CN111116232A - Synthesis method of formaldehyde gas sensor sensitive material - Google Patents
Synthesis method of formaldehyde gas sensor sensitive material Download PDFInfo
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- CN111116232A CN111116232A CN201911284155.1A CN201911284155A CN111116232A CN 111116232 A CN111116232 A CN 111116232A CN 201911284155 A CN201911284155 A CN 201911284155A CN 111116232 A CN111116232 A CN 111116232A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/505—Tin oxide
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The invention relates to the technical field of gas detection, and discloses a method for synthesizing a formaldehyde gas sensor sensitive material, which comprises the following steps: printing a metallic tin layer on the ceramic sheet printed with the prong electrodes, and carrying out annealing treatment; performing ultrasonic treatment, washing with deionized water and ethanol for multiple times, and drying; placing the ceramic wafer in a reaction kettle for hydrothermal reaction; immersing the grown tin oxide precursor into fresh hydrogen peroxide H2O2(30 wt.%) and NH monohydrate3·H2Adding O (25 wt%) into the mixed solution, washing with distilled water, and drying in air; annealing the nanowire array at constant temperature in an oxygen-enriched environment; finally, rutile type tin dioxide nano SnO2The NW was cooled to room temperature. By the mode, the invention can provide more active sites and greatly improveThe response value of the sensor guarantees the corresponding long-term stability of the sensitive material, and the binding force of the sensitive material can be improved to a great extent.
Description
Technical Field
The invention relates to the technical field of gas detection, in particular to a method for synthesizing a sensitive material of a formaldehyde gas sensor.
Background
The indoor air pollution source is caused by furniture pollution to a great extent, and interlayer glue, carpets, paints and most plastic products in new furniture release organic small molecule gases (VOCs), and the gases contain a large amount of formaldehyde gas which easily causes human diseases. In this regard, the world health organization and the administrative department of environmental protection in china have established corresponding formaldehyde release standards. Therefore, in recent years, the demand for formaldehyde detection equipment, particularly high-selectivity and high-sensitivity formaldehyde detection equipment, is increasing.
At present, most of sensitive materials of formaldehyde gas sensors are zinc oxide and tin dioxide as sensitive substrate materials, wherein the tin dioxide is an important n-type semiconductor, has a proper conduction band valence band position and low cost, and is a key research point of sensitive materials of semiconductor sensors.
The tin dioxide of the nano structure can generate different performances due to different shapes, and the tin dioxide of the one-dimensional nano structure has peculiar physical and chemical characteristics.
1) The tin dioxide with the one-dimensional structure has a large specific surface area, the morphology has great advantages for being used as a gas sensor, and the tin dioxide can have more active sites to obtain target gas;
2) the one-dimensional nanowire structure can provide a good electronic channel;
3) the one-dimensional structure can effectively avoid crystal growth and prolong the service life.
Because most of the existing tin oxide nanowires are in a powder state and are coated on the additional heat sheet by thick film and thin film printing and dot diagram of a dispenser or other modes, the whole states of the nanowires are mutually crossed and staggered, and the original advantages are greatly reduced. Therefore, the conventional formaldehyde semiconductor gas sensor has low response sensitivity, poor selectivity and zero drift even after long-term use.
In addition, the firmness of the bonding of the powder sensitive material and the substrate is also an important factor for the stable performance of the sensor.
Disclosure of Invention
The invention mainly solves the technical problem of providing a method for synthesizing a sensitive material of a formaldehyde gas sensor, which can provide more active sites, greatly improve the response value of the sensor, ensure the corresponding long-term stability of the sensitive material and greatly improve the binding force of the sensitive material.
