CN111579600A - Camellia flower-shaped ZnO/SnO-SnO2Composite material and preparation method and application thereof - Google Patents
Camellia flower-shaped ZnO/SnO-SnO2Composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111579600A CN111579600A CN202010596580.0A CN202010596580A CN111579600A CN 111579600 A CN111579600 A CN 111579600A CN 202010596580 A CN202010596580 A CN 202010596580A CN 111579600 A CN111579600 A CN 111579600A
- Authority
- CN
- China
- Prior art keywords
- sno
- zno
- camellia
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses camellia-shaped ZnO/SnO-SnO2Camellia-shaped ZnO/SnO-SnO as well as preparation method and application thereof2The composite material is formed by self-assembling two-dimensional ZnO slices, SnO-SnO2The mixture was uniformly anchored to the ZnO sheet. Firstly, synthesizing SnO-SnO by a hydrothermal method2The nanoparticles are mixed. Then, using a solvothermal method and AOT as a soft template, and adding the prepared SnO-SnO2Adding the mixed nano particles into a reaction system, and finally calcining the composite material at 400 ℃ for 2h to obtain camellia-shaped ZnO/SnO-SnO2A composite material. The invention compounds SnO-SnO on the basis of zinc oxide2The nanometer particles improve the sensitivity and the selectivity to amine gas, have better selectivity to triethylamine at the working temperature of 100 ℃, and the sensitivity to 100ppm of triethylamine reaches 780.
Description
Technical Field
The invention relates to camellia-shaped ZnO/SnO-SnO2Preparation of composite material and application in amine sensor.
Background
Amines are volatile organic compounds, some of which are toxic and harmful and also have malodour. Such substances are mainly produced in the industrial processes of the manufacture of dyes and dye intermediates, rubber accelerators and antioxidants, photographic developers and also in the synthesis of pharmaceuticals, the production of fragrances, the curing of plastics and the manufacture of resins, the construction of coatings, lacquers, etc. The existence of amine substances in the atmosphere has great harm to the environment and human health. During the death and decay of fish and shellfish, Triethylamine (TEA) gas is released, the concentration increasing with decreasing freshness of the fish. TEA gas is not only toxic, but also flammable and explosive, and seriously harms human health, such as skin burn, headache, nausea and the like. It is extremely damaging to the respiratory system and can lead to pulmonary edema and even death. The environmental TEA concentration is limited to 10ppm according to the Occupational Safety and Health Administration (OSHA). The literature reports that ZnO-SnO with hollow interior is synthesized by adopting a two-step method2Heterojunction nanotubes (Sensors)&Activators: b. Chemical 279, 2019, 410-417), the prepared triethylamine sensor has a high operating temperature and the response value remains very low after irradiation with ultraviolet laser. CN108931559A discloses a boron-doped graphene modified Au @ ZnO core-shell heterogeneous triethylamine sensor, which realizes triethylamine detection at near room temperature (50 ℃) by utilizing the high specific surface area of graphene and the p-type semiconductor characteristic of boron-doped graphene. However, the method still has the defects of low sensitivity, complicated preparation and the like. M-toluidine, which has a contact limit of 2ppm, is a strong methemoglobin former and can irritate the urinary bladder and cause hematuria. Contact with the skin can cause symptoms such as burning of the face, severe headache, dizziness, dyspnea, etc. And the danger of combustion and explosion caused by naked fire, high heat or strong oxidant, and high heatAnd toxic gas is decomposed. Aniline is a carcinogenic substance and can cause chronic poisoning and damage to liver, kidney, skin, etc. Few reports on aniline sensors have been made, and CN103336034A discloses an aniline gas sensor and a preparation method thereof. The ZnS/PTCDA core-shell nano-particles are synthesized by a two-step method, and the prepared gas sensor can realize the selectivity of the p-aniline, but the selectivity of the p-aniline under low concentration is not outstanding. The existing amine sensor still has the defects of high working temperature, poor sensitivity and the like. Therefore, there is a need to develop a high sensitivity, low operating temperature, low cost and stable amine gas sensor.
