CN105928930A - Refrigeration tank with gas sensing function - Google Patents

Abstract

The invention provides a refrigeration tank with a gas sensing function. A gasochromic gas sensor is installed on the outer surface of the refrigeration tank and comprises a sensitive unit, a heating unit and a data reading unit, wherein the heating unit and the data reading unit are connected with a tungsten oxide gas-sensitive film of the sensitive unit, the heating unit is used as a heating source for the tungsten oxide gas-sensitive film in operation, and the sensitive unit is of a double-layer structure with a hollow-structure central part. The refrigeration tank is based on the gas-sensitive property and gasochromic property of a WO3 nano-material, can realize visual detection of hydrogen, has the advantages of short reaction response time, high sensitivity, convenience in usage and easiness in operation, and achieves the purpose of accurate and timely detection of hydrogen leakage.

Description

A kind of refrigerant tank with gas sensing function

Technical field

The application relates to refrigerant tank field, is specifically related to a kind of refrigerant tank with gas sensing function.

Background technology

Refrigerant tank is a kind of important pasture mechanized equipment, it is adaptable to milk plant's cooling collection storage fresh milk, Make to cool down raw milk and keep optimum state, prevent bacterial reproduction from producing.

In working yet with refrigerant tank, general employing hydrogen freezes, along with the prolongation of service life, It is susceptible to the leakage of hydrogen, serious harm user and the personal safety as well as the property safety of equipment.

Summary of the invention

For overcoming problem present in correlation technique, the application provides a kind of with gas sensing function Refrigerant tank.

First aspect according to the embodiment of the present application, it is provided that a kind of refrigeration with gas sensing function Tank, the outer surface of described refrigerant tank is provided with gas-discoloration gas sensor, described gas-discoloration gas Sensor is based on WO₃Gas sensitive and WO₃Gas-discoloration material；Described gas-discoloration gas sensing Device includes sensing unit, heating unit and data-reading unit；Described heating unit and digital independent list Unit is connected with the tungsten oxide air-sensitive film of sensing unit；Described heating unit is as tungsten oxide air-sensitive film Heating source during work；Data-reading unit process tungsten oxide air-sensitive film conductivity variations signal with The concentration value of display object gas；Described sensing unit is the double-decker of hollow structure, forms bilayer A face structure and the B face structure of structure are staggered relatively, distance 500 μm, A face structure and B face knot The periphery of structure handing-over uses colloid to seal；Described A face include quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve right NO₂The detection of gas, described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃ Gas-discoloration layer is WO₃Nano wire film doping ZnTPP-2-NO₂, utilize the gas-discoloration principle can To realize the Visual retrieval to hydrogen；It is additionally provided with 2 for object gas in the structure of described B face The air-vent penetrated.In A face, described SnO₂Granularity less than 80nm, described WO₃Air-sensitive Thin film layer thickness is 350nm；In B face, described WO₃Nanowire length about 1 μm, diameter about 60 nm。

Second aspect according to the embodiment of the present application, it is provided that a kind of refrigerant tank with gas sensing function Preparation method, it is preferable that the making of the sensing unit of described gas-discoloration gas sensor include with Lower step:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixing Gas, regulates Ar:O₂Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected For solvent, take 3.8g ZnTPP-2-NO₂It is configured to the solution of 5.0mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

The technical scheme that embodiments herein provides includes following beneficial effect:

1. configuration aspects, creative employing double membrane structure, the air-sensitive combining tungsten oxide material is special Property and gas-discoloration characteristic, increase the range of application of device；

2. tungsten oxide air-sensitive film passes through magnetically controlled sputter method system based on Film-mode resistor sensor, thin film Make, by controlling partial pressure of oxygen and doped stannum oxide in manufacturing process so that thin film is to NO₂Selectivity All it is greatly improved with sensitivity；

3. tungsten oxide gas chromism film is tungsten oxide nano doping tetraphenylporphyrin zinc derivative (ZnTPP-2-NO2) material, this dopant material, as catalyst, substantially increases tungsten oxide nanometer Line is to H₂Reactivity, improve sensitivity, and achieve " smell-seeing " to hydrogen and measure.