In order to solve the technical problems, the invention adopts a technical scheme that: the synthesis method of the formaldehyde gas sensor sensitive material comprises the following steps:
step 1: printing a metallic tin layer on the ceramic sheet printed with the prong electrodes, and annealing the printed metallic tin layer to obtain a tin oxide thin layer;
step 2: carrying out ultrasonic treatment on the ceramic wafer, washing the ceramic wafer for multiple times by using deionized water and ethanol, and drying the ceramic wafer to ensure that the surface microstructure of the tin oxide thin layer is uneven tin oxide particles which can be used as a seed layer for growth of tin oxide nanowires;
and step 3: placing the ceramic wafer in a reaction kettle to carry out hydrothermal reaction for 1-36h, and growing a tin oxide precursor, wherein the morphology of the tin oxide precursor is the morphology of the array arrangement nano wires;
and 4, step 4: immersing the grown tin oxide precursor (ceramic wafer) into a fresh first solution, washing with a large amount of distilled water after a period of time, and then placing in the air for natural drying to obtain a nanowire array; wherein the first solution comprises hydrogen peroxide H2O2(30 wt.%) and NH monohydrate3·H2O(25wt％)，H2O2And NH3·H2The volume ratio of O is 1-10: 10-1;
and 5: annealing the nanowire array in an oxygen-rich environment at a constant temperature of 200-800 ℃ for 0.1-5h to obtain rutile type tin dioxide nano SnO2NW；
Step 6: the rutile type stannic oxide nano SnO2The NW was cooled to room temperature.
Preferably, the specific operation of step 1 is as follows:
A. preparing a ceramic wafer printed with fork tooth electrodes, and cleaning for later use;
B. weighing tin powder with the particle size of 10-100 microns, then adding terpineol which is 1-3 times of the mass of the tin powder, span 85 (sorbitan trioleate) which is 0.01-0.5 time of the mass of the tin powder and ethyl cellulose which is 0.01-0.2 time of the mass of the tin powder, and fully and uniformly mixing to obtain printing slurry of metallic tin;
C. selecting a silk-screen printing plate with a proper pattern according to actual conditions, and carrying out silk-screen printing on the surface of the ceramic plate on a printing machine by using indexes that the printing gap is 0.1-50 microns and the pressure is 5-200Pa so as to obtain a metallic tin layer with the thickness of 1-10 microns;
D. and annealing the printed ceramic wafer at the constant temperature of 120-800 ℃ for 0.5-5h to volatilize organic matters, thereby obtaining the tin oxide thin layer with a certain pattern.
Preferably, in step 3: the lining of the reaction kettle is made of polytetrafluoroethylene; the mixed solution in the reaction kettle comprises water, 2-butanone, ethanol, hydrochloric acid (the concentration is 37%) and tetrabutyl stannate (Sn (OBun)4), wherein the water accounts for 0-50% of the mixed solution, the 2-butanone accounts for 5-20% of the mixed solution, the ethanol accounts for 0-10% of the mixed solution, the hydrochloric acid accounts for 20-80% of the mixed solution, and the tetrabutyl stannate accounts for 1-11% of the mixed solution; the mixed solution in the reaction kettle is controlled at a constant temperature, and the constant temperature is 120-300 ℃.
Preferably, in step 5: the oxygen flow of the oxygen-enriched environment is 0.5-1.0Lmin-1。
The invention has the beneficial effects that: the tin oxide nanowire structure has a large specific surface area, can provide more active sites, and greatly improves the response value of a sensor; in addition, the nanowire structure arranged in the array can provide a more unobstructed electronic channel, and the internal resistance of the sensitive material is reduced; moreover, the nanowire structure belongs to in-situ growing nanowires, the binding force of materials ensures the corresponding long-term stability of sensitive materials, and meanwhile, the nanowire structure arranged in an array can effectively prevent crystal grains from growing up and prolong the service life of the sensor. Finally, the nanowire structure is controllable, and a foundation can be provided for subsequent gas sensor research.
