CN101041463A - Method for preparation of multifarious Sb2O3 nanostructure - Google Patents

Method for preparation of multifarious Sb2O3 nanostructure Download PDF

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CN101041463A
CN101041463A CN 200710051648 CN200710051648A CN101041463A CN 101041463 A CN101041463 A CN 101041463A CN 200710051648 CN200710051648 CN 200710051648 CN 200710051648 A CN200710051648 A CN 200710051648A CN 101041463 A CN101041463 A CN 101041463A
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nanometer
nanostructured
reaction
oxygen
sheet
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CN100486899C (en
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黄在银
谭学才
柴春芳
唐世华
吴健
周泽广
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Guangxi University for Nationalities
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Guangxi University for Nationalities
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Abstract

The invention discloses a preparing method of multi-branched structure of Sb2O3, nanometer array, nanometer rod and nanometer slice, which comprises the following steps: making elemental carbon (graphite powder, activated char and carbon nanometer pipe) and nanometer ATO powder as raw material; setting Ar as carrier gas; adopting CVD method; leading into O2 of 1sccm till reaching design temperature; setting heating-up temperature at 1000-1200 deg.c, reacting time at 1-2.5 h and Ar flow rate at 30-70sccm; proceeding a series of reaction; getting the product.

Description

A kind ofly prepare multiple Sb 2O 3The method of nanostructured
Technical field
The present invention relates to a kind ofly take simple substance carbon as reducing agent, adopt chemical vapour deposition technique (CVD) high temperature reduction ATO nano particle to prepare multiple Sb 2O 3The method of nanostructured.
Background technology
Along with the develop rapidly of society, the densification of the densification of urban population, dwelling house and utilities buildings such as office building and commerce and trade, high stratification, the Hazard Factor of fire and occurrence frequency also increase thereupon in social life and the production field.The loss that causes of various countries' fire in recent years is in rising trend.In order to nip in the bud, western countries especially advanced industrial countries such as the U.S., Japan, West Europe are devoted to the development of Fire Retardant Industry one after another.The Fire Retardant Industry of China is started late, but obtains development to a certain degree over nearly 10 years.Sb 2O 3Be a kind of additive flame retardant, be widely used as various plastic flame fillers, also can be used as the catalyst of the fire retardant of canvas, paper, paint, coating etc. and petrochemical industry, synthetic fibers etc.China's antimony reserves occupy first place, the world, and the outlet of a large amount of antimony oxygen or antimony slab is arranged every year.But China's antimony oxygen production technology is more backward, the product of producing does not satisfy the demand that becomes more meticulous (ultrapure, Gao Bai, granularity is little and be evenly distributed) of industry such as domestic weaving, these production departments have to allow Western industrialized economy earn a large amount of secondary economic benefits by with the Hesperian converted products of high price import.Therefore, change the backward production technology of China's antimony oxygen, research and develop the antimony oxygen product of ultra-fine high-purity high whiteness, social benefit and economic benefit are widely arranged.
