CN114609197B - Gas-sensitive material, preparation method and NH (NH) thereof 3 Application in gas sensor - Google Patents
Gas-sensitive material, preparation method and NH (NH) thereof 3 Application in gas sensor Download PDFInfo
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- CN114609197B CN114609197B CN202210299257.6A CN202210299257A CN114609197B CN 114609197 B CN114609197 B CN 114609197B CN 202210299257 A CN202210299257 A CN 202210299257A CN 114609197 B CN114609197 B CN 114609197B
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000035945 sensitivity Effects 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 239000010931 gold Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229930192474 thiophene Natural products 0.000 claims description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000011258 core-shell material Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 229920000123 polythiophene Polymers 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- -1 ammonium heptamolybdate tetrahydrate Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 51
- 239000000126 substance Substances 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 101100509438 Leishmania major NSNH gene Proteins 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000004685 tetrahydrates Chemical class 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
Abstract
The invention provides a method based on MoO 3 @MoS 2 Composite material of/PTH, preparation method and application in ammonia gas sensor, relates to the field of gas detection, wherein MoO 3 @MoS 2 Occupying MoO 3 @MoS 2 20% by mass of/PTH; the working temperature is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4; the preparation method comprises the following steps: firstly, preparing flower-shaped MoO by a hydrothermal method 3 In MoO 3 Preparation of MoO for precursor 3 @MoS 2 Then preparing MoO by an in-situ polymerization method 3 @MoS 2 A PTH gas sensitive material; moO is carried out 3 @MoS 2 Coating PTH material on gold electrode coated Al 2 O 3 The surface of the ceramic tube is made into a gas sensor. The invention utilizes MoO prepared by an in-situ polymerization method 3 @MoS 2 The gas sensitive material of/PTH has higher sensitivity to ammonia gas, faster response time and recovery time.
Description
Technical Field
The invention relates to the technical field of functional nano material preparation, and also relates to the technical field of gas sensor detection, in particular to a gas sensitive material, a preparation method and application thereof in a gas sensor.
Background
In recent years, the rapid development of modern industry, environmental and ecological problems are more and more emphasized, environmental protection and monitoring of harmful substances become urgent, and air pollution is closely related to human health, and detection of harmful gases is more and more required. Ammonia is a common gas in daily life, and is not only a raw material of many chemical products, but also excreted waste gas of many chemical products, when the index concentration of ammonia exceeds a certain range, the ammonia will cause damage to our body, therefore, we need to monitor the ammonia concentration to ensure the product quality and environmental safety.
At present, many types of chemical resistance sensors exist in the world, and most of sensors using metal semiconductors as sensitive materials are semiconductor sensors, and the sensitivity of the semiconductor sensors is high, but the use temperature is high, and the gas selectivity is poor, so that a novel resistance sensor is urgently needed, and the applicability and the selectivity of the sensor are improved. The polythiophene in the conductive polymer is considered as a sensing material with great prospect because of the advantages of easy polymerization, high conductivity, good thermal stability, environmental stability and the like, and the synergistic effect or complementary effect between the polythiophene and the inorganic component has great significance for improving the gas-sensitive performance of components.
In recent years, new two-dimensional materials have evolved rapidly, with MoS 2 The polymer has the characteristics of good conductivity, strong adsorption capacity, high reactivity, good flexibility and the like, and has a natural band gap. MoS (MoS) 2 Is a strict two-dimensional material, has large specific surface area, unsaturated bonds at the edge, and the like, and provides living time for gas molecule adsorption reactionSex loci. These characteristics make MoS 2 The material becomes a hot spot for researching the gas-sensitive sensing material. MoS (MoS) 2 The gas sensor is insensitive to certain gases, so that the gas-sensitive performance is improved by adopting doping and compounding means, and a new thought is provided for the development of gas-sensitive devices with excellent performances such as low detection limit, high responsivity, short response/recovery time, low production cost and the like.
MoO 3 The material is a broadband transition metal oxide semiconductor material, has a special layer structure and good oxidation-reduction catalytic activity, has stable physical and chemical properties, can well control the morphology structure by controlling the reaction conditions, and improves the gas-sensitive performance of the material by doping and heterojunction construction.