Drawings
FIG. 1 is a microscopic morphology of a tin dioxide nanowire in the sensitive material of the formaldehyde gas sensor of the invention;
FIG. 2 is a microscopic morphology image of the tin dioxide nanowire amplified in the formaldehyde gas sensor sensitive material of the invention.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Please refer to fig. 1 and 2
A method for synthesizing a formaldehyde gas sensor sensitive material comprises the following steps:
step 1: printing a metallic tin layer on the ceramic sheet printed with the prong electrodes, and annealing the printed metallic tin layer to obtain a tin oxide thin layer;
step 2: carrying out ultrasonic treatment on the ceramic wafer, washing the ceramic wafer for multiple times by using deionized water and ethanol, and drying the ceramic wafer to ensure that the surface microstructure of the tin oxide thin layer is uneven tin oxide particles which can be used as a seed layer for growth of tin oxide nanowires;
and step 3: placing the ceramic wafer in a reaction kettle to carry out hydrothermal reaction for 10h (the reaction time can be any time between 1h and 36h and comprises 1h and 36h per se), and growing a tin oxide precursor, wherein the morphology of the tin oxide precursor is the morphology of the array arrangement nano wires; the lining of the reaction kettle is made of polytetrafluoroethylene;
the mixed solution in the reaction kettle comprises water, 2-butanone, ethanol, hydrochloric acid (with a concentration of 37%) and tetrabutyl stannate (sn (obun)4), the water accounts for 0% (which may be any value between 0-50%, including 0% and 50% itself), the 2-butanone accounts for 11% (which may be any value between 5-20%, including 5% and 20% itself), the ethanol accounts for 7% (which may be any value between 0-10%, including 0% and 10% itself), the hydrochloric acid accounts for 75% (which may be any value between 20-80%, including 20% and 80% itself), the tetrabutyl stannate accounts for 7% (which may be any value between 1-11%, including 1% and 11% by itself); controlling the constant temperature of the mixed solution in the reaction kettle, wherein the constant temperature is 120-300 ℃ (the temperature value can be any value between 120-300 ℃, including 120 ℃ and 300 ℃);
and 4, step 4: immersing the grown tin oxide precursor (ceramic wafer) into a fresh first solution, washing with a large amount of distilled water after 10 minutes, and then placing in the air for natural drying to obtain a nanowire array (the nanowire array has better crystallinity and is more stable compared with the tin oxide precursor before immersion); wherein the first solution comprises hydrogen peroxide H2O2(30 wt.%) and NH monohydrate3·H2O(25wt％)，H2O2And NH3·H2The volume ratio of O is 3: 8 (the ratio can be any ratio between 1: 10 and 10: 1, including 1: 10 and 10: 1 per se);
and 5: nanowire arrays were grown at an oxygen flow of 0.6Lmin-1(the oxygen flow may be 0.5-1.0Lmin-1Any flow value between, including 0.5Lmin-1And 1.0Lmin-1Self) in oxygen-enriched environment for 2h (the annealing time can be any time between 0.1-5h, including 0.1h and 5h per se), the constant temperature is 500 ℃ (the constant temperature can be any value between 200 and 800 ℃, including 200 ℃ and 800 ℃), and the rutile type tin dioxide nano SnO can be obtained2NW；
Step 6: the rutile type stannic oxide nano SnO2The NW (ceramic wafer) was cooled to room temperature.
The specific operation of the step 1 is as follows:
A. preparing a ceramic wafer printed with fork tooth electrodes, and cleaning for later use;
B. weighing 100g of tin powder with the particle size of 50 micrometers (the particle size can be 10-100 micrometers and comprises 10 micrometers and 100 micrometers per se), then adding 200g of terpineol, 30g of span 85 (sorbitan trioleate) and 10g of ethyl cellulose (the mass of the terpineol can be 1-3 times of that of the tin powder, wherein the times comprise 1 time and 3 times of that of the terpineol per se, the mass of the span 85 can be 0.01-0.5 time of that of the tin powder, the times comprise 0.01 time and 0.5 time of that of the ethyl cellulose, the mass of the ethyl cellulose can be 0.01-0.2 time of that of the tin powder, and the times comprise 0.01 time and 0.2 time of that of the ethyl cellulose), and fully mixing to obtain the printing slurry of metallic tin;
C. selecting a silk-screen printing plate with a proper pattern according to actual conditions, and carrying out silk-screen printing on the surface of the ceramic sheet on a printing machine by using an index with a printing gap of 0.1 micrometer (the gap value can be any gap value between 0.1 and 50 micrometers and comprises 0.1 micrometer and 50 micrometers per se) and a pressure of 5Pa (the pressure value can be any pressure value between 5 and 200Pa and comprises 5Pa and 200Pa per se) to obtain a metallic tin layer with the thickness of 1 micrometer (different thickness values can be obtained according to different printing gaps and pressures, and the thickness of the metallic tin layer can be any thickness value between 1 and 10 micrometers and comprises 1 micrometer and 10 micrometers per se);
D. and (3) annealing the printed ceramic wafer at a constant temperature of 300 ℃ (the temperature value can be any value between 120 ℃ and 800 ℃, including 120 ℃ and 800 ℃ per se) for 3h (the annealing time can be any time between 0.5h and 5h, including 0.5h and 5h per se), volatilizing organic matters, and obtaining a tin oxide thin layer with a certain pattern.