Along with deepening continuously of research, people have developed a series of preparation Sb 2O 3The method of nanostructured, this wherein prepares in the majority with wet method, also have Using Gas Evaporation Method, plasma method etc.Yi Lisong etc. are with SbCl 3, concentrated hydrochloric acid, ethanol and benzene etc. are raw material, have prepared Sb through processes such as stirring, precipitation, decant dryings 2O 3Nano particle [ultra-fine Sb 2O 3Synthetic and the flame-retarding characteristic of micro mist, Zhongshan University's journal collection of essay, 1998 (4): 102-106]; Sun Qiuxiang, carries out products therefrom to obtain Sb after centrifugation, washing, the drying take antimonous sulfate, sulfuric acid, ammoniacal liquor, sodium chloride and sodium phosphate trimer as raw material after the series of complex reaction 2O 3Nanocrystalline [the standby nanometer Sb of 3 in Inert Thick Salt Media legal system 2O 3,, chemistry and bioengineering, 2006,23 (1): 30-32]; Zhong Yongke etc. are with SbCl 3, TEA, absolute ethyl alcohol, NaOH be raw material, with SbCl 3Ethanol solution stir the lower (SbCl in the ethanol solution that contains NaOH (3.0mol/L), TEA that joins 3: NaOH: TEA=1: 3.0: 2.0, mol ratio), will obtain Sb after the white depositions ageing that obtain, centrifugation, the drying 2O 3Nanocrystalline powder [the nanocrystalline preparation of oblique side's antimony oxide, plastic additive, 2002, (6): 19-22]; What book Son is take metallic antimony as raw material, and plasma generator, stibium trioxide stove are that capital equipment adopts plasma method to prepare Sb 2O 3[plasma is produced Sb to nano-powder 2O 3Device and technology, nonferrous metallurgy, 2002,2 (1): 26-29]; Deng etc. are take antimony powder, polyvinylpyrrolidone, ethylenediamine as raw material, and stirring reaction 5h under the room temperature will obtain a large amount of Sb after the white precipitate filtration that obtain, washing, the drying 2O 3Nano wire [A Simple Solution Route toSingle-Crystalline Sb 2O 3Nanowires with Rectangular Cross Sections, J.Phys.Chem.B, 2006,110:18225-18230]; Ye etc. are with Sb 2S 3Be raw material, 500 ℃ of lower heating 90min obtain Sb in tube furnace 2O 3Nanotube [A facile vapor-solid synthetic route to Sb2O3 fibrils and tubules, Chem.Phys.Lett., 2002,363:34-38]; Zhang etc. are with SbCl 3, CTAB, ethanol, NaBH 4Be raw material, adopt hydro-thermal method to prepare Sb by controlling certain temperature 2O 3[the Shape-controlled growthof one-dimensional Sb such as nanobelt, nanometer rods, nanotube, nanofiber 2O 3Nanomaterials, Nanotechnology, 2004,15:762-765].
Existing Sb 2O 3Nanostructured preparation method's deficiency:
1. medicine is various, the operating process complexity.
2. energy consumption height, the production cost height.
Summary of the invention
The present invention adopts chemical vapour deposition technique (CVD) preparation Sb 2O 3The method of nanostructured take simple substance carbon and ATO powder as raw material, is passing into oxygen under certain reaction condition, simple substance carbon passes through series reaction with the ATO powder, has generated Sb in the crystallizing field growth substrate 2O 3Apparatus derivatorius, nanometer stick array, nanometer rods and nanometer sheet.
The preparation method is as follows:
1. simple substance carbon and nano ATO are mixed so that mass ratio 1: 1～6 scopes are interior, grind for some time.
2. the ceramic boat that the mixed powder after an amount of grinding will be housed places the vitrified pipe middle part, and the Si sheet that is of a size of 1 * 1cm places the carrier gas downstream, apart from the about 13cm of powder mix place.
3. sealing vitrified pipe, feeding flow velocity is the high-purity Ar of 200sccm, time 2h is to drain entrap bubble in the vitrified pipe.
4. flow velocity 50～100sccm of maintenance Ar starts pipe examination stove and begins heating, and temperature of reaction is 1000～1200 ℃, the feeding flow velocity is the oxygen of 1sccm to system, reaction times 1～2h.
5. question response finishes, and system naturally cools to room temperature, takes out the Si sheet, and it is to be measured to collect sample.
The invention provides the multiple Sb of preparation 2O 3The method of nanostructured has following advantage:
1. required raw material types is few, and technical process is simple, and is easy to operate.
2. product purity height, crystal property is good.
3. the product pattern is various.
4. clean environment firendly.