The CN105510403A is prepared by forming a quasi-periodic structure on the surface of a monocrystalline silicon wafer by adopting a chemical or physical etching method and detecting ammonia by forming an electrode through thermal evaporation coating, but the process has high equipment requirement, high operation requirement and high production cost, and is not beneficial to large-scale application. CN102978578A adopts a sputtering method to prepare an ammonia gas sensor of a copper oxide doped tin dioxide matrix, and the sensor has high sensitivity and short response recovery time, but has high working temperature and large volume. CN104502415a invented an ammonia gas sensor based on noble metal composite material, which has good gas-sensitive property but high cost. CN110702752 invented a catalytic gas sensor, but its recovery time is long. CN102103103a discloses a sensor for detecting ammonia gas and a preparation method thereof, and the sensor is made of an organic thin film transistor for detecting ammonia gas, but the transistor sensor has the disadvantages of complex processing technology, long manufacturing period, harsh manufacturing conditions and unfriendly chemical reagents used in the preparation process.
In view of the above, the invention provides a gas sensor and application thereof in ammonia gas detection, which are used for solving the defect that the gas sensor can work only when the temperature of the gas sensor is raised or under an ultraviolet lamp in the prior art.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a MoO 3 @MoS 2 A method for preparing a PTH gas-sensitive material and application thereof in a gas-sensitive sensor.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a gas-sensitive material is MoO 3 @MoS 2 PTH by using MoO 3 Is nuclear and takes MoS 2 Forming core-shell structure MoO for shell 3 @MoS 2 Then polymerized with thiophene monomer, wherein MoO 3 And MoS 2 MoO of core-shell structure 3 @MoS 2 Accounting for 10 to 30 percent of the mass fraction of the material.
As a preferred mode, the flower-shaped nano molybdenum trioxide is prepared by a hydrothermal method, and then MoO is prepared 3 And MoS 2 Is prepared by an in-situ polymerization method 3 @MoS 2 /PTH。
Preferably, the gas-sensitive material is a sheet stacking structure, the MoO 3 @MoS 2 The working temperature of the PTH gas-sensitive material is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4.
The invention also provides a preparation method of the gas-sensitive material, which comprises the following steps:
s1: preparing flower-like molybdenum trioxide: the molar ratio was set to 1: heptamolybdic acid tetrahydrate of 10 to 3:10 (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and ammonium sulfate (NH) 4 ) 2 SO 4 Dissolving in 50mL of deionized water, then continuously adding 0.93mol of ammonia water and a proper amount of deionized water to a volume of 70mL, uniformly stirring the obtained solution, then adding 1.817g of thioacetamide, uniformly stirring to obtain a clear solution, transferring the solution into a 100mL of hydrothermal reaction kettle, and heating at 180-240 ℃ for 24 hours; naturally cooling to room temperature, collecting the obtained precipitate, washing with deionized water and ethanol for several times, and vacuum drying at 60deg.C for 10 hr;
s2: preparation of MoO 3 @MoS 2 : 1mM MoO was weighed out 3 The powder is dispersed in 100mL of mixed solution of water and ethanol by ultrasonic, the volume ratio of the water to the ethanol in the mixed solution is 2:3, and the uniform powder is obtainedMoO of quality 3 After the dispersion, thiourea and MoO with different molar ratios are added 3 ：H 2 NSNH 2 The molar ratio of (2) is 1:1-1:10, after thiourea is completely dissolved, transferring the whole mixed dispersion liquid into a hydrothermal kettle with the capacity of 100mL, wherein the filling ratio of the hydrothermal kettle is 70%, the hydrothermal temperature is 180-220 ℃, and the hydrothermal time is 18-24h; after the reaction is finished, cooling to room temperature, respectively centrifugally washing with water and ethanol for several times, and drying to obtain MoO 3 @MoS 2 ；
S3: preparing a material, namely weighing anhydrous ferric chloride, dissolving the anhydrous ferric chloride in chloroform, wherein the molar ratio of thiophene monomers to the anhydrous ferric chloride is 3:1, stirring for 1h to obtain dark green turbid liquid, and weighing thiophene monomers and MoO 3 @MoS 2 Dissolving in chloroform, thiophene monomer and MoO 3 @MoS 2 The mass ratio of (2) is 10:1-10:3, the dispersion liquid of thiophene and molybdenum disulfide is obtained by ultrasonic treatment for 1h, the dispersion liquid is slowly dripped into ferric chloride turbid night, and the reaction is stirred for 9h at room temperature; evaporating the solvent at room temperature after the reaction is completed, adding a proper amount of 1mol/L HCI, and stirring for 12 hours at room temperature; and washing the obtained product with HCl for a plurality of times, washing with deionized water, and drying at 60-80 ℃ for 6-8 hours.
