CN103926285A - Method for manufacturing hydrogen sensor by using precious metal doped titanium dioxide nanometer powder - Google Patents
Method for manufacturing hydrogen sensor by using precious metal doped titanium dioxide nanometer powder Download PDFInfo
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- CN103926285A CN103926285A CN201410154763.1A CN201410154763A CN103926285A CN 103926285 A CN103926285 A CN 103926285A CN 201410154763 A CN201410154763 A CN 201410154763A CN 103926285 A CN103926285 A CN 103926285A
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- titanium dioxide
- hydrogen
- precious metal
- nanometer powder
- hydrogen sensor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/005—Specially adapted to detect a particular component for H2
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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
Abstract
The invention belongs to the technical field of hydrogen sensor manufacturing and relates to a method for manufacturing a hydrogen sensor by using precious metal doped titanium dioxide nanometer powder. The method comprises the following steps: (1) mixing titanium dioxide nanometer powder and precious metal powder accounting for 1-10% of the titanium dioxide nanometer powder in weight; (2) mixing the doped titanium dioxide nanometer powder and deionized water, grinding, pelleting, and pressing to form a blank body by a mold; (3) sintering the blank body at the temperature being 350-600 DEG C for 0.5-2h; and (4) forming paired metal electrodes on the surface of a sintered nanometer block. The hydrogen sensor manufactured by adopting the method is very good in response to hydrogen, and can reduce the working temperature until the room temperature.
Description
Technical field
The invention belongs to hydrogen gas sensor preparing technical field, especially relate to a kind of method that precious metal doping titanic oxide nano is prepared hydrogen gas sensor.
Background technology
In various fields such as chemical industry, semiconductor, food processing and energy production, all need environment density of hydrogen to carry out Real-Time Monitoring.Current hydrogen gas sensor generally can be divided into several large classes of heat-conduction-type, catalytic combustion-type, galvanochemistry type and semi-conductor type.Wherein the sensitivity of heat conduction and catalytic combustion-type sensor is on the low side, and not good to hydrogen selective; Electrochemical hydrogen gas sensor at room temperature has higher sensitivity and response speed faster, is most widely used at present.But the electrolytic solution of its use easily leaks, volatilizees, make this hydrogen gas sensor life-span shorter, and price is also more expensive; Semiconductor type sensor, owing to having good stability, simple in structure, low price and being easy to the features such as compound, is specially adapted to the detection of reducibility gas, just more and more causes people's extensive attention.
Traditional oxide semiconductor type hydrogen sensor remains the shortcomings such as high in power consumption, sensitivity is low, working temperature is higher.More common tin oxide hydrogen gas sensor on market for example, it is by serigraphy, on ceramic substrate, to form thick film, then becomes porous ceramics through high temperature sintering.And there is a heater circuit at the back side of ceramic substrate, tin oxide ceramics is heated, make its resistance to hydrogen, have compared with large response and complete detection under higher temperature.And high-temperature heating not only makes device circuitry more complicated, and hydrogen is flammable explosive gas, more increased the risk in test process.Therefore people are in the urgent need to being operated in the semiconductor hydrogen gas sensor of room temperature.
The resistance that it is found that the metal-oxide semiconductor (MOS) of many nanostructureds at room temperature has good response to hydrogen.But these nano materials or be a kind of one-dimentional structure, comprise nano wire at present, nanometer rods, nanobelt, nanotube etc., or be their complex, comprise nano-array, Nanostructure Network, etc.These nanostructured ubiquity consistance are poor, are not suitable for the problems such as production in enormous quantities, seriously restricted their business application in hydrogen gas sensor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that precious metal doping titanic oxide nano is prepared hydrogen gas sensor.
The present invention has the precious metal material of splitting action by doping to hydrogen molecule, makes hydrogen at room temperature be broken down into highly active hydrogen atom, and hydrogen atom reacts with titania and makes its resistance decline, thereby makes the hydrogen gas sensor can be at working and room temperature.
The present invention be take titanic oxide nano material as raw material, by traditional ceramic preparation technology, comprises compressing tablet, sintering, electrode preparation, and prepared material property high conformity, can mass production meets the requirement of hydrogen gas sensor commercial applications.
Technical scheme of the present invention comprises the steps:
1) the noble metal powder of titanic oxide nano material and titanic oxide nano material quality 1 ~ 10% is mixed;
2) the titanic oxide nano material after doping is mixed with deionized water, grind granulation, adopt mould to be pressed into base substrate;
3) by base substrate sintering 0.5-2 hour under 350-600 degree celsius temperature;
4) the nano block surface after sintering is formed into right metal electrode.
Step 2), in, the pressure that is pressed into idiosome can be 10MPa.
In step 3), by base substrate sintering 0.5-2 hour under 350-600 degree celsius temperature, make between titanium dioxide granule to form and connect, but do not occur serious grain growth, densification is also incomplete, thereby obtains having some strength, the block of certain porosity.
In step 4), by methods such as sputter, photoetching, at block surface, be formed into right metal electrode.Described metal electrode can be platinum, gold, silver etc.Metal electrode will form in pairs, to the resistance between two electrodes is measured.
