CN104391010A - Cr2O3-ZnO composite nano material as well as preparation method and application thereof - Google Patents
Cr2O3-ZnO composite nano material as well as preparation method and application thereof Download PDFInfo
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- CN104391010A CN104391010A CN201410661273.0A CN201410661273A CN104391010A CN 104391010 A CN104391010 A CN 104391010A CN 201410661273 A CN201410661273 A CN 201410661273A CN 104391010 A CN104391010 A CN 104391010A
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Abstract
The invention discloses a Cr2O3-ZnO composite nano gas sensitive material as well as a preparation method and application thereof. A coprecipitation method is adopted. The preparation method is characterized in that nano particles are prepared by adopting absolute ethyl alcohol or water is adopted as a solvent and adopting a coprecipitation technique at a low temperature under an alkalescent condition; the ratio of Cr2O3 to ZnO in the nano particles is controlled by adjusting the quantities of Cr salt and Zn salt in a precursor; precipitates are dried and annealed to obtain Cr2O3-ZnO nano particles with high specific surface area and high degree of crystallinity. The preparation method of a product is simple, the cost is low, the specific surface area is large, the ratio of Cr2O3 to ZnO in the nano particles is easy to control, and the prepared nano particles have the advantages of uniform particle size distribution, high stability and the like; the prepared nano particles can be applied to the fields of gas sensors, gas catalytic purification and the like.
Description
Technical field
The present invention relates to the technology of preparing of metal oxide nano-material, specifically refer to a kind of Cr
2o
3the preparation method of-ZnO composite nano materials.
Background technology
Air is one of the mankind's important environmental factor of depending on for existence, but developing rapidly along with industrial technology in modern times, the harm that inflammable, explosive, toxic and harmful brings also manifests thereupon, these gases not only threaten the security of the lives and property of people, but also the environment that the destruction ecosystem and the mankind depend on for existence.Wherein oxides of nitrogen (NOx) is one of primary pollution source causing atmospheric pollution, and discharge capacity is in the trend increased year by year.In order to human survival health, environmental improvement, commercial production and safety, the Tesing and Solution of oxides of nitrogen is become to the Main way in International Environmental Protection field; It is also proposed requirement that is higher, that upgrade to the stability of gas sensor, reliability, sensitivity, the gas sensing technology greatly developing oxides of nitrogen is very urgent.Analysis method for gases main at present has the instrumental analysis etc. such as infrared absorption, analysis of thermal conductivity, chromatography of gases, but due to expensive, field monitoring can not be realized, limit its application.Therefore developing low-cost, highly sensitive, portable gas sensor become the important directions of Developing.
Causing when metal oxide semiconductor material contacts with gas with carrier moving is that the physical property such as conductivity, surface potential of feature changes, and utilizes this character can detect composition and the concentration of gas to be measured.This sensor has the response time and the advantage such as release time is fast, price is low, become output in the world maximum, use one of the widest sensor.Nano zinc oxide material, owing to having higher specific surface area and good photoelectricity, photocatalysis performance, has boundless application prospect at gas sensor domain.ZnO nano material has larger specific surface area, and surfactivity room is many, has stronger ion-exchange performance, is conducive to reactant and reacts in active sites in catalytic process.But all there is response, poor selectivity based on the gas sensor of ZnO nano material to gases such as ethanol, acetone, formaldehyde, NOx, seriously constrain the development of gas sensor in practical application area.
As semiconductor functional material, the surface imperfection that its gas sensing property causes primarily of self crystal structure, surface chemical state, Lacking oxygen determines, also very responsive to a small amount of doping, therefore by the sensitivity and the selectivity that change the pattern of material, doping vario-property can improve air-sensitive response.Cr
2o
3as important catalysis material, application widely, the present invention is had to be intended to expand Cr in the field of purification of NO
2o
3application, preparation Cr
2o
3-ZnO composite nano materials, improves the gas-selectively of ZnO, prepares the gas sensor material for NO.
Summary of the invention
For overcoming the deficiencies in the prior art, this method provides a kind of Cr
2o
3-ZnO composite nanometer particle and its preparation method and application.