Disclosure of Invention
The invention aims to solve the technical problem of providing ZnO/SnO-SnO with high sensitivity, low power consumption and excellent selectivity to amine gas aiming at the defects of low sensitivity, high working temperature and the like of amine sensors2Composite materials and methods for making the same.
In order to solve the technical problems, the following technical scheme is adopted:
the camellia-shaped ZnO/SnO-SnO of the invention2The composite material is formed by self-assembling two-dimensional ZnO slices, SnO-SnO2The hybrid nanoparticles are anchored to the ZnO sheet.
The camellia-shaped ZnO/SnO-SnO of the invention2The preparation method of the composite material comprises the following steps: firstly, synthesizing SnO-SnO by a hydrothermal method2The nanoparticles are mixed. Then, using a solvothermal method and AOT as a soft template, and adding the prepared SnO-SnO2Adding the mixed nano particles into a reaction system, and finally calcining the composite material at 400 ℃ for 2h to obtain camellia-shaped ZnO/SnO-SnO2A composite material.
The camellia-flower-shaped ZnO/SnO-SnO2The preparation method of the composite material comprises the following specific steps:
(1) preparing tin oxide: dissolving a precipitant I in a mixed solution of low-carbon alcohol and deionized water, adding a divalent tin compound after stirring and dissolving, adding a precipitant II into the mixed solution under a stirring state, and stirring to obtain a suspension; after high-temperature reaction, calcining in inert atmosphere to obtain SnO-SnO2Mixing;
(2) preparing a zinc salt solution: dissolving a surfactant in a mixed solution of low-carbon alcohol and deionized water, and adding zinc salt into the surfactant solution to prepare a zinc salt solution;
(3) preparation of camellia-shaped ZnO/SnO-SnO2The composite material comprises the following components: adding a precipitator II into the zinc salt solution obtained in the step (2), stirring, and adding SnO-SnO2The mixture is obtained into suspension; after the high-temperature reaction, washing, drying and calcining the obtained product to obtain camellia-shaped ZnO/SnO-SnO2A composite material.
Further, the divalent tin compound is SnC2O4、SnSO4、Na2SnO2Or SnCl2.2H2O; the precipitator I is hexamethylenetetramine, ammonia water or NaOH; the precipitator II is urea, ethanolamine or sodium citrate; the lower alcohol is methanol, ethanol or ethylene glycol; the volume ratio of the low-carbon alcohol to the deionized water is 1 (0.1-1.7).
Further, the concentration of the divalent tin compound in the suspension obtained in the step (1) is 0.0025-0.0375mol/L, the mass ratio of the divalent tin compound to the precipitating agent I is 1 (0.3-1), and the mass ratio of the divalent tin compound to the precipitating agent II is 1: (0.5-1.5).
Further, the temperature of the high-temperature reaction in the step (1) is 120 ℃, and the reaction time is 12 hours; the calcining temperature is 400 ℃, and the calcining time is (1-3) h.
Further, in the step (2), the surfactant is an anionic surfactant or a cationic surfactant, the anionic surfactant is a sodium succinate anionic surfactant, and the cationic surfactant is an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant, an onium salt cationic surfactant, an amine oxide cationic surfactant or a heterocyclic cationic surfactant.
Further, the zinc salt in the step (2) is zinc acetate, zinc nitrate or zinc chloride; the ratio of the zinc salt to the amount of surfactant is 1 (0.3-1.2).
Further, zinc salt in the step (3)The mass ratio of the precipitant II to the precipitant II is 1: (0.5-1.5); SnO-SnO2The addition amount of the mixture is based on 1mmol of zinc salt, and SnO-SnO is required2The mass of the mixture is 0.0045-0.225 g.
Further, the reaction temperature in the step (3) is 110-; the calcining temperature is 400 ℃, and the calcining time is 1-3 h.
The camellia-shaped ZnO/SnO-SnO2The composite material is used as a gas sensor in the aspect of amine sensors.
The key point of the innovation of the invention is to prepare three-dimensional camellia-shaped ZnO/SnO-SnO2A composite material. The ZnO triethylamine sensor has a lot of materials, but the working temperature is high and the sensitivity is low. When the working temperature is 100 ℃, the invention has better selectivity to triethylamine and the sensitivity to 100ppm triethylamine reaches 780. At 160 ℃, excellent selectivity to m-toluidine was shown. When the temperature is continuously increased to 240 ℃, camellia-shaped ZnO/SnO-SnO2The sensitivity of the composite material to aniline is highest.
