CN1490618A - Zeolite based tin peroxide gas sensitive material and preparation - Google Patents
Zeolite based tin peroxide gas sensitive material and preparation Download PDFInfo
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- CN1490618A CN1490618A CNA031419216A CN03141921A CN1490618A CN 1490618 A CN1490618 A CN 1490618A CN A031419216 A CNA031419216 A CN A031419216A CN 03141921 A CN03141921 A CN 03141921A CN 1490618 A CN1490618 A CN 1490618A
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- molecular sieve
- zeolite molecular
- zeolite
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Abstract
The material can be obtained by dipping zeolite molecular sieve in tin salt solution and then to carry on steaming for dry and baking for forming nano-crystal of tin dioxide on surface of the zeolite.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to Zeolite-based nano tin dioxide gas-sensitive material and preparation method thereof.
Background technology
Gas sensor is used increasingly extensive at aspects such as control automatically, environment measurings, be the message elements of widespread demand in industrial and agricultural production and the national defense construction.Gas sensitive is a material base of making the high-performance gas sensor.Practical application is very strict at performance requirements such as sensitivity, selectivity, stability, serviceable life, the range of linearity, response speeds to the air-sensitive sensing material.At present, the main type of practical gas sensor has catalytic combustion type, semiconductor-type, solid electrolyte formula, temperature conductivity varying type etc., and wherein semiconductor-type is most widely used, research is maximum.(Chinese invention patent, application number: 99115842.3), this material is in proportion trickle powder Al to have invented the manufacture method of tin dioxide-base nanometer crystal gas-sensitive material and tin ash thick film methylmethane gas sensitive thereof as Hui Chun and Xu Ailan
2O
3, SiO
2Adding has in the butter of tin solution of specific pH value scope with the Pd catalyzer, is carrying out hydrothermal chemical reaction and activation processing more than 100 ℃, thereby obtains the tin dioxide nanocrystal composite granule.People such as Meng Guangyao have invented acetylene, alcohol gas-sensitive material and preparation method (Chinese invention patent, application number: 98125730.5), this material is a raw material with the oxide or the salt of cadmium, indium, samarium, make that to contain the ion mol ratio be Cd: Sm: In=1.65-1.5: 0.5-0.4: 2 mixed solutions, with alkali lye co-precipitation, washing, filtration, oven dry, formed in 4 hours 800 ℃ of roastings.People such as Peng Shaoyi have invented a kind of preparation method of superfine tin dioxide powder, and (Chinese invention patent, application number: 94117467.0), this invention utilizes the synthetic SnO of inorganic salts-organic solvent system supercritical fluid drying technology
2Ultrafine particle by different doping, can be made all gases (CO, H
2, C
2H
5OH etc.) carry out slug type or the thick-film type gas sensitive that low temperature detects.Jap.P. (JP2000356616-A) has been reported that the tin dioxide film of two different components is deposited in succession and has been constituted in the substrate of insulation carbonic oxide and inflammable gas sensor sensitive, the skin of this tin dioxide film contains the Pd of 0.05-1.0% and the Pt of 0.5-5%, and internal layer contains the Pt of 0.5-5%.Jap.P. (JP2000321231-A) has been reported a kind of preparation method of combustible gas sensor, this sensor is to be deposited in the substrate with double-level-metal oxide semiconductor (tin ash) to constitute, and the skin of its sensitive material layer is single tin ash for the tin ash internal layer that antimony mixes.
