CN101671050B - Method for preparing nano SnO2 material by utilizing exothermal reaction - Google Patents

Method for preparing nano SnO2 material by utilizing exothermal reaction Download PDF

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CN101671050B
CN101671050B CN2009102722834A CN200910272283A CN101671050B CN 101671050 B CN101671050 B CN 101671050B CN 2009102722834 A CN2009102722834 A CN 2009102722834A CN 200910272283 A CN200910272283 A CN 200910272283A CN 101671050 B CN101671050 B CN 101671050B
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reaction
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sno
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CN101671050A (en
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张国栋
任正元
李玲
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Hubei Fortune Technology Co., Ltd.
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Wuhan University WHU
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Abstract

The invention relates to a method for preparing nano SnO2 material by utilizing exothermal reaction, which comprises the following steps: firstly, uniformly mixing the powder in mass percent: 10-35% of Al powder, 30-55% of Cu2O, 16-36% of Fe2O3, 2-15% of MnO2, 5-12% of SnO2, 0-2% of CaO and 1-3% of CaF2, and then putting the mixed powder in a reaction unit; secondly, using a magnesium ribbon to ignite pyrophoric powder so as to ignite the reaction powder; and finally, utilizing a gathering unit which is arranged above the reaction unit before the ignition to collect the nano SnO2 material. Through utilizing the invention to prepare nano stannic oxide, the process is simple, the circle is short, and the cost is low; the obtained SnO2 product is pure, the diameters of particles are uniform, and the generation efficiency of the product is high, thereby the invention can be easily used for industrialized production.