The invention has the beneficial effects that: the invention compounds SnO-SnO on the basis of zinc oxide2The nanometer particles improve the sensitivity and selectivity to amine gas; the sensitivity of the working temperature of 100 ℃ to 100ppm triethylamine gas is up to 780, which is lower than the working temperature of the existing triethylamine sensor; the sensitivity to 100ppm m-toluidine gas at the working temperature of 160 ℃ is as high as 42.5; the sensitivity to aniline is highest when the temperature is raised to 240 ℃. The method has high yield and low preparation cost; the shape and size of the material are uniform; has higher response to amine gas and is easy to realize industrialization.
Drawings
FIG. 1 shows camellia-like ZnO/SnO-SnO prepared in example 22XRD pattern of the composite.
FIG. 2 is a Field Emission Scanning Electron Microscope (FESEM) photograph of the camellia-like ZnO nanomaterial prepared in example 2.
FIG. 3 shows camellia-like ZnO/SnO-SnO prepared in example 22Field emission scanning electron microscope (FES) for composite materialsEM) photograph.
FIG. 4 shows camellia-like ZnO/SnO-SnO prepared in example 22XPS spectra of the composite.
FIG. 5 shows camellia-like ZnO/SnO-SnO prepared in example 22The composite material gas sensor is used for testing the selectivity of different harmful gases (100 ppm).
FIG. 6 shows different amounts of camellia-shaped ZnO/SnO-SnO prepared in example 22Response curve of composite gas sensor to 100ppm triethylamine gas.
FIG. 7 shows camellia-like ZnO/SnO-SnO prepared in example 22And (3) testing the cyclicity of the composite material gas sensor to 100ppm triethylamine.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 1mmol of hexamethylenetetramine, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 1.5mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol of Sapamine A cationic surfactant, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a stable water phase solution;
(5) 1mmol of zinc acetate is weighed, added to the aqueous solution and stirred for 1h, then 1.5mmol of urea is added and stirred again for 1 h. 0.0045g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 110 ℃ for reacting for 3h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 2
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 1mmol of hexamethylenetetramine, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol of sodium succinate anionic surfactant (AOT), adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1 h. 0.0076g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 12h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times respectivelyDrying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
FIG. 1 shows the camellia-like ZnO/SnO-SnO obtained in this example2XRD spectrogram of the composite material, the products are ZnO and SnO-SnO2The complex of (1). Fig. 2-3 are FESEM photographs of the materials. The pure ZnO material is in a camellia shape, ZnO/SnO-SnO2In the composite material, SnO-SnO2The mixed nano-particles are evenly anchored on the flower-shaped ZnO sheet layer. FIG. 4 shows the camellia-like ZnO/SnO-SnO obtained in this example2XRS spectrogram of the composite material, and Gaussian fitting is carried out on Sn spectrum to generate Sn4+And Sn2+Characteristic peak of (2). FIG. 5 shows the camellia-like ZnO/SnO-SnO obtained in this example2Gas sensitivity test of composite material based on camellia-shaped ZnO/SnO-SnO2The gas sensor made of the composite material shows excellent selectivity to different amine gases at different working temperatures. FIGS. 6 to 7 show the camellia-like ZnO/SnO-SnO obtained in this example2Gas sensitivity test of composite materials to triethylamine, SnO-SnO2The material with the compounding amount of 10% has the best gas-sensitive performance to triethylamine and has good reproducibility.
