CN103353470A - Gas sensor based on mesoporous indium oxide gas-sensitive material and preparation method - Google Patents
Gas sensor based on mesoporous indium oxide gas-sensitive material and preparation method Download PDFInfo
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- CN103353470A CN103353470A CN201310274638XA CN201310274638A CN103353470A CN 103353470 A CN103353470 A CN 103353470A CN 201310274638X A CN201310274638X A CN 201310274638XA CN 201310274638 A CN201310274638 A CN 201310274638A CN 103353470 A CN103353470 A CN 103353470A
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Abstract
The invention relates to a gas sensor based on a mesoporous indium oxide gas-sensitive material and a preparation method. The mesoporous indium oxide gas-sensitive material is used as a sensing layer of the sensor. According to the invention, mesoporous indium oxide prepared by using a nanometer casting method is used as the gas-sensitive material, the concentration of prepared coating slurry is 0.02 to 0.2 g/mL, and the thickness of the sensing layer of the gas sensor prepared through coating is 500 nm to 300 mu m. The preparation method for the gas sensor is simple to operate and easy to realize; the gas sensor has a large gas-sensitive specific surface area, greater than 150 m<2>/g; the preparation method is favorable for improving gas-sensitive performance of the prepared gas sensor, and the prepared gas sensor has optimal ethanol sensing performance of greater than 18, optimal acetone sensing performance of greater than 15 and optimal methanol sensing performance of greater than 12, all higher than the performance of frequently used industrial gas sensors.
Description
Technical field
The invention belongs to the inorganic porous material application.Relate in particular a kind of method of utilizing the nanometer casting method oppositely to copy preparation porous oxidation indium gas sensitive and being applied to the gas sensor of high air-sensitive property energy.
Background technology
The advantages such as the gas sensitive device based on metal-oxide semiconductor (MOS) is cheap owing to having, gas sensing property good, be easy to assembling, volume is little are widely used in life and industrial gasses sensory field.In order further to promote its gas sensing performance, the important directions that is designed to development of the nanostructured of gas sensitive comprises structure and the three-dimensional nanometer materials such as the materials such as zero-dimension nano particle gas sensitive, one-dimensional nano line rod, two-dimensional nano sheet dish.Wherein the preparation of three-dimensional meso-hole nanostructured gas sensitive has attracted to pay close attention to widely, this is because it had both had the bigger serface of zero dimension one dimension and two-dimensional nano material, the advantage in many adsorption activity site, the drawback of having avoided again these nano materials easily to reunite in application process simultaneously; The mesopore orbit size both had been beneficial to the effective adsorption area that increases gas molecule between 2-50nm, be beneficial to again the mass transfer distance that reduces gas molecule, thereby can its air-sensitive performance of Effective Raise and reduce the response time.Soft template method and hard template method (nanometer casting method) are two kinds of common methods of preparation mesoporous material, wherein soft template method is when the preparation metal oxide materials, because the poor high temperature stability of soft template, mesopore orbit easily caves in the process of high temperature removal soft template, causes mesoporous order on the low side; And hard template method has effectively been avoided this problem, and this is because hard template at high temperature can stable existence, plays good hard supporting role, thereby guarantees that calcining turns brilliant process intermediary hole duct and well preserved.Has very large relevance between the mesoporous appearance structure of mesopore metal oxide and its air-sensitive performance.The prepared mesoporous metallic oxide material of hard template method is owing to turning inevitable volumetric contraction in the brilliant process at present, its mesoporous order and particle size are less, the method of repeatedly filling has improvement to a certain degree, but because the duct has Partial Blocking in the first time in the filling process, therefore follow-up filling process just produces effects limited, has therefore affected the further lifting of its air-sensitive performance.How to seek optimum mesopore metal oxide hole shape looks structure, thus prepare high sensing capabilities and high selectivity can gas sensitive become the key that promotes the gas sensitive device performance.Our research is found by the ratio of change calcining vessel aperture area with sample size, can control the effusion speed that turns in the brilliant process water and byproduct gas in the precursor, thereby control turns brilliant process and carries out in solid phase or liquid phase, thereby the mesoporous order pattern of the prepared mesoporous metallic oxide material of final regulation and control.