Zeolite molecular sieve is the inorganic poromerics of a class that is widely used in fields such as absorption, heterocatalysis, gas separation and ion-exchange.In recent years, the zeolitization scholar chooses zeolite molecular sieve as main body, with pure material, as has functional organism, inorganic salts, the nanometer object that metal and metal oxide go out to have controlled micromechanism as object in zeolite cavity interior orientation growth or assembly arranged evenly, thereby be built into new zeolite-nano composite material [Chem.Mater.1992,4,511.], wait that as Zou LiCl is assembled into the STI zeolite quietly and form a kind of wet sensitive sensing material [Chem.Lett.2001,8,810], someone is coated on surface acoustic wave (SAW) device with zeolite as air-sensitive film, crystal microbalance (QCM) is gone up [1.J.Am.Chem.Soc.1989,111,7640.2.J.Phys.Chem.1992,96,9387.3.Microporousand Mesoporous Materials, 1998,23,287.4.Journal of Analytical Chemistry1999,54 (5), 449.] and semi-girder (Cantilever) go up [Microporous and Mesoporous Materials1998,21,403], survey the variation of minimum gas adsorbance according to frequency shift.Also there is the people that the complex of ruthenium is fixed in the zeolite molecular sieve supercage as oxygen sensor [Abstracts of Papers of the American Chemical Society.222:354-Phys, Part 2 Aug 2001.], Jap.P. (JP5279015-A) has reported that doing substrate with monocrystalline silicon prepares zeolite membrane in the above as gas or moisture sensor, Jap.P. (JP5279014-A) has reported that doing substrate with quartz prepares zeolite membrane in the above as moisture sensor, and United States Patent (USP) (US5151110-A) has been reported and coated zeolite molecular sieve as chemoselective sensor etc. on piezoelectric crystal.But the outside surface growing nano sized metal oxide crystal at zeolite does not appear in the newspapers so far as the gas sensing material, and load on the tin dioxide nano-particle of outer surface of zeolite, contact easilier, strengthened the thermal stability of nano particle, be suitable as very much sensing material with reactant molecule.
Summary of the invention
The object of the present invention is to provide that a kind of cost of manufacture is low, Heat stability is good, highly sensitive Zeolite-based nano tin dioxide gas-sensitive material and preparation method thereof.
The new zeolite base nano tin dioxide gas-sensitive material that the present invention proposes is to be immersed in the solubility pink salt by zeolite molecular sieve, the compound substance that roasting forms in air then, and its substrate is a zeolite molecular sieve, outside surface is a tin dioxide nano-particle.
Among the present invention, used zeolite base material can be the natural or synthesis zeolite of 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, as the MFI (ZSM-5) of 10 oxygen unit ring, TON (ZSM-22), FER (ZSM-35), natural stilbite STI etc.; The FAU of 12 oxygen unit ring (Y, X), LAL (L), MTN (ZSM-12), BEA (β), MOR (mordenite), AlPO
4-5, (SO such as MTW
2/ Al
2O
3Scope 3～∞), and the presoma of tin ash is soluble pink salt class is as the halogenide of tin, nitrate, sulfate, acetate, alkoxide etc.
The concrete preparation method of above-mentioned Zeolite-based nano tin dioxide gas-sensitive material is: the pink salt of solubility is dissolved in the corresponding solvent, be made into the solution of concentration at 1-5mol/L, zeolite molecular sieve with finished product is immersed in wherein then, and the mass ratio of soluble-salt and zeolite molecular sieve is 0.1-1; Take out, oven dry, 300-700 ℃ of following roasting, the time of roasting was generally 1-10 hour, can make the Zeolite-based nano tin dioxide gas-sensitive material.
New material feature provided by the invention can be tested with the following method:
1.X-x ray diffraction.This material is the compound substance that zeolite molecular sieve and nano-metal-oxide are formed, and can provide the strong diffraction peak of zeolite molecular sieve and the broadening characteristic diffraction peak of tin ash in x-ray diffraction pattern, judges with this whether nano-stannic oxide forms.
2. transmission electron microscope.Can be clear that existence and the size of nano-stannic oxide by transmission electron microscope at the zeolite molecular sieve grain surface.
3. air-sensitive performance.With this material compressing tablet, both sides connect electrode, and the resistor of contacting is being measured the resistance change of this material under different temperatures, concentration and different gas parts under the constant voltage, thereby records the air-sensitive performance of this material.
(A) is the x-ray diffraction pattern of typical NaY (FAU type) zeolite molecular sieve among Fig. 1, (B) be the x-ray diffraction pattern of nano-stannic oxide and the formed compound substance of NaY zeolite, the weak peak of three broadenings that arrow is represented among the figure belongs to 110 of tin ash, 101, (its diffraction d value is respectively 3.35 to the diffraction peak of 211 3 crystal faces, 2.64 and 1.77 ), from the broadening of three diffraction peaks the strongest of tin ash, illustrate that the nano particle of tin ash forms.The result of transmission electron microscope has confirmed that further nano-stannic oxide forms (Fig. 2) at zeolite surface, and from transmission electron microscope photo, the size of nano-stannic oxide particle is about the 5-8 nanometer.Fig. 3 is the air-sensitive performance experiment at the tin dioxide nano-particle of NaY zeolite surface formation, ordinate is a resistance, horizontal ordinate is the time, curve among the figure in the time of 280 ℃ with the nitrogen that contains 1% hydrogen and nitrogen in the resistance variations by gas sensitive alternately 15 minutes time the at interval, curve from figure is found out, through after the several cycles, the resistance variations of material does not descend, show material stability reliably, we place test more afterwards in three months with this material, and air-sensitive performance does not descend, under the compressing tablet situation, this gas sensitive has corresponding in the time of 280 ℃ to the hydrogen of 100ppm, the corresponding time was less than 1 second.