A kind of Cr
2o
3the preparation method of-ZnO composite nanometer particle, adopt coprecipitation, it is characterized in that, concrete steps are as follows:
Presoma as zinc source and chromium source is dissolved in obtained solution A in solvent; Solution B is for providing OH
-ammoniacal liquor or the aqueous solution of hexamethylene tetramine; By solution A and solution B mixing, mixed method is get the water of 20 ~ 200 milliliters or ethanol is heated to 30 ~ 80 DEG C, jointly instills in water or ethanol by solution A and solution B; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO; By Cr
2o
3-ZnO at 70 ~ 120 DEG C dry 6 ~ 12 hours, by dried powder mull, then anneal 2 ~ 5 hours under air atmosphere, annealing temperature 300 DEG C ~ 600 DEG C, namely obtains Cr
2o
3-ZnO composite nanometer particle.
Described zinc source is one or both potpourris in zinc nitrate, zinc chloride, zinc acetate; Described chromium source is one in chromic nitrate, chromium chloride or potpourri.
Described solvent is one or both the potpourri in deionized water, ethanol, ethylene glycol.
Described zinc source and the mol ratio in chromium source are 1:30 ~ 1:1; Zinc source and chromium source ion total concentration are 0.4M ~ 3M.
A kind of Cr
2o
3-ZnO composite nanometer particle, is characterized in that, prepares according to above-mentioned arbitrary described method.
A kind of Cr
2o
3-ZnO composite nanometer particle is at NO
xthe application of gas sensor.
That the invention provides a kind of simple possible, that there is very well optionally gas sensor material preparation method, solve the problem of the gas sensor poor selectivity based on ZnO nano material, make the gas sensor based on metal oxide have better selectivity, higher sensitivity.
Method of the present invention utilizes coprecipitation to prepare Cr
2o
3-ZnO nano particle, by Cr in Cr and Zn presoma molar weight regulation and control nano particle in change system
2o
3with the ratio of ZnO; Device is easy to prepare, gas sensitive is coated in ceramic pipe surface, and preparation technology is simple, reproducible.
The invention has the advantages that: the present invention is by Cr
2o
3-ZnO composite nanometer particle is applied to gas sensor domain, is a kind of novel gas sensitive, effectively can improves selectivity and the sensitivity of gas sensor; Nano particle has larger specific surface area, homogeneous domain size distribution, fabulous stability; Preparation method of the present invention is simple, is conducive to large-scale popularization.
Accompanying drawing explanation
Fig. 1 is Cr of the present invention
2o
3the SEM figure of-ZnO composite nanometer particle.
Fig. 2 is Cr of the present invention
2o
3the energy spectrogram of-ZnO composite nanometer particle.
Fig. 3 is Cr of the present invention
2o
3-ZnO composite nanometer particle is to the gas response curve of NO.
Embodiment
Embodiment 1:
Zinc nitrate and chromium chloride are dissolved in obtained solution A in 30ml water by Cr:Zn mol ratio 1:10, and ion concentration is 1M; Solution B is the ammoniacal liquor of 30 ml; By solution A and solution B mixing, mixed method is that the water getting 60 ml is heated to 70 DEG C, solution A and solution B is jointly instilled in water; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO powder; By Cr
2o
3-ZnO powder at 80 DEG C dry 12 hours, by dried powder mull, then anneals 3 hours under air atmosphere, annealing temperature 500 DEG C.
Product SEM, EDX after annealing are characterized its structure and component, the Cr of Fig. 1,2 reaction conditions gained for this reason
2o
3the pattern of-ZnO nano particle, constitutional diagram.As can be seen from SEM figure, the product of preparation is the uniform particle sizes of nano particle, nano particle, is about about 10 nm; As can be seen from energy spectrogram, have Zn, Cr and O element in product, the atomic ratio of Zn and Cr is 1:7, suitable with rate of charge.Fig. 3 is the air-sensitive response curve that sample records NO 330 DEG C time, and the concentration of NO is 100 ppm.This lays a good foundation for the application of metal oxide in gas sensor.
Embodiment 2:
Zinc chloride chromic nitrate is dissolved in aqueous solvent obtained solution A by Cr:Zn mol ratio 1:5, and ion concentration is 0.5M; Solution B is ammoniacal liquor; By solution A and solution B mixing, mixed method is that the water getting 100 ml is heated to 60 DEG C, solution A and solution B is jointly instilled in ethanol; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO powder; By Cr
2o
3-ZnO powder at 100 DEG C dry 6 hours, by dried powder mull, then anneals 5 hours under air atmosphere, annealing temperature 600 DEG C.