Preferably, in S1, the solution is transferred to a hydrothermal reaction vessel and reacted at 180℃for 24h.
Preferably, in S2, moO is weighed with a molar ratio of 1:3 3 And H 2 NSNH 2 Added to the solution.
In the preferred mode, in S3, thiophene monomer and MoO with the mass ratio of 10:2 are weighed 3 @MoS 2 Dissolved in chloroform.
The invention also provides a gas-sensitive material in NH 3 The application in the gas sensor is as follows: moO is carried out 3 @MoS 2 PTH sensitive material coating and gold electrode coated Al 2 O 3 The surface of the ceramic tube is made into a gas-sensitive sensing element.
Preferably, the NH is 3 The preparation method of the gas-sensitive sensing element comprises the following steps: taking MoO 3 @MoS 2 Grinding PTH powder product for 10min, adding absolute ethanol, mixing, grinding to paste, and uniformly applying the pasteGold electrode coated Al 2 O 3 Evaporating ethanol at room temperature on the surface of the ceramic tube, and welding a gold electrode on the ceramic base.
The invention has the beneficial effects that: the invention provides a gas sensor which can detect ammonia gas with different concentrations under the condition of normal temperature and visible light and has the advantages of good responsiveness, high sensitivity, quick response and recovery time and strong selectivity; and the preparation is simple, the production cost is low, and the method is suitable for ammonia gas detection in certain environments. The technical defect that the gas sensor can work only under high temperature or ultraviolet light in the prior art is overcome.
Drawings
FIG. 1 shows a flower-like MoO of the present invention 3 SEM images of (a). (a) Low magnification and (b) high magnification
FIG. 2 is an SEM image of the polythiophene of the present invention. (a) Low magnification and (b) high magnification
FIG. 3 shows MoO of the present invention 3 @MoS 2 SEM image of PTH. (a) Low magnification and (b) high magnification
FIG. 4 shows MoO according to the present invention 3 @MoS 2 XPS map of/PTH.
FIG. 5 shows PTH and MoO of the present invention 3 @MoS 2 、MoO 3 @MoS 2 FTIR plot of/PTH.
FIG. 6 shows the MoO at room temperature according to the present invention 3 @MoS 2 Response curve of PTH to ammonia gas at no concentration.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
The embodiment provides a gas-sensitive material which is MoO 3 @MoS 2 /PTHBy using MoO 3 Is nuclear and takes MoS 2 Forming core-shell structure MoO for shell 3 @MoS 2 Then polymerized with thiophene monomer, wherein MoO 3 And MoS 2 MoO of core-shell structure 3 @MoS 2 Accounting for 10 to 30 percent of the mass fraction of the material.
The gas-sensitive material is of a sheet stacking structure, and the MoO 3 @MoS 2 The working temperature of the PTH gas-sensitive material is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4.