Description

Utilize thermopositive reaction to prepare nano SnO 2The method of material
Technical field
The invention belongs to the functional materials preparation field, relate in particular to and a kind ofly utilize thermopositive reaction to prepare nano SnO 2The method of material.
Background technology
In recent ten years, along with the high speed development of electronic science and technology, various electron devices are granular day by day.Simultaneously, for the various chemical substances that comprised in the air are carried out effective Detection ﹠ Controling, it is economical and practical, a kind of method fast and effectively that gas sensory detects.At present, the gas sensitive of studying both at home and abroad and using mainly contains Fe 2O 3, ZnO, ZnS, SnO 2, TiO 2, WO 3Deng, wherein with SnO 2Be main.SnO 2It is a kind of broad-spectrum semiconductor sensing modulator material, gas sensor with its preparation has the characteristics highly sensitive, that working temperature is low, is widely used in the detection and the forecast of various inflammable gass, industrial gaseous waste, environmental pollution gas and other various obnoxious flavoures.In addition, SnO 2Have the specific electroconductibility and the characteristic of infrared radiation reflecting; visible light had good permeability; have excellent chemical stability in the aqueous solution, it also has been widely used in fields such as piezoresistance, photoelectron device, liquid-crystal display, solar cell, transparency conductive electrode, anti-infrared detection protections.With SnO 2Be the moisture sensor of base preparation, also have been widely used in places such as improving indoor environment, goods and materials storage, precision instrument and equipment machine room and Library, the Art Museum, museum.
At present, preparation nano SnO 2Material has a lot of methods, and method commonly used has: room temperature mechanochemical method, the precipitator method, hydrothermal synthesis method, sol-gel method etc.But this several method all has the shortcoming of oneself: the room temperature mechanochemical method also can't be controlled preferably to speed of response; The product purity that the precipitator method obtain is lower, and particle diameter is bigger; The hydrothermal synthesis method experiment condition is comparatively complicated, needs to carry out in autoclave; Chinese patent CN19356666A discloses the method that a kind of sol-gel method prepares the stannic oxide nanometer material, this method is even with phospho-molybdic acid and stannic hydroxide powder mixes, add dehydrated alcohol furnishing pulpous state, 65-80 ℃ following constant temperature 4-10 hour, dry 2-6h calcines the nano tin dioxide material that obtains modification with retort furnace again; But this method need be used the phospho-molybdic acid modification, complex process, and need to use a large amount of ethanol, improve preparation cost and be unfavorable for suitability for industrialized production.Chinese patent CN101298338A discloses a kind of electronic-beam radiation synthesizing method of nanometer tin dioxide rod, this method can not use any catalyzer just can make the stannic oxide nanometer material at normal temperatures and pressures, yet, this method is to the equipment requirements height, simultaneously, need to consume a large amount of electric energy, be unfavorable for industrialization promotion.
Thermopositive reaction is the common reaction of chemical field, does not also have relevant report but use it for the preparation nano material.
Summary of the invention
Purpose of the present invention is exactly to prepare nano SnO in order to overcome existing method 2The weak point of material provides a kind of preparation nano SnO based on thermopositive reaction 2The method of material makes the nano SnO of preparation 2Not only purity is higher for material, size distribution is even, and good dispersity and nothing or light the reunion.
Realize that technical scheme of the present invention is: a kind ofly utilize thermopositive reaction to prepare nano SnO 2The method of material is characterized in that, comprises the steps:
(1) the massfraction ratio is respectively: Al powder 10-35%, Cu 2O 30-55%, Fe 2O 316-36%, MnO 22-15%, SnO 25-12%, CaO 0-2%, CaF 2The medicinal powder of 1-3% mixes, in the reaction unit of then mixed powder being packed into;
(2) light pyrophoric powders with magnesium rod and then ignite this reaction medicinal powder;
(3) collection device that has been placed on the reaction unit top before the utilization igniting is collected nano SnO 2Material;
The particle diameter of above-mentioned mixed powder is the 50-200 order;
Above-mentioned reaction unit is the crystal vessel that carries through hole;
The outside of above-mentioned collection device is the shell with high temperature steel preparation, and the inside of shell is made up of the grid of high temperature steel preparation, and it comprises upper die and lower die two portions, and counterdie is provided with aperture, and jack is used to insert magnesium rod.
The invention has the beneficial effects as follows: this contrive equipment is simple, experiment condition is gentle and its cost is low, technology is simple, does not need catalyzer, resultant purity is higher, size distribution evenly, good dispersity and nothing or light nano SnO of reuniting 2Material.
Description of drawings
Below in conjunction with accompanying drawing this invention is further specified.
Fig. 1 is the X-ray diffractogram of product of the present invention.
Fig. 2 is the scanning electron microscope diagram of product of the present invention.
Fig. 3 is the preparation nano SnO 2The instrument assembling section of material.
Fig. 4 is a nano SnO 2Material collection device counterdie vertical view.
Wherein, 1-patrix, 2-counterdie, 3-jack, 4-reaction unit.
Embodiment
The present invention is based on thermopositive reaction and prepares nano SnO 2Reaction unit is the crystal vessel that carries through hole, in the process of thermopositive reaction, thereby utilizes the metallic compound chemical reaction heat as thermal source preparation nano SnO 2Material.
The present invention realizes in the following way:
With Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Mix the medicinal powder of preparation feedback according to a certain percentage, with magnesium rod and pyrophoric powders this chemical reaction that ignites, wherein pyrophoric powders consists of 2g potassium permanganate and 1g sulphur powder.In this reaction process, Al is as reductive agent and Cu 2O, Fe 2O 3, MnO 2React and a spot of SnO Deng oxide powder 2Also participated in reaction.
2Al+3Cu 2O＝Al 2O 3+6Cu
2Al+Fe 2O 3＝Al 2O 3+2Fe
4Al+3MnO 2＝2Al 2O 3+3Mn
These reactions are thermopositive reaction.Redox reaction taking place rapidly after mixed powder is ignited, discharge a large amount of heats in reaction process, make resultant Cu, Fe, the Mn fusing of reaction, obtain superheated hybrid metal liquid, generates slag Al in reaction 2O 3-CaO-CaF 2Protection under, liquid metal temperature can reach more than 2000, and tindioxide distils at 1800～1900.Tindioxide quick cooled and solidified in uphill process generates particulate state, drops on the matrix of stainless steel grid, becomes the nucleus of next step crystal growth.The tindioxide molecular cluster that forms in reaction process is at the heterogeneous forming core of particle surface and be grown to serve as needed nano SnO gradually 2Material.In the reaction process, do not have the existence of catalyzer, a kind of method of new nano material preparation is provided.
