CN116237020A - Self-assembled monolayer film modified tin diselenide sensing material and preparation method and application thereof - Google Patents
Self-assembled monolayer film modified tin diselenide sensing material and preparation method and application thereof Download PDFInfo
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- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical class [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011540 sensing material Substances 0.000 title claims abstract description 59
- 239000002094 self assembled monolayer Substances 0.000 title claims abstract description 29
- 239000013545 self-assembled monolayer Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 38
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 38
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000002356 single layer Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 12
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 150000003342 selenium Chemical class 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- VIEXQFHKRAHTQS-UHFFFAOYSA-N chloroselanyl selenohypochlorite Chemical compound Cl[Se][Se]Cl VIEXQFHKRAHTQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 66
- 230000035945 sensitivity Effects 0.000 abstract description 16
- -1 3-aminopropyl triethoxysilane modified tin diselenide Chemical class 0.000 description 26
- 239000000463 material Substances 0.000 description 26
- 230000004044 response Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002135 nanosheet Substances 0.000 description 12
- 239000000376 reactant Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 230000004043 responsiveness Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 208000017574 dry cough Diseases 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 210000003800 pharynx Anatomy 0.000 description 1
- 208000005333 pulmonary edema Diseases 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 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
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Abstract
The invention belongs to the technical field of gas sensing materials, and particularly relates to a self-assembled monolayer film modified tin diselenide sensing material, and a preparation method and application thereof. The sensing material is used for modifying tin diselenide by using 3-aminopropyl triethoxy silane to self-assemble an organic monolayer film on the surface of the tin diselenide. The 3-aminopropyl triethoxy silane can greatly improve the adsorption capacity of the sensing material to nitrogen dioxide, so that the sensing material has higher sensitivity, specificity and stability under the condition of room temperature, and is very suitable for being applied to the detection and adsorption of nitrogen dioxide.
Description
Technical Field
The invention belongs to the technical field of gas sensing materials. More particularly, relates to a self-assembled monolayer film modified tin diselenide sensing material, a preparation method and application thereof.
Background
With the rapid increase of the conservation amount of motor vehicles in China, a large amount of tail gas is discharged into the atmosphere. Because nitrogen dioxide in tail gas has strong irritation, long-term inhalation of human beings can cause discomfort and dry cough of the pharynx and even cause injuries such as delayed pulmonary edema. Therefore, the gas-sensitive sensing material which has the advantages of high specificity, high responsivity, high sensitivity and the like for detecting the nitrogen dioxide is designed and developed, and has very important value for protecting the green environment and the health of human beings.
The layered metal disulfide is a novel two-dimensional material, and is often used for room temperature detection of gas due to the advantages of large specific surface area, high carrier concentration, rich gas adsorption sites and the like. Tin diselenide, as representative thereof, has a great adsorption energy for nitrogen dioxide, calculated according to the first principle of nature, indicating that it has a specific recognition capacity for nitrogen dioxide. The responsiveness of gas sensors based on tin diselenide is generally low, and some method strategies are required to improve the gas-sensitive response capability, such as that disclosed in chinese patent application CN109521063a, a petal-like SnSe 2 The nitrogen dioxide gas sensor comprises a gas-sensitive material and a heating substrate, wherein the petal-shaped tin diselenide nano gas-sensitive material is coated on the surface of the heating substrate, and although the sensitivity of the tin diselenide is improved to a certain extent, the petal-shaped tin diselenide needs a special and complex preparation process, and the detection needs to be carried out at a high temperature of 90-150 ℃, so that the energy consumption is high and the use is inconvenient.
Therefore, there is an urgent need to provide a tin diselenide gas-sensitive sensing material with high nitrogen dioxide responsiveness, good sensitivity and convenient use.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of complex preparation method, low material responsiveness and low sensitivity of the existing tin diselenide gas-sensitive material, and provides the self-assembled monolayer film modified tin diselenide sensing material with high nitrogen dioxide responsiveness, good sensitivity and convenient use.
The invention aims to provide a preparation method of the self-assembled monolayer film modified tin diselenide sensing material.