Description of drawings
Fig. 1 wherein, (A) is the x-ray diffraction pattern of NaY (FAU type) zeolite molecular sieve for the x-ray diffraction pattern of material of the present invention, (B) is the x-ray diffraction pattern of nano-stannic oxide and the formed compound substance of NaY zeolite.
Fig. 2 is the Electronic Speculum figure of material of the present invention.
Fig. 3 is the air-sensitive performance experiment diagram of material of the present invention.
Embodiment
Further describe the present invention below by embodiment:
Embodiment 1: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 3ml, and stirring and dissolving with 1g NaY zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, both got product, be designated as SnO
2-NaY.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano-stannic oxide crystal grain forms at the NaY zeolite surface, and it is of a size of the 5-8 nanometer.Through air-sensitive performance test proof, this material shows good air-sensitive performance to reducibility gas such as carbon monoxide, hydrogen.
Embodiment 2: the SnCl that takes by weighing 0.4g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g EFR zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-FER shows with X-ray diffraction, transmissioning electric mirror test: the size at the nano-stannic oxide particle of EFR zeolite surface production is about 10 nanometers.The air-sensitive performance test shows: this material shows good air-sensitive performance to reducibility gas such as carbon monoxide, hydrogen.
Embodiment 3: the SnCl that takes by weighing 0.4g
22H
2O is positioned in the magnetic boat, adds the deionized water of 2ml, and stirring and dissolving with 1g TON zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-TON characterizes demonstration with X-ray diffraction, transmission electron microscope: the nano-stannic oxide particle size that generates on TON zeolite grain surface is about 10 nanometers.The air-sensitive performance test shows: this material shows good air-sensitive performance to reducibility gas such as carbon monoxide, hydrogen.
Embodiment 4: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 3ml, and stirring and dissolving with 1g BEA zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-BEA, this product show that through X-ray diffraction, transmission electron microscope the size of the tin ash particle that generates on BEA zeolite grain surface is about 10 nanometers.The air-sensitive performance test shows: this material shows good air-sensitive performance to reducibility gas such as carbon monoxide, hydrogen.
Embodiment 5: the SnCl that takes by weighing 0.5g
22H
2O is positioned in the magnetic boat, adds the deionized water of 3ml, and stirring and dissolving with 1g ZSM-5 zeolite molecular sieve dipping wherein, stirs, 100 ℃ of heating, evaporating water was put into muffle furnace with the magnetic boat, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, can get product, be designated as SnO
2-ZSM-5, X-ray diffraction, transmission electron microscope characterize proof: the size of the tin ash particle that generates on ZSM-5 zeolite grain surface is about 15 nanometers.The air-sensitive performance test shows: this material shows good air-sensitive performance to reducibility gas such as carbon monoxide, hydrogen.
Claims (5)
1, a kind of Zeolite-based nano tin dioxide gas-sensitive material is to be immersed in the solubility pink salt by zeolite molecular sieve, and the compound substance that roasting forms in air is characterized in that its substrate is a zeolite molecular sieve then, and outside surface is a tin dioxide nano-particle.
2, gas sensitive according to claim 1 is characterized in that zeolitic material is the natural or synthetic zeolite molecular sieve of 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures.
3, gas sensitive according to claim 2, the zeolite molecular sieve that it is characterized in that 10 oxygen membered ring channel structures adopts MFI (ZSM-5), TON (ZSM-22), FER (ZSM-35), or natural stilbite STI's is a kind of, the zeolite molecular sieve of 12 oxygen unit ring adopt FAU (Y, X), LAL (L), MTN (ZSM-12), BEA (β), MOR, AlPO
4-5, MTW's is a kind of.
4, gas sensitive according to claim 1 is characterized in that solubility pink salt as the tin ash presoma is a kind of in halogenide, nitrate, sulfate, acetate, the pure salt.
