CN105181755A - Ammonia gas sensor and preparation technology thereof - Google Patents

Ammonia gas sensor and preparation technology thereof Download PDF

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CN105181755A
CN105181755A CN201510524167.2A CN201510524167A CN105181755A CN 105181755 A CN105181755 A CN 105181755A CN 201510524167 A CN201510524167 A CN 201510524167A CN 105181755 A CN105181755 A CN 105181755A
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graphene
titania
titanium dioxide
gas sensor
ammonia gas
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CN105181755B (en
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李晓干
赵阳阳
王雪燕
王兢
唐祯安
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The invention discloses an ammonia gas sensor, which comprises a gas sensitive material and a substrate. The gas sensitive material is painted on the substrate surface and comprises graphene modified titanium dioxide composite nano particles with a bridge connection structure. The composite nano particle comprises graphene and titanium dioxide, and the graphene is arranged between titanium dioxide as a bridge. Graphene accounts for 0.2 to 20 wt% of the composite nano material. The thickness of the gas sensitive material coating is 0.4 to 0.5 [mu]m. The substrate is made of Si or Al2O3 and is provided with an Au electrode. The gas sensitive material of the ammonia gas sensor is composed of graphene modified titanium dioxide composite nano particles with a bridge connection structure, can respond to NH3 gas more selectively, restoratively, and stably, and has a lower work temperature.

Description

Ammonia gas sensor and preparation technology thereof
Technical field
The invention belongs to technical field of nano material, be specifically related to ammonia gas sensor and preparation technology thereof.
Background technology
In prior art gas sensor be mainly used in the detection of CO gas, the detection of methane gas, the detection of coal gas, freon (R11, R12) detection, exhale in the detection of ethanol, the detection of human oral cavity halitosis etc.It converts electric signal to by gaseous species and with concentration dependent information, according to the power of these electric signal just can obtain with gas to be measured in the environment there is the relevant information of situation, thus can carry out detecting, monitor, report to the police; Can also be formed by interface circuit and computing machine and automatically detect, control and warning system.Wherein, though ammonia is present in air with low concentration, the ammonia of low concentration still has harmful effect to the healthy of people and environmental pollution, and therefore how rapid and accurate determination goes out the content of ammonia, for the improvement of air ambient provides foundation, become a large hot issue of those skilled in the art.
Since 2004, individual layer two-dimensional graphene is paid close attention to greatly because its special charge transport ability and the premium properties in heat, light and machinery etc. cause people, and the Schedin of Univ Manchester UK etc. are recently reported the potential application of Graphene for advanced chemical sensor.But with the Graphene derivative of surface functional group as graphene oxide (GO) or reductibility Graphene (rGO), compared with the metal oxide of tradition research, also there is characteristic of semiconductor, the application of chemical sensor may be more suitable for.The chemical sensor of reductibility Graphene (rGO) and compound thereof is used to start by large quantifier elimination, such as it is found that reductibility Graphene (rGO) and metal oxide compound effectively can improve the gas-sensitive property of sensor, mainly because compound combines available characteristics different in its composition, improve the machinery of compound, chemistry and electrology characteristic.Metal oxide that is present and reductibility Graphene (rGO) compound mainly contains SnO 2, ZnO, WO 3deng, the ZnO-rGO compound of the synthesis such as domestic Jilin University LiuSen is to NO 2show the response higher than single composition, and obviously shorten response and release time.The Russo etc. of Aveiro university of Portugal has prepared Pt – SnO 2/ rGO nanostructured shows under low temperature H relative to one matter in compound 2good response characteristic.For ammonia gas sensor, the Lu of Univ Wisconsin-Madison USA etc. make sensor by the partial reductive Graphene obtained of annealing under Ar environment, can to NO 2and NH 3response, and for NH 3response unstable.