Aspect and advantage that the application adds will part be given in the following description, and part will be from following Description in become obvious, or recognized by the practice of the application.It should be appreciated that above It is only exemplary and explanatory that general description and details hereinafter describe, and can not limit the application.

Accompanying drawing explanation

Accompanying drawing herein is merged in description and constitutes the part of this specification, it is shown that meet this Inventive embodiment, and for explaining the principle of the present invention together with description.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.

Fig. 2 is the flow chart preparing the sensing unit in Fig. 1.

Wherein: 1-quartz glass substrate, 2-interdigital electrode layer, 3-WO₃Air-sensitive film layer, 4-hollow Structure, 5-WO₃Gas-discoloration layer.

Detailed description of the invention

Here will illustrate exemplary embodiment in detail, its example represents in the accompanying drawings.Below Description when relating to accompanying drawing, unless otherwise indicated, the same numbers in different accompanying drawings represents identical or phase As key element.Embodiment described in following exemplary embodiment does not represent and present invention phase one The all embodiments caused.On the contrary, they only with as appended claims describes in detail, this The example of the consistent apparatus and method of some aspects of invention.

Following disclosure provides many different embodiments or example for realizing the difference of the application Structure.In order to simplify disclosure herein, hereinafter parts and setting to specific examples are described. Certainly, they are the most merely illustrative, and are not intended to limit the application.Additionally, the application is permissible Repeat reference numerals and/or letter in different examples.This repetition is to simplify and clearly mesh , itself it is more than the relation between various embodiment being discussed and/or arranging.Additionally, the application The various specific technique provided and the example of material, but those of ordinary skill in the art can anticipate Know the applicability to other techniques and/or the use of other materials.It addition, described below first is special Levy Second Eigenvalue " on " structure can include what the first and second features were formed as directly contacting Embodiment, it is also possible to include the embodiment that other feature is formed between the first and second features, this Sample the first and second feature is not likely to be directly contact.

In the description of the present application, it should be noted that unless otherwise prescribed and limit, term " peace Dress ", should be interpreted broadly " being connected ", " connection ", for example, it may be mechanical connection or electrically connect, also Can be the connection of two element internals, can be to be joined directly together, it is also possible to indirect by intermediary It is connected, for the ordinary skill in the art, above-mentioned term can be understood as the case may be Concrete meaning.

Modern society, along with economic and industry development, mankind's consumption to various natural resourcess Being continuously increased, owing to pursuing the shortcoming of economic goal and environmental consciousness, the pollution problem of environment is the tightest Weight.Meanwhile, show gas aspect, in productive life discharge various inflammable, explosive, have The leakage of gas in poisonous gas and environment, pollution are also that people's property safety is big with the one of personal safety Threaten.Therefore, gas sensor technology is one of important topic of current research.Gas sensor is A kind of can change and the device effectively monitored or device by perception surrounding target gas levels, It is based on physical principle or chemical reaction etc., the type of gas sensor mainly has semiconductor gas Dependent sensor, electrochemical gas sensor, catalytic combustion type gas sensor, optical profile type gas sensing Device etc..WO₃It is a kind of preferably controllable color change material, can realize visible ray and near-infrared radiation saturating Cross continuously adjusting of rate.Amorphous WO from Deb reported first in 1969₃The electrochromism effect of thin film Since Ying, find the performance such as its gas-discoloration, photochromic, thermochromism successively, meanwhile, as Transition metal oxide, Tungstic anhydride. is to some gas, such as NO₂、NO、NH₃、H₂、H₂S etc. All show sensitivity characteristic；Compared with electrochromic device, WO₃Gas-discoloration device has system structure Simply, the advantage such as relative inexpensiveness, therefore its gas-discoloration characteristic is combined with gas-sensitive property, Great significance to gas sensing optics type senser element.

The operation principle of the gas sensor used in the application is: gas sensor is sensing technology One important branch.Gas sensor can be divided into dissimilar according to structure and material etc., wherein, The sensitive prime material that Metal Oxide Gas Sensors is used is broad stopband N-shaped metal-oxide half Conductor, it all shows good sensitivity characteristic to multiple gases.