The concrete preparation method of nano tin dioxide material is: take by weighing the Al powder of a certain amount of 50-200 purpose, Cu according to the ratio that configures 2O, Fe 2O 3, MnO 2, SnO 2, CaO and CaF 2, and with stirrer these medicinal powder are mixed.To dry by the thermopositive reaction mould that graphite is made with oxy-acetylene flame, remove the water vapour in the mould; Remove oxy-acetylene flame, the medicinal powder that mixes is packed into react in the mould, and will react the medicinal powder compacting, to aggravate the carrying out of this reaction.On the medicinal powder of compacting, evenly spread some pyrophoric powderss, then the Mg bar of scale removal is inserted on the pyrophoric powders as safety fuse, the Mg bar that ignites, this reaction is just carried out.Before the magnesium rod that ignites, the reaction mould above collection device is installed, and the reaction mould comprise patrix 1 and counterdie 2 two portions, counterdie is provided with jack 3, jack is used to insert magnesium rod, it is assembled shown in Fig. 3,4.Reaction finishes the back just can obtain needed nano SnO 2Material.
The prepared nano SnO of the present invention 2The feature of material can be tested with following method:
The 1X ray diffraction.This material is a nano SnO 2Material can provide the characteristic diffraction peak of tindioxide in X-ray diffraction spectrum, judge with this whether nano-stannic oxide generates.
2 scanning electronic microscope.Can be clearly seen that the shape characteristic of nano-stannic oxide by scanning electronic microscope, and can estimate the size of its diameter roughly.
Specific embodiment
The present invention is further described below in conjunction with embodiment, and the explanation of following examples will help to understand the present invention, but do not limit content of the present invention.
Embodiment 1
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 13: 55: 16 according to the massfraction ratio: 2: 12: 0.5: 1.5 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just mixed uniformly medicinal powder can be poured in the dewatered thermopositive reaction mould and with the medicinal powder compacting then.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the thermopositive reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.
The gained nano SnO 2The X-ray diffraction of material and scanning electronic microscope characterization result are seen Fig. 1 and Fig. 2.By Fig. 1 and Fig. 2 as can be seen: in the X-ray diffractogram of Fig. 1, the crystal face of strong diffraction peak is (110), according to SnO 2PDF card comparison know that it is SnO 2, from the diffraction peak position of X-ray diffraction as can be seen, the nano SnO of gained 2Material purity is very high, and to calculate its diameter according to the Scherrer formula be 53.70912nm; Fig. 2 is the picture of the scanning electronic microscope of this product, as can be seen from Figure 2 the nano SnO of gained of the present invention 2Material particle size is evenly distributed, good dispersity and nothing or light nano SnO of reuniting 2Material, Fig. 2 also further confirm nano SnO 2Product generates and its diameter is about 50nm.
Embodiment 2
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 20: 36: 22 according to the ratio of massfraction: 8: 12: 1: 1 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just can pour into mixed uniformly medicinal powder in the dewatered exothermic welding mould then and the medicinal powder compacting.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the heat release welding reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.This product characterizes proof through X-ray diffraction and scanning electronic microscope: the nano-stannic oxide product that purity is very high generates, and its mean diameter is about 60nm.
Embodiment 3
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 12: 50: 16 according to the ratio of massfraction: 9: 10: 0: 3 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just can pour into mixed uniformly medicinal powder in the dewatered exothermic welding mould then and the medicinal powder compacting.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the heat release welding reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.This product characterizes proof through X-ray diffraction and scanning electronic microscope: the nano-stannic oxide product that purity is very high generates, and its mean diameter is about 60nm.
Embodiment 4
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 15: 30: 33 according to the ratio of massfraction: 15: 5: 1: 1 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just can pour into mixed uniformly medicinal powder in the dewatered exothermic welding mould then and the medicinal powder compacting.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the heat release welding reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.This product characterizes proof through X-ray diffraction and scanning electronic microscope: the nano-stannic oxide product that purity is very high generates, and its mean diameter is about 55nm.
Embodiment 5
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 35: 30: 20 according to the ratio of massfraction: 2: 10: 2: 1 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just can pour into mixed uniformly medicinal powder in the dewatered exothermic welding mould then and the medicinal powder compacting.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the heat release welding reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.This product characterizes proof through X-ray diffraction and scanning electronic microscope: the nano-stannic oxide product that purity is very high generates, and its mean diameter is about 50nm.
Embodiment 6
At first with Al powder, Cu 2O, Fe 2O 3, MnO 2, SnO 2, CaO, CaF 2Seven kinds of materials are 10: 30: 36 according to the ratio of massfraction: 10: 9: 2: 3 take by weighing and with stirrer with they uniform mixing.Remove moisture in the thermopositive reaction mould with oxy-acetylene flame, just can pour into mixed uniformly medicinal powder in the dewatered exothermic welding mould then and the medicinal powder compacting.Evenly sprinkle pyrophoric powders on the medicinal powder of compacting, insert the Mg bar on its pyrophoric powders, the Mg bar that ignites is preceding with nano SnO 2The material collection device is installed on the heat release welding reaction mould, and it is assembled as shown in Figure 3, and reaction finishes the back just can obtain nano SnO 2Material.This product characterizes proof through X-ray diffraction and scanning electronic microscope: the nano-stannic oxide product that purity is very high generates, and its mean diameter is about 55nm.

