CN114646669B - Preparation method and application of tin disulfide/tin diselenide transverse heterostructure gas-sensitive material - Google Patents
Preparation method and application of tin disulfide/tin diselenide transverse heterostructure gas-sensitive material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical compound [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011669 selenium Substances 0.000 claims abstract description 27
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 19
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 51
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- -1 selenium ions Chemical class 0.000 claims description 7
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 7
- 230000005684 electric field Effects 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 45
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 239000012071 phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 2
- NRDVCAXHUJWZEY-UHFFFAOYSA-N selenium(2-) tin(4+) Chemical compound [Se-2].[Se-2].[Sn+4] NRDVCAXHUJWZEY-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 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 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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Abstract
A preparation method and application of a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material. The invention belongs to the field of gas-sensitive materials, and particularly relates to a preparation method and application of a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material. The invention aims to solve the problems of low working sensitivity and slow response/recovery of a gas sensor at room temperature caused by low charge transmission efficiency due to a large number of defects and weak built-in electric field caused by lattice mismatch and discontinuous heterogeneous interfaces among components of a heterostructure prepared by the existing liquid phase method. The method comprises the following steps: preparing a SnS 2 template by a solvothermal synthesis method, and then synthesizing the SnS 2/SnSe2 transverse heterostructure gas-sensitive material by using selenium dioxide as a selenium source, using 1-octadecene and oleylamine as solvents and adopting a liquid phase ion replacement method. The gas-sensitive material is used for a gas-sensitive sensor, and can detect NO 2 with the concentration level of ppb to ppm at room temperature, and has high room temperature sensitivity and high response and recovery speed.
Description
Technical Field
The invention belongs to the field of gas-sensitive materials, and particularly relates to a preparation method and application of a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material.
Background
Nitrogen dioxide (NO 2) is a common and highly toxic gas mainly derived from industrial fuel combustion and motor vehicle exhaust emissions, and is one of the main muzzles for inducing acid rain and photochemical smog. It can damage respiratory system, induce asthma, cancer and other serious diseases, and threaten human health. Therefore, development of a high-performance NO 2 gas sensor for environmental monitoring, hazard warning and safety protection is imperative, and in particular development of a novel gas-sensitive material with high sensitivity and rapid response/recovery characteristics at room temperature. The conventional heterostructure material based on the two-dimensional layered material generally lacks of an interface optimization design, and due to the problems of a plurality of defects of an interface, weak built-in electric field and low interface charge transmission efficiency, the two-phase material for constructing the heterostructure cannot fully exert the respective excellent characteristics, so that a gas sensor working at room temperature is difficult to simultaneously have high sensitivity and quick response/recovery characteristics.
Two-dimensional/two-dimensional vertical heterojunctions and two-dimensional/two-dimensional lateral heterojunctions have recently been developed around heterostructure materials based on two-dimensional layered materials. The two-dimensional/two-dimensional lateral heterojunction exhibits superior performance to the two-dimensional/two-dimensional vertical heterojunction due to the stronger chemical interactions and exposed active interfaces. The method is formed by seamlessly connecting different two-dimensional materials in the same plane by means of strong covalent bonds, has the characteristics of few interface defects and low lattice mismatch rate of each functional element, and can effectively improve the charge transfer capacity of the interface. At present, the heterojunction is formed into a transverse heterostructure by a thin film growth mode such as molecular beam epitaxy or vapor deposition. However, these vapor phase epitaxy techniques require severe reaction conditions (e.g., atmosphere concentration, gas flow, rate of temperature rise), low yields, high costs, and contamination of transfer process interfaces, making it difficult to achieve mass production of materials. More importantly, the application of the two-dimensional/two-dimensional transverse heterostructure in the field of gas sensitive materials is still blank at present. Therefore, there is a need to develop new preparation techniques with simple reaction, high yield and low cost to synthesize high quality two-dimensional/two-dimensional lateral heterostructures in large quantities for manufacturing high performance NO 2 gas sensors.
Disclosure of Invention
The invention provides a preparation method and application of a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material, and aims to solve the problems that lattice mismatch among components of a heterostructure prepared by an existing liquid phase method and discontinuous heterogeneous interfaces lead to a plurality of defects and weak built-in electric field, so that charge transmission efficiency is low, and further the gas sensor has low working sensitivity at room temperature and slow response/recovery.