The sensitive mechanism of metal oxide semiconductor gas sensor is: sensitive material is made into as thin Films etc. are beneficial to contact the structure of air, under heating state, when it is exposed in air, and sensitive material The total surface of material is to adsorb a certain amount of oxonium ion, forms surface potential barrier and space charge layer, can make The sheet electron concentration of sensitive material declines, and then electrical conductivity declines；When object gas is reproducibility gas (such as CO, H during body₂), this reducibility gas can adsorb on sensitive material surface, and with surface Oxygen reacts, and makes sheet electron concentration increase, and electrical conductivity rises therewith；When object gas is oxidation (such as NO during property gas₂), the absorption on sensitive material surface of this oxidizing gas further increases The adsorbance of oxygen so that the electrical conductivity of sensitive material declines further；I.e. the concentration of object gas with The electrical conductivity of sensitive material has dependency, thus, by measure sensitive material electrical conductivity change thus Measure the concentration of object gas.

After gas-discoloration refers to that material arrives some gas, because the reversible chemical reaction occurred makes Material produces the colour developing effect that the light to wavelengths characteristic absorbs, and the absorption spectrum of material can change, Macro manifestations is the change of material color.Specific to WO₃After contact hydrogen, it can with hydrogen generation Back reaction, can form tungsten bronze structure (H_xWO₄), owing to this structure is blue, show as WO₃ The color of thin film can be blue by original transparent color, again because the change of thin film color can make it saturating The light intensity crossed changes, i.e. the light transmittance of thin film changes, therefore can be by measuring thin film The concentration of determination of light transmittance hydrogen.

The application is based on WO₃The gas-discoloration character of material and air-sensitive character, will by double membrane structure It combines；On the one hand, WO₃Air-sensitive film can measure NO in the case of external power supply and heating₂ Concentration, on the other hand, can not heat with not powered etc. have particular/special requirement in the environment of, WO₃Air-sensitive Thin-film material shows limitation, now can pass through WO₃Gas chromism film is to H₂Detect.

Embodiment 1:

There is provided a kind of refrigerant tank with gas sensing function, described refrigerant tank outer surface that gas is installed to cause Variable color gas sensor, described gas-discoloration gas sensor is based on WO₃Gas sensitive and WO₃Gas Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃ Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃Nanometer Line film doping ZnTPP-2-NO₂, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face, Described SnO₂Granularity less than 80nm, described WO₃Air-sensitive film layer thickness is 350nm；B In face, described WO₃Nanowire length about 1 μm, diameter about 60nm；

Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute Show, comprise the following steps:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixing Gas, regulates Ar:O₂Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected For solvent, take 3.8g ZnTPP-2-NO₂It is configured to the solution of 5.0mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.

Data test:

In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical Enter by air and finite concentration NO₂The mixed gas of configuration, keeps 30min, is again passed through pure air, Record WO₃The resistance value of air-sensitive film layer, respectively R (NO₂) and R (air), define air-sensitive Sensitivity is: S=R (NO₂)/R (air), response time is defined as being passed through resistance after test gas Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film NO in 8ppm concentration₂Gas medium sensitivity is 38；Best-case Response Time is 17s；Through 100 Secondary testing fatigue, electrical response value drops to original 86%.WO₃Air-sensitive film shows well Sensitivity, response time and repeatability.

In B face, use spectrophotometer to variable concentrations H₂WO in atmosphere₃Gas-discoloration layer is carried out Light transmittance is tested, and defines T₀For not leading to H₂Time sample light transmittance, T is for being passed through finite concentration H₂ Time sample light transmittance, relative light transmission:, be passed through H₂When concentration is 5000ppm, the most thoroughly Light rate with wavelength change, minimum 4%, be 59.7% to the maximum, and through about 10min, relatively Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens Color performance.

Test finds, this refrigerant tank is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively Greatly, it is achieved that beyond thought effect, there is certain actual application value.

Embodiment 2:

There is provided a kind of refrigerant tank with gas sensing function, described refrigerant tank outer surface that gas is installed to cause Variable color gas sensor, described gas-discoloration gas sensor is based on WO₃Gas sensitive and WO₃Gas Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃ Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃Nanometer Line film doping ZnTPP-2-NO₂, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face, Described SnO₂Granularity less than 55nm, described WO₃Air-sensitive film layer thickness is 500nm；B In face, described WO₃Nanowire length about 1 μm, diameter about 60nm；

Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute Show, comprise the following steps:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixing Gas, regulates Ar:O₂Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 330 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 8h, then take out quartz glass substrate and spend ionized water cleaning；(4) selection chloroform is Solvent, takes 2.8g ZnTPP-2-NO₂It is configured to the solution of 5.4mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.