The metallic tin layer with the thickness of 1-10 microns can be obtained by adjusting the viscosity and solid content of the tin paste, the coating gap used for printing and the coating pressure parameters. Experiments for countless times prove that the too thin metal tin layer can cause the insufficient bonding force and the too large resistance of the metal tin layer and the too thick metal tin layer can increase the cost.
Metallic tin having a specific thickness can be printed on the ceramic sheet on which the tine electrodes are printed using screen printing, allowing easy control of the macroscopic shape of the sensitive material desired. And annealing the printed metallic tin layer, thereby not only effectively removing organic matters in the printing slurry, but also improving the binding force between the metallic tin layer and the ceramic wafer. The tin oxide thin layer is obtained by printing metal tin on the ceramic sheet and annealing, so that the shape of the metal tin layer can be well controlled, the printing thickness of the metal tin layer can be controlled, and the consistency of products can be greatly improved.
The tin oxide nanowires (in-situ growth nanowires) arranged in parallel are grown from the metallic tin by a hydrothermal method, and the electrochemical properties of the nanowires in a special shape can be perfectly embodied. The ratio of 2-butanone, ethanol and hydrochloric acid in the hydrothermal reaction is changed, the ratio of the diameter to the length of the nanowire can be controlled, and different electrochemical characteristics are reacted, so that the optimal concentration ratio responding to formaldehyde is found. In the experiment, the 2-butanone, the ethanol, the water and the hydrochloric acid are respectively divided into 30 parts of gradient solution, and hydrothermal reaction is respectively carried out, so that the nano wires with different diameters and lengths can be obtained. Statistical analysis shows that the ratio of the diameter to the length of the nanowire is smaller and smaller when the proportion of water is smaller and the proportion of the organic solvent is larger under the condition of ensuring that the content of hydrochloric acid is higher.
The solvent types in the hydrothermal synthesis are four, and the ratio of the diameter to the length of the tin dioxide nanowire can be effectively controlled by adjusting the proportion of the solvents, so that the nanowires with different gas response performances can be obtained. The shape determines the performance, and the synthesis method of the formaldehyde sensitive material with the highest formaldehyde selectivity, the highest sensitivity and the fastest response recovery time can be found by utilizing different shapes.
The in-situ grown tin oxide nanowire is prepared by a hydrothermal method, and the nanowire and the printed tin layer are integrated, so that the binding force of a sensitive material can be improved to a great extent, and the stability of a conductive channel is ensured. Compared with the preparation method of synthesizing the powdered tin oxide nanowire and coating the powdered tin oxide nanowire on the substrate, the preparation method can better embody that the in-situ growth preparation method has higher response stability.
The formaldehyde gas sensor sensitive material prepared by the synthesis method has a very low detection limit on formaldehyde, can accurately detect ppb level gas, and has response recovery time less than 1 s. The tin dioxide nanowire in the sensitive material is an in-situ growth nanowire, the combination with the substrate is very firm, and the nanowire structure arranged in an array can effectively prevent crystal grains from growing, so that the long-term use stability of the sensor is greatly guaranteed.