It is another object of the invention to provide the use of the self-assembled monolayer film modified tin diselenide sensing material.
The above object of the present invention is achieved by the following technical scheme:
the self-assembled monolayer film technique is an ordered molecular film that spontaneously forms long-chain organic molecules on a specific substrate material by chemisorption and self-organization. The technology has the characteristics of simple operation, high film forming stability and the like. And according to the difference of the tail end functional groups of the assembled organic molecules, the adsorption capacity of different gas molecules can be changed, so that the selectivity and the responsiveness of the gas sensitivity of the substrate are enhanced.
Therefore, the invention provides a self-assembled monolayer film modified tin diselenide sensing material, which is characterized in that 3-aminopropyl triethoxysilane is self-assembled on the surface of tin diselenide to form an organic monolayer film to modify tin diselenide.
The tin diselenide is a semiconductor type material, the tin diselenide is modified by using 3-aminopropyl triethoxy silane to form an organic monolayer film through self-assembly on the surface of the tin diselenide, the resistance of the self-assembled monolayer film modified tin diselenide sensing material is stabilized to be more than 53000 omega when the self-assembled monolayer film modified tin diselenide sensing material is in air, when the self-assembled monolayer film modified tin diselenide sensing material contacts nitrogen dioxide molecules, nitrogen dioxide can capture free electrons in the self-assembled monolayer film modified tin diselenide sensing material, and as the tin diselenide presents N-type semiconductor property, the loss of electrons can lead to the decrease of the conductivity of the gas sensing material and the increase of the resistance, and the concentration of nitrogen dioxide in the environment can be obtained through measuring the relation between the resistance change and the concentration of nitrogen dioxide.
In addition, the invention also provides a preparation method of the self-assembled monolayer film modified tin diselenide sensing material, which specifically comprises the following steps:
and (3) uniformly dispersing the tin diselenide in an ethanol solution, adding 3-aminopropyl triethoxysilane, fully contacting and reacting completely, and carrying out post-treatment to obtain the finished product.
Further, the method of uniform dispersion is ultrasound. Preferably, the power of the ultrasonic wave is 100-200W, and the ultrasonic wave time is 20-40 minutes.
Further, the mass volume ratio of the tin diselenide to the 3-aminopropyl triethoxysilane is (50-200) mg/mL.
Further, the ethanol volume fraction of the ethanol solution is 80-95%.
Further, after the tin diselenide is placed in the ethanol solution, the mass concentration of the tin diselenide is (1-5) mg/mL.
Further, the sufficient contact is performed by stirring, which may be magnetic stirring, at a stirring rate of (300 to 500) rpm.
Further, the time for the complete contact reaction is 1 to 12 hours.
Further, the preparation method of the tin diselenide comprises the following steps:
dissolving tin salt and selenium salt in water, adding hydrazine hydrate, fully mixing and reacting completely, fully performing hydrothermal reaction at 160-180 ℃, and performing post-treatment to obtain the finished product. According to the method, the reducibility of hydrazine hydrate is utilized to reduce tin salt and selenium salt into simple substances, and the two simple substances are combined under a hydrothermal condition to generate tin diselenide.
Further, the tin salt is selected from one or more of stannous chloride, stannous sulfate and stannic methane sulfonate.
Still further, the selenium salt is selected from one or more of selenium dioxide, selenium powder, and selenium chloride.
Further, the mass volume ratio of the tin salt to the selenium salt to the water is (0.4-0.5): (20-40) g/mL.
Further, the volume-mass ratio of the hydrazine hydrate to the tin salt is 1 (200-300) mL/mg.
Further, the well-mixed reaction is performed in combination with magnetic stirring at a stirring rate of (300-500) rpm for 20-40 minutes.
Further, the hydrothermal reaction time is 20 to 24 hours.
Further, the post-treatment specifically includes: after water and absolute ethyl alcohol are alternately washed for three times, the reactant is dried for 10 to 14 hours at the temperature of 60 to 80 ℃.