Therefore, prepare a kind of processing step simple, cost is low and to NH 3selectivity high, working temperature easily reaches, stability and the strong ammonia gas sensor of restorability become those skilled in the art's technical matters urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of to NH 3response high, stability is strong, the ammonia gas sensor of ammonia level can be detected effectively, accurately and rapidly, technical scheme is: comprise gas sensitive and substrate, described gas sensitive is coated in described substrate surface, it is characterized in that, described gas sensitive composition comprises the titania composite nanometer particle of the graphene modified with bridging structure; Described composite nanometer particle comprises Graphene and titania, and described Graphene bridge joint is between described titania.
As preferred technical scheme, the massfraction that described Graphene accounts for composite nano materials is 0.2% ~ 20%.
As preferred technical scheme, described gas sensitive coating thickness is 0.4 ~ 0.5 μm.
As preferred technical scheme, described substrate is Si substrate with Au electrode or Al 2o 3substrate.
As preferred technical scheme, described titania is spherical, and the particle diameter of described titania is 1 μm ~ 5 μm.
Further preferably, described titania is mono-dispersion microballoon.
The present invention also provides the preparation technology of described ammonia gas sensor, comprises the following steps:
Step one, prepares positively charged titanium dioxide microballoon sphere: modify the surface of titanium dioxide microballoon sphere, makes microsphere surface positively charged;
Step 2, prepares graphene dispersing solution: be distributed to by the graphene oxide of a mass parts in the water of 6-8 mass parts, ultrasonic process, adjust ph to 3.5 ~ 4.5;
Step 3, the positively charged titanium dioxide microballoon sphere 0.04g-0.40g getting step one gained joins in 5ml-80ml absolute ethyl alcohol, regulates pH to 6.5 ~ 7.5, under stirring, add the graphene dispersing solution 49mg-65mg of step 2 gained, regulate pH to 5.5 ~ 6.5; Centrifugal after stirring, obtain sediment and be dissolved in the ethanol water of the 60-75% of 10ml-30ml, carry out hydro-thermal reaction, temperature of reaction 175 ~ 185 DEG C, reaction time 15 ~ 17h;
Step 4, is placed in Ar environment by step 3 gained solution and calcines, calcining heat 395-405 DEG C, and calcination time is 1 ~ 3h, must have the titania composite nanometer particle of the graphene modified of bridging structure;
Step 5, getting titania composite nanometer particle 4mg ~ 5mg that step 4 gained has a graphene modified of bridging structure is dispersed in deionized water, form the dispersion liquid of 8mg/ml ~ 10mg/ml, get 40 μ L ~ 50 μ L dispersion again to described substrate surface, 40 ~ 60 DEG C of dry 5-15min.
The preparation of titanium dioxide microballoon sphere of the present invention is not limited to specific method, can adopt the template of prior art, sol-gel process, hydro-thermal method, vapor phase method, Hydrolyze method etc.
As preferred technical scheme, in described step one, prepare positively charged titanium dioxide microballoon sphere and adopt following processing mode: 0.3g-0.5g titanium dioxide microballoon sphere particle is dissolved in 180ml-240ml absolute ethyl alcohol, ultrasonic process; Add 2ml-3ml aminopropyl trimethoxysilane, condensing reflux 3 ~ 5h.
As preferred technical scheme, described step 2, ultrasonic power is 240 ~ 260W, and ultrasonic time is 25 ~ 35min; Described graphene oxide is through shearing pre-service; Described step 3, centrifugal rotating speed is 2500r-3000r, and centrifugation time is 5min-10min.The graphene oxide scissor cut of bulk is fragmentated and (is most preferably less than 1x1mm 2fragment), Graphene can be made enough little in the solution.Still more preferably, described graphene oxide is preferably sheet individual layer.
As preferred technical scheme, the coating method in described step 5 comprises spraying, roller coating or dipping.