The preparation method of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material comprises the following steps:
1. Adding thiourea into deionized water solution under the condition of electromagnetic stirring, obtaining a mixed solution after the thiourea is dissolved, adding tin tetrachloride pentahydrate into the mixed solution under the condition of electromagnetic stirring, magnetically stirring for 10-60 min, adding the mixed solution into a solvothermal reaction kettle, reacting for 8-24 h at 160-200 ℃, centrifuging, washing the centrifuged product with absolute ethyl alcohol for 3-5 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven to obtain SnS 2 powder; the molar ratio of the thiourea to the penta-water stannic chloride is (2-8) 1, and the concentration of the penta-water stannic chloride in the mixed solution is 0.01-0.6 mol/L;
2. Adding SnS 2 powder into a 1-octadecene solution under the conditions of electromagnetic stirring and inert atmosphere, and obtaining a reaction solution after SnS 2 is dispersed; the concentration of SnS 2 in the reaction solution is 0.01-0.6 mol/L;
3. Adding SeO 2 into an oleylamine solution under the condition of electromagnetic stirring, and obtaining a selenium precursor solution after SeO 2 is dissolved; the concentration of selenium ions in the selenium precursor solution is 0.01-0.8 mol/L;
4. Putting the reaction solution and the selenium precursor solution into a flask, reacting for 30-300 min at 200-320 ℃, centrifuging, washing the product obtained by centrifuging with cyclohexane for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven to obtain the SnS 2/SnSe2 transverse heterostructure gas-sensitive material; the mol ratio of the reaction solution to the solute in the selenium precursor solution is (0.5-10): 1.
The application of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material prepared in the mode is that the SnS 2/SnSe2 transverse heterostructure gas-sensitive material is used for low-concentration NO 2 sensing.
The invention has the beneficial effects that:
1. According to the invention, a two-dimensional layered metal sulfide SnS 2 is used as a template, a Se ion precursor is used for carrying out a liquid-phase topological ion exchange reaction, so that selenide SnSe 2 is induced to grow along the lateral topology of the edge of SnS 2, and a SnS 2/SnSe2 lateral heterostructure with an atomic-level continuous interface is prepared. The method for preparing the transverse heterojunction gas-sensitive material has the advantages of low cost and simple preparation process, and is suitable for large-scale batch synthesis.
2. Compared with the traditional heterostructure material, the SnS 2/SnSe2 transverse heterostructure material has the advantages that lattices among components of the SnS 2/SnSe2 transverse heterostructure are highly matched, and an atomic-level continuous interface is formed. The interface defect is few, the built-in electric field intensity is high, and the charge transmission efficiency is high.
3. The SnS 2/SnSe2 transverse heterostructure gas-sensitive material prepared by the invention works at room temperature to realize high response multiplying power, high sensitivity and rapid response/recovery of NO 2 gas detection: the sensitivity was as high as 322% ppm -1, and the response rate and response/recovery time to 4ppm NO 2 were 1165% and 86/77s, respectively.
Drawings
FIG. 1 is a scanning electron microscope image of a lateral heterostructure of SnS 2/SnSe2 obtained in the first embodiment;
FIG. 2 is an X-ray diffraction (XRD) pattern of the lateral heterostructure of SnS 2/SnSe2 with different SnSe 2 contents, and I is pure SnS 2 powder; XRD curves of SnS 2/SnSe2 transverse heterostructures of 2%,10% and 30% mass fraction SnSe 2, respectively;
FIG. 3 is an EDX elemental plane distribution diagram of a lateral heterostructure of SnS 2/SnSe2 obtained in example I;
FIG. 4 is a High Resolution Transmission Electron Microscope (HRTEM) image of pure SnS 2;
fig. 5 is a HRTEM image of the SnS 2/SnSe2 lateral heterostructure obtained in the first embodiment;
FIG. 6 is a graph showing response/recovery curves of the SnS 2/SnSe2 lateral heterostructure gas sensitive material obtained in example I for different concentrations of NO 2 at room temperature;
FIG. 7 is a graph showing the sensitivity of the SnS 2/SnSe2 lateral heterostructure gas-sensitive material obtained in example I as a function of NO 2 concentration at room temperature;
FIG. 8 is a response/recovery curve of a SnS 2/SnSe2 lateral heterostructure gas sensitive material obtained in example one versus 4 ppm.
