CN104865292A - Nitrogen dioxide gas sensor based on o-aminophenyl substituted porphyrin nanometer material - Google Patents
Nitrogen dioxide gas sensor based on o-aminophenyl substituted porphyrin nanometer material Download PDFInfo
- Publication number
- CN104865292A CN104865292A CN201510205948.5A CN201510205948A CN104865292A CN 104865292 A CN104865292 A CN 104865292A CN 201510205948 A CN201510205948 A CN 201510205948A CN 104865292 A CN104865292 A CN 104865292A
- Authority
- CN
- China
- Prior art keywords
- gas sensor
- bis
- conductive glass
- amino phenyl
- interdigital electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention belongs to the technical field of material chemicals, and particularly relates to a preparation method of a gas sensor based on 5, 10-dual- aminophenyl-15, 20- diphenyl porphyrin nanometer material and its application. The gas sensor takes an ITO conductive glass sheet as a carrier, and an interdigital electrode is etched on the ITO conductive glass sheet; a gas sensitive material is dropped and coated on the interdigital electrode of the ITO conductive glass sheet so as to form a NO2 gas sensor. The nitrogen dioxide gas sensor provided by the invention has the advantages of low response concentration and high sensitivity; moreover, the Nitrogen dioxide gas sensor is simple in preparation, low in production cost, and green and environment-friendly, and can be applied to test concentration of NO2 in automobile exhaust and power plant exhaust gas under the room temperature.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of nitrogen dioxide gas sensor based on 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material and application thereof.
Background technology
In the production and life of society, can touch various gas needs to carry out checking and controlling.Such as room air pollution as the benzaldehyde in chemical fibre carpet, cosmetics, finishing material and new composite furniture etc., the benzene homologues in paint, coating, binder, wood-based plate, foam heat insulating material, plastic plate wallpaper etc.; The Detection & Controling of the oxides of nitrogen (as nitrogen dioxide) in Chemical Manufacture and vehicle exhaust; The testing and alarm of coal mine gas concentration; The monitoring of environmental pollution states; Gas leak etc.
Wherein, nitrogen dioxide (NO
2) be have pungency, strong oxidizing property, can be combustion-supporting toxic gas, be also a kind of important atmosphere pollution.It is mainly derived from the industrial processes of Vehicular exhaust, the fuel combustion of heat power station and other industry and nitric acid, nitrogenous fertilizer, very harmful to human body, thus carries out detection to it and has very important value.
The more semiconductor gas sensor of current research mainly comprises metal-oxide semiconductor (MOS) gas sensor and organic semiconductor gas transducer.The class gas sensor that metal-oxide semiconductor (MOS) gas sensor is current most study, practical value is the highest, but its preparation technology, production cost are compared to organic semiconductor sensor more complicated, metal-oxide semiconductor (MOS) gas sensor needs working temperature at 200 ~ 400 DEG C, and organic semiconductor sensor can carry out work at normal temperatures, greatly can improve the practicality of gas sensor, the study hotspot making development of new organic semiconducting materials prepare organic semiconductor sensor to become emerging; The invention reside in and a kind of new nitrogen dioxide gas sensor is provided.
The sensitivity (S) of gas sensor is the index of gas sensor to tested gas sensitization degree.S=Rg/Ra, wherein Rg is the resistance value of sensitive layer in gas to be measured, and Ra is the aerial resistance value of sensitive layer.
Summary of the invention
The invention provides a kind of nitrogen dioxide gas sensor based on 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material, at room temperature can carry out detection toxic gas nitrogen dioxide (NO
2) existence and concentration, its performance and preparation technology are obviously better than hot type, have good practical application meaning and commercial value.
First aspect present invention provides a kind of gas sensor element for measuring nitrogen dioxide gas, and described sensor element comprises ITO electro-conductive glass substrate (1), interdigital electrode (2) and porphyrin nano material coating (3); Described interdigital electrode (2) is etched in ITO electro-conductive glass substrate (1), described material coating (3) droplet is coated in the substrate of ITO electro-conductive glass and obtains in interdigital electrode, it is characterized in that, the component of described material coating is 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material, described 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin has the chemical constitution shown in formula I.