Data test:

In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical Enter by air and finite concentration NO₂The mixed gas of configuration, keeps 30min, is again passed through pure air, Record WO₃The resistance value of air-sensitive film layer, respectively R (NO₂) and R (air), define air-sensitive Sensitivity is: S=R (NO₂)/R (air), response time is defined as being passed through resistance after test gas Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film NO in 8ppm concentration₂Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100 Secondary testing fatigue, electrical response value drops to original 86%.WO₃Air-sensitive film shows well Sensitivity, response time and repeatability.

In B face, use spectrophotometer to variable concentrations H₂WO in atmosphere₃Gas-discoloration layer is carried out Light transmittance is tested, and defines T₀For not leading to H₂Time sample light transmittance, T is for being passed through finite concentration H₂ Time sample light transmittance, relative light transmission:, be passed through H₂When concentration is 5000ppm, the most thoroughly Light rate with wavelength change, minimum 7%, be 65% to the maximum, and through about 10min, the most thoroughly Light rate tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, table Now transparent being become blue for thin film color from original, response time is short, shows good gas-discoloration Performance.

Test finds, this refrigerant tank is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively Greatly, it is achieved that beyond thought effect, there is certain actual application value.

Embodiment 3:

There is provided a kind of refrigerant tank with gas sensing function, described refrigerant tank outer surface that gas is installed to cause Variable color gas sensor, described gas-discoloration gas sensor is based on WO₃Gas sensitive and WO₃Gas Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses glue Body seals；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, Described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃ Nano wire film doping ZnTPP-2-NO₂, utilize that gas-discoloration principle can realize hydrogen is visual Change detection；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.A face In, described SnO₂Granularity less than 50nm, described WO₃Air-sensitive film layer thickness is 400nm； In B face, described WO₃Nanowire length about 5 μm, diameter about 60nm；

Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute Show, comprise the following steps:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1.5 μm, cover at interdigital electrode mask Lower exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating One layer of Cr film thick for 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz Substrate of glass is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixed Close gas, regulate Ar:O₂Ratio is 5:1, and operating pressure is 3.5Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 22g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.7g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected For solvent, take 3.8g ZnTPP-2-NO₂It is configured to the solution of 5.0mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.

Data test:

In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical Enter by air and finite concentration NO₂The mixed gas of configuration, keeps 30min, is again passed through pure air, Record WO₃The resistance value of air-sensitive film layer, respectively R (NO₂) and R (air), define air-sensitive Sensitivity is: S=R (NO₂)/R (air), response time is defined as being passed through resistance after test gas Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film NO in 8ppm concentration₂Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100 Secondary testing fatigue, electrical response value drops to original 86%.WO₃Air-sensitive film shows well Sensitivity, response time and repeatability.

In B face, use spectrophotometer to variable concentrations H₂WO in atmosphere₃Gas-discoloration layer is carried out Light transmittance is tested, and defines T₀For not leading to H₂Time sample light transmittance, T is for being passed through finite concentration H₂ Time sample light transmittance, relative light transmission:, be passed through H₂When concentration is 5000ppm, the most thoroughly Light rate with wavelength change, minimum 8%, be 56.7% to the maximum, and through about 10min, relatively Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens Color performance.

Test finds, this refrigerant tank is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively Greatly, it is achieved that beyond thought effect, there is certain actual application value.

Embodiment 4:

There is provided a kind of refrigerant tank with gas sensing function, described refrigerant tank outer surface that gas is installed to cause Variable color gas sensor, described gas-discoloration gas sensor is based on WO₃Gas sensitive and WO₃Gas Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃ Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃Nanometer Line film doping ZnTPP-2-NO₂, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face, Described SnO₂Granularity less than 50nm, described WO₃Air-sensitive film layer thickness is 700nm；B In face, described WO₃Nanowire length about 7 μm, diameter about 50nm；

Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute Show, comprise the following steps:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixing Gas, regulates Ar:O₂Ratio is 5:3, and operating pressure is 2.4Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected For solvent, take 3.8g ZnTPP-2-NO₂It is configured to the solution of 5.0mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.