Enforcement of the present invention comprises following technique effect:
1, the present invention adopts sol-gel process, the precipitation method to obtain titania nanoparticles, can prepare the Nano microsphere of morphology controllable, and simultaneously it also has that equipment investment is little, the simple advantage of technological process.
2, sol-gel process of the present invention, the precipitation method obtain titanium dioxide granule precursor, realize the TiO with the graphene modified of bridging structure by hydro-thermal method 2nano particle, the Graphene with bridging structure of acquisition and titania composite nanometer particle stable chemical nature, to NH 3gas-sensitive property is good, the conductivity of compound is high.
3, the reduction of graphene oxide of the present invention, complete with the titania compound realizing graphene modified, preparation process is few and technique is simpler simultaneously.
4, the titania composite nanometer particle with the graphene modified of bridging structure of the present invention's acquisition, titanium dioxide granule is evenly distributed.
5, the gas sensitive of ammonia gas sensor of the present invention is the titania composite nanometer particle of the graphene modified with bridging structure, and this gas sensitive shows NH 3the better selectivity of response performance of gas, restorative, the performance such as stability and lower working temperature.
Accompanying drawing explanation
Accompanying drawing 5 width of the present invention;
The titania composite nanometer particle X-ray diffractogram of Fig. 1 graphene modified of the present invention;
The titania composite nanometer particle Raman collection of illustrative plates of Fig. 2 graphene modified of the present invention;
The titania composite nanometer particle electronic transmission microscopic appearance figure of Fig. 3 graphene modified of the present invention;
Fig. 4 ammonia gas sensor of the present invention when room temperature to about 5 ~ 50ppmNH 3resistance variations response diagram;
Fig. 5 ammonia gas sensor of the present invention when room temperature to several escaping gas and NH 3response comparison diagram.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment graphene oxide purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., XF002-1, sheet footpath 0.5--5um thickness 0.5--1.2nm.
Embodiment 1
Ammonia gas sensor, comprises gas sensitive and substrate, and gas sensitive is evenly coated in described substrate surface, and gas sensitive composition comprises the titania composite nanometer particle of the graphene modified with bridging structure, and gas sensitive coating thickness is 0.4 ~ 0.5 μm.There is the titania composite nanometer particle of the graphene modified of bridging structure, comprise Graphene and titania, described bridging structure refers to that Graphene bridge joint is between described titania, and the massfraction that described Graphene accounts for composite nanometer particle is 4.7%, and preparation method comprises the following steps:
Step one, prepare titanium dioxide microballoon sphere particle: be dissolved in 800ml absolute ethyl alcohol (ethanol) by the hexadecylamine (hexadecylamine) of 5.3g, then 3.2mlKCl (0.1mol/L) solution is added, stirring at normal temperature in stirring in water bath device, add 17.6ml isopropyl titanate (titanium (IV) isopropoxide), stirring at normal temperature 5min.The white titania suspension obtained leaves standstill 18h at normal temperatures, then collects titanium dioxide microballoon sphere particle with filtrator, and with washes of absolute alcohol titanium dioxide microballoon sphere particle three times; In order to control the formation of microsphere particle, need the scope of strict temperature control, temperature range is 15 DEG C of-20 DEG C of the bests, and high temperature is unfavorable for the formation of spherical structure;
Step 2, titanium dioxide microballoon sphere particle surface positive charge process: titanium dioxide microballoon sphere particle 0.4g step one prepared is dissolved in 200ml absolute ethyl alcohol, ultrasonic 30min.Add 2ml aminopropyl trimethoxysilane (APTMS), condensing reflux 4h.Then the titania of washes of absolute alcohol gained is used, to remove residual APTMS completely, the titanium dioxide microballoon sphere particle prepared by collecting with filtration unit;
Step 3, prepares graphene dispersing solution: be distributed to by the graphene oxide of 8mg in 50ml deionized water, after the ultrasonic 1h of ultrasonic machine, obtains graphene dispersing solution;