Second aspect present invention provides the preparation method of gas sensor element described in first aspect present invention, and the method comprises the following steps:
1) preparation of ITO electro-conductive glass interdigital electrode
1. on ITO transparent conducting glass after cleaning, spin coating last layer bears photoresist, is then inserted 70 DEG C of constant temperature 10min in drying box;
2. paint sheet for mask plate with the light being designed with interdigital electrode pattern, under litho machine, expose development and rinsing afterwards in 18 seconds;
3. style clearly of developing is carried out 140 DEG C and bake 40min, in the mixed liquor of hydrochloric acid and nitric acid after etching, remove residual acid and photoresist with deionized water and negative glue cleaning fluid, obtain the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
2) above-mentioned ITO electro-conductive glass is cleaned up;
3) 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano droplets of material is coated onto step 2) in the interdigital electrode of ITO substrate that obtains, dry, namely obtain the gas sensor of gas sensor;
Wherein, step 1) described cleaning step is: the substrate of ITO electro-conductive glass is used toluene, acetone, ethanol successively, and deionized water is ultrasonic cleaning 5-10min respectively, then dry for standby;
Third aspect present invention provides one to prepare the method for 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material, and the method comprises the following steps:
1) 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin is joined in good solvent, filter;
2) to step 1) inject in gained filtrate or drip poor solvent, sealing, leave standstill 3 ~ 4 days, obtain 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin aggregation;
Wherein, 5,10 ,-two p-amino phenyl-15,20-diphenyl porphyrin (mol) and good solvent (ml) molar volume are than being 1:5 ~ 100, preferred 1:4 ~ 80;
The volume ratio of poor solvent and good solvent is 1:3 ~ 10; Described good solvent be selected from methenyl choloride, methylene chloride one or both; Described poor solvent be selected from methyl alcohol, normal hexane one or both.
In one embodiment of the invention, the preparation method of above-mentioned aggregation comprises the following steps:
(1) raw material 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin is joined in methenyl choloride, then filter, obtain 5,10, the chloroform soln of-two p-amino phenyl-15,20-diphenyl porphyrins.
(2) carefully and be lentamente injected into by poor solvent in the chloroform soln of 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin, the volume ratio of poor solvent and methenyl choloride is 1:3 ~ 10, and sealing, left at room temperature is about 3-4 days, obtains aggregation.
Fourth aspect present invention protection 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin is for the preparation of the purposes of nitrogen dioxide gas sensor.
Gas sensor provided by the invention is characterised in that can carry out low concentration (1-40ppm) range detection to nitrogen dioxide at normal temperatures;
5,10-bis-p-amino phenyl-15, the 20-diphenyl porphyrin nano materials that the present invention is prepared in methyl alcohol are to NO
2minimum response concentration 2ppm, sensitivity is 1.24 at this concentration; 5,10-bis-p-amino phenyl-15, the 20-diphenyl porphyrin nano materials prepared in normal hexane are to NO
2minimum response concentration 4ppm, sensitivity is 1.02 at this concentration.
The advantage of gas sensor of the present invention:
(1) gas sensor of the present invention's use is to toxic gas NO
2response concentration low, improve the sensitivity to gas absorption reaction, and in low concentration of NO
2to response sensitivity, there is good linear rule in scope.
(2) gas sensor that the present invention uses can at room temperature carry out, without potential safety hazard.
(3) gas-sensitive sensor structure that uses of the present invention and preparation technology simple, with low cost, be convenient to batch production.
Accompanying drawing explanation
The structural representation of Fig. 1 gas sensor element;
The cross sectional representation of Fig. 2 gas sensor;
Gas sensor prepared by the aggregation that Fig. 3 embodiment 1 obtains is to NO
2concentration time curve (room temperature condition);
Gas sensor prepared by the aggregation that Fig. 4 embodiment 2 obtains is to NO
2concentration time curve (room temperature condition);
Gas sensor prepared by the aggregation that Fig. 5 embodiment 1 obtains is to NO
2sensitivity-concentration curve (room temperature condition);
Gas sensor prepared by the aggregation that Fig. 6 embodiment 2 obtains is to NO
2sensitivity-concentration curve (room temperature condition);
In figure, 1 is transparent conducting glass (ITO) substrate, and 2 is interdigital electrode, and 3 is material coating.