The 3-aminopropyl triethoxy silane can adjust the energy band structure of the gas sensing material, regulate and control the active site of tin diselenide, and the amino group at the tail end of the 3-aminopropyl triethoxy silane has unique adsorption characteristic on nitrogen dioxide, so that the adsorption capacity of the sensing material on nitrogen dioxide is greatly improved, and the sensing material has higher sensitivity, specificity and stability under the room temperature condition and is very suitable for being applied to the detection and adsorption of nitrogen dioxide.
Therefore, the invention also claims the application of the self-assembled monolayer film modified tin diselenide sensing material in nitrogen dioxide detection.
Further protecting the application of the self-assembled monolayer film modified tin diselenide sensing material in nitrogen dioxide adsorption.
The invention has the following beneficial effects:
the invention provides a self-assembled monolayer film modified tin diselenide sensing material, which is characterized in that 3-aminopropyl triethoxysilane is used for self-assembling to form an organic monolayer film on the surface of tin diselenide to modify tin diselenide. The 3-aminopropyl triethoxy silane can greatly improve the adsorption capacity of the sensing material to nitrogen dioxide, so that the sensing material has higher sensitivity, specificity and stability under the condition of room temperature, and is very suitable for being applied to the detection and adsorption of nitrogen dioxide.
Drawings
FIG. 1 is a scanning electron microscope STEM-EDS diagram of a tin diselenide gas-sensitive sensor material modified by 3-aminopropyl triethoxysilane in example 1 of the present invention.
FIG. 2 is a TEM high resolution contrast fringe pattern of a 3-aminopropyl triethoxysilane modified tin diselenide gas sensitive sensor material of example 1 of the present invention.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of the tin diselenide gas sensor material modified by 3-aminopropyl triethoxysilane in the embodiment 1 of the invention on Sn 3d, se 3d, N1 s and Si 2 p.
FIG. 4 is a graph showing the dynamic response recovery of 500ppb nitrogen dioxide for a 3-aminopropyl triethoxysilane modified tin diselenide gas sensor material of example 1 of the present invention.
FIG. 5 is a graph showing the dynamic response recovery curves, linear relations and long-term stability results of the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material of example 1 of the present invention for nitrogen dioxide gases with different concentrations.
FIG. 6 is a statistical chart of sensitivity data of 3-aminopropyl triethoxysilane modified tin diselenide gas sensor material of example 1 of the present invention to 5ppm different gases.
FIG. 7 is a statistical chart of the resistance value measurement results of the 3-aminopropyl triethoxysilane modified tin diselenide gas sensing material in the embodiment 1 of the present invention.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of self-assembled monolayer film modified tin diselenide gas sensor Material
1. The preparation method of the self-assembled monolayer film modified tin diselenide gas-sensitive sensing material specifically comprises the following steps:
s1, preparing a tin diselenide nano sheet: 451mg of stannous chloride dihydrate and 443mg of selenium dioxide are dissolved in 30mL of deionized water, 2mL of hydrazine hydrate is added into the solution dropwise, and the solution is magnetically stirred for 30 minutes at the rotation speed of 400rpm to complete the reaction; transferring the obtained reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃; washing the reactant for multiple times, and drying at 60 ℃ for 12 hours to obtain tin diselenide nano-sheets;
s2, performing ultrasonic treatment on the tin diselenide nano-sheets obtained in the step S1 in 20mL of ethanol/water (volume ratio is 95:5) solution for 30 minutes at 150W to obtain uniform dispersion; adding 0.5mL of 3-aminopropyl triethoxysilane into the dispersion liquid, and magnetically stirring at 400rpm for 3 hours to complete the reaction; and after washing for many times, drying the reactant at 60 ℃ for 12 hours to obtain the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material.
2. Determination of physicochemical Properties
(1) The scanning electron microscope STEM-EDS diagram of the 3-aminopropyl triethoxysilane modified tin diselenide gas sensing material obtained in the embodiment is measured, and the result is shown in FIG. 1. From the figure, the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material presents a remarkable two-dimensional lamellar structure, and Sn, se, O, si is uniformly distributed in the material.
(2) TEM high-resolution contrast fringe pattern of the tin diselenide gas-sensitive sensing material modified by 3-aminopropyl triethoxysilane obtained in the embodiment is measured, and the result is shown in FIG. 2. The interplanar spacing of the material can be determined by measurement, further proving the presence of tin diselenide.