Data test:

In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical Enter by air and finite concentration NO₂The mixed gas of configuration, keeps 30min, is again passed through pure air, Record WO₃The resistance value of air-sensitive film layer, respectively R (NO₂) and R (air), define air-sensitive Sensitivity is: S=R (NO₂)/R (air), response time is defined as being passed through resistance after test gas Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film NO in 8ppm concentration₂Gas medium sensitivity is 35；Best-case Response Time is 15s；Through 100 Secondary testing fatigue, electrical response value drops to original 86%.WO₃Air-sensitive film shows well Sensitivity, response time and repeatability.

In B face, use spectrophotometer to variable concentrations H₂WO in atmosphere₃Gas-discoloration layer is carried out Light transmittance is tested, and defines T₀For not leading to H₂Time sample light transmittance, T is for being passed through finite concentration H₂ Time sample light transmittance, relative light transmission:, be passed through H₂When concentration is 5000ppm, the most thoroughly Light rate with wavelength change, minimum 4%, be 63.7% to the maximum, and through about 10min, relatively Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens Color performance.

Test finds, this refrigerant tank is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively Greatly, it is achieved that beyond thought effect, there is certain actual application value.

Embodiment 5:

There is provided a kind of refrigerant tank with gas sensing function, described refrigerant tank outer surface that gas is installed to cause Variable color gas sensor, described gas-discoloration gas sensor is based on WO₃Gas sensitive and WO₃Gas Cause off-color material；Described gas-discoloration gas sensor includes that sensing unit, heating unit and data are read Take unit；The tungsten oxide air-sensitive film of described heating unit and data-reading unit and sensing unit is even Connect；Heating source when described heating unit works as tungsten oxide air-sensitive film；At data-reading unit The conductivity variations signal of reason tungsten oxide air-sensitive film is to show the concentration value of object gas.

Fig. 1 is the schematic diagram of sensing unit in the gas-discoloration gas sensor that the present invention uses.Reference Fig. 1, this sensing unit is the double-decker of hollow structure, forms double-deck A face structure and B Face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses colloid Seal；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃ Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃Nanometer Line film doping ZnTPP-2-NO₂, utilize gas-discoloration principle can realize the inspection of the visualization to hydrogen Survey；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face.In A face, Described SnO₂Granularity less than 100nm, described WO₃Air-sensitive film layer thickness is 400nm；B In face, described WO₃Nanowire length about 5 μm, diameter about 100nm；

Fig. 2 is according to the flow chart preparing sensing unit shown in an exemplary embodiment, such as Fig. 2 institute Show, comprise the following steps:

S1, preparation A face structure, including following enforcement step: (1) takes certain size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water ultrasonic cleaning 20min；(2) Spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, under interdigital electrode mask covers Exposure 6s, cleans with deionized water after being then passed through development 50s, uses magnetically controlled sputter method plating one Cr film thick for layer 300nm, as interdigital electrode layer, then removes photoresist；(3) by quartz glass Glass substrate is put in magnetic control sputtering device, is evacuated to 5 × 10^-4Below Pa, is passed through Ar and O₂Mixing Gas, regulates Ar:O₂Ratio is 5:1, and operating pressure is 2.4Pa, is purity 99.96% at target Metal W target magnetic control sputtering 28min, target is the metal tin target magnetron sputtering 2min of purity 98%, Obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step: (1) takes same size (4cm × 4cm) Quartz glass substrate, sequentially pass through acetone, ethanol, deionized water, NaOH aqueous solution, go from Sub-water ultrasonic cleaning, the time is 20min；(2) take 20g sodium tungstate to be dissolved in 200ml water, Add excess concentrated hydrochloric acid obtain active tungstic acid precipitation, is filtered, then with deionized water cleaning until Can't detect chloride ion, then active tungstic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, spin coating In quartz glass substrate, 350 DEG C process 1h and obtain Seed Layer, and thickness is 20nm；(3) tungsten is taken Acid sodium powder 4.12g is dissolved in 60ml deionized water, and regulating its pH with 3M HCl solution is 2.0, Be subsequently adding 2.5g (0.3M) ammonium sulfate as controlling agent, quartz glass substrate is lain in from In sub-water, after stirring 1 hour, pour in rustless steel hydrothermal reaction kettle, be heated to 150 DEG C in an oven Keep 10h, then take out quartz glass substrate and spend ionized water cleaning；(4) chloroform is selected For solvent, take 3.8g ZnTPP-2-NO₂It is configured to the solution of 5.6mg/ml, supersound process 20min, Make solution uniform, by dripping glue mode by made solution drop coating at quartz glass substrate surface, set rotation Painting speed is 3400rpm, and spin-coating time is 70s, finally by quartz glass substrate at vacuum drying oven In be dried 12h at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂WO₃Nano wire film, i.e. WO₃ Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.