The embodiment also provides a preparation method of the gas-sensitive material, which comprises the steps of preparing flower-shaped nano molybdenum trioxide by a hydrothermal method, and then preparing MoO 3 And MoS 2 Is prepared by an in-situ polymerization method 3 @MoS 2 /PTH。
The method specifically comprises the following steps:
s1: preparing flower-like molybdenum trioxide: the molar ratio was set to 1: heptamolybdic acid tetrahydrate of 10 (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and ammonium sulfate (NH) 4 ) 2 SO 4 Dissolving in 50mL of deionized water, then continuously adding 0.93mol of ammonia water and a proper amount of deionized water to a volume of 70mL, uniformly stirring the obtained solution, then adding 1.817g of thioacetamide, uniformly stirring to obtain a clear solution, transferring the solution into a 100mL of hydrothermal reaction kettle, and heating at 180 ℃ for 24 hours; naturally cooling to room temperature, collecting the obtained precipitate, washing with deionized water and ethanol for several times, and vacuum drying at 60deg.C for 10 hr;
s2: preparation of MoO 3 @MoS 2 : 1mM MoO was weighed out 3 Dispersing the powder in 100mL of mixed solution of water and ethanol by ultrasonic, wherein the volume ratio of the water to the ethanol in the mixed solution is 2:3, and homogenizing to obtain MoO 3 After the dispersion, thiourea and MoO with different molar ratios are added 3 ：H 2 NSNH 2 The molar ratio of (2) is 1:1, after thiourea is completely dissolved, transferring the whole mixed dispersion liquid into a hydrothermal kettle with the capacity of 100mL, wherein the filling ratio of the hydrothermal kettle is 70%, the hydrothermal temperature is 180 ℃, and the hydrothermal time is 24 hours; after the reaction is finished, cooling to room temperatureCentrifugally washing with water and ethanol for several times, and drying to obtain MoO 3 @MoS 2 ；
S3: preparing a material, namely weighing anhydrous ferric chloride, dissolving the anhydrous ferric chloride in chloroform, wherein the molar ratio of thiophene monomers to the anhydrous ferric chloride is 3:1, stirring for 1h to obtain dark green turbid liquid, and weighing thiophene monomers and MoO 3 @MoS 2 Dissolving in chloroform, thiophene monomer and MoO 3 @MoS 2 Ultrasonic treatment is carried out for 1h to obtain dispersion liquid of thiophene and molybdenum disulfide, the dispersion liquid is slowly dripped into ferric chloride turbid liquid, and stirring reaction is carried out for 9h at room temperature; evaporating the solvent at room temperature after the reaction is completed, adding a proper amount of 1mol/L HCI, and stirring for 12 hours at room temperature; the resulting product was washed with HCl multiple times and then with deionized water and dried at 60 ℃ for 6 hours.
Example 2
The embodiment provides a gas-sensitive material which is MoO 3 @MoS 2 PTH by using MoO 3 Is nuclear and takes MoS 2 Forming core-shell structure MoO for shell 3 @MoS 2 Then polymerized with thiophene monomer, wherein MoO 3 And MoS 2 MoO of core-shell structure 3 @MoS 2 Accounting for 10 to 30 percent of the mass fraction of the material.
The gas-sensitive material is of a sheet stacking structure, and the MoO 3 @MoS 2 The working temperature of the PTH gas-sensitive material is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4.
The embodiment also provides a preparation method of the gas-sensitive material, which comprises the steps of preparing flower-shaped nano molybdenum trioxide by a hydrothermal method, and then preparing MoO 3 And MoS 2 Is prepared by an in-situ polymerization method 3 @MoS 2 /PTH。
The method specifically comprises the following steps:
s1: preparing flower-like molybdenum trioxide: heptamolybdic acid tetrahydrate in a molar ratio of 3:10 was reacted as (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and ammonium sulfate (NH) 4 ) 2 SO 4 Dissolving in 50mL deionized water, then continuously adding 0.93mol ammonia water and proper amount of deionized water to a constant volume of 70mL, and adding the mixture into the mixtureThe obtained solution is stirred uniformly, 1.817g of thioacetamide is added and stirred uniformly to obtain a clear solution, and then the solution is transferred into a 100mL hydrothermal reaction kettle and heated for 24 hours at 240 ℃; naturally cooling to room temperature, collecting the obtained precipitate, washing with deionized water and ethanol for several times, and vacuum drying at 60deg.C for 10 hr;
