CN100432012C - Nanometer gas-sensing material of ternary composite metal oxide and production thereof - Google Patents
Nanometer gas-sensing material of ternary composite metal oxide and production thereof Download PDFInfo
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- CN100432012C CN100432012C CNB2005100663693A CN200510066369A CN100432012C CN 100432012 C CN100432012 C CN 100432012C CN B2005100663693 A CNB2005100663693 A CN B2005100663693A CN 200510066369 A CN200510066369 A CN 200510066369A CN 100432012 C CN100432012 C CN 100432012C
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Abstract
The present invention relates to a novel nanometer gas sensitive material of ternary composite metal oxide and a production thereof. The composite metal oxide is prepared by a wet chemical controllable reaction, namely preparing ZnO-SnO2 presoma by a coprecipitation method firstly. Third component metal oxide is added into the presoma by a secondary precipitation method so as to obtain a ternary metal composite oxide material with a chemical formula of MO-ZnO-SnO2. The preparation processes need to control the controllable preparation parameters of compound composition, the total concentration of metal salt solutions, the mol ratio of Zn/Sn, a precipitation pH value, aging time, etc. The weight percentage composition of the third component metal oxide MO in the MO-ZnO-SnO2 is 2% to 30%, and the MO is mainly transition metal oxides or alkali metal oxides. The grain size distribution of the ternary composite material is 30 to 90 nm, and specific surface area is 20 to 100m<2>/g. The ternary metal oxide composite material is used as a gas sensitive material and has good sensitivity and selectivity.
Description
Technical field:
The present invention relates to a kind of nanometer gas-sensing material of ternary composite metal oxide and preparation method thereof.
Background technology:
SnO
2Be a kind of N-N-type semiconductorN metal oxide, can be used as the gas sensitive that detects reductibility and oxidizing gas, present available SnO
2The based sensor ubiquity poor stability, and sensitivity and selectivity are not ideal enough, special in the sintering process of sensor production temperature 〉=600 ℃ often because SnO
2Grain growth or reunite reduces sensitivity and selectivity greatly.Investigators generally believe that the sensitivity characteristic of gas sensitive and its particle size and thermostability are closely related, development along with nano material, transmitter also enters a new stage, nano structural material is because its unique dimensional effect and surface effects, it is very responsive to light, electricity, temperature and gas adsorption, can cause the response that electricity is led or other signals change rapidly, so be especially suitable for use as the gas sensor sensitive material.The improvement and the hot of research and development of gas sensitive mainly concentrate on complex metal oxides and mixed metal oxide at present.Document [1]: Journal of Materials Chemistry, 1998,8 (9): people such as S.R.Davis utilizes sol-gel method to prepare SnO in 2065～2071
2And doped with Cu
2+, Fe
3+Nanocrystalline SnO
2Gas sensitive has been studied in air these materials to the response of carbon monoxide and the relation of sintering temperature, and the result shows that they increase along with crystal grain carbon monoxide sensitivity and reduce, and add metallic cation and can hinder grain growing.Document [2]: Chinese Journal of ChemicalEngineering, 2004,12 (2): in 282～285, human sol-gel methodes such as Lijing Ma have prepared nano-scale γ-Fe
2O
3-SiO
2The composite air-sensitive material, and studied it to CH
4, H
2With the gas-sensitive property of reducing gas such as ethanol, and further improve its sensitivity by the doping small amount of precious metals.Document [3]: Sensorsand Actuators B, people such as B.P.J.de Lacy Costello is with SnO in 1999,61,199～207
2With ZnO be that raw material obtains SnO through mechanically mixing
2With the mixture gas sensitive of ZnO, under 350 ℃ of service temperatures, measure its sensitivity characteristic to n-propyl alcohol and dimethyl sulphide (DMDS) steam, the result shows to have best sensitivity when the Zn/Sn of mixture mol ratio is 1: 1.
From above-mentioned document as seen, SnO
2Carry out the catalysis gas-sensitive property that recombination energy improves matrix material with another kind of metal oxide.But exist that operation steps is complicated, sensitivity and selectivity be not ideal enough, and mostly concentrate on organic compound steam such as alcohols and reducing gas detected, to NO
x, CO, SO
2Deng the rarely found report of the detection of environment toxic gas, particularly at ZnO-SnO
2The method of adding the 3rd component composition on the basis of nano composite material is not appeared in the newspapers so far.
Summary of the invention
The object of the present invention is to provide a kind of novel tertiary complex metal oxides gas-sensitive nano material and preparation method thereof.This complex metal oxides is at ZnO-SnO
2Compound the 3rd component metals oxide compound obtains a kind of novel ternary composite metal oxide material on the basis, and this ternary composite metal oxide material can improve the performance of the semiconductor transducer of testing environment toxic gas as gas sensitive.