Description of drawings
Fig. 1 (a) is Sb of the present invention 2O 3The EDS spectrogram of apparatus derivatorius;
Fig. 1 (b) is Sb of the present invention 2O 3The wide journey scanning of the XPS of apparatus derivatorius spectrogram;
Fig. 1 (c) is Sb of the present invention 2O 3The XPS core level spectrogram of apparatus derivatorius;
Fig. 2 is Sb of the present invention 2O 3The SEM photo figure of apparatus derivatorius comprises (a), (b), (c), (d) four pictures among the figure;
Fig. 3 (a) is Sb of the present invention 2O 3The EDS spectrogram of nanometer stick array;
Fig. 3 (b) is Sb of the present invention 2O 3The wide journey scanning of the XPS of nanometer stick array spectrogram;
Fig. 3 (c) is Sb of the present invention 2O 3The XPS core level spectrogram of nanometer stick array;
Fig. 4 is Sb of the present invention 2O 3The SEM photo figure of nanometer stick array comprises (a), (b), (c), (d) four pictures among the figure;
Fig. 5 (a) is Sb of the present invention 2O 3The EDS spectrogram of nanometer rods;
Fig. 5 (b) is Sb of the present invention 2O 3The wide journey scanning of the XPS of nanometer rods spectrogram;
Fig. 5 (c) is Sb of the present invention 2O 3The XPS core level spectrogram of nanometer rods;
Fig. 6 is Sb of the present invention 2O 3The SEM photo figure of nanometer rods comprises (a), (b) two pictures among the figure;
Fig. 7 (a) is Sb of the present invention 2O 3The EDS spectrogram of nanometer sheet;
Fig. 7 (b) is Sb of the present invention 2O 3The wide journey scanning of the XPS of nanometer sheet spectrogram;
Fig. 7 (c) is Sb of the present invention 2O 3The XPS core level spectrogram of nanometer sheet;
Fig. 8 is Sb of the present invention 2O 3The SEM photo figure of nanometer sheet.
Embodiment
The present invention reaches the O that passes into simple substance carbon (can be graphite powder, also can be active carbon or CNT) and nano ATO when reaching design temperature 2, be that 1000～1200 ℃, reaction time are that 1～2h and Ar are carrier gas in heating-up temperature, flow velocity is under 50～100sccm condition, through series reaction, has generated Sb 2O 3Apparatus derivatorius, nanometer stick array, nanometer rods and nanometer sheet.
The CVD method is the present comparatively preparation method of a kind of nanostructure commonly used.It utilizes material to evaporate at a certain temperature, react, and by carrier gas with the vapor transport that generates to the deposition region, because the different nanostructureds that deposit the generation different-shape of degree of supersaturation and deposition substrate.
Carbon reduction method is CVD method a kind of method commonly used, its primary process is: simple substance carbon can be gac, also can be that the reaction of graphite or carbon nanotube and oxide compound generates oxide gas at a low price or simple substance carbon regenerates the expection oxide compound with oxygen reaction, and under the effect of carrier gas on the Si sheet the certain nanostructure of deposition generation.This method equipment is simple, operational safety, and also synthetic product is pure.Mechanism of the present invention is as described below:
SnO 2+C→Sn+CO (1)
Sb 2O 4+C→Sb+CO (2)
Sb+O 2→Sb 2O 3 (3)
Grow (2h) owing to feed the time of Ar before the heating, flow velocity also higher (200sccm), therefore, Sn when system is heated to certain temperature in the raw material and the oxide compound of Sb are Sn and Sb simple substance by graphite reduction fully, shown in reaction (1) and (2).The fusing point of Sn (232 ℃) is far below the fusing point (630.7 ℃) of Sb, and therefore, simple substance Sn volatilizees prior to Sb, and is transported to the vitrified pipe downstream or is directly discharged reactive system by Ar.When system is warming up to the temperature of setting, in system, pass into a certain amount of oxygen, under the high temperature, simple substance Sb and oxygen reaction generate gaseous state Sb 2O 3(reaction (3)), and be transported to crystallizing field by Ar, generate different Sb in not isotopic Si sheet deposition 2O 3Nanostructured.