About the device in above-described embodiment, the concrete mode that wherein modules performs to operate exists About the embodiment of the method has been described in detail, explanation will be not set forth in detail herein.

Data test:

In A face, air-sensitive test completes on Testing system of gas-sensor built, is put into by the device made In quartz ampoule, heating unit heats makes the operating temperature of sensing unit be 120 DEG C, after stable, logical Enter by air and finite concentration NO₂The mixed gas of configuration, keeps 30min, is again passed through pure air, Record WO₃The resistance value of air-sensitive film layer, respectively R (NO₂) and R (air), define air-sensitive Sensitivity is: S=R (NO₂)/R (air), response time is defined as being passed through resistance after test gas Change to the time required for the 80% of maximum changes in resistance.Test finds, this tungsten oxide air-sensitive film NO in 8ppm concentration₂Gas medium sensitivity is 30；Best-case Response Time is 15s；Through 100 Secondary testing fatigue, electrical response value drops to original 83%.WO₃Air-sensitive film shows well Sensitivity, response time and repeatability.

In B face, use spectrophotometer to variable concentrations H₂WO in atmosphere₃Gas-discoloration layer is carried out Light transmittance is tested, and defines T₀For not leading to H₂Time sample light transmittance, T is for being passed through finite concentration H₂ Time sample light transmittance, relative light transmission:, be passed through H₂When concentration is 5000ppm, the most thoroughly Light rate with wavelength change, minimum 7%, be 56.7% to the maximum, and through about 10min, relatively Light transmittance tends towards stability, it is seen that be passed through with tested gas, and tungsten oxide gas-discoloration layer light transmittance declines, Showing as thin film color and transparent become blue from original, response time is short, shows good gas mutagens Color performance.

Test finds, this refrigerant tank is provided with gas-discoloration gas sensor, utilizes gas-discoloration principle Can realize the Visual retrieval to hydrogen, and response time is short, highly sensitive, color change interval is relatively Greatly, it is achieved that beyond thought effect, there is certain actual application value.

Those skilled in the art, after considering description and putting into practice invention disclosed herein, will readily occur to Other embodiments of the present invention.The application is intended to any modification of the present invention, purposes or fits Answering property changes, and these modification, purposes or adaptations are followed the general principle of the present invention and wrap Include the undocumented common knowledge in the art of the application or conventional techniques means.Description and reality Executing example and be considered only as exemplary, true scope and spirit of the invention are referred to by claim below Go out.

It should be appreciated that the invention is not limited in essence described above and illustrated in the accompanying drawings Really structure, and various modifications and changes can carried out without departing from the scope.The scope of the present invention is only Limited by appended claim.