Embodiment 3:
Using zinc acetate and the chromic nitrate presoma as zinc source and chromium source, be dissolved in obtained solution A in etoh solvent by Cr:Zn mol ratio 1:30, ion concentration is 3M; Solution B is the aqueous solution of hexamethylene tetramine; By solution A and solution B mixing, mixed method is that the water getting 200ml is heated to 80 DEG C, solution A and solution B is jointly instilled in water; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO powder; By Cr
2o
3-ZnO powder at 70 DEG C dry 10 hours, by dried powder mull, then anneals 4 hours under air atmosphere, annealing temperature 450 DEG C.
Embodiment 4:
Using zinc nitrate and the chromic nitrate presoma as zinc source and chromium source, be dissolved in obtained solution A in aqueous solvent by Cr:Zn mol ratio 1:1, ion concentration is 2M; Solution B is ammoniacal liquor; By solution A and solution B mixing, mixed method is that the ethanol getting 20ml is heated to 30 DEG C, solution A and solution B is jointly instilled in ethanol; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO powder; By Cr
2o
3-ZnO powder at 100 DEG C dry 8 hours, by dried powder mull, then anneals 2 hours under air atmosphere, annealing temperature 400 DEG C.
Embodiment 5:
Using the presoma of a kind of or potpourri in zinc nitrate and chromium chloride as zinc source and chromium source, be dissolved in obtained solution A in aqueous solvent by Cr:Zn mol ratio 1:20, ion concentration is 1M; Solution B is ammoniacal liquor; By solution A and solution B mixing, mixed method is heated to 60 DEG C for the water getting 20 ~ 200ml, solution A and solution B is jointly instilled in water; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO powder; By Cr
2o
3-ZnO powder at 80 DEG C dry 12 hours, by dried powder mull, then anneals 4 hours under air atmosphere, annealing temperature 500 DEG C.
Claims (6)
1. a Cr
2o
3the preparation method of-ZnO composite nanometer particle, adopt coprecipitation, it is characterized in that, concrete steps are as follows:
Presoma as zinc source and chromium source is dissolved in obtained solution A in solvent; Solution B is for providing OH
-ammoniacal liquor or the aqueous solution of hexamethylene tetramine; By solution A and solution B mixing, mixed method is get the water of 20 ~ 200 milliliters or ethanol is heated to 30 ~ 80 DEG C, jointly instills in water or ethanol by solution A and solution B; By mixed solution left standstill 1 hours, centrifugally obtain Cr
2o
3-ZnO; By Cr
2o
3-ZnO at 70 ~ 120 DEG C dry 6 ~ 12 hours, by dried powder mull, then anneal 2 ~ 5 hours under air atmosphere, annealing temperature 300 DEG C ~ 600 DEG C, namely obtains Cr
2o
3-ZnO composite nanometer particle.
2. Cr according to claim 1
2o
3the preparation method of-ZnO composite nanometer particle, is characterized in that, described zinc source is one or both potpourris in zinc nitrate, zinc chloride, zinc acetate; Described chromium source is one in chromic nitrate, chromium chloride or potpourri.
3. Cr according to claim 1
2o
3the preparation method of-ZnO composite nanometer particle, is characterized in that, described solvent is one or both the potpourri in deionized water, ethanol, ethylene glycol.
4. Cr according to claim 1
2o
3the preparation method of-ZnO composite nanometer particle, is characterized in that, described zinc source and the mol ratio in chromium source are 1:30 ~ 1:1; Zinc source and chromium source ion total concentration are 0.4M ~ 3M.
5. a Cr
2o
3-ZnO composite nanometer particle, is characterized in that, according to above-mentioned arbitrary claim, method prepares.
6. Cr according to claim 5
2o
3-ZnO composite nanometer particle is at NO
xthe application of gas sensor.
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Cited By (1)
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| CN104749235A (en) * | 2015-03-12 | 2015-07-01 | 宁波大学 | High-selectivity compensation type CO sensor and preparation method thereof |
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Application publication date: 20150304 |
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