Claims (3)

1. one kind is utilized thermopositive reaction to prepare nano SnO 2The method of material is characterized in that, comprises the steps:
(1) the massfraction ratio is respectively: Al powder 10-35%, Cu 2O 30-55%, Fe 2O 316-36%, MnO 22-15%, SnO 25-12%, CaO 0-2%, CaF 2The medicinal powder of 1-3% mixes, in the reaction unit (4) of then mixed powder being packed into;
(2) light pyrophoric powders with magnesium rod and then ignite this reaction medicinal powder;
(3) collection device that has been placed on reaction unit (4) top before the utilization igniting is collected nano SnO 2Material;
The particle diameter of described mixed powder is the 50-200 order.
2. according to claim 1ly utilize thermopositive reaction to prepare nano SnO 2The method of material is characterized in that: described reaction unit is the crystal vessel that carries through hole.
3. according to claim 1ly utilize thermopositive reaction to prepare nano SnO 2The method of material, it is characterized in that: the outside of described collection device is the shell with the high temperature steel preparation, and the inside of shell is made up of the grid of high temperature steel preparation, and it comprises patrix (1) and counterdie (2) two portions, counterdie is provided with jack (3), and jack is used to insert magnesium rod.
CN2009102722834A 2009-09-28 2009-09-28 Method for preparing nano SnO2 material by utilizing exothermal reaction Expired - Fee Related CN101671050B (en)

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CN102001700B (en) * 2010-12-07 2012-05-23 武汉大学 Method for synthesizing SnO2 nanoribbon by utilizing self-propagating high-temperature reaction
CN104445378B (en) * 2014-12-17 2016-05-25 武汉大学 A kind of synthetic method of tin ash sub-micrometer rod
CN105905931B (en) * 2016-04-20 2017-08-25 武汉大学 A kind of method of utilization Self-propagating Reaction Synthesis spherical alumina nano particle
CN107364885B (en) * 2017-06-29 2019-05-31 武汉大学苏州研究院 A method of utilizing the spherical bismuth oxide of Self-propagating Reaction Synthesis submicron order
CN108593718A (en) * 2018-05-22 2018-09-28 广东美的制冷设备有限公司 Gas sensor sensitive material and preparation method thereof
CN113406155B (en) * 2021-06-23 2022-08-05 长春理工大学 Tin oxide/polyacid/tungsten oxide three-layer coaxial nanofiber gas sensing material and preparation method thereof

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