Claims (2)

1. the refrigerant tank with gas sensing function, it is characterised in that described refrigerant tank appearance Face is provided with gas-discoloration gas sensor, and described gas-discoloration gas sensor is based on WO₃Air-sensitive Material and WO₃Gas-discoloration material；Described gas-discoloration gas sensor includes sensing unit, adds Hot cell and data-reading unit；The oxidation of described heating unit and data-reading unit and sensing unit Tungsten air-sensitive film connects；Heating source when described heating unit works as tungsten oxide air-sensitive film；Number According to reading the conductivity variations signal of cell processing tungsten oxide air-sensitive film to show the dense of object gas Angle value；Described sensing unit is the double-decker of hollow structure, formed double-deck A face structure and B face structure is staggered relatively, distance 500 μm, and the periphery of A face structure and the handing-over of B face structure uses Colloid seals；Described A face includes quartz glass substrate, interdigital electrode layer and WO₃Air-sensitive film layer, WO₃Air-sensitive film layer is doping SnO₂WO₃Thin film, it is possible to achieve to NO₂The detection of gas, Described B face includes quartz glass substrate and WO₃Gas-discoloration layer, WO₃Gas-discoloration layer is WO₃ Nano wire film doping ZnTPP-2-NO₂, utilize that gas-discoloration principle can realize hydrogen is visual Change detection；2 it are additionally provided with for air-vent that object gas penetrates in the structure of described B face；A face In, described SnO₂Granularity less than 80nm, described WO₃Air-sensitive film layer thickness is 350nm； In B face, described WO₃Nanowire length about 1 μm, diameter about 60nm.

2. the preparation a kind of refrigerant tank with gas sensing function described in claim 1, its feature Being, wherein, the making of the sensing unit of described gas-discoloration gas sensor comprises the following steps:

S1, preparation A face structure, including following enforcement step:

(1) take the quartz glass substrate of certain size (4cm × 4cm), sequentially pass through acetone, second Alcohol, deionized water ultrasonic cleaning 20min；

(2) spin coating one layer photoetching glue in quartz glass substrate, thickness 1 μm, cover in interdigital electrode Masterplate exposes 6s under covering, and cleans with deionized water after being then passed through development 50s, uses magnetic control to spatter Cr film thick for shooting method one layer of 300nm of plating, as interdigital electrode layer, then removes photoresist；

(3) quartz glass substrate is put in magnetic control sputtering device, be evacuated to 5 × 10^-4Below Pa, It is passed through Ar and O₂Mixed gas, regulate Ar:O₂Ratio is 5:1, and operating pressure is 2.4Pa, Target is the metal W target magnetic control sputtering 28min of purity 99.96%, and target is the gold of purity 98% Belong to stannum target magnetic control sputtering 2min, obtain the SnO that adulterates₂WO₃Thin film, i.e. WO₃Air-sensitive film layer；

S2, preparation B face structure, including following enforcement step:

(1) take the quartz glass substrate of same size (4cm × 4cm), sequentially pass through acetone, second Alcohol, deionized water, NaOH aqueous solution, deionized water ultrasonic cleaning, the time is 20min；

(2) taking 20g sodium tungstate to be dissolved in 200ml water, the concentrated hydrochloric acid adding excess obtains Porous Tungsten Acid precipitation, is filtered, then cleans until can't detect chloride ion with deionized water, then by activity Wolframic acid precipitation is dissolved in hydrogen peroxide, prepares colloidal sol, is spun in quartz glass substrate, at 350 DEG C Reason 1h obtains Seed Layer, and thickness is 20nm；

(3) take sodium tungstate powder 4.12g and be dissolved in 60ml deionized water, regulate with 3M HCl solution Its pH is 2.0, is subsequently adding 2.1g (0.3M) ammonium sulfate as controlling agent, by quartz glass substrate The end, keeps flat in deionized water, after stirring 1 hour, pours in rustless steel hydrothermal reaction kettle, at baking oven In be heated to 150 DEG C keep 10h, then take out quartz glass substrate spend ionized water clean；

(4) selecting chloroform is solvent, takes 3.8g ZnTPP-2-NO₂It is configured to 5.0mg/ml's Solution, supersound process 20min, make solution uniform, by dripping glue mode by made solution drop coating at stone English glass basic surface, sets spin speed as 3400rpm, and spin-coating time is 70s, finally by stone English substrate of glass is dried 12h in vacuum drying oven at 60 DEG C, obtain the ZnTPP-2-NO that adulterates₂'s WO₃Nano wire film, i.e. WO₃Gas-discoloration layer；

S3, assembling: by staggered relatively to the A face completed, B face structure, distance 500 μm, A The periphery of face structure and the handing-over of B face structure uses colloid to seal, and obtains described gas-discoloration gas sensing The sensing unit of device.