Detailed Description
The first embodiment is as follows: the preparation method of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material in the embodiment comprises the following steps:
1. Adding thiourea into deionized water solution under the condition of electromagnetic stirring, obtaining a mixed solution after the thiourea is dissolved, adding tin tetrachloride pentahydrate into the mixed solution under the condition of electromagnetic stirring, magnetically stirring for 10-60 min, adding the mixed solution into a solvothermal reaction kettle, reacting for 8-24 h at 160-200 ℃, centrifuging, washing the centrifuged product with absolute ethyl alcohol for 3-5 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven to obtain SnS 2 powder; the molar ratio of the thiourea to the penta-water stannic chloride is (2-8) 1, and the concentration of the penta-water stannic chloride in the mixed solution is 0.01-0.6 mol/L;
2. Adding SnS 2 powder into a 1-octadecene solution under the conditions of electromagnetic stirring and inert atmosphere, and obtaining a reaction solution after SnS 2 is dispersed; the concentration of SnS 2 in the reaction solution is 0.01-0.6 mol/L;
3. Adding SeO 2 into an oleylamine solution under the condition of electromagnetic stirring, and obtaining a selenium precursor solution after SeO 2 is dissolved; the concentration of selenium ions in the selenium precursor solution is 0.01-0.8 mol/L;
4. Putting the reaction solution and the selenium precursor solution into a flask, reacting for 30-300 min at 200-320 ℃, centrifuging, washing the product obtained by centrifuging with cyclohexane for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven to obtain the SnS 2/SnSe2 transverse heterostructure gas-sensitive material; the mol ratio of the reaction solution to the solute in the selenium precursor solution is (0.5-10): 1.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: in the first step, the molar ratio of the thiourea to the stannic chloride pentahydrate is 5:1. Other steps and parameters are the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the concentration of the tin tetrachloride pentahydrate in the mixed solution in the first step is 0.02mol/L. Other steps and parameters are the same as in the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: and in the second step, the concentration of the SnS 2 reaction solution is 0.1mol/L. Other steps and parameters are the same as in one to three embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and in the third step, the concentration of selenium ions in the selenium precursor solution is 0.05mol/L. Other steps and parameters are the same as in one to four embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: and in the third step, the concentration of selenium ions in the selenium precursor solution is 0.1mol/L. Other steps and parameters are the same as in one to five embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: in the fourth step, the reaction is carried out for 60min at the temperature of 300 ℃ and then centrifugal separation is carried out. Other steps and parameters are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: in the fourth step, the reaction is carried out for 60min at the temperature of 280 ℃ and then centrifugal separation is carried out. Other steps and parameters are the same as in one of the first to seventh embodiments.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: in the fourth step, the reaction is carried out for 18min at the temperature of 300 ℃ and then centrifugal separation is carried out. Other steps and parameters are the same as in one to eight embodiments.
Detailed description ten: the application of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material in the embodiment is that the SnS 2/SnSe2 transverse heterostructure gas-sensitive material is used for low-concentration NO 2 sensing.
The following examples are used to verify the benefits of the present invention:
Embodiment one: the preparation method of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material comprises the following steps:
1. Adding 5mmoL thiourea into 60mL of deionized water solution under electromagnetic stirring, after thiourea is dissolved, adding 1mmoL penta-water stannic chloride into the mixed solution under the electromagnetic stirring condition, magnetically stirring for 30min, adding into a solvothermal reaction kettle, reacting for 12h at 180 ℃ and then centrifugally separating, washing the product obtained by centrifugation with absolute ethyl alcohol for 3 times, washing with deionized water for 3 times, and drying in a vacuum drying oven to obtain SnS 2 powder;
2. Adding the 0.1mmoL SnS 2 powder prepared in the first step into 10mL of 1-octadecene solution under electromagnetic stirring and inert atmosphere protection, and performing ultrasonic dispersion to obtain a reaction solution;
3. Adding 0.1mmoL SeO 2 into 1mL of oleylamine solution under electromagnetic stirring, and stirring at 60 ℃ to dissolve SeO 2 to obtain selenium precursor solution;
4. And (3) filling the reaction solution in the second step and the selenium precursor solution in the third step into a flask, reacting for 60min at the temperature of 300 ℃, centrifuging, cleaning the product obtained by centrifuging by cyclohexane for 3 times, cleaning by absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven to obtain the SnS 2/SnSe2 transverse heterostructure gas-sensitive material.