Indium oxide is a kind of Semiconductor gas sensors material commonly used, can be applicable to measure part oxidizing gas and partial reduction gas.The indium oxide gas sensor of using at present is difficult to take into account high air-sensitive property and high selectivity owing to not possessing the bigger serface of meso-hole structure and many avtive spot features, thereby the appearance structure that therefore requires further improvement material promotes its comprehensive air-sensitive performance.
Summary of the invention
The objective of the invention is to overcome the difficult compatible high air-sensitive property of existing indium oxide gas sensor and and the problem of high selectivity, a kind of gas sensor preparation method take mesoporous indium oxide as gas sensitive is provided.
Technical scheme of the present invention is as follows:
A kind of gas sensor based on the mesoporous indium oxide gas sensitive is with the sensing layer of mesoporous indium oxide gas sensitive as sensor.
The preparation method of sensor of the present invention adopts the mesoporous indium oxide for preparing with the nanometer casting method as gas sensitive, and it is 0.02-0.2g/mL that preparation applies slurry concentration, and the sensing layer thickness through applying the preparation gas sensor is 500nm～300um.
The preparation method of mesoporous indium oxide gas sensitive of the present invention is: be by the ratio (10 of control calcining vessel aperture area with the calcining mixt sample size on the basis of nanometer casting method
-6– 1m
2/ g), regulate and control the mesoporous order pattern of prepared mesoporous metallic oxide material, concrete mechanism and preparation method see also document (Xiaohong Sun etc., Container Effect in Nanocasting Synthesis of Mesoporous Metal Oxides "; Journal of the American Chemical Society; 2011,133,14542 – 14545); The hard template that the nanometer casting method adopts is the ordered meso-porous silicon oxide material, by nanometer casting preparation ordered mesoporous indium oxide gas sensitive.
Described ordered meso-porous silicon oxide hard template refers to one of KIT-6 molecular sieve, SBA-15 molecular sieve or MCM-41 molecular sieve.
Described ordered meso-porous silicon oxide hard template is 0.1-100 with the quality of five water indium nitrate precursors than scope.
Calcination temperature range in the described nanometer casting method preparation process is 200-800 ℃, and the temperature retention time scope is 0.2-20h.
The preparation flow of mesoporous indium oxide gas sensitive is: the ordered meso-porous silicon oxide hard template is distributed in the alcohol solvent, add five water indium nitrate precursors, the stirring at room dipping, thereby the indium precursor is immersed in the silicon oxide mesoporous duct, then volatilize alcohol solvent, and the calcined mixed matter sample that obtains is encased in the calcining vessel with certain opening area calcining and insulation certain hour under certain calcining heat.Then method centrifugal after stirring with sodium hydroxide solution obtains order mesoporous indium oxide material to remove the monox template.
The invention provides a kind of gas sensor based on the mesoporous indium oxide gas sensitive and prepare the method for gas sensor.The mesoporous appearance structure of material can decide by the ratio of control calcining vessel aperture area with the calcining mixt sample size.The gas sensitive thickness of gas sensor can apply the concentration of slurry and apply number of times by control and determine.This gas sensor preparation method realization simple to operate, easy has large air-sensitive specific surface area, greater than 150m
2/ g; And be conducive to improve the air-sensitive performance of prepared gas sensor, the best sensing capabilities of ethanol is greater than 18, the best sensing capabilities of acetone is greater than 15, and the best sensing capabilities of methyl alcohol is greater than 12, and (gas sensing performance S is defined as S=R all to be higher than industry gas sensor performance commonly used
Air/ R
Gas, R wherein
AirBe the resistance value that sensor is measured, R in air
GasThe resistance value of in mensurated gas composition, measuring for sensor).
Description of drawings
Fig. 1 is the sensor of made and the schematic diagram of sensing layer thereof.
Fig. 2 is the small angle X-ray diffraction figure of the prepared indium oxide gas sensitive of embodiment 1, and significantly the X-ray diffraction peak shows that prepared indium oxide material has the order mesoporous structure of height;
Fig. 3 is the big angle X-ray diffractogram of the prepared indium oxide gas sensitive of embodiment 2, all diffraction peaks are corresponding one by one with bixbyite indium oxide standard diffracting spectrum (JCPDS No.06-0416), show that prepared indium oxide is the pure phase indium oxide, and have high crystallinity;
Fig. 4 is the transmission electron microscope photo of the prepared indium oxide gas sensitive of embodiment 3, as we can clearly see from the figure orderly meso-hole structure.