The chemical formula of ternary composite metal oxide provided by the invention is:
MO-ZnO-SnO
2
Wherein MO represents the 3rd component metals oxide compound, and its quality percentage composition is 2%～30% according to the quality percentage composition of compound back metal oxide; MO, ZnO, SnO
2Between combine with chemical bond or intermolecular forces; The Zn/Sn mol ratio is 0.2～4: 1 preferred 0.6～1.5 in this ternary composite metal oxide: 1; MO mainly is Al
2O
3, In
2O
3, TiO
2, MgO etc.; The size distribution of this ternary composite nano air-sensitive material is 30～90nm, and specific surface area is 20～100m
2/ g.When the quality percentage composition of MO is 5%～20%, has better air-sensitive performance;
The preparation method of ternary composite metal oxide is as follows:
In reaction vessel, with solubility Zn
2+Salt and solubility Sn
4+Salt is pressed positively charged ion Zn
2+/ Sn
4+Mol ratio is that 0.2～4: 1 ratio is dissolved in and is made into Sn in the deionized water
4+And Zn
2+Total mol concentration is the mixing salt solution of 0.02～0.20mol/L, at rotating speed is under the violent stirring of 100～500rpm, be that about 12% dilute ammonia solution slowly is added drop-wise in the above-mentioned mixing solutions until the pH value with concentration be 4.0～9.0, form the precipitation presoma, after treating that precipitation fully, add the 3rd component soluble metal salts solution immediately, the add-on of the 3rd component metals salt is 2～30% to determine that preferable content is 5%～20% by the quality percentage composition of compound back metal oxide; Slowly drip 12% dilute ammonia solution while stirring, regulating the pH value is 7.0～10.0, make its secondary sedimentation, treat to leave standstill aging 12～48hr, discharging after precipitation fully, filter, thorough washing is the inclusion-free negatively charged ion in filtrate, and the throw out dry 4～7hr under 90～120 ℃ of temperature with obtaining places stoving oven to rise to 400～1000 ℃ with the temperature rise rate of 3～10 ℃/min again, roasting 4～8hr obtains MO-ZnO-SnO
2Composite oxide powder.
Wherein solubility Zn salt is: Zn (NO
3)
26H
2O, ZnCl
2, Zn (SO
4)
27H
2O etc.; Solubility Sn salt is: SnCl
45H
2O, Sn (NO
3)
45H
2O etc.; The 3rd component metals salt is transition metal or alkalimetal oxide: as AlCl
36H
2O, InCl
34H
2O, TiCl
4, Mg (NO
3) 6H
2O etc.
The composite nano-powder of the above-mentioned metal oxide that makes is used phase structure, specific surface and the granule-morphology thereof of X-ray diffraction (XRD), specific surface test (BET) and transmission electron microscope (TEM) measuring powder respectively.SnO
2Be cubic crystalline phase, rutile structure spherical in shape, ZnO and the 3rd component metal oxide are amorphous dispersion state, and diameter of particle is distributed as 30～90nm, and specific surface is 20～100m
2/ g.
The air-sensitive performance test:
The nano-metal composite oxide powder that makes is depressed to thin rounded flakes in 8～15MPa, and its diameter is about 8～15mm, and thickness is 1～3mm, makes gas sensor.The gas sensor of making is placed a silica tube, bubbling air or gas to be measured and Air mixing gas, be heated to 100～400 ℃ of service temperatures, and the constant operation electric current is 0.50～2.00 μ A, treats to survey respectively after stable it in air and the magnitude of voltage U in the gas mixture
aAnd U
gFor reducing gas such as CO, CH
4Deng, sensitivity S is defined as element voltage and the ratio U that detects element voltage in the atmosphere in the air
a/ U
gOr the ratio R of both resistance
a/ R
gAnd for oxidizing gas, as NO
2, NO etc., sensitivity S is defined as U
g/ U
aOr R
g/ R
aUnder the different operating temperature, measured NO with this method
2With the sensitivity and the selectivity of gas such as CO, the result shows: the ternary composite metal oxide matrix material of the present invention's preparation has sensitivity preferably and selectivity.
The ternary composite metal oxide MO-ZnO-SnO of the present invention's preparation
2Do not see bibliographical information, this complex metal oxides has nanocrystalline grain size, bigger serface, and the second component ZnO and the 3rd component MO are unformed high dispersion state, can suppress SnO in temperature-rise period
2Grain growth, thus make material have thermally-stabilised and structural stability.It is simple, easy to operate that the preparation method that the present invention adopts has equipment, experiment condition gentleness, advantage such as reaction conditions is controlled, and is with low cost.