s2: preparation of MoO 3 @MoS 2 : 1mM MoO was weighed out 3 Dispersing the powder in 100mL of mixed solution of water and ethanol by ultrasonic, wherein the volume ratio of the water to the ethanol in the mixed solution is 2:3, and homogenizing to obtain MoO 3 After the dispersion, thiourea and MoO with different molar ratios are added 3 ：H 2 NSNH 2 The molar ratio of (2) is 1:10, after thiourea is completely dissolved, transferring the whole mixed dispersion liquid into a hydrothermal kettle with the capacity of 100mL, wherein the filling ratio of the hydrothermal kettle is 70%, the hydrothermal temperature is 220 ℃, and the hydrothermal time is 18 hours; after the reaction is finished, cooling to room temperature, respectively centrifugally washing with water and ethanol for several times, and drying to obtain MoO 3 @MoS 2 ；
S3: preparing a material, namely weighing anhydrous ferric chloride, dissolving the anhydrous ferric chloride in chloroform, wherein the molar ratio of thiophene monomers to the anhydrous ferric chloride is 3:1, stirring for 1h to obtain dark green turbid liquid, and weighing thiophene monomers and MoO 3 @MoS 2 Dissolving in chloroform, thiophene monomer and MoO 3 @MoS 2 Ultrasonic treatment is carried out for 1h to obtain dispersion liquid of thiophene and molybdenum disulfide, the dispersion liquid is slowly dripped into ferric chloride turbid liquid, and stirring reaction is carried out for 9h at room temperature; evaporating the solvent at room temperature after the reaction is completed, adding a proper amount of 1mol/L HCI, and stirring for 12 hours at room temperature; and washing the obtained product with HCl for a plurality of times, washing with deionized water, and drying at 60-80 ℃ for 6-8 hours.
Example 3
The embodiment provides a gas-sensitive material which is MoO 3 @MoS 2 PTH by using MoO 3 Is nuclear and takes MoS 2 Forming core-shell structure MoO for shell 3 @MoS 2 Then polymerized with thiophene monomer, wherein MoO 3 And MoS 2 MoO of core-shell structure 3 @MoS 2 Accounting for 10 to 30 percent of the mass fraction of the material.
The gas-sensitive material is of a sheet stacking structure, and the MoO 3 @MoS 2 The working temperature of the PTH gas-sensitive material is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4.
The embodiment also provides a preparation method of the gas-sensitive material, which comprises the steps of preparing flower-shaped nano molybdenum trioxide by a hydrothermal method, and then preparing MoO 3 And MoS 2 Is prepared by an in-situ polymerization method 3 @MoS 2 /PTH。
The method specifically comprises the following steps:
s1: preparing flower-like molybdenum trioxide: the molar ratio was set to 2: heptamolybdic acid tetrahydrate of 10 (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and ammonium sulfate (NH) 4 ) 2 SO 4 Dissolving in 50mL of deionized water, then continuously adding 0.93mol of ammonia water and a proper amount of deionized water to a volume of 70mL, uniformly stirring the obtained solution, then adding 1.817g of thioacetamide, uniformly stirring to obtain a clear solution, transferring the solution into a 100mL of hydrothermal reaction kettle, and heating at 200 ℃ for 24 hours; naturally cooling to room temperature, collecting the obtained precipitate, washing with deionized water and ethanol for several times, and vacuum drying at 60deg.C for 10 hr;
s2: preparation of MoO 3 @MoS 2 : 1mM MoO was weighed out 3 Dispersing the powder in 100mL of mixed solution of water and ethanol by ultrasonic, wherein the volume ratio of the water to the ethanol in the mixed solution is 2:3, and homogenizing to obtain MoO 3 After the dispersion, thiourea and MoO with different molar ratios are added 3 ：H 2 NSNH 2 The molar ratio of (2) is 1:3, after thiourea is completely dissolved, transferring the whole mixed dispersion liquid into a hydrothermal kettle with the capacity of 100mL, wherein the filling ratio of the hydrothermal kettle is 70%, the hydrothermal temperature is 200 ℃, and the hydrothermal time is 20h; after the reaction is finished, cooling to room temperature, respectively centrifugally washing with water and ethanol for several times, and drying to obtain MoO 3 @MoS 2 ；
S3: preparing a material, namely weighing anhydrous ferric chloride, dissolving the anhydrous ferric chloride in chloroform, wherein the molar ratio of thiophene monomer to the anhydrous ferric chloride is 3:1, stirring for 1h to obtain dark green turbid liquid, and weighing thiophene monomerBody and MoO 3 @MoS 2 Dissolving in chloroform, thiophene monomer and MoO 3 @MoS 2 Ultrasonic treatment is carried out for 1h to obtain dispersion liquid of thiophene and molybdenum disulfide, the dispersion liquid is slowly dripped into ferric chloride turbid liquid, and stirring reaction is carried out for 9h at room temperature; evaporating the solvent at room temperature after the reaction is completed, adding a proper amount of 1mol/L HCI, and stirring for 12 hours at room temperature; the resulting product was washed with HCl multiple times and then with deionized water and dried at 70 ℃ for 7 hours.