(3) XPS graphs of Sn 3d, se 3d, N1 s and Si 2p of the 3-aminopropyl triethoxysilane modified tin diselenide gas sensing material obtained in the embodiment are measured, and the results are shown in FIG. 3. It can be seen that tin diselenide is present and that the surface is assembled with 3-aminopropyl triethoxysilane molecules.
(4) The dynamic response recovery curve of the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment to nitrogen dioxide gas with the concentration of 500ppb is measured by adopting a dynamic gas distribution method, and the result is shown in fig. 4. The graph shows that the material has better response characteristic to nitrogen dioxide, and the resistivity of the nitrogen dioxide, namely the sensitivity, reaches 318%.
(5) The dynamic response recovery curve and linear relation of the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment to nitrogen dioxide gas with different concentrations (100 ppb, 200ppb, 300ppb, 400ppb, 500 ppb) are measured by adopting a dynamic gas distribution method, the result is seen in fig. 5, the response of the material to nitrogen dioxide with different concentrations shows stepwise change, the sensitivity of the response change is increased along with the increase of the concentration of nitrogen dioxide, and R is linearly fitted 2 =0.997; for the 3-aminopropyl triethoxysilane modified tin diselenide gas sensor material obtained in this example, the sensor material pair was measured once every five days for 100The responses of 300, 500ppb nitrogen dioxide were measured for a total of 30 days to observe the stability of the material, and as a result, referring to fig. 5, it can be seen from the graph that the sensing material exhibited stable response values to various concentration gases within 30 days.
(6) The sensitivity of the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in this example to different gases was measured (resistance values Rg and Ra of the sensing device in target gas and air were measured, respectively, and the sensitivity s= (Rg-Ra)/Ra was calculated by the following formula), and the result is shown in fig. 6. The figure shows that the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material has higher selectivity to nitrogen dioxide.
(7) The resistance value of the 3-aminopropyl triethoxysilane modified tin diselenide gas sensor material obtained in this example was measured, and the result is shown in FIG. 7. The graph shows that the resistance value of the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment is more than 53000 omega when the material is in air.
The topographical features of the following examples are similar to those of example 1 and are not repeated.
Example 2 preparation of self-assembled monolayer film modified tin diselenide gas sensor Material
The preparation method of the self-assembled monolayer film modified tin diselenide gas-sensitive sensing material specifically comprises the following steps:
s1, preparing a tin diselenide nano sheet: 451mg of stannous chloride dihydrate and 443mg of selenium dioxide are dissolved in 30mL of deionized water, 2mL of hydrazine hydrate is added into the solution dropwise, and the solution is magnetically stirred for 30 minutes at the rotation speed of 400rpm to complete the reaction; transferring the obtained reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃; washing the reactant for multiple times, and drying at 60 ℃ for 12 hours to obtain tin diselenide nano-sheets;
s2, preparing a gas-sensitive sensing material: carrying out ultrasonic treatment on the tin diselenide nano-sheets obtained in the step S1 in 20mL of ethanol/water (volume ratio is 95:5) solution for 30 minutes at 150W to obtain uniform dispersion liquid; adding 0.5mL of 3-aminopropyl triethoxysilane into the dispersion liquid, and magnetically stirring at 400rpm for 1 hour to complete the reaction; and after washing for many times, drying the reactant at 60 ℃ for 12 hours to obtain the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material.
The 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment has good response characteristic to nitrogen dioxide gas with the concentration of 500ppb at 25 ℃, and the nitrogen dioxide resistance response rate is 253 percent.