Step 4, titania (APTMS-TreatedTiO prepared by 0.16g step 2 2) be dissolved in the absolute ethyl alcohol of 40ml and obtain solution a, recording its pH value is 5, in faintly acid, add ammonia spirit, adjust its pH to 7, obtain solution b, (55mg) graphene dispersing solution pH value prepared by survey step 3 is 5, in faintly acid, adds HCl solution, adjust its pH value to 4, obtain solution c, solution b is in magnetic stirring apparatus environment, by solution c slowly down in solution b, adjust its pH value to be 6, slowly stir 1h, obtain solution d;
Step 5, solution d centrifuge prepared by step 4, centrifuge speed is at 2500r-3000r, the gray precipitate thing obtained is dissolved in the mixed liquor of the absolute ethyl alcohol of 10ml and the deionized water of 5ml, obtain solution e, be put in reactor by solution e and carry out hydrothermal treatment consists, hydrothermal conditions is keep 16h at 180 DEG C; Then by material 400 DEG C of calcining 2h in Ar environment, the titania nanoparticles of the graphene modified with bridging structure is prepared into;
Step 6, getting the titania nanoparticles 4mg ~ 5mg with the graphene modified of bridging structure that step 5 obtains is dispersed in deionized water, form the dispersion liquid of 8mg/ml ~ 10mg/ml, get 40 μ L ~ 50 μ L dispersion to substrate surface, after 50 DEG C of dry 10min, obtain ammonia gas sensor.
Fig. 1 illustrates the X-ray diffractogram with the titania composite nanometer particle of the graphene modified of bridging structure prepared by embodiment 1, prepared nano particle contains TiO 2;
Accompanying drawing 2 is Raman collection of illustrative plates with the titania composite nanometer particle of the graphene modified of bridging structure prepared by embodiment 1, and the titania composite nanometer particle of prepared graphene modified has D peak and the G peak of typical reductibility Graphene.
Fig. 3 gives the electronic transmission microscopic appearance figure with the titania composite nanometer particle of the graphene modified of bridging structure prepared by embodiment 1, the titania composite nanometer particle of prepared graphene modified has obvious bridge joint micromechanism.
Embodiment 2
Ammonia gas sensor, comprise gas sensitive and substrate, described gas sensitive is evenly coated in described substrate surface, and described gas sensitive composition comprises the titania composite nanometer particle of the graphene modified with bridging structure, and described gas sensitive coating thickness is 0.4 ~ 0.5 μm.There is the titania composite nanometer particle of the graphene modified of bridging structure, comprise Graphene and titania, described bridging structure refers to that Graphene bridge joint is between described titania, and the massfraction that described Graphene accounts for composite nanometer particle is 1.9%, and preparation method comprises the following steps:
Step one, prepare titanium dioxide microballoon sphere particle: be dissolved in 800ml absolute ethyl alcohol (ethanol) by the hexadecylamine (hexadecylamine) of 5.3g, then 3.2mlKCl (0.1mol/L) solution is added, stirring at normal temperature in stirring in water bath device, add 17.6ml isopropyl titanate (titanium (IV) isopropoxide), stirring at normal temperature 5min.The white titania suspension obtained leaves standstill 18h at normal temperatures, then collects titanium dioxide microballoon sphere particle with filtrator, and with washes of absolute alcohol titanium dioxide microballoon sphere particle three times;
Step 2, titanium dioxide microballoon sphere particle surface positive charge process: titanium dioxide microballoon sphere particle 0.4g step one prepared is dissolved in 200ml absolute ethyl alcohol, ultrasonic 30min.Add 2ml aminopropyl trimethoxysilane (APTMS), condensing reflux 4h.Then the titania of washes of absolute alcohol gained is used, to remove residual APTMS completely, the titanium dioxide microballoon sphere particle prepared by collecting with filtration unit;
Step 3, prepares graphene dispersing solution: be distributed to by the graphene oxide of 8mg in 50ml deionized water, after the ultrasonic 1h of ultrasonic machine, obtains graphene dispersing solution;
