniacal liquor is 6mol/L, with ammoniacal liquor, the pH of solution is transferred to 10.
Described reactor pressure is 10-40MPa, and temperature is 323-383K, and the dwell time is 60-120 minute.
Described ultrasonic power is 150W.
Described distilled water consumption is SnCl 4.5H 2o and SbCl 3the 1%-50% of total mass.；
Described calcining temperature is 500-800 DEG C.
SnCl of the present invention 4.5H 2o and SbCl 3mass ratio be between 10:1-10:0.3;
The total mass of two kinds of tensio-active agents of the present invention is SnCl 4.5H 2o and SbCl 3total mass 0.5%-3% between, and the mass ratio of two kinds of tensio-active agents is 1:1;
Pressure of the present invention is 10MPa-40MPa;
Time of the present invention is between 60min-120min;
The tin-antiomony oxide nano material adopting the method for the invention to prepare has meso-hole structure, and specific surface area is comparatively large, greatly improves the function of tin-antiomony oxide, extends potential using value.
Accompanying drawing explanation
Fig. 1 is the TEM photo of embodiment one mesoporous tin oxide antimony.
Embodiment
Further illustrate the present invention below by embodiment, instead of limit the scope of the invention.
Embodiment 1:
A certain amount of SnCl is accurately taken according to formula 4.5H 2o, SbCl 3and tensio-active agent (SnCl 4.5H 2o and SbCl 3mass ratio be 10:0.3, the quality of tensio-active agent polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer is SnCl 4.5H 2o and SbCl 3total mass 0.25%, surfactant B YK180 quality be SnCl 4.5H 2o and SbCl 3total mass 0.25%), added in a certain amount of distilled water that (consumption of distilled water is SnCl 4.5H 2o and SbCl 3total mass 10%), be 10 with ammoniacal liquor by pH regulator, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Ultrasonic power controls at 50W, controls certain pressure (10Pa) and temperature (323K), and pressurize certain hour (60min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, can obtain presoma, this persursor material is calcined 4h at 500 DEG C and obtains final product, Fig. 1 is the TEM photo of embodiment one mesoporous tin oxide antimony.
Embodiment 2:
A certain amount of SnCl is accurately taken according to formula 4.5H 2o, SbCl 3and tensio-active agent (SnCl 4.5H 2o and SbCl 3mass ratio be 10:0.5, the quality of tensio-active agent polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer is SnCl 4.5H 2o and SbCl 3total mass 0.5%, surfactant B YK180 quality be SnCl 4.5H 2o and SbCl 3total mass 0.5%), added in a certain amount of distilled water that (consumption of distilled water is SnCl 4.5H 2o and SbCl 3total mass 10%), be 10 with ammoniacal liquor by pH regulator, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Ultrasonic power controls at 50W, controls certain pressure (20Pa) and temperature (353K), and pressurize certain hour (80min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, can presoma be obtained, this persursor material is calcined 4h at 600 DEG C and obtains final product.
Embodiment 3:
A certain amount of SnCl is accurately taken according to formula 4.5H 2o, SbCl 3and tensio-active agent (SnCl 4.5H 2o and SbCl 3mass ratio be 10:0.7, the quality of tensio-active agent polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer is SnCl 4.5H 2o and SbCl 3total mass 1%, surfactant B YK180 quality be SnCl 4.5H 2o and SbCl 3total mass 1%), added in a certain amount of distilled water that (consumption of distilled water is SnCl 4.5H 2o and SbCl 3total mass 10%), be 10 with ammoniacal liquor by pH regulator, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Ultrasonic power controls at 50W, controls certain pressure (30MPa) and temperature (370K), and pressurize certain hour (100min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, can presoma be obtained, this persursor material is calcined 4h at 700 DEG C and obtains final product.
Embodiment 4:
A certain amount of SnCl is accurately taken according to formula 4.5H 2o, SbCl 3and tensio-active agent (SnCl 4.5H 2o and SbCl 3mass ratio be 10:1, the quality of tensio-active agent polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer is SnCl 4.5H 2o and SbCl 3total mass 1.5%, surfactant B YK180 quality be SnCl 4.5H 2o and SbCl 3total mass 1.5%), added in a certain amount of distilled water that (consumption of distilled water is SnCl 4.5H 2o and SbCl 3total mass 10%), be 10 with ammoniacal liquor by pH regulator, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Ultrasonic power controls at 50W, controls certain pressure (40MPa) and temperature (383K), and pressurize certain hour (120min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, can presoma be obtained, this persursor material is calcined 4h at 800 DEG C and obtains final product.