The present invention be take titanic oxide nano material as raw material, the noble metal powders such as certain density Pt, Pd, Au adulterate, by pressure forming, make the base substrate of definite shape, through suitable temperature sintering, obtain having the nano block of certain porosity, by the method for sputter, on nano block surface, prepare metal electrode again, just can access the hydrogen gas sensor at room temperature hydrogen with good response.
The inventive method technique is simply controlled, the consistance of sample, reproducible, and by doped precious metal, control sintering temperature to obtain having the nano block of certain porosity, the hydrogen gas sensor of preparing based on this block has good response to hydrogen, can effectively reduce its working temperature, until room temperature.
Accompanying drawing explanation
Fig. 1, the nano titania block of 550 ℃ of sintering of the 5wt%Pt that adulterates in embodiment 2.
The response of the nano titania block resistance room temperature of 550 ℃ of sintering of 5wt%Pt of adulterating in Fig. 2 embodiment 2 to 1% hydrogen.
Embodiment
Embodiment 1: the commercially available nanometer titanium dioxide photocatalysis material P25 of take is raw material, adds the Pd powder of 1wt%, take deionized water as medium, by bowl mill ball milling 4 hours, 110 degrees Celsius of oven dry, then using deionized water as cementing agent, in agate mortar, grind granulation.By mould, the pressure of 10MPa of take is pressed into diameter as 12 millimeters, and thickness is the disk of 1 millimeter.In batch-type furnace to this disk 350 degrees Celsius of thermal treatments 2 hours, cool to room temperature with the furnace and take out.By magnetron sputtering, on a surface of disk, form a pair of wide 2 millimeters, long 5 millimeters, at a distance of the Pt electrodes of 3 millimeters.This is drawn electrode welding pair of lead wires, be connected to measure two resistance between electrode with ohmer.Hydrogen in environment can make the resistance measuring significantly decline, and the density of hydrogen amplitude that more high resistance declines is larger, according to the resistance measuring, can carry out the measurement of environment density of hydrogen.
Embodiment 2: the commercially available nanometer titanium dioxide photocatalysis material P25 of take is raw material, with deionized water, be made into suspending liquid, the Pt powder that adds 5wt%, by magnetic agitation 4 hours, it is mixed, by centrifuging, go out to be mixed with the P25 of platinum powder, 110 degrees Celsius of oven dry, using deionized water as cementing agent again, in agate mortar, grind granulation.By mould, the pressure of 10MPa of take is pressed into diameter as 12 millimeters, and thickness is the disk of 1 millimeter.In batch-type furnace to this disk 550 degrees Celsius of thermal treatments 2 hours, cool to room temperature with the furnace and take out.From accompanying drawing 1, can see, the pottery that this condition obtains, titania majority is less than 100 nanometers, has more space.This is diffused into ceramic inside for hydrogen is very favorable.By magnetron sputtering, on a surface of disk, form a pair of wide 2 millimeters, long 5 millimeters, at a distance of the Au electrodes of 3 millimeters.This is drawn electrode welding pair of lead wires, between this is to electrode, apply the DC voltage of 15 volts, and measure by this electric current between electrode.The resistance of titania reduces along with the increase of density of hydrogen, and density of hydrogen is larger, and the electric current measuring is just larger, and the resistance calculating according to Ohm law is just larger, sees accompanying drawing 2, in a tubular furnace, when passing into 1%H
2+ N
2time, the resistance that meter is calculated declines 500 times rapidly, and after passing into air, resistance recovers rapidly again, and repeatability is good.According to the corresponding relation of resistance and density of hydrogen, by the resistance measuring, just can know tested density of hydrogen.
Embodiment 3: the commercially available nanometer titanium dioxide photocatalysis material P25 of take is raw material, adds the Au powder of 10wt%, mixes 4 hours, then using alcohol as cementing agent in agate mortar, grinds granulation in agate mortar.By mould, the pressure of 10MPa of take is pressed into diameter as 12 millimeters, and thickness is the disk of 1 millimeter.In batch-type furnace to this disk 600 degrees Celsius of thermal treatments 0.5 hour, cool to room temperature with the furnace and take out.By magnetron sputtering, on a surface of disk, form a pair of wide 2 millimeters, long 5 millimeters, at a distance of the Pt electrodes of 3 millimeters.This is drawn electrode welding pair of lead wires, be connected with ohmer, this is drawn electrode welding pair of lead wires, be connected to measure two resistance between electrode with ohmer, hydrogen in environment can make the resistance measuring significantly decline, and the density of hydrogen amplitude that more high resistance declines is larger, according to the resistance measuring, can carry out the measurement of environment density of hydrogen.
Claims (5)
1. precious metal doping titanic oxide nano is prepared the method for hydrogen gas sensor, it is characterized in that, comprises the steps:
1) the noble metal powder of titanic oxide nano material and titanic oxide nano material quality 1 ~ 10% is mixed;
2) the titanic oxide nano material after doping is mixed with deionized water, grind granulation, adopt mould to be pressed into base substrate;
3) by base substrate sintering 0.5-2 hour under 350-600 degree celsius temperature;
4) the nano block surface after sintering is formed into right metal electrode.