Example 3 preparation of self-assembled monolayer film modified tin diselenide gas sensor Material
The preparation method of the self-assembled monolayer film modified tin diselenide gas-sensitive sensing material specifically comprises the following steps:
s1, preparing a tin diselenide nano sheet: 451mg of stannous chloride dihydrate and 443mg of selenium dioxide are dissolved in 30mL of deionized water, 2mL of hydrazine hydrate is added into the solution dropwise, and the solution is magnetically stirred for 30 minutes at the rotation speed of 400rpm to complete the reaction; transferring the obtained reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃; washing the reactant for multiple times, and drying at 60 ℃ for 12 hours to obtain tin diselenide nano-sheets;
s2, preparing a gas-sensitive sensing material: carrying out ultrasonic treatment on the tin diselenide nano-sheets obtained in the step S1 in 20mL of ethanol/water (volume ratio is 95:5) solution for 30 minutes at 150W to obtain uniform dispersion liquid; adding 0.5mL of 3-aminopropyl triethoxysilane into the dispersion liquid, and magnetically stirring at 400rpm for 6 hours to complete the reaction; and after washing for many times, drying the reactant at 60 ℃ for 12 hours to obtain the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material.
The 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment has good response characteristic to 500ppb nitrogen dioxide gas at 25 ℃, and the nitrogen dioxide resistance response rate, namely the sensitivity is 228%.
Example 4 preparation of self-assembled monolayer film modified tin diselenide gas sensor Material
The preparation method of the self-assembled monolayer film modified tin diselenide gas-sensitive sensing material specifically comprises the following steps:
s1, preparing a tin diselenide nano sheet: 451mg of stannous chloride dihydrate and 443mg of selenium dioxide are dissolved in 30mL of deionized water, 2mL of hydrazine hydrate is added into the solution dropwise, and the solution is magnetically stirred for 30 minutes at the rotation speed of 400rpm to complete the reaction; transferring the obtained reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃; washing the reactant for multiple times, and drying at 60 ℃ for 12 hours to obtain tin diselenide nano-sheets;
s2, preparing a gas-sensitive sensing material: carrying out ultrasonic treatment on the tin diselenide nano-sheets obtained in the step S1 in 20mL of ethanol/water (volume ratio is 95:5) solution for 30 minutes at 150W to obtain uniform dispersion liquid; 0.5mL of 3-aminopropyl triethoxysilane is added into the dispersion liquid, and the mixture is magnetically stirred at 400rpm for 12 hours to complete the reaction; and after washing for many times, drying the reactant at 60 ℃ for 12 hours to obtain the 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material.
The 3-aminopropyl triethoxysilane modified tin diselenide gas-sensitive sensing material obtained in the embodiment has good response characteristic to 500ppb nitrogen dioxide gas at 25 ℃, and the nitrogen dioxide resistance response rate, namely the sensitivity is 186%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A self-assembled monolayer film modified tin diselenide sensing material is characterized in that 3-aminopropyl triethoxysilane is used for self-assembling on the surface of tin diselenide to form an organic monolayer film to modify tin diselenide.
2. The method for preparing the self-assembled monolayer film modified tin diselenide sensing material of claim 1, which is characterized by comprising the following steps:
and (3) uniformly dispersing the tin diselenide in an ethanol solution, adding 3-aminopropyl triethoxysilane, fully contacting and reacting completely, and carrying out post-treatment to obtain the finished product.
3. The method of claim 2, wherein the method of uniform dispersion is ultrasound.
4. The preparation method according to claim 3, wherein the mass-volume ratio of the tin diselenide to the 3-aminopropyl triethoxysilane is (50-200) mg/mL.
5. The method according to claim 3, wherein the ethanol solution has an ethanol volume fraction of 80 to 95%.
6. The preparation method according to claim 2, wherein the preparation method of tin diselenide comprises the following steps:
dissolving tin salt and selenium salt in water, adding hydrazine hydrate, fully mixing and reacting completely, fully performing hydrothermal reaction at 160-200 ℃, and performing post-treatment to obtain the finished product.
7. The method according to claim 6, wherein the tin salt is one or more selected from stannous chloride, stannous sulfate and tin methane sulfonate.
8. The preparation method according to claim 6, wherein the selenium salt is one or more selected from selenium dioxide, selenium powder and selenium chloride.
9. Use of the self-assembled monolayer film modified tin diselenide sensing material of claim 1 in nitrogen dioxide detection.
10. Use of the self-assembled monolayer film modified tin diselenide sensing material of claim 1 for nitrogen dioxide adsorption.
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