The present invention is raw materials used:
The nano ATO powder, Graphite Powder 99, gac, carbon nanotube, high-purity Ar, high purity oxygen gas.
The used high temperature pipe examination of the present invention stove model: the GGL-5 high temperature pipe examination stove that Hefei Kai Er nanotechnology limited liability company produces.
The used vitrified pipe specification of the present invention: long 75cm, internal diameter 2cm, wall thickness 0.3cm.
The used ceramic boat specification of the present invention: long 8cm, dark 1cm, wall thickness 0.2cm.
The used Si sheet of the present invention specification: 1 * 1cm.
The various Sb of the present invention 2O 3Nanostructured preparation method is as follows:
Embodiment 1.Sb 2O 3The preparation of apparatus derivatorius
Be that 6: 1 ATO nano particle and graphite powder mixture grind and be placed in the ceramic boat half an hour with the 3g mass ratio, and this ceramic boat is placed the earthenware middle part, the Si sheet places the downstream apart from mixed powder original position 13cm place.Earlier in system, pass into the high-purity Ar 2h that flow velocity is 200sccm before the heating, to drain intrasystem air; Then with the Ar velocity of flow adjust to 100sccm, start tube furnace, when the system that treats is warming up to rapidly 1200 ℃ (about 10min), in system, pass into the oxygen that flow velocity is 1sccm, system begins cooling behind the 2h, keep the flow velocity of Ar constant this moment, closes oxygen, and the system for the treatment of takes out the Si sheet after naturally cooling to room temperature.
Investigate its composition with electronic spectrum (EDS) and x-ray photoelectron spectroscopy (XPS), (FE-SEM) observes its pattern with field emission scanning electron microscope.EDS and XPS spectrum figure show that product is Sb 2O 3, as shown in Figure 1.Find that through scanning electron microscopic observation the deposit on the Si sheet is Sb 2O 3Apparatus derivatorius Figure 2 shows that Sb 2O 3The SEM photo of apparatus derivatorius.
Embodiment 2.Sb 2O 3The preparation of nanometer stick array
Be that 4: 1 ATO nano particle and activated carbon mixture are ground and be placed in the ceramic boat half an hour with the 3g mass ratio, and this ceramic boat is placed the earthenware middle part, the Si sheet places the downstream apart from medicine original position 13cm place.Earlier in system, pass into the high-purity Ar 2h that flow velocity is 200sccm before the heating, to drain intrasystem air; Then with the Ar velocity of flow adjust to 80sccm, start tube furnace, when the system that treats is warming up to rapidly 1150 ℃ (about 10min), in system, pass into the oxygen that flow velocity is 1sccm, 1.5h rear system begins cooling, keep the flow velocity of Ar constant this moment, closes oxygen, and the system for the treatment of takes out the Si sheet after naturally cooling to room temperature.
Investigate its composition with electronic spectrum (EDS) and x-ray photoelectron spectroscopy (XPS), (FE-SEM) observes its pattern with field emission scanning electron microscope.EDS and XPS spectrum figure show that product is Sb 2O 3, as shown in Figure 3.Find that through scanning electron microscopic observation the deposit on the Si sheet is nanometer stick array, Figure 4 shows that Sb 2O 3The SEM photo of nanometer stick array.
Embodiment 3.Sb 2O 3The preparation of nanometer rods
Be that 2: 1 ATO nano particle and activated carbon mixture are ground and be placed in the ceramic boat half an hour with the 3g mass ratio, and this ceramic boat is placed the earthenware middle part, the Si sheet places the downstream apart from medicine original position 13cm place.Earlier in system, pass into the high-purity Ar 2h that flow velocity is 200sccm before the heating, to drain intrasystem air; Then with the Ar velocity of flow adjust to 50sccm, start tube furnace, when the system that treats is warming up to rapidly 1150 ℃ (about 10min), in system, pass into the oxygen that flow velocity is 1sccm, system begins cooling behind the 1h, keep the flow velocity of Ar constant this moment, closes oxygen, and the system for the treatment of takes out the Si sheet after naturally cooling to room temperature.