The mass fraction of SnSe 2 in the SnS 2/SnSe2 transverse heterostructure gas-sensitive material obtained by the method of the first embodiment is about 10% of SnSe 2, a scanning electron microscope image of the SnSe 2 is shown in fig. 1, and it can be seen that the morphology of the SnS 2/SnSe2 transverse heterostructure retains the nano sheet structure of the original SnS 2 powder. As shown in a curve III in FIG. 2, compared with pure SnS 2 (curve I), the XRD spectrum of the material has the (001), (100), (101), (102), (003) and (110) crystal plane diffraction peaks of SnS 2 and SnSe 2 crystal phases simultaneously in the XRD spectrum of the lateral heterostructure of SnS 2/SnSe2, and the diffraction peaks are mainly caused by the fact that selenium atoms replace part of sulfur atoms in SnS 2, so that the SnSe 2 crystal phase is generated. Fig. 3 is an HRTEM image of pure SnS 2 with a interplanar spacing of 0.586nm attributed to the (001) plane of hexagonal-phase SnS 2 crystals. Fig. 4 is a plane distribution picture of EDX element, which shows that the solution ion substitution reaction preferentially occurs at the edge position of SnS 2 nano-sheet, and SnSe 2 and SnS 2 form a two-dimensional/two-dimensional transverse heterostructure along the basal plane direction. HRTEM tests further demonstrate that selenium atoms partially replace sulfur atoms in SnS 2 to generate SnSe 2,SnS2 and SnSe 2 crystals, which are seamlessly connected by a good continuous interface, and form a transverse heterostructure along the direction of a two-dimensional basal plane. FIG. 5 is a HRTEM image of pure SnS 2 with a (001) interplanar spacing of 0.586nm; in the HRTEM image of the SnS 2/SnSe2 transverse heterostructure in fig. 5, the (100) interplanar spacing of SnSe 2 is 0.336 nm, and the (100) interplanar spacing of SnS 2 is 0.321nm, which are joined together by an atomically continuous interface in the transverse direction along the basal plane.
The SnS 2/SnSe2 transverse heterostructure gas-sensitive material is dissolved in ethanol to prepare a solution of 10mg/mL, after ultrasonic treatment is carried out for 10min, a dispersion liquid of the SnS 2/SnSe2 transverse heterostructure is obtained, the SnS 2/SnSe2 transverse heterostructure is dispersed and dripped on the surface of an electrode slice by a instilling method, the electrode slice is dried for 1h at the temperature of 70 ℃, after the ethanol solvent volatilizes, a uniform film is formed on the surface of the electrode by the SnS 2/SnSe2 transverse heterostructure, and the electrode slice can be directly used for gas-sensitive performance test.
The gas-sensitive performance was tested by the electrochemical workstation, and the response rate R of the sensor was defined as: the test results are shown in fig. 6, and the test results show that, under the room-temperature working condition, the gas sensor prepared by using the SnS 2/SnSe2 transverse heterostructure gas-sensitive material obtained in example one can obviously increase the resistance value of the sensor after adsorbing NO 2 gas, and as the concentration of NO 2 increases, the response multiplying power of the sensor also obviously increases. FIG. 7 is a graph showing the response rate of a gas sensor prepared from the SnS 2/SnSe2 transverse heterostructure gas-sensitive material obtained in example I, wherein the response rate of the gas sensor changes with the concentration of NO 2, the concentration of NO 2 is between 0.05 and 6ppm, and the response rate of the sensor changes approximately linearly with the concentration of NO 2. The sensitivity S of the sensor is defined as the slope value of the response rate versus concentration linear relationship. As can be seen from fig. 7, the sensitivity of the gas sensor prepared from the SnS 2/SnSe2 transverse heterostructure gas sensitive material was 322% ppm -1. The response/recovery time of the sensor is defined as the time required from the start of response/recovery to a 90% change in response magnification. From FIG. 8, it is understood that the response/recovery time of the gas sensor prepared from the SnS 2/SnSe2 transverse heterostructure gas sensitive material to 4ppm is 86/77s.
Embodiment two: the present embodiment is different from the first embodiment in that: in the second step, the powder 0.3mmoL SnS 2 prepared in the first step is added into 10mL of 1-octadecene solution under electromagnetic stirring and inert atmosphere protection. Other steps and parameters are the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the second embodiment is that: in step three, 0.01mmoL SeO 2 was added to 1mL of oleylamine solution under electromagnetic stirring. Other steps and parameters are the same as in the first embodiment.
Embodiment four: the first difference between this embodiment and the second embodiment is that: in step three, 0.05mmoL SeO 2 was added to 1mL of oleylamine solution with electromagnetic stirring. Other steps and parameters are the same as in the first embodiment.
Fifth embodiment: the first difference between this embodiment and the second embodiment is that: in the fourth step, the reaction is carried out at the temperature of 280 ℃ and then centrifugal separation is carried out. Other steps and parameters are the same as in the first embodiment.
Example six: the first difference between this embodiment and the second embodiment is that: and step four, reacting for 180min, and centrifuging. Other steps and parameters are the same as in the first embodiment.