The 3rd component metals oxide compound dispersion property is good, and gas to be measured is had high absorption property, has improved ZnO-SnO
2Gas sensitive is to NO
xSensitivity and selectivity Deng gas.
Description of drawings
Fig. 1 is the Al of embodiment 1 preparation
2O
3-ZnO-SnO
2TEM figure.
Embodiment
Embodiment 1
Al
2O
3-ZnO-SnO
2Preparation
Accurately take by weighing 5.2602g Zn (NO
3)
26H
2O and 2.9747g SnCl
45H
2O is dissolved in the 500mL deionized water and is made into mixing salt solution, at rotating speed is under the 400rpm violent stirring, be that about 12% dilute ammonia solution slowly is added drop-wise in the above-mentioned mixing solutions until the pH value with concentration be 8.0, form the precipitation presoma, treat to add 0.7658g AlCl immediately after precipitation fully
36H
2O, and be that slowly to drip concentration under the 400rpm violent stirring be 12% dilute ammonia solution at rotating speed, regulating pH value is 9.0, aging 24hr is left standstill in secondary sedimentation, and filtration, thorough washing does not almost have Cl in filtrate
-And NO
3 -, the throw out that obtains is dry 5hr under 100 ℃ of temperature, roasting 6hr in 600 ℃ of air atmospheres, and wherein temperature rise rate is 3 ℃/min, obtains Al
2O
3-ZnO-SnO
2Composite metal oxide powder, wherein Zn
2+/ Sn
4+Mol ratio is 2: 3, Al
2O
3The mass percent that accounts for composite oxides is 5%.TEM (Fig. 1) by this matrix material finds out that its median size is about 45nm; The specific surface that records this matrix material with BET is 90.4m
2/ g.
Embodiment 2
With embodiment 1, just with AlCl
36H
2The add-on of O becomes 1.6165g, prepares Al
2O
3-ZnO-SnO
2Composite metal oxide powder, wherein Zn
2+/ Sn
4+Mol ratio is 2: 3, Al
2O
3The mass percent that accounts for composite oxides is 10%.The median size of matrix material is about 38nm, and specific surface area is 100.5m
2/ g.
Embodiment 3
With embodiment 1, just with AlCl
36H
2The add-on of O becomes 3.6374g, prepares Al
2O
3-ZnO-SnO
2Composite metal oxide powder, wherein Zn
2+/ Sn
4+Mol ratio is 2: 3, Al
2O
3The mass percent that accounts for composite oxides is 20%.The median size of matrix material is about 60nm, and specific surface area is 56.7m
2/ g.
Embodiment 4
With embodiment 1, just with AlCl
36H
2O changes Mg (NO into
3)
2.6H
2O prepares MgO-ZnO-SnO
2Composite oxide powder, wherein Zn
2+/ Sn
4+Mol ratio is 2: 3, and the mass percent that MgO accounts for composite oxides is 10%.The median size of matrix material is about 45nm, and specific surface is 81.5m
2/ g.
The sensitivity test example
The gas sensitive that embodiment 1～4 is made is measured it to 450ppmNO under the different operating temperature respectively
2Sensitivity, the result is as shown in table 1:
Table 1
The selectivity test example
The composite air-sensitive material that obtains with embodiment 2 carries out the selectivity examination, under 200 ℃ of service temperatures, measures it respectively to NO
2, CO, NO and CH
4Sensitivity, the result is as shown in table 2:
Table 2
To each gas sensitivity test result as can be seen, under 200 ℃ of service temperatures, this metal oxide composite air-sensitive material is to 450ppm CO, NO and CH
4Sensitivity be respectively 43.2,20.6 and 3.4, under the same conditions to NO
2Sensitivity is up to 532, NO
2Selectivity to CO and NO is respectively 12.3 and 25.8, and CH
4Noiseless effect.
Claims (5)
1. nanometer gas-sensing material of ternary composite metal oxide, its chemical formula is:
MO-ZnO-SnO
2
Wherein MO represents the 3rd component metals oxide compound, and MO is Al
2O
3, In
2O
3, TiO
2Or MgO, the quality percentage composition of MO is 2%～30% according to the quality percentage composition of compound back metal oxide; MO, ZnO, SnO
2Between combine with chemical bond or intermolecular forces, wherein the Zn/Sn mol ratio is 0.2～4: 1; The size distribution of this ternary composite metal oxide is 30～90nm, and specific surface area is 20～100m
2/ g.
2. nanometer gas-sensing material of ternary composite metal oxide according to claim 1, the quality percentage composition that it is characterized in that MO in the ternary composite metal oxide is 5%～20%; The Zn/Sn mol ratio is 0.6～1.5: 1.