Investigate its composition with electronic spectrum (EDS) and x-ray photoelectron spectroscopy (XPS), (FE-SEM) observes its pattern with field emission scanning electron microscope.EDS and XPS spectrum figure show that product is Sb 2O 3, as shown in Figure 5.Find that through scanning electron microscopic observation the deposit on the Si sheet is nanometer rods, Figure 6 shows that Sb 2O 3The SEM photo of nanometer rods.
Embodiment 4.Sb 2O 3The preparation of nanometer sheet
Be that 1: 1 ATO nano particle and CNT mixture grind and be placed in the ceramic boat half an hour with the 3g mass ratio, and this ceramic boat is placed the earthenware middle part, the Si sheet places the downstream apart from medicine original position 13cm place.Earlier in system, pass into the high-purity Ar 2h that flow velocity is 200sccm before the heating, to drain intrasystem air; Then with the Ar velocity of flow adjust to 50sccm, start tube furnace, when the system that treats is warming up to rapidly 1100 ℃ (about 7min), in system, pass into the oxygen that flow velocity is 1sccm, system begins cooling behind the 1h, keep the flow velocity of Ar constant this moment, closes oxygen, and the system for the treatment of takes out the Si sheet after naturally cooling to room temperature.
Investigate its composition with electronic spectrum (EDS) and x-ray photoelectron spectroscopy (XPS), (FE-SEM) observes its pattern with field emission scanning electron microscope.EDS and XPS spectrum figure show that product is Sb 2O 3, as shown in Figure 7.Find that through scanning electron microscopic observation the deposit on the Si sheet is nanometer sheet, Figure 8 shows that Sb 2O 3The SEM photo of nanometer sheet.

Claims (4)

1. one kind prepares multiple Sb 2O 3The method of nanostructured, be to adopt chemical vapour deposition technique (CVD), it is characterized in that take simple substance carbon and nano ATO powder as raw material, take Ar as carrier gas, in high-temperature pipe examination stove under certain reaction condition with oxygen reaction, prepare multiple Sb in the crystallizing field growth substrate 2O 3The nanostructured product.
2. the multiple Sb of preparation according to claim 1 2O 3The method of nanostructured, the mass ratio that it is characterized in that simple substance carbon and ATO is 1: 1～6, reaction condition is: the Ar 2h that passes into 200sccm before heating, 1000～1200 ℃ of reaction temperatures, reaction time 1～2h, argon gas flow velocity are 50～100sccm, oxygen gas flow rate 1sccm.
3. the multiple Sb of preparation according to claim 1 2O 3The method of nanostructured is characterized in that the Sb that generates 2O 3Nanostructured product shape cap has Sb 2O 3Apparatus derivatorius, nanometer stick array, nanometer rods and nanometer sheet.
4. the multiple Sb of preparation according to claim 1 2O 3The method of nanostructured, the growth substrate that it is characterized in that crystallizing field are the Si sheets.
CNB2007100516481A 2007-03-09 2007-03-09 Method for preparation of multifarious Sb2O3 nanostructure Expired - Fee Related CN100486899C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466726A (en) * 2013-09-27 2013-12-25 夏国栋 Method for directly synthesizing high conductivity nickel sulfide two-dimension nanosheet array in large scale
CN107123552A (en) * 2017-05-08 2017-09-01 华北电力大学（保定） A kind of antimony based composites, its preparation method and its application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103466726A (en) * 2013-09-27 2013-12-25 夏国栋 Method for directly synthesizing high conductivity nickel sulfide two-dimension nanosheet array in large scale
CN107123552A (en) * 2017-05-08 2017-09-01 华北电力大学（保定） A kind of antimony based composites, its preparation method and its application

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