The SnS 2/SnSe2 transverse heterostructure prepared by the embodiment is high in yield, low in cost and easy to control, and the technical bottleneck that methods such as vapor deposition and molecular beam epitaxy cannot be prepared in batches and strict reaction conditions are needed is solved. In addition, the gas sensor prepared based on the SnS 2/SnSe2 transverse heterostructure gas-sensitive material solves the problems of low working sensitivity and slow response/recovery time of the gas sensor at room temperature due to the fact that lattice mismatch among components of the heterostructure prepared by a liquid phase method and discontinuous heterogeneous interfaces are caused, defects are many, a built-in electric field is weak, and therefore charge transmission efficiency is low. The SnS 2/SnSe2 transverse heterostructure sensor has high response multiplying power, high sensitivity and quick response/recovery performance under the room temperature working condition, and is mainly characterized in that different components of the SnS 2/SnSe2 transverse heterostructure prepared by a liquid phase ion replacement method are matched in lattice height, so that an atomic-level continuous seamless interface is provided, interface defects are reduced, a built-in electric field is enhanced, and charge transmission efficiency is improved. At the same time, the unique lateral heterostructure fully exposes the highly active interfacial region to the surface, increasing the active sites for gas adsorption.
Claims (10)
1. The preparation method of the tin disulfide/tin diselenide transverse heterostructure gas-sensitive material is characterized by comprising the following steps of:
1. Adding thiourea into deionized water solution under the condition of electromagnetic stirring, obtaining a mixed solution after the thiourea is dissolved, adding tin tetrachloride pentahydrate into the mixed solution under the condition of electromagnetic stirring, magnetically stirring for 10-60 min, adding the mixed solution into a solvothermal reaction kettle, reacting for 8-24 h at 160-200 ℃, centrifuging, washing the centrifuged product with absolute ethyl alcohol for 3-5 times, washing with deionized water for 3-5 times, and drying in a vacuum drying oven to obtain SnS 2 powder; the molar ratio of the thiourea to the penta-water stannic chloride is (2-8) 1, and the concentration of the penta-water stannic chloride in the mixed solution is 0.01-0.6 mol/L;
2. Adding SnS 2 powder into a 1-octadecene solution under the conditions of electromagnetic stirring and inert atmosphere, and obtaining a reaction solution after SnS 2 is dispersed; the concentration of SnS 2 in the reaction solution is 0.01-0.6 mol/L;
3. Adding SeO 2 into an oleylamine solution under the condition of electromagnetic stirring, and obtaining a selenium precursor solution after SeO 2 is dissolved; the concentration of selenium ions in the selenium precursor solution is 0.01-0.8 mol/L;
4. Putting the reaction solution and the selenium precursor solution into a flask, reacting for 30-300 min at 200-320 ℃, centrifuging, washing the product obtained by centrifuging with cyclohexane for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying in a vacuum drying oven to obtain the SnS 2/SnSe2 transverse heterostructure gas-sensitive material; the mol ratio of the reaction solution to the solute in the selenium precursor solution is (0.5-10): 1.
2. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material according to claim 1, wherein in the step one, the molar ratio of thiourea to tin tetrachloride pentahydrate is 5:1.
3. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas sensitive material according to claim 1, wherein the concentration of tin tetrachloride pentahydrate in the mixed solution in the first step is 0.02mol/L.
4. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material according to claim 1, wherein the concentration of the SnS 2 reaction solution in the second step is 0.1mol/L.
5. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas sensitive material according to claim 1, wherein in the third step, the concentration of selenium ions in the selenium precursor solution is 0.05mol/L.
6. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas sensitive material according to claim 1, wherein in the third step, the concentration of selenium ions in the selenium precursor solution is 0.1mol/L.
7. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material according to claim 1, wherein in the fourth step, the gas-sensitive material is centrifugally separated after being reacted for 60 minutes at 300 ℃.
8. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material according to claim 1, wherein in the fourth step, the gas-sensitive material is centrifugally separated after being reacted for 60 minutes at a temperature of 280 ℃.
9. The method for preparing a tin disulfide/tin diselenide transverse heterostructure gas-sensitive material according to claim 1, wherein in the fourth step, the gas-sensitive material is centrifugally separated after being reacted for 18min at 300 ℃.
10. The application of the tin disulfide/tin diselenide transverse heterostructure gas sensitive material prepared by the method of claim 1, wherein the SnS 2/SnSe2 transverse heterostructure gas sensitive material is used for low-concentration NO 2 sensing.
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