Embodiment
Embodiment 1: with ordered meso-porous silicon oxide SBA-15 as hard template, the mass ratio of itself and five water indium nitrate precursors is 100, the room temperature ethanol infusion process is immersed in the silicon oxide mesoporous duct indium precursor, then volatilize alcohol solvent, and be to calcine in the crucible of 10-6 the ratio that the calcining mixt that obtains is encased in vessel port area and calcining mixt sample size, sintering temperature is 200 ℃, and temperature retention time is 20h.Then method centrifugal after stirring with sodium hydroxide solution obtains order mesoporous indium oxide material to remove the monox template.
As shown in Figure 1, the schematic diagram of the sensor of making and sensing layer thereof.It is 0.1g/mL that the preparation mesoporous indium oxide applies slurry concentration, and with the coating pen slurry evenly is coated on the outside surface of ceramic die of gold electrode, forming indium oxide sensing layer thickness is 1um, dries after each coating is finished to apply under infrared lamp next time again, spends the night at last and dries in the shade.The ceramic die that then will be coated with the mesoporous indium oxide gas sensitive is welded on the sensor base, simultaneously the NI-G heater strip is passed ceramic die and also is welded on the connecting line and adds a cover the outer cover collar and be assembled into complete senser element and test its air-sensitive performance.Its ethanol to 100ppm has best selective, and its sensing capabilities is 18.2.As shown in Figure 2, the small angle X-ray diffraction figure of prepared indium oxide gas sensitive, significantly the X-ray diffraction peak shows that prepared indium oxide material has the order mesoporous structure of height.
Embodiment 2: with ordered meso-porous silicon oxide MCM-41 as hard template, the mass ratio of itself and five water indium nitrate precursors is 10, the room temperature ethanol infusion process is immersed in the silicon oxide mesoporous duct indium precursor, then volatilize alcohol solvent, and be to calcine in 1 the crucible the ratio that the calcining mixt that obtains is encased in vessel port area and calcining mixt sample size, sintering temperature is 400 ℃, and temperature retention time is 5h.Then method centrifugal after stirring with sodium hydroxide solution obtains order mesoporous indium oxide material to remove the monox template.
It is 0.2g/mL that the preparation mesoporous indium oxide applies slurry concentration, and with the coating pen slurry evenly is coated on the outside surface of ceramic die of gold electrode, forming indium oxide sensing layer thickness is 300um, dries after each coating is finished to apply under infrared lamp next time again, spends the night at last and dries in the shade.The ceramic die that then will be coated with the mesoporous indium oxide gas sensitive is welded on the sensor base, simultaneously the NI-G heater strip is passed ceramic die and also is welded on the connecting line and adds a cover the outer cover collar and be assembled into complete senser element.Its acetone to 100ppm has best selective, and its sensing capabilities is 15.9.As shown in Figure 3, the big angle X-ray diffractogram of prepared indium oxide gas sensitive, all diffraction peaks are corresponding one by one with bixbyite indium oxide standard diffracting spectrum (JCPDS No.06-0416), show that prepared indium oxide is the pure phase indium oxide, and have high crystallinity.
Embodiment 3: with ordered meso-porous silicon oxide KIT-6 as hard template, the mass ratio of itself and five water indium nitrate precursors is 0.1, the room temperature ethanol infusion process is immersed in the silicon oxide mesoporous duct indium precursor, then volatilize alcohol solvent, and be 10 with the ratio that the calcining mixt that obtains is encased in vessel port area and calcining mixt sample size
-4Crucible in calcine, sintering temperature is 800 ℃, temperature retention time is 0.2h.Then method centrifugal after stirring with sodium hydroxide solution obtains order mesoporous indium oxide material to remove the monox template.
It is 0.02g/mL that the preparation mesoporous indium oxide applies slurry concentration, and with the coating pen slurry evenly is coated on the outside surface of ceramic die of gold electrode, forming indium oxide sensing layer thickness is 500nm, dries after each coating is finished to apply under infrared lamp next time again, spends the night at last and dries in the shade.The ceramic die that then will be coated with the mesoporous indium oxide gas sensitive is welded on the sensor base, simultaneously the NI-G heater strip is passed ceramic die and also is welded on the connecting line and adds a cover the outer cover collar and be assembled into complete senser element.Its methyl alcohol to 100ppm has best selective, and its sensing capabilities is 12.5.As shown in Figure 4, the transmission electron microscope photo of prepared indium oxide gas sensitive, as we can clearly see from the figure orderly meso-hole structure.