Example 3
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 0.6mmol of hexamethylenetetramine, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 1 hr to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol of CTAC cationic surfactant, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1 h. 0.0045g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 150 ℃ for reacting for 12h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 4
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 0.3mmol of hexamethylenetetramine, adding 10ml of absolute ethyl alcohol and 30ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 0.5mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 3 hr to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol of Soromine A cationic surfactant, adding 10ml of absolute ethyl alcohol and 30ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 0.5mmol of urea, and stirring again for 1 h. 0.0225g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) sealing the suspension in a high-pressure autoclave with a polytetrafluoroethylene inner container, reacting at 90 deg.C for 1h, rapidly heating to 180 deg.C, and reactingThe reaction solution is left for 12 hours and then naturally cooled to the room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 5
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 1mmol of hexamethylenetetramine, adding 15ml of absolute ethyl alcohol and 25ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 0.5mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol CTAB cationic surfactant, adding 15ml of absolute ethyl alcohol and 25ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 0.5mmol of urea, and stirring again for 1 h. 0.0045g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 3h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 3 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 6
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 1mmol of hexamethylenetetramine, adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 1mmol of sodium citrate, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 0.3mmol of sodium succinate anionic surfactant (AOT), adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of sodium citrate, and stirring again for 1 h. 0.0076g of SnO-SnO was added2Mixing the nanometer materials, and continuously stirring until the solution forms suspension liquid;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 9h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 1 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 7
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) weighing 1mmol of hexamethylenetetramine, adding 25ml of absolute ethyl alcohol and 15ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, stirring for 1h, then adding 1mmol of ethanolamine, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. The product is reacted with distilled waterWashing with anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1.2mmol of sodium succinate anionic surfactant (AOT), adding 25ml of absolute ethyl alcohol and 15ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of ethanolamine, and stirring again for 1 h. 0.0076g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 15h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 8
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) taking 35ml of absolute ethyl alcohol and 5ml of deionized water, and carrying out ultrasonic treatment for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, adding 1mmol of NaOH, stirring for 1 hour, then adding 1mmol of urea, and stirring again for 1 hour until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol sodium succinate anionic surfactant (AOT), adding 35ml absolute ethyl alcohol and 5ml deionized water, and ultrasonically dissolving for 10min to form uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1 h. Adding 0.0076g SnO-SnO2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 20h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
Example 9
The camellia-like ZnO/SnO-SnO of the embodiment2The preparation method of the composite material comprises the following steps:
(1) taking 30ml of absolute ethyl alcohol and 10ml of deionized water, and carrying out ultrasonic treatment for 10min to form a uniform and stable aqueous phase solution;
(2) weighing 1mmol of stannous chloride, adding the stannous chloride into the aqueous phase solution, adding 500 mu l of ammonia water, stirring for 1h, then adding 1mmol of urea, and stirring again for 1h until the solution forms a suspension;
(3) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting at the constant temperature of 120 ℃ for 12 hours, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12h, calcining at 400 deg.C in inert atmosphere for 2h to obtain SnO-SnO2Mixing the nano materials.
(4) Weighing 1mmol of sodium succinate anionic surfactant (AOT), adding 30ml of absolute ethyl alcohol and 10ml of deionized water, and ultrasonically dissolving for 10min to form a uniform and stable aqueous phase solution;
(5) weighing 1mmol of zinc acetate, adding the zinc acetate into the aqueous phase solution, stirring for 1h, then adding 1mmol of urea, and stirring again for 1 h. 0.0076g of SnO-SnO was added2Continuously stirring the mixed nano materials until the solution forms suspension;
(6) and (3) sealing the suspension in an autoclave with a polytetrafluoroethylene inner container, reacting for 1h at 90 ℃, rapidly heating to 120 ℃ for reacting for 22h, and naturally cooling to room temperature. Washing the product with distilled water and anhydrous ethanol for 3 times, drying at 60 deg.C for 12 hr, calcining at 400 deg.C in inert atmosphere for 2 hr to obtain flos Camelliae Japonicae-shaped ZnO/SnO-SnO2A composite material.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. Camellia flower-shaped ZnO/SnO-SnO2A composite material characterized by: the camellia-shaped ZnO/SnO-SnO2The composite material is formed by self-assembling two-dimensional ZnO slices, SnO-SnO2The mixture was uniformly anchored to the ZnO sheet.