The tin oxide nanowire structure has a large specific surface area, can provide more active sites, and greatly improves the response value of a sensor; in addition, the nanowire structure arranged in the array can provide a more unobstructed electronic channel, and the internal resistance of the sensitive material is reduced; moreover, the nanowire structure belongs to in-situ growing nanowires, the binding force of materials ensures the corresponding long-term stability of sensitive materials, and meanwhile, the nanowire structure arranged in an array can effectively prevent crystal grains from growing up and prolong the service life of the sensor. Finally, the nanowire structure is controllable, and a foundation can be provided for subsequent gas sensor research.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (4)
1. A method for synthesizing a formaldehyde gas sensor sensitive material is characterized by comprising the following steps:
step 1: printing a metallic tin layer on the ceramic sheet printed with the prong electrodes, and annealing the printed metallic tin layer to obtain a tin oxide thin layer;
step 2: carrying out ultrasonic treatment on the ceramic wafer, washing the ceramic wafer for multiple times by using deionized water and ethanol, and drying the ceramic wafer to ensure that the surface microstructure of the tin oxide thin layer is uneven tin oxide particles which can be used as a seed layer for growth of tin oxide nanowires;
and step 3: placing the ceramic wafer in a reaction kettle to carry out hydrothermal reaction for 1-36h, and growing a tin oxide precursor, wherein the morphology of the tin oxide precursor is the morphology of the array arrangement nano wires;
and 4, step 4: immersing the grown tin oxide precursor (ceramic wafer) into a fresh first solution, washing with a large amount of distilled water, and then placing in the air for natural drying to obtain a nanowire array; wherein the first solution comprises hydrogen peroxide H2O2(30 wt.%) and NH monohydrate3·H2O(25wt％)，H2O2And NH3·H2The volume ratio of O is 1-10: 10-1;
and 5: annealing the nanowire array in an oxygen-rich environment at a constant temperature of 200-800 ℃ for 0.1-5h to obtain rutile type tin dioxide nano SnO2NW；
Step 6: the rutile type stannic oxide nano SnO2The NW was cooled to room temperature.
2. The method for synthesizing the formaldehyde gas sensor sensitive material as claimed in claim 1, wherein the specific operation of step 1 is as follows:
A. preparing a ceramic wafer printed with fork tooth electrodes, and cleaning for later use;
B. weighing tin powder with the particle size of 10-100 microns, then adding terpineol which is 1-3 times of the mass of the tin powder, span 85 (sorbitan trioleate) which is 0.01-0.5 time of the mass of the tin powder and ethyl cellulose which is 0.01-0.2 time of the mass of the tin powder, and fully and uniformly mixing to obtain printing slurry of metallic tin;
C. screen printing is carried out on the surface of the ceramic wafer on a printing machine by using the indexes that the printing gap is 0.1-50 microns and the pressure is 5-200Pa to obtain a metallic tin layer with the thickness of 1-10 microns;
D. and annealing the printed ceramic wafer at the constant temperature of 120-800 ℃ for 0.5-5h to volatilize organic matters, thereby obtaining the tin oxide thin layer with a certain pattern.
3. The method for synthesizing the formaldehyde gas sensor sensitive material as claimed in claim 1 or 2, wherein in step 3: the lining of the reaction kettle is made of polytetrafluoroethylene; the mixed solution in the reaction kettle comprises water, 2-butanone, ethanol, hydrochloric acid (the concentration is 37%) and tetrabutyl stannate (Sn (OBun)4), wherein the water accounts for 0-50% of the mixed solution, the 2-butanone accounts for 5-20% of the mixed solution, the ethanol accounts for 0-10% of the mixed solution, the hydrochloric acid accounts for 20-80% of the mixed solution, and the tetrabutyl stannate accounts for 1-11% of the mixed solution; the mixed solution in the reaction kettle is controlled at a constant temperature, and the constant temperature is 120-300 ℃.