Performance testing
MoO for 3 examples 3 @MoS 2 Characterization of PTH gas sensitive materials:
MoO prepared by using a scanning electron microscope, a Fourier infrared spectrometer and an X-ray photoelectron spectrometer 3 @MoS 2 Physical or chemical characterization is carried out on the PTH gas-sensitive material to obtain the graph 1, the graph 2, the graph 3, the graph 4 and the graph 5 respectively:
FIG. 1 is MoO 3 From the scanning electron microscope image of (2), the synthesized MoO can be seen 3 Is of a flower-shaped structure;
FIG. 2 is a scanning electron microscope image of polythiophene, from which it can be seen that the synthetic polythiophene in the form of a rod is connected in a network structure;
FIG. 3 is MoO 3 @MoS 2 Scanning electron microscope image of/PTH, from which it can be seen that PTH was successful in MoO 3 @MoS 2 Successful polymerization is carried out;
FIG. 4 is MoO 3 @MoS 2 X-ray photoelectron spectrum of PTH: the composite material is composed of C, O, S, mo and four elements, and four peaks at 164.41eV, 229.08eV, 285.07eV and 532.33eV are respectively attributed to the binding energy of S2p, mo3d, C1S and O1S.
FIG. 5 shows PTH, moO 3 @MoS 2 、MoO 3 @MoS 2 FT-IR picture of PTH, moO 3 @MoS 2 the/PTH nanocomposite shows peaks similar to PTH. 785.03cm -1 Corresponds to the C-H surface extension vibration of the 2, 5-substituted thiophene ring generated by the polymerization of thiophene monomers. 670.5cm -1 The peak at which is C-S bond flexural vibration 462.92cm -1 The peak band at which is attributable to the C-S-C bondThe ring deformation mode proves that thiophene is in MoO 3 @MoS 2 And the polymerization was successful.
EXAMPLE 4 MoO preparation 3 @MoS 2 PTH ammonia gas sensor
Taking MoO 3 @MoS 2 Grinding PTH powder product for 10min, adding absolute ethanol, mixing, grinding to paste, and uniformly coating the paste on gold electrode coated Al 2 O 3 Evaporating ethanol at room temperature on the surface of the ceramic tube, and welding a gold electrode on the ceramic base to obtain NH 3 A gas sensor.
MoO for example 4 3 @MoS 2 Sensitivity of PTH ammonia gas sensor for testing
The sensitivity of the gas sensitive material is measured by adopting a static gas distribution method: moO produced at room temperature 3 @MoS 2 the/PTH sensor is respectively added with ammonia gas with different concentrations for testing, and S=R/R is used for testing 0 The formula calculates the sensitivity of different concentrations, where R is the resistance value of the sensor after exposure to ammonia, R 0 Is the initial resistance value of the sensor in the air to obtain MoO 3 @MoS 2 Sensitivity of the PTH gas sensitive material to 50ppm, 100ppm, 200ppm, 300ppm, 500ppm, 800ppm is shown in FIG. 6.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.