Embodiment
Below the specific embodiment of the invention is further described
Embodiment 15,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material preparation method
Pipette 1mL methenyl choloride, add 3mg 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin, ultrasonicly make it dissolve, then filter, in assembling bottle, obtain the chloroform soln of 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin.Poor solvent normal hexane carefully and is lentamente injected into 5,10-bis-p-amino phenyl-15, in the chloroform soln of 20-diphenyl porphyrin, the volume ratio of methyl alcohol and methenyl choloride is 1:3, sealing, and left at room temperature is about 3-4 days, can see that aggregate material occurs in assembling bottle, i.e. 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano materials.
Embodiment 25,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material preparation method
Pipette 1mL methenyl choloride, add 3mg 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin, ultrasonicly make it dissolve, then filter, in assembling bottle, obtain the chloroform soln of 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin.Poor solvent methyl alcohol carefully and is lentamente injected into 5,10-bis-p-amino phenyl-15, in the chloroform soln of 20-diphenyl porphyrin, the volume ratio of methyl alcohol and methenyl choloride is 1:3, sealing, and left at room temperature is about 3-4 days, can see that aggregate material occurs in assembling bottle, i.e. 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano materials.
The preparation of embodiment 35,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material silica nitrogen dependent sensor
(1) preparation of ITO electro-conductive glass interdigital electrode
1. on ITO transparent conducting glass after cleaning, spin coating last layer bears photoresist, is then inserted 70 DEG C of constant temperature 10min in drying box; 2. paint sheet for mask plate to design figuratum light, under litho machine, expose development and rinsing afterwards in 18 seconds; 3. style clearly of developing is carried out 140 DEG C and bake 40min, in the mixed liquor of hydrochloric acid and nitric acid after etching, remove residual acid and photoresist with deionized water and negative glue cleaning fluid, obtain the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
(2) ITO substrate is used toluene successively, acetone, ethanol, deionized water is ultrasonic cleaning 5-10min respectively, then dry for standby;
(3) respectively embodiment 1 and embodiment 2 are prepared 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano droplets of material is coated onto in the interdigital electrode of the ITO substrate that step (2) obtains, and dries, namely obtains the gas sensor of gas sensor;
The performance measurement of embodiment 4 nitrogen dioxide gas sensor
Air-sensitive proving installation is built by laboratory, and air-sensitive test process carries out under fixed-bias transistor circuit 5V between a comparatively gentle environment (under room temperature, external atmosphere pressure and dry air) and two electrodes.Use the accurate source/measuring unit of testing tool: Agilent B290a.
Two kinds of gas sensors are at NO
2in low strength range, response sensitivity has good linear rule.The contrast of two kinds of gas sensors is known, 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin in methyl alcohol aggregation gas sensor than 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin, in normal hexane, aggregation gas sensor is slightly well.
Claims (5)
1., for measuring a gas sensor element for nitrogen dioxide gas, described sensor element comprises ITO electro-conductive glass substrate (1), interdigital electrode (2) and material coating (3); Described interdigital electrode (2) is etched in ITO electro-conductive glass substrate (1), described material coating (3) drips and is coated in the substrate of ITO electro-conductive glass, it is characterized in that, the component of described material coating is 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano material.
2. prepare a method for gas sensor element described in claim 1, the method comprises the following steps:
1) preparation of ITO electro-conductive glass interdigital electrode;
2) above-mentioned ITO electro-conductive glass is cleaned up;
3) 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano droplets of material is coated onto step 2) in the interdigital electrode of ITO substrate that obtains, dry, namely obtain the gas sensor of gas sensor.