4. The method for synthesizing the formaldehyde gas sensor sensitive material as claimed in claim 1, wherein in step 5: the oxygen flow of the oxygen-enriched environment is 0.5-1.0Lmin-1。
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Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284474A (en) * | 1999-08-17 | 2001-02-21 | 惠春 | Tin dioxide-base nanometer crystal gas-sensitive material and its preparation |
| US20030067003A1 (en) * | 2001-09-28 | 2003-04-10 | Gole James L. | Tin oxide nanostructures |
| CN1746131A (en) * | 2005-05-19 | 2006-03-15 | 北京化工大学 | Gas-sensing material with noble metal doped composite metal oxide and its production |
| KR100791812B1 (en) * | 2006-07-03 | 2008-01-04 | 한국과학기술연구원 | Tin oxide nanowire-based gas sensor and method for manufacturing the same |
| CN101172644A (en) * | 2007-10-16 | 2008-05-07 | 上海大学 | Method of producing quadrangular shaped tin oxide nano wire |
| CN101549884A (en) * | 2009-05-27 | 2009-10-07 | 清华大学 | Method for synthesizing tin dioxide nano-particle |
| CN102290248A (en) * | 2011-06-10 | 2011-12-21 | 浙江东晶电子股份有限公司 | Method for preparing efficient compound light anode of dye sensitized solar cell |
| CN102336431A (en) * | 2011-06-28 | 2012-02-01 | 西北大学 | SnO2 flowerlike structure nano material and hydrothermal preparation method for the same |
| CN102350094A (en) * | 2011-09-05 | 2012-02-15 | 北京航空航天大学 | Oil and water separator based on micron-nano hiberarchy net membrane and preparation and application method thereof |
| CN102863018A (en) * | 2012-08-30 | 2013-01-09 | 云南锡业股份有限公司 | Preparation method of nanometer tin dioxide particles |
| CN103412008A (en) * | 2013-08-21 | 2013-11-27 | 东北大学 | Pd-doped SnO2 nanowire gas sensor for detecting H2 under low temperature, and preparation method thereof |
| CN103526165A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Transparent conducting thin film as well as preparation method thereof, display base plate and display device |
| CN104122304A (en) * | 2014-07-22 | 2014-10-29 | 苏州能斯达电子科技有限公司 | Preparation method of sensor based on stannic oxide functionalized graphene |
| CN204129000U (en) * | 2014-07-18 | 2015-01-28 | 苏州能斯达电子科技有限公司 | A kind of MEMS gas sensor |
| CN104698041A (en) * | 2013-12-06 | 2015-06-10 | 纳米新能源生命科技（唐山）有限责任公司 | An ethanol sensor based on a zinc oxide nanometer structure and a preparing method thereof |
| CN105236472A (en) * | 2015-09-30 | 2016-01-13 | 西北大学 | Preparation method of SnO2 nano-wire array |
| CN105609310A (en) * | 2016-01-21 | 2016-05-25 | 湘潭大学 | Surface modification method for SnO<2>-based photo-anode |
| CN105668618A (en) * | 2016-04-15 | 2016-06-15 | 广东工业大学 | Stannic oxide nanowire and preparation method thereof |
| CN105928934A (en) * | 2016-04-21 | 2016-09-07 | 林业城 | Anti-lightening power distribution cabinet based on gasochromic gas sensor |
| CN105954201A (en) * | 2016-04-21 | 2016-09-21 | 林业城 | Balloon aerating device which can inspect hydrogen leakage |
| CN106971852A (en) * | 2017-04-14 | 2017-07-21 | 上海为然环保科技有限公司 | A kind of DSSC of modified light anode structure |
| CN106970118A (en) * | 2017-03-28 | 2017-07-21 | 吉林大学 | A kind of CoO/SnO2Composition of sensitive material and preparation method thereof |
| CN108217717A (en) * | 2017-12-19 | 2018-06-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Mn doping stannic oxide gas sensitives and products thereof and application |
| CN108732207A (en) * | 2018-04-17 | 2018-11-02 | 上海理工大学 | A kind of sensitive material used in formaldehyde examination and preparation method and application |
| CN109911929A (en) * | 2019-03-29 | 2019-06-21 | 东北大学 | A kind of Pt is catalyst preparation SnO2The methods and applications of nano material |
| CN110047915A (en) * | 2019-04-12 | 2019-07-23 | 西交利物浦大学 | One kind is based on two-dimensional semiconductor material film transistor and preparation method thereof |
| CN209747517U (en) * | 2019-04-12 | 2019-12-06 | 西交利物浦大学 | Two-dimensional semiconductor material based thin film transistor |
-
2019
- 2019-12-13 CN CN201911284155.1A patent/CN111116232A/en active Pending