Claims (7)
1. A gas sensitive material characterized in that: the material is MoO 3 @MoS 2 PTH by using MoO 3 Is nuclear and takes MoS 2 Forming core-shell structure MoO for shell 3 @MoS 2 Then polymerized with thiophene monomer, wherein MoO 3 And MoS 2 Core-shell junction of (2)MoO structure 3 @MoS 2 Accounting for 10 to 30 percent of the mass fraction of the material; wherein PTH is polythiophene;
the preparation method specifically comprises the following steps:
s1: preparing flower-like molybdenum trioxide: the molar ratio was set to 1: ammonium heptamolybdate tetrahydrate (NH) 10 to 3:10 4 ) 6 Mo 7 O 24 ·4H 2 O and ammonium sulfate (NH) 4 ) 2 SO 4 Dissolving in 50mL of deionized water, then continuously adding 0.93mol of ammonia water and a proper amount of deionized water to a volume of 70mL, uniformly stirring the obtained solution, then adding 1.817g of thioacetamide, uniformly stirring to obtain a clear solution, transferring the solution into a 100mL of hydrothermal reaction kettle, and heating at 180-240 ℃ for 24 hours; naturally cooling to room temperature, collecting the obtained precipitate, washing with deionized water and ethanol for several times, and vacuum drying at 60deg.C for 10 hr;
s2: preparation of MoO 3 @MoS 2 : 1mM MoO was weighed out 3 The powder is dispersed in 100mL of mixed solution of water and ethanol by ultrasonic, the volume ratio of the water to the ethanol in the mixed solution is 2:3, and the homogenized MoO is obtained 3 After the dispersion, thiourea and MoO with different molar ratios are added 3 ：H 2 NCSNH 2 The molar ratio of (2) is 1:1-1:10, after thiourea is completely dissolved, transferring the whole mixed dispersion liquid into a hydrothermal kettle with the capacity of 100mL, wherein the filling ratio of the hydrothermal kettle is 70%, the hydrothermal temperature is 180-220 ℃, and the hydrothermal time is 18-24h; after the reaction is finished, cooling to room temperature, respectively centrifugally washing with water and ethanol for several times, and drying to obtain MoO 3 @MoS 2 ；
S3: preparing a material, namely weighing anhydrous ferric chloride, dissolving the anhydrous ferric chloride in chloroform, wherein the molar ratio of thiophene monomers to the anhydrous ferric chloride is 3:1, stirring for 1h to obtain dark green turbid liquid, and weighing thiophene monomers and MoO 3 @MoS 2 Dissolving in chloroform, thiophene monomer and MoO 3 @MoS 2 The mass ratio of (2) is 10:1-10:3, and thiophene and MoO are obtained after 1h of ultrasonic treatment 3 @MoS 2 Slowly dripping the dispersion into the ferric chloride turbid liquid, and stirring at room temperature for reaction for 9 hours; evaporating the solvent at room temperature after the reaction is completed, adding a proper amount of 1mol/L hydrochloric acid, and stirring for 12h at room temperatureThe method comprises the steps of carrying out a first treatment on the surface of the Washing the obtained product with hydrochloric acid for multiple times, washing with deionized water, and drying at 60-80 ℃ for 6-8 hours.
2. A gas sensitive material according to claim 1, wherein: the gas-sensitive material is of a sheet stacking structure, and the MoO 3 @MoS 2 The working temperature of the PTH gas-sensitive material is room temperature, and the sensitivity to 50ppm ammonia gas reaches 1.4, wherein PTH is polythiophene.
3. A gas sensitive material according to claim 1, wherein: in S1, the solution is transferred to a hydrothermal reaction kettle and reacted for 24 hours at 180 ℃.
4. A gas sensitive material according to claim 1, wherein: s2, weighing MoO with the molar ratio of 1:3 3 And H 2 NCSNH 2 Added to the solution.
5. A gas sensitive material according to claim 1, wherein: s3, weighing thiophene monomer and MoO with the mass ratio of 10:2 3 @MoS 2 Dissolved in chloroform.
6. A gas-sensitive material as claimed in claim 1 in NH 3 The application in the gas sensor, characterized by: moO is carried out 3 @MoS 2 Coating PTH gas sensitive material on Al coated by gold electrode 2 O 3 NH is produced on the surface of the ceramic tube 3 A gas sensing element wherein PTH is polythiophene.
7. The gas-sensitive material of claim 6 in NH 3 The application in the gas sensor, characterized by: the NH is 3 The preparation method of the gas-sensitive sensing element comprises the following steps: taking MoO 3 @MoS 2 Grinding powder product of PTH gas sensitive material for 10min, adding absolute ethanol, mixing, grinding to paste, and uniformly coating the paste on gold electrode coated Al 2 O 3 Evaporating ethanol at room temperature on the surface of ceramic tube, and then evaporating goldThe electrode is welded on the ceramic base; wherein PTH is polythiophene.
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