Step 4, the titania (APTMS-TreatedTiO2) 0.4g step 2 prepared is dissolved in the absolute ethyl alcohol of 60ml and obtains solution a, recording its pH value is 5, in faintly acid, add ammonia spirit, adjust its pH to 7, obtain solution b, (55mg) graphene dispersing solution pH value prepared by survey step 3 is 5, in faintly acid, add HCl solution, adjust its pH value to 4, obtain solution c, solution b, in magnetic stirring apparatus environment, by solution c slowly down in solution b, adjusts its pH value to be 6, slow stirring 1h, obtains solution d;
Step 5, solution d centrifuge prepared by step 4, centrifuge speed is at 2500r-3000r, the gray precipitate thing obtained is dissolved in the mixed liquor of the absolute ethyl alcohol of 10ml and the deionized water of 5ml, obtain solution e, be put in reactor by solution e and carry out hydrothermal treatment consists, hydrothermal conditions is keep 16h at 180 DEG C; Then by material 400 DEG C of calcining 2h in Ar environment, the titania nanoparticles of the graphene modified with bridging structure is prepared into;
Step 6, getting the titania nanoparticles 4mg ~ 5mg with the graphene modified of bridging structure that step 5 obtains is dispersed in deionized water, form the dispersion liquid of 8mg/ml ~ 10mg/ml, get 40 μ L ~ 50 μ L dispersion to substrate surface, after 50 DEG C of dry 10min, obtain ammonia gas sensor.
Embodiment 3
A kind of novel ammonia gas sensor, comprise gas sensitive and substrate, described gas sensitive is evenly coated in described substrate surface, and described gas sensitive composition comprises the titania composite nanometer particle of the graphene modified with bridging structure, and described gas sensitive coating thickness is 0.4 ~ 0.5 μm.There is the titania composite nanometer particle of the graphene modified of bridging structure, comprise Graphene and titania, described bridging structure refers to that Graphene bridge joint is between described titania, and the massfraction that described Graphene accounts for composite nanometer particle is 9.0%, and preparation method comprises the following steps:
Step one, prepare titanium dioxide microballoon sphere particle: be dissolved in 800ml absolute ethyl alcohol (ethanol) by the hexadecylamine (hexadecylamine) of 5.3g, then 3.2mlKCl (0.1mol/L) solution is added, stirring at normal temperature in stirring in water bath device, add 17.6ml isopropyl titanate (titanium (IV) isopropoxide), stirring at normal temperature 5min.The white titania suspension obtained leaves standstill 18h at normal temperatures, then collects titanium dioxide microballoon sphere particle with filtrator, and with washes of absolute alcohol titanium dioxide microballoon sphere particle three times;
Step 2, titanium dioxide microballoon sphere particle surface positive charge process: titanium dioxide microballoon sphere particle 0.4g step one prepared is dissolved in 200ml absolute ethyl alcohol, ultrasonic 30min.Add 2ml aminopropyl trimethoxysilane (APTMS), condensing reflux 4h.Then the titania of washes of absolute alcohol gained is used, to remove residual APTMS completely, the titanium dioxide microballoon sphere particle prepared by collecting with filtration unit;
Step 3, prepares graphene dispersing solution: be distributed to by the graphene oxide of 8mg in 50ml deionized water, after the ultrasonic 1h of ultrasonic machine, obtains graphene dispersing solution;
Step 4, the titania (APTMS-TreatedTiO2) 0.08g step 2 prepared is dissolved in the absolute ethyl alcohol of 10ml and obtains solution a, recording its pH value is 5, in faintly acid, add ammonia spirit, adjust its PH to 7, obtain solution b, (55mg) graphene dispersing solution pH value prepared by survey step 3 is 5, in faintly acid, add HCl solution, adjust its pH value to 4, obtain solution c, solution b, in magnetic stirring apparatus environment, by solution c slowly down in solution b, adjusts its pH value to be 6, slow stirring 1h, obtains solution d;
Step 5, solution d centrifuge prepared by step 4, centrifuge speed is at 2500r-3000r, the gray precipitate thing obtained is dissolved in the mixed liquor of the absolute ethyl alcohol of 8ml and the deionized water of 4ml, obtain solution e, be put in reactor by solution e and carry out hydrothermal treatment consists, hydrothermal conditions is keep 16h at 180 DEG C; Then by material 400 DEG C of calcining 2h in Ar environment, the titania nanoparticles of the graphene modified with bridging structure is prepared into;
Step 6, getting the titania nanoparticles 4mg ~ 5mg with the graphene modified of bridging structure that step 5 obtains is dispersed in deionized water, form the dispersion liquid of 8mg/ml ~ 10mg/ml, get 40 μ L ~ 50 μ L dispersion to substrate surface, after 50 DEG C of dry 10min, obtain ammonia gas sensor.