5, a kind of preparation method as one of claim 1-4 described gas sensitive, it is characterized in that concrete steps are as follows: the pink salt of described solubility is dissolved in the corresponding solvent, be made into the solution of concentration at 1-5mol/L, with described zeolite molecular sieve dipping wherein, the mass ratio of soluble-salt and zeolite molecular sieve is 0.1-1 then; Take out, oven dry, 300-700 ℃ of following roasting, the time of roasting is to get final product in 1-10 hour.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100411730C (en) * | 2006-05-22 | 2008-08-20 | 苏州科技学院 | Zeolite based nano-titanium dioxide double function material and its prepn. method |
| CN100427943C (en) * | 2006-06-22 | 2008-10-22 | 上海交通大学 | Production of tubing network-structured nano-stannic oxide gas-sensing material |
| CN100429145C (en) * | 2005-06-17 | 2008-10-29 | 中南大学 | Method for assemble nanometer stannic oxide using layered phyllosilicate porous material |
| CN101609059B (en) * | 2009-07-22 | 2013-04-03 | 西南科技大学 | Oxide/silicate mineral fiber nano composite air-sensitive film and preparation method thereof |
| CN103556303A (en) * | 2013-10-19 | 2014-02-05 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN104056657A (en) * | 2014-07-11 | 2014-09-24 | 中国科学院上海硅酸盐研究所 | Hierarchical pore SnO2/ZSM-5 alcohol fuel battery anode catalyst and preparation method thereof |
| CN107024513A (en) * | 2016-02-01 | 2017-08-08 | 武汉清琪科技有限公司 | Gas sensor, gas sensitive devices and system |
| CN108046829A (en) * | 2017-12-20 | 2018-05-18 | 东北大学 | A kind of nonmetallic mineral porous substrate and its preparation method and application |
| CN108589260A (en) * | 2018-04-08 | 2018-09-28 | 上海理工大学 | A kind of preparation method for detecting the graded structure tin dioxide gas-sensitive material of formaldehyde gas |
| CN110589875A (en) * | 2019-09-17 | 2019-12-20 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| 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 |
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2003
- 2003-07-29 CN CN 03141921 patent/CN1288082C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429145C (en) * | 2005-06-17 | 2008-10-29 | 中南大学 | Method for assemble nanometer stannic oxide using layered phyllosilicate porous material |
| CN100411730C (en) * | 2006-05-22 | 2008-08-20 | 苏州科技学院 | Zeolite based nano-titanium dioxide double function material and its prepn. method |
| CN100427943C (en) * | 2006-06-22 | 2008-10-22 | 上海交通大学 | Production of tubing network-structured nano-stannic oxide gas-sensing material |
| CN101609059B (en) * | 2009-07-22 | 2013-04-03 | 西南科技大学 | Oxide/silicate mineral fiber nano composite air-sensitive film and preparation method thereof |
| CN103556303B (en) * | 2013-10-19 | 2015-06-10 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN103556303A (en) * | 2013-10-19 | 2014-02-05 | 山东大学 | Preparation method of tin oxide fiber precursor and tin oxide crystal fibers |
| CN104056657A (en) * | 2014-07-11 | 2014-09-24 | 中国科学院上海硅酸盐研究所 | Hierarchical pore SnO2/ZSM-5 alcohol fuel battery anode catalyst and preparation method thereof |
| CN104056657B (en) * | 2014-07-11 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Multi-stage porous SnO 2/ ZSM-5 methanol fuel cell anode catalyzer and preparation method thereof |
| CN107024513A (en) * | 2016-02-01 | 2017-08-08 | 武汉清琪科技有限公司 | Gas sensor, gas sensitive devices and system |
| CN108046829A (en) * | 2017-12-20 | 2018-05-18 | 东北大学 | A kind of nonmetallic mineral porous substrate and its preparation method and application |
| CN108589260A (en) * | 2018-04-08 | 2018-09-28 | 上海理工大学 | A kind of preparation method for detecting the graded structure tin dioxide gas-sensitive material of formaldehyde gas |
| CN108589260B (en) * | 2018-04-08 | 2021-07-13 | 上海理工大学 | Preparation method of tin dioxide gas-sensitive material with hierarchical structure for detecting formaldehyde gas |
| CN110589875A (en) * | 2019-09-17 | 2019-12-20 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| CN110589875B (en) * | 2019-09-17 | 2021-10-26 | 复旦大学 | Gas-sensitive nano material based on single-layer ordered tin oxide nano bowl branched zinc oxide nanowire structure, preparation process and application thereof |
| 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 |
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| CN1288082C (en) | 2006-12-06 |
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