2. method according to claim 1, is characterized in that, described noble metal is Pt, Pd or Au.
3. method according to claim 1 and 2, is characterized in that step 2) in, the pressure that is pressed into idiosome is 10MPa.
4. method according to claim 1 and 2, is characterized in that, in step 4), by sputter or photoetching method, at block surface, is formed into right metal electrode.
5. method according to claim 4, is characterized in that, described metal electrode is platinum, gold or silver-colored.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410154763.1A CN103926285B (en) | 2014-04-17 | 2014-04-17 | Precious metal doping titanic oxide nano prepares the method for hydrogen gas sensor |
| PCT/CN2015/076697 WO2015158272A1 (en) | 2014-04-17 | 2015-04-16 | Method for manufacturing hydrogen gas sensor by using noble metal doped titanium dioxide nano-powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410154763.1A CN103926285B (en) | 2014-04-17 | 2014-04-17 | Precious metal doping titanic oxide nano prepares the method for hydrogen gas sensor |
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| Publication Number | Publication Date |
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| CN103926285A true CN103926285A (en) | 2014-07-16 |
| CN103926285B CN103926285B (en) | 2016-04-27 |
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| CN201410154763.1A Expired - Fee Related CN103926285B (en) | 2014-04-17 | 2014-04-17 | Precious metal doping titanic oxide nano prepares the method for hydrogen gas sensor |
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| WO (1) | WO2015158272A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015158272A1 (en) * | 2014-04-17 | 2015-10-22 | 武汉大学 | Method for manufacturing hydrogen gas sensor by using noble metal doped titanium dioxide nano-powder |
| 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 |
| CN107290397A (en) * | 2017-06-04 | 2017-10-24 | 郑州大学 | The preparation method and hydrogen gas sensor of a kind of hydrogen gas sensor |
| CN107884453A (en) * | 2017-11-13 | 2018-04-06 | 青海民族大学 | A kind of TiO 2 nanotubes modified array Schottky junction hydrogen sensor of palladium and preparation method thereof |
| CN107894448A (en) * | 2017-11-09 | 2018-04-10 | 福州大学 | A kind of light of boron doped titanic oxide helps gas sensor and preparation method and application |
| CN114235904A (en) * | 2021-12-17 | 2022-03-25 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3702769A1 (en) | 2019-02-27 | 2020-09-02 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Capacitive hydrogen sensor |
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| CN101625335A (en) * | 2009-08-19 | 2010-01-13 | 河北理工大学 | Thick-film type limited current hydrogen sensor and preparation method thereof |
| CN102495045A (en) * | 2011-11-07 | 2012-06-13 | 华中科技大学 | Hydrogen sensitive material for optical fiber hydrogen sensor and preparation method of hydrogen sensitive material |
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| CN103926285B (en) * | 2014-04-17 | 2016-04-27 | 武汉大学 | Precious metal doping titanic oxide nano prepares the method for hydrogen gas sensor |
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- 2014-04-17 CN CN201410154763.1A patent/CN103926285B/en not_active Expired - Fee Related
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2015
- 2015-04-16 WO PCT/CN2015/076697 patent/WO2015158272A1/en active Application Filing
Patent Citations (6)
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| US20050224360A1 (en) * | 2004-04-02 | 2005-10-13 | The Penn Research Foundation | Titania nanotube arrays for use as sensors and method of producing |
| CN101290310A (en) * | 2007-04-20 | 2008-10-22 | 中国科学院大连化学物理研究所 | Piezoelectric type hydrogen sensor and its preparation and uses |
| CN102297881A (en) * | 2011-05-26 | 2011-12-28 | 东南大学 | Preparation method of titanium dioxide nanotube based hydrogen sensor |
| US20140051567A1 (en) * | 2011-08-18 | 2014-02-20 | University Of Central Florida Research Foundation, Inc. | Method of forming supported doped palladium containing oxidation catalysts |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015158272A1 (en) * | 2014-04-17 | 2015-10-22 | 武汉大学 | Method for manufacturing hydrogen gas sensor by using noble metal doped titanium dioxide nano-powder |
| 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 |
| CN107024513B (en) * | 2016-02-01 | 2021-08-24 | 武汉市义光亿科贸有限公司 | Gas sensor, gas sensing device and system |
| CN107290397A (en) * | 2017-06-04 | 2017-10-24 | 郑州大学 | The preparation method and hydrogen gas sensor of a kind of hydrogen gas sensor |
| CN107894448A (en) * | 2017-11-09 | 2018-04-10 | 福州大学 | A kind of light of boron doped titanic oxide helps gas sensor and preparation method and application |
| CN107884453A (en) * | 2017-11-13 | 2018-04-06 | 青海民族大学 | A kind of TiO 2 nanotubes modified array Schottky junction hydrogen sensor of palladium and preparation method thereof |
| CN114235904A (en) * | 2021-12-17 | 2022-03-25 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
| CN114235904B (en) * | 2021-12-17 | 2022-11-01 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
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| Publication number | Publication date |
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| CN103926285B (en) | 2016-04-27 |
| WO2015158272A1 (en) | 2015-10-22 |
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