3. preparation method according to claim 2, is characterized in that, step 1) preparation method of described ITO electro-conductive glass interdigital electrode is:
1. on ITO transparent conducting glass after cleaning, spin coating last layer bears photoresist, is then inserted 70 DEG C of constant temperature 10min in drying box;
2. paint sheet for mask plate with the light being designed with interdigital electrode pattern, under litho machine, expose development and rinsing afterwards in 18 seconds;
3. style clearly of developing is carried out 140 DEG C and bake 40min, in the mixed liquor of hydrochloric acid and nitric acid after etching, remove residual acid and photoresist with deionized water and negative glue cleaning fluid, obtain the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
4. the preparation method of 55,10-bis-p-amino phenyl-15,20-diphenyl porphyrin nano materials described in claim 2 step 3, the method comprises the following steps:
1) 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin is joined in good solvent, filter;
2) to step 1) inject in gained filtrate or drip poor solvent, sealing and standing 3 ~ 4 days, filter, obtain 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin aggregation;
Preparation method according to claim 2, is characterized in that, 5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin (mol) and good solvent (ml) molar volume are than being 1:5 ~ 100, preferred 1:4 ~ 80;
The volume ratio of poor solvent and good solvent is 1:3 ~ 10;
Described good solvent be selected from methenyl choloride, methylene chloride one or both;
Described poor solvent be selected from methyl alcohol, normal hexane one or both.
5.5,10-bis-p-amino phenyl-15,20-diphenyl porphyrin is for the preparation of the purposes of nitrogen dioxide gas sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510205948.5A CN104865292B (en) | 2015-04-27 | 2015-04-27 | A kind of nitrogen dioxide gas sensor based on o-aminophenyl substitution porphyrin nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510205948.5A CN104865292B (en) | 2015-04-27 | 2015-04-27 | A kind of nitrogen dioxide gas sensor based on o-aminophenyl substitution porphyrin nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104865292A true CN104865292A (en) | 2015-08-26 |
| CN104865292B CN104865292B (en) | 2017-12-15 |
Family
ID=53911272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510205948.5A Expired - Fee Related CN104865292B (en) | 2015-04-27 | 2015-04-27 | A kind of nitrogen dioxide gas sensor based on o-aminophenyl substitution porphyrin nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104865292B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223237A (en) * | 2015-09-10 | 2016-01-06 | 济南大学 | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO 2gas sensor |
| CN106349248A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | Metalloporphyrin complex and preparation method and application thereof |
| CN106349247A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube and preparation method and application thereof |
| CN107219280A (en) * | 2017-07-21 | 2017-09-29 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
| CN107356648A (en) * | 2017-07-21 | 2017-11-17 | 济南大学 | It is a kind of to be used to determine gas sensor element of ethanol and its preparation method and application |
| CN109030577A (en) * | 2018-07-04 | 2018-12-18 | 吉林大学 | Room temperature NH3 sensor and preparation method thereof based on DPA-Ph-DBPzDCN and golden interdigital electrode |
| CN110068588A (en) * | 2019-04-28 | 2019-07-30 | 济南大学 | For detecting NO2Organo-mineral complexing nano material and gas sensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242584A (en) * | 1988-03-24 | 1989-09-27 | Yoshio Imai | Aromatic diamine |
| CN103439304A (en) * | 2013-08-19 | 2013-12-11 | 中国科学院合肥物质科学研究院 | Double-transmission fluorescent chemical sensor and preparation method and application thereof |
| CN103674946A (en) * | 2013-12-18 | 2014-03-26 | 东南大学 | Color-sensitive gas sensing array based on nanofiber gas enrichment and preparation method thereof |
-
2015
- 2015-04-27 CN CN201510205948.5A patent/CN104865292B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242584A (en) * | 1988-03-24 | 1989-09-27 | Yoshio Imai | Aromatic diamine |
| CN103439304A (en) * | 2013-08-19 | 2013-12-11 | 中国科学院合肥物质科学研究院 | Double-transmission fluorescent chemical sensor and preparation method and application thereof |
| CN103674946A (en) * | 2013-12-18 | 2014-03-26 | 东南大学 | Color-sensitive gas sensing array based on nanofiber gas enrichment and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| J.M. PEDROSA ET AL.: "Characterization and fast optical response to NO2 of porphyrin LB films", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