Patent Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284474A (en) * | 1999-08-17 | 2001-02-21 | 惠春 | Tin dioxide-base nanometer crystal gas-sensitive material and its preparation |
| US20030067003A1 (en) * | 2001-09-28 | 2003-04-10 | Gole James L. | Tin oxide nanostructures |
| CN1746131A (en) * | 2005-05-19 | 2006-03-15 | 北京化工大学 | Gas-sensing material with noble metal doped composite metal oxide and its production |
| KR100791812B1 (en) * | 2006-07-03 | 2008-01-04 | 한국과학기술연구원 | Tin oxide nanowire-based gas sensor and method for manufacturing the same |
| CN101172644A (en) * | 2007-10-16 | 2008-05-07 | 上海大学 | Method of producing quadrangular shaped tin oxide nano wire |
| CN101549884A (en) * | 2009-05-27 | 2009-10-07 | 清华大学 | Method for synthesizing tin dioxide nano-particle |
| CN102290248A (en) * | 2011-06-10 | 2011-12-21 | 浙江东晶电子股份有限公司 | Method for preparing efficient compound light anode of dye sensitized solar cell |
| CN102336431A (en) * | 2011-06-28 | 2012-02-01 | 西北大学 | SnO2 flowerlike structure nano material and hydrothermal preparation method for the same |
| CN102350094A (en) * | 2011-09-05 | 2012-02-15 | 北京航空航天大学 | Oil and water separator based on micron-nano hiberarchy net membrane and preparation and application method thereof |
| CN102863018A (en) * | 2012-08-30 | 2013-01-09 | 云南锡业股份有限公司 | Preparation method of nanometer tin dioxide particles |
| CN103412008A (en) * | 2013-08-21 | 2013-11-27 | 东北大学 | Pd-doped SnO2 nanowire gas sensor for detecting H2 under low temperature, and preparation method thereof |
| CN103526165A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Transparent conducting thin film as well as preparation method thereof, display base plate and display device |
| CN104698041A (en) * | 2013-12-06 | 2015-06-10 | 纳米新能源生命科技（唐山）有限责任公司 | An ethanol sensor based on a zinc oxide nanometer structure and a preparing method thereof |
| CN204129000U (en) * | 2014-07-18 | 2015-01-28 | 苏州能斯达电子科技有限公司 | A kind of MEMS gas sensor |
| CN104122304A (en) * | 2014-07-22 | 2014-10-29 | 苏州能斯达电子科技有限公司 | Preparation method of sensor based on stannic oxide functionalized graphene |
| CN105236472A (en) * | 2015-09-30 | 2016-01-13 | 西北大学 | Preparation method of SnO2 nano-wire array |
| CN105609310A (en) * | 2016-01-21 | 2016-05-25 | 湘潭大学 | Surface modification method for SnO<2>-based photo-anode |
| CN105668618A (en) * | 2016-04-15 | 2016-06-15 | 广东工业大学 | Stannic oxide nanowire and preparation method thereof |
| CN105928934A (en) * | 2016-04-21 | 2016-09-07 | 林业城 | Anti-lightening power distribution cabinet based on gasochromic gas sensor |
| CN105954201A (en) * | 2016-04-21 | 2016-09-21 | 林业城 | Balloon aerating device which can inspect hydrogen leakage |
| CN106970118A (en) * | 2017-03-28 | 2017-07-21 | 吉林大学 | A kind of CoO/SnO2Composition of sensitive material and preparation method thereof |
| CN106971852A (en) * | 2017-04-14 | 2017-07-21 | 上海为然环保科技有限公司 | A kind of DSSC of modified light anode structure |
| CN108217717A (en) * | 2017-12-19 | 2018-06-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Mn doping stannic oxide gas sensitives and products thereof and application |
| CN108732207A (en) * | 2018-04-17 | 2018-11-02 | 上海理工大学 | A kind of sensitive material used in formaldehyde examination and preparation method and application |
| CN109911929A (en) * | 2019-03-29 | 2019-06-21 | 东北大学 | A kind of Pt is catalyst preparation SnO2The methods and applications of nano material |
| CN110047915A (en) * | 2019-04-12 | 2019-07-23 | 西交利物浦大学 | One kind is based on two-dimensional semiconductor material film transistor and preparation method thereof |
| CN209747517U (en) * | 2019-04-12 | 2019-12-06 | 西交利物浦大学 | Two-dimensional semiconductor material based thin film transistor |
Non-Patent Citations (2)
| Title |
|---|
| HUI HUANG等: "Semiconductor gas sensor based on tin oxide nanorods prepared by plasma-enhanced chemical vapor deposition with postplasma treatment", 《APPLIED PHYSICS LETTERS》 * |
| 吴承玲等: "SnO2纳米晶体的液相法可控合成研究进展", 《吴承玲等》 * |
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