2. Camellia-like ZnO/SnO-SnO according to claim 12The preparation method of the composite material is characterized by comprising the following steps:
(1) preparing tin oxide: dissolving a precipitant I in a mixed solution of low-carbon alcohol and deionized water, adding a divalent tin compound after stirring and dissolving, adding a precipitant II into the mixed solution under a stirring state, and stirring to obtain a suspension; after high-temperature reaction, calcining in inert atmosphere to obtain SnO-SnO2Mixing;
(2) preparing a zinc salt solution: dissolving a surfactant in a mixed solution of low-carbon alcohol and deionized water, and adding zinc salt into the surfactant solution to prepare a zinc salt solution;
(3) preparation of camellia-shaped ZnO/SnO-SnO2The composite material comprises the following components: adding a precipitator II into the zinc salt solution obtained in the step (2), stirring, and adding SnO-SnO2The mixture is obtained into suspension; after the high-temperature reaction, washing, drying and calcining the obtained product to obtain camellia-shaped ZnO/SnO-SnO2A composite material.
3. Camellia-like ZnO/SnO-SnO according to claim 22Of composite materialsThe preparation method is characterized by comprising the following steps: the divalent tin compound is SnC2O4、SnSO4、Na2SnO2Or SnCl2.2H2O; the precipitator I is hexamethylenetetramine, ammonia water or NaOH; the precipitator II is urea, ethanolamine or sodium citrate; the lower alcohol is methanol, ethanol or ethylene glycol; the volume ratio of the low-carbon alcohol to the deionized water is 1 (0.1-1.7).
4. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: the concentration of the divalent tin compound in the suspension obtained in the step (1) is 0.0025-0.0375mol/L, the mass ratio of the divalent tin compound to the precipitating agent I is 1 (0.3-1), and the mass ratio of the divalent tin compound to the precipitating agent II is 1: (0.5-1.5).
5. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: the temperature of the high-temperature reaction in the step (1) is 120 ℃, and the reaction time is 12 h; the calcining temperature is 400 ℃, and the calcining time is (1-3) h.
6. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: in the step (2), the surfactant is an anionic surfactant or a cationic surfactant, the anionic surfactant is a sodium succinate anionic surfactant, and the cationic surfactant is an amine salt cationic surfactant, a quaternary ammonium salt cationic surfactant, an onium salt cationic surfactant, an amine oxide cationic surfactant or a heterocyclic cationic surfactant.
7. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: the zinc salt in the step (2) is zinc acetate, zinc nitrate or zinc chloride; the ratio of the zinc salt to the amount of surfactant is 1 (0.3-1.2).
8. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: the mass ratio of the zinc salt to the precipitant II in the step (3) is 1: (0.5-1.5); SnO-SnO2The addition amount of the mixture is based on 1mmol of zinc salt, and SnO-SnO is required2The mass of the mixture is 0.0045-0.225 g.
9. Camellia-like ZnO/SnO-SnO according to claim 22The preparation method of the composite material is characterized by comprising the following steps: the reaction temperature in the step (3) is 110-180 ℃, and the reaction time is 3-22 h; the calcining temperature is 400 ℃, and the calcining time is 1-3 h.
10. Camellia-like ZnO/SnO-SnO according to claim 12The composite material is used as a gas sensor in the aspect of amine sensors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596580.0A CN111579600B (en) | 2020-06-28 | 2020-06-28 | Camellia flower-shaped ZnO/SnO-SnO 2 Composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010596580.0A CN111579600B (en) | 2020-06-28 | 2020-06-28 | Camellia flower-shaped ZnO/SnO-SnO 2 Composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111579600A true CN111579600A (en) | 2020-08-25 |
| CN111579600B CN111579600B (en) | 2022-11-22 |
Family