| 王丽 等: "溶液自组装法制备卟啉纳米材料研究进展", 《化工进展》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105223237A (en) * | 2015-09-10 | 2016-01-06 | 济南大学 | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO 2gas sensor |
| CN105223237B (en) * | 2015-09-10 | 2017-12-26 | 济南大学 | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO2Gas sensor |
| CN106349248A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | Metalloporphyrin complex and preparation method and application thereof |
| CN106349247A (en) * | 2016-08-09 | 2017-01-25 | 济南大学 | 5-p-hydroxyphenyl-10,15,20-trichlorophenyl porphyrin nanotube and preparation method and application thereof |
| CN106349247B (en) * | 2016-08-09 | 2018-10-19 | 济南大学 | A kind of 5- p-hydroxybenzenes -10,15,20- trichlorophenyl porphyrin nano pipes and its preparation method and application |
| CN106349248B (en) * | 2016-08-09 | 2018-10-23 | 济南大学 | A kind of Metalloporphyrins and its preparation method and application |
| CN107219280A (en) * | 2017-07-21 | 2017-09-29 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
| CN107356648A (en) * | 2017-07-21 | 2017-11-17 | 济南大学 | It is a kind of to be used to determine gas sensor element of ethanol and its preparation method and application |
| CN107219280B (en) * | 2017-07-21 | 2019-07-05 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
| CN109030577A (en) * | 2018-07-04 | 2018-12-18 | 吉林大学 | Room temperature NH3 sensor and preparation method thereof based on DPA-Ph-DBPzDCN and golden interdigital electrode |
| CN110068588A (en) * | 2019-04-28 | 2019-07-30 | 济南大学 | For detecting NO2Organo-mineral complexing nano material and gas sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104865292B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104865292A (en) | Nitrogen dioxide gas sensor based on o-aminophenyl substituted porphyrin nanometer material | |
| CN104897733A (en) | P-aminophenyl substituted porphyrin aggregate material-based nitrogen dioxide gas-sensitive sensor | |
| CN110095509B (en) | Ti3C2 Tx/polyaniline composite film ammonia gas sensor and preparation method and application thereof | |
| CN110412087B (en) | Isopropanol gas sensor based on nanocube material and preparation method thereof | |
| CN109030577B (en) | Room temperature NH3Sensor and preparation method thereof | |
| CN101566597B (en) | Preparation method of ammonia-sensitive material for detecting ammonia concentration in air | |
| CN107011340A (en) | A kind of schiff bases fluorescence probe and its synthetic method and application | |
| CN105223237A (en) | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO 2gas sensor | |
| CN106680336B (en) | The preparation of redox graphene/Phthalocyanine Zinc composite membrane and its be applied to NO2Gas-monitoring | |
| Firooz et al. | Selective and sensitive optical chemical sensor for the determination of Hg (II) ions based on tetrathia-12-crown-4 and chromoionophore I | |
| CN105842287B (en) | For detecting the nano material and gas sensor element of nitrogen dioxide | |
| CN110283173B (en) | Perylene bisimide compound and preparation method and application thereof | |
| Georgescu-State et al. | Electrochemical platform based on molecularly imprinted polymer with zinc oxide nanoparticles and multiwalled carbon nanotubes modified screen-printed carbon electrode for amaranth determination | |
| CN105784773A (en) | Nitrogen dioxide gas sensitive sensor based on amino phenyl substituted porphyrin nanomaterial | |
| CN104897739B (en) | A kind of organic semiconductor nano material and preparation method thereof and purposes and a kind of nitrogen dioxide gas sensor | |
| CN105158306A (en) | Preparation method of gas sensor for volatile organic matter detection | |
| CN106349248B (en) | A kind of Metalloporphyrins and its preparation method and application | |
| CN105891267B (en) | A kind of nitrogen dioxide gas sensor replacing porphyrin nano material based on an aminophenyl | |
| CN106188111A (en) | A kind of porphyrin phthalocyanine double-level-metal coordination compound and its preparation method and application | |
| CN101566595A (en) | Preparation method of ammonia-sensitive material for detecting ammonia concentration in air | |
| CN110068588A (en) | For detecting NO2Organo-mineral complexing nano material and gas sensor | |
| CN102953059B (en) | Manufacture method of acetone gas sensitive sensor based on titanium dioxide doped by zinc oxide | |
| CN108752516A (en) | The preparation method of MIP, formaldehyde chemical sensor and preparation method thereof | |
| CN105891132B (en) | A kind of preparation method of highly sensitive optics ammonia-sensitive material | |
| CN105203617B (en) | A kind of electrochemical gas sensor and preparation method thereof for detecting ethyl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171215 Termination date: 20200427 |