The performance test of embodiment 4 ammonia gas sensor
Under sensor prepared by embodiment 1-3 is placed in air atmosphere, working temperature is room temperature, then introduces NH 3gas molecule.By multimeter survey sensor at air with at the variable concentrations NH taking air as background 3resistance variations under atmosphere, as the signal of sensor.The ammonia gas sensor contrast accompanying drawing prepared for embodiment 1 is illustrated, and Fig. 4 gives prepared sensor and is being about the NH of 10 ~ 50ppm 3under atmosphere, the situation of change of sensor resistance.Sensor is (about 8min) after a few minutes, and sensor resistance change (i.e. induced signal) reaches 90% of peak value.Fig. 5 gives prepared sensor for several escaping gas such as ethanol, methyl alcohol and NH 3response contrast at room temperature, can find that this sensor is to NH 3response be the several times of other gases.
The present invention adopts sol-gel process, the precipitation method to obtain titania nanoparticles, connects TiO by realizing reduced graphene in hydro-thermal method 2nano particle, the effect of hydrothermal treatment consists has two: the first, generate Graphene connect TiO as bridge 2the micromechanism of nano particle; The second, graphene oxide is reduced to reductibility graphene oxide, hydro-thermal is chronic, can obtain higher reduction degree.Finally calcine in Ar environment, other organism can be removed, and ensure that C atom is not oxidized by oxygen.The TiO with the graphene modified of bridging structure obtained 2composite nanometer particle, as the gas sensitive principal ingredient of ammonia gas sensor of the present invention.What the present invention prepared is coated with the ammonia gas sensor of this gas sensitive to NH 3the response of gas has better selectivity, restorative, the performance such as stability and lower working temperature.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.

Claims (10)

1. ammonia gas sensor, comprises gas sensitive and substrate, and described gas sensitive is coated in described substrate surface, it is characterized in that, described gas sensitive composition comprises the titania composite nanometer particle of the graphene modified with bridging structure; Described composite nanometer particle comprises Graphene and titania, and described Graphene bridge joint is between described titania.
2. ammonia gas sensor according to claim 1, is characterized in that, the massfraction that described Graphene accounts for composite nano materials is 0.2% ~ 20%.
3. ammonia gas sensor according to claim 1, is characterized in that, described gas sensitive coating thickness is 0.4 ~ 0.5 μm.
4. ammonia gas sensor according to claim 1, is characterized in that, described substrate is Si substrate with Au electrode or Al 2o 3substrate.
5. ammonia gas sensor according to claim 1, is characterized in that, described titania is spherical, and the particle diameter of described titania is 1 μm ~ 5 μm.
6. ammonia gas sensor according to claim 5, is characterized in that, described titania is mono-dispersion microballoon.