Claims (6)

1. a method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co, it is characterized in that, concrete steps are as follows:
(1) stannic chloride pentahydrate SnCl is accurately taken according to formula 4.5H 2o, butter of antimony SbCl 3, ammoniacal liquor and two component tensio-active agent, added in distilled water, stir and make it fully dissolve and be prepared into solution; Wherein, in two component tensio-active agent, the mass ratio of polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer: BYK180 is 1:1, SnCl 4.5H 2o:SbCl 3mass ratio be 10:0.3-1, two component tensio-active agent: (SnCl 4.5H 2o+SbCl 3) mass ratio be 0.5-3:100;
(2) inserted in supercritical reaction still by the mixing solutions of above-mentioned steps (1), open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor by high-pressure pump after being pressurizeed;
Open Vltrasonic device, control certain pressure and temperature, and pressurize certain hour;
(3) open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, obtain presoma powder;
(4) by collect powder at 500-800 DEG C of temperature lower calcination, be mesoporous tin oxide antimony powder of the present invention end.
2. the method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co according to claim 1, it is characterized in that, described ammoniacal liquor is 6mol/L, with ammoniacal liquor, the pH of solution is transferred to 10.
3. the method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co according to claim 1, it is characterized in that, described reactor pressure is 10-40MPa, and temperature is 323-383K, and the dwell time is 60-120 minute.
4. the method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co according to claim 1, it is characterized in that, described ultrasonic power is 150W.
5. the method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co according to claim 1, it is characterized in that, described distilled water consumption is SnCl 4.5H 2o and SbCl 3the 1%-50% of total mass.
6. the method for mesoporous tin oxide antimony material prepared by ultrasonic wave added supercritical co according to claim 1, it is characterized in that, described calcining temperature is 500-800 DEG C.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112335681A (en) * 2020-11-08 2021-02-09 上海聚治新材料科技有限公司 Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent
CN116477662A (en) * 2023-04-27 2023-07-25 深圳市汇投智控科技有限公司 Gas-sensitive material, sensor and preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2025915A (en) * 1978-07-12 1980-01-30 Matsushita Electric Ind Co Ltd Process of preparing conductive tin dioxide powder
CN1597520A (en) * 2004-09-27 2005-03-23 大连理工大学 Method of preparing nanometer magnesium oxide using uniform precipitation-supercritical carbon dioxide drying method
CN102010197A (en) * 2010-09-29 2011-04-13 大连交通大学 Method for preparing antimony-doped tin oxide (ATO) nano powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2025915A (en) * 1978-07-12 1980-01-30 Matsushita Electric Ind Co Ltd Process of preparing conductive tin dioxide powder
CN1597520A (en) * 2004-09-27 2005-03-23 大连理工大学 Method of preparing nanometer magnesium oxide using uniform precipitation-supercritical carbon dioxide drying method
CN102010197A (en) * 2010-09-29 2011-04-13 大连交通大学 Method for preparing antimony-doped tin oxide (ATO) nano powder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112335681A (en) * 2020-11-08 2021-02-09 上海聚治新材料科技有限公司 Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent
CN112335681B (en) * 2020-11-08 2022-07-26 上海聚治新材料科技有限公司 Preparation method of layered unsaturated load silver-zinc-copper composite antibacterial and antiviral agent
CN116477662A (en) * 2023-04-27 2023-07-25 深圳市汇投智控科技有限公司 Gas-sensitive material, sensor and preparation method

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