Claims (2)
1. the gas sensor based on the mesoporous indium oxide gas sensitive is characterized in that with the sensing layer of mesoporous indium oxide gas sensitive as sensor.
2. the preparation method of the sensor of claim 1, it is characterized in that adopting the mesoporous indium oxide for preparing with the nanometer casting method as gas sensitive, it is 0.02-0.2g/mL that preparation applies slurry concentration, and the sensing layer thickness through applying the preparation gas sensor is the 500nm-300um scope.
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| CN104495912A (en) * | 2014-12-15 | 2015-04-08 | 宁夏大学 | Triple-mesopore indium oxide formaldehyde gas-sensitive material and preparation method thereof |
| CN104569081A (en) * | 2015-02-04 | 2015-04-29 | 吉林大学 | Ethanol gas sensor based on In2O3 microflower/SnO2 nanoparticle composite material and preparation method of sensor |
| CN104897727A (en) * | 2015-05-22 | 2015-09-09 | 兰州大学 | Gas sensor for high-sensitivity multi-gas detection |
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN107024518A (en) * | 2017-04-18 | 2017-08-08 | 中国工程物理研究院化工材料研究所 | Three-dimensional structure nano indium oxide gas sensor and preparation method thereof |
| CN110357606A (en) * | 2019-08-01 | 2019-10-22 | 东北大学 | A kind of In based on zeolite substrate2O3Nano material preparation and its application |
| CN111233516A (en) * | 2020-04-01 | 2020-06-05 | 蚌埠学院 | Preparation method and application of oxygen detection sensor material |
| CN113092543A (en) * | 2021-04-09 | 2021-07-09 | 中国科学院上海微***与信息技术研究所 | Gas sensing material and preparation method and application thereof |
| CN113740390A (en) * | 2021-09-01 | 2021-12-03 | 山东大学 | Nickel-doped indium oxide nanoparticles and preparation method and application thereof |
| CN113842906A (en) * | 2020-06-25 | 2021-12-28 | 现代自动车株式会社 | Catalyst for converting carbon dioxide into methanol by hydrogenation and method for preparing same |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN104495912A (en) * | 2014-12-15 | 2015-04-08 | 宁夏大学 | Triple-mesopore indium oxide formaldehyde gas-sensitive material and preparation method thereof |
| CN104569081A (en) * | 2015-02-04 | 2015-04-29 | 吉林大学 | Ethanol gas sensor based on In2O3 microflower/SnO2 nanoparticle composite material and preparation method of sensor |
| CN104897727A (en) * | 2015-05-22 | 2015-09-09 | 兰州大学 | Gas sensor for high-sensitivity multi-gas detection |
| CN107024518A (en) * | 2017-04-18 | 2017-08-08 | 中国工程物理研究院化工材料研究所 | Three-dimensional structure nano indium oxide gas sensor and preparation method thereof |
| CN110357606A (en) * | 2019-08-01 | 2019-10-22 | 东北大学 | A kind of In based on zeolite substrate2O3Nano material preparation and its application |
| CN111233516A (en) * | 2020-04-01 | 2020-06-05 | 蚌埠学院 | Preparation method and application of oxygen detection sensor material |
| CN111233516B (en) * | 2020-04-01 | 2022-05-17 | 蚌埠学院 | Preparation method and application of oxygen detection sensor material |
| CN113842906A (en) * | 2020-06-25 | 2021-12-28 | 现代自动车株式会社 | Catalyst for converting carbon dioxide into methanol by hydrogenation and method for preparing same |
| CN113092543A (en) * | 2021-04-09 | 2021-07-09 | 中国科学院上海微***与信息技术研究所 | Gas sensing material and preparation method and application thereof |
| CN113740390A (en) * | 2021-09-01 | 2021-12-03 | 山东大学 | Nickel-doped indium oxide nanoparticles and preparation method and application thereof |
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Application publication date: 20131016 |