ID=72122068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010596580.0A Active CN111579600B (en) | 2020-06-28 | 2020-06-28 | Camellia flower-shaped ZnO/SnO-SnO 2 Composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111579600B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112110477A (en) * | 2020-10-09 | 2020-12-22 | 郑州轻工业大学 | 2D porous Ce-doped ZnO nanosheet for aniline room temperature detection and preparation method and application thereof |
| CN112268940A (en) * | 2020-10-30 | 2021-01-26 | 郑州轻工业大学 | MO for aniline gas sensor2/MO3NMNPs hollow microsphere material and preparation method thereof |
| CN112844363A (en) * | 2021-01-12 | 2021-05-28 | 山东科技大学 | Preparation of tubular ZnO-SnO by biological template method2Composite nanomaterial |
| CN115385372A (en) * | 2022-08-16 | 2022-11-25 | 中科检测技术服务(广州)股份有限公司 | Moisture-proof high-selectivity response triethylamine gas-sensitive material constructed based on bimetallic MOF route and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103776870A (en) * | 2014-02-27 | 2014-05-07 | 河南理工大学 | ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material |
| CN105548275A (en) * | 2016-01-14 | 2016-05-04 | 吉林大学 | Acetone sensor based on NiO/ZnO heterostructure nanoflower sensitive material and preparation method of acetone sensor |
| CN105692692A (en) * | 2016-03-23 | 2016-06-22 | 云南大学 | Synthesis technology for petal-shaped SnO2 nano-arrays |
| JP2018009814A (en) * | 2016-07-11 | 2018-01-18 | 富士通株式会社 | Gas sensor array, gas measurement device, and gas measurement method |
| CN108896622A (en) * | 2018-05-09 | 2018-11-27 | 广东美的制冷设备有限公司 | The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof |
| CN109019673A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of SnO2-In2O3The preparation method of nanocomposite |
| CN109607593A (en) * | 2019-01-10 | 2019-04-12 | 沈阳化工大学 | A kind of preparation and its application of NiO-ZnO flower-like structure composite material |
-
2020
- 2020-06-28 CN CN202010596580.0A patent/CN111579600B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103776870A (en) * | 2014-02-27 | 2014-05-07 | 河南理工大学 | ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material |
| CN105548275A (en) * | 2016-01-14 | 2016-05-04 | 吉林大学 | Acetone sensor based on NiO/ZnO heterostructure nanoflower sensitive material and preparation method of acetone sensor |
| CN105692692A (en) * | 2016-03-23 | 2016-06-22 | 云南大学 | Synthesis technology for petal-shaped SnO2 nano-arrays |
| JP2018009814A (en) * | 2016-07-11 | 2018-01-18 | 富士通株式会社 | Gas sensor array, gas measurement device, and gas measurement method |
| CN108896622A (en) * | 2018-05-09 | 2018-11-27 | 广东美的制冷设备有限公司 | The SnO of heterojunction structure2- ZnO gas sensitive and preparation method thereof |
| CN109019673A (en) * | 2018-08-01 | 2018-12-18 | 济南大学 | A kind of SnO2-In2O3The preparation method of nanocomposite |
| CN109607593A (en) * | 2019-01-10 | 2019-04-12 | 沈阳化工大学 | A kind of preparation and its application of NiO-ZnO flower-like structure composite material |
Non-Patent Citations (5)
| Title |
|---|
| QIAN MA ET AL.: ""Construction of SnS2/ZIF-8 derived flower-like porous SnO2/ZnO heterostructures with enhanced triethylamine gas sensing performance"", 《MATERIALS LETTERS》 * |
| TIANYE YANG ET AL.: ""ZnO-SnO2 heterojunction nanobelts: Synthesis and ultraviolet light irradiation to improve the triethylamine sensing properties"", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| WENRU LI ET AL.: ""Different morphologies of ZnO and their triethylamine sensing properties"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 姜江一鸣: ""多孔ZnO-SnO2异质结构的制备及气敏特性研究"", 《山东化工》 * |
| 张赫: ""氧化锌形貌调控、改性及其对胺气体性能研究"", 《工程科技Ⅰ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112110477A (en) * | 2020-10-09 | 2020-12-22 | 郑州轻工业大学 | 2D porous Ce-doped ZnO nanosheet for aniline room temperature detection and preparation method and application thereof |
| CN112110477B (en) * | 2020-10-09 | 2022-08-19 | 郑州轻工业大学 | 2D porous Ce-doped ZnO nanosheet for aniline room temperature detection and preparation method and application thereof |
| CN112268940A (en) * | 2020-10-30 | 2021-01-26 | 郑州轻工业大学 | MO for aniline gas sensor2/MO3NMNPs hollow microsphere material and preparation method thereof |
| CN112268940B (en) * | 2020-10-30 | 2024-04-16 | 郑州轻工业大学 | MO for aniline gas sensor 2 /MO 3 NMNPs hollow microsphere material and preparation method thereof