7. the preparation technology of ammonia gas sensor described in claim 1-6 any one, is characterized in that, comprise the following steps:
Step one, prepares positively charged titanium dioxide microballoon sphere: modify the surface of titanium dioxide microballoon sphere, makes microsphere surface positively charged;
Step 2, prepares graphene dispersing solution: be distributed to by the graphene oxide of a mass parts in the water of 6-8 mass parts, ultrasonic process, adjust ph to 3.5 ~ 4.5;
Step 3, the positively charged titanium dioxide microballoon sphere 0.04g-0.40g getting step one gained joins in 5ml-80ml absolute ethyl alcohol, regulates pH to 6.5 ~ 7.5, under stirring, add the graphene dispersing solution 49mg-65mg of step 2 gained, regulate pH to 5.5 ~ 6.5; Centrifugal after stirring, obtain sediment and be dissolved in the ethanol water of the 60-75% of 10ml-30ml, carry out hydro-thermal reaction, temperature of reaction 175 ~ 185 DEG C, reaction time 15 ~ 17h;
Step 4, is placed in Ar environment by step 3 gained solution and calcines, calcining heat 395-405 DEG C, and calcination time is 1 ~ 3h, must have the titania composite nanometer particle of the graphene modified of bridging structure;
Step 5, getting titania composite nanometer particle 4mg ~ 5mg that step 4 gained has a graphene modified of bridging structure is dispersed in deionized water, form the dispersion liquid of 8mg/ml ~ 10mg/ml, get 40 μ L ~ 50 μ L dispersion again to described substrate surface, 40 ~ 60 DEG C of dry 5-15min.
8. technique according to claim 7, is characterized in that, in described step one, prepares positively charged titanium dioxide microballoon sphere and adopts following processing mode: be dissolved in 180ml-240ml absolute ethyl alcohol by 0.3g-0.5g titanium dioxide microballoon sphere particle, ultrasonic process; The 2ml-3ml aminopropyl trimethoxysilane condensing reflux 3 ~ 5h added.
9. technique according to claim 7, is characterized in that, described step 2, and ultrasonic power is 240 ~ 260W, and ultrasonic time is 25 ~ 35min; Described graphene oxide is through shearing pre-service; Described step 3, centrifugal rotating speed is 2500r-3000r, and centrifugation time is 5min-10min.
10. preparation technology according to claim 7, is characterized in that, the coating method in described step 5 comprises spraying, roller coating or dipping.
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CN105548277A (en) * 2016-01-14 2016-05-04 苏州大学 Ammonia gas sensor based on squaric acid derivatives and preparation method and application of ammonia gas sensor
CN105572174A (en) * 2016-01-14 2016-05-11 苏州大学 Acetic acid gas sensor based on azobenzene compound and preparation method and application of acetic acid gas sensor
CN105548277B (en) * 2016-01-14 2018-03-23 苏州大学 A kind of ammonia gas sensor based on squaric acid derivertives and its production and use
CN105572174B (en) * 2016-01-14 2018-07-06 苏州大学 A kind of acetic gas sensor of azo-based benzene-like compounds and its preparation method and application
CN110763737A (en) * 2018-11-22 2020-02-07 上海因士环保科技有限公司 Nano conductive material/polymer composite gas sensor and preparation method thereof
CN110763737B (en) * 2018-11-22 2022-05-31 因士(上海)科技有限公司 Preparation method of nano conductive material/polymer composite gas sensor
CN109613070A (en) * 2019-01-02 2019-04-12 大连理工大学 One kind being based on two dimension MXene/SnO2Ammonia gas sensor, preparation process and the application of hetero-junctions
CN109613070B (en) * 2019-01-02 2021-04-20 大连理工大学 Ammonia gas sensor based on two-dimensional MXene/SnO2 heterojunction, preparation process and application
CN113960123A (en) * 2021-11-03 2022-01-21 北京印刷学院 Ammonia-sensitive flexible intelligent package for detecting freshness of fish

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