3. the preparation method of a nanometer gas-sensing material of ternary composite metal oxide, step is:
In reaction vessel, with solubility Zn
2+Salt and solubility Sn
4+Salt is pressed positively charged ion Zn
2+/ Sn
4+Mol ratio is that 0.2～4: 1 ratio is dissolved in and is made into Sn in the deionized water
4+And Zn
2+Total mol concentration is the mixing salt solution of 0.02～0.20mol/L, at rotating speed is under the violent stirring of 100～500rpm, be that about 12% dilute ammonia solution slowly is added drop-wise in the above-mentioned mixing solutions until the pH value with concentration be 4.0～9.0, form precipitation presoma ZnO-SnO
2After treating that precipitation fully, add the 3rd component soluble metal salts solution immediately, the add-on of the 3rd component metals salt is 2～30% to determine by the quality percentage composition of compound back metal oxide, slowly drip 12% dilute ammonia solution while stirring, regulating the pH value is 7.0～10.0, make its secondary sedimentation, treat to leave standstill aging 12～48hr after precipitation fully, discharging is filtered, and thorough washing is the inclusion-free negatively charged ion in filtrate, with the throw out dry 4～7hr under 90～120 ℃ of temperature that obtains, place stoving oven to rise to 400～1000 ℃ with the temperature rise rate of 3～10 ℃/min again, roasting 4～8hr obtains MO-ZnO-SnO
2Composite oxide powder.
4. the preparation method of nanometer gas-sensing material of ternary composite metal oxide according to claim 3 is characterized in that, solubility Zn salt is: Zn (NO
3)
26H
2O, ZnCl
2Or Zn (SO
4)
27H
2O, solubility Sn salt is: SnCl
45H
2O or Sn (NO
3)
45H
2O; The 3rd component soluble metallic salt is soluble transition metal salt or soluble alkali metal salts; The add-on of the 3rd component metals salt is 5%～20% to determine by the quality percentage composition of compound back metal oxide.
5. the preparation method of nanometer gas-sensing material of ternary composite metal oxide according to claim 4: it is characterized in that the 3rd component soluble metallic salt is AlCl
36H
2O, InCl
35H
2O, TiCl
4Or Mg (NO
3)
26H
2O.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101256166B (en) * | 2008-04-16 | 2012-05-09 | 北京航空航天大学 | Method of preparing zinc oxide/titanium dioxide composite self-assembly thin film gas sensitive device |
| CN101493430B (en) * | 2009-02-17 | 2012-05-30 | 武汉工程大学 | Hydrogen sulfide gas sensitive, preparation, and method for making hydrogen sulfide gas sensitive device |
| CN104391010A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cr2O3-ZnO composite nano material as well as preparation method and application thereof |
| CN104950014A (en) * | 2015-05-24 | 2015-09-30 | 北京化工大学 | Chlorinated hydrocarbons volatile gas sensing material and preparation method thereof |
| CN105424757B (en) * | 2016-01-11 | 2019-08-13 | 济南大学 | The polynary metal oxide of high air-sensitive property energy, preparation method and application |
| CN108226233B (en) * | 2018-01-08 | 2020-01-31 | 中国工程物理研究院化工材料研究所 | Hierarchical ZnO @ ZnO nanocomposite gas-sensitive material and preparation method thereof |
| CN110274934A (en) * | 2018-03-14 | 2019-09-24 | 全球能源互联网研究院有限公司 | A kind of gas sensitive and preparation method thereof |
| CN109112697A (en) * | 2018-08-06 | 2019-01-01 | 佛山市南海区佳妍内衣有限公司 | Novel health-care underwear textile fabric |
Citations (2)
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|---|---|---|---|---|
| CN1043830A (en) * | 1989-10-16 | 1990-07-11 | 云南大学 | The manufacture method of zinc metastannate gas |
| KR20020031439A (en) * | 2000-10-20 | 2002-05-02 | 정명식 | Gas sensor having good sensitivity and selectivity to carbon monoxide gas and process for the preparation thereof |
-
2005
- 2005-04-26 CN CNB2005100663693A patent/CN100432012C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043830A (en) * | 1989-10-16 | 1990-07-11 | 云南大学 | The manufacture method of zinc metastannate gas |
| KR20020031439A (en) * | 2000-10-20 | 2002-05-02 | 정명식 | Gas sensor having good sensitivity and selectivity to carbon monoxide gas and process for the preparation thereof |
Non-Patent Citations (4)
| Title |
|---|
| SnO2-ZnO二元系半导体陶瓷材料特性. 季秉厚等.内蒙古大学学报，第29卷第1期. 1998 |
| SnO2-ZnO二元系半导体陶瓷材料特性. 季秉厚等.内蒙古大学学报，第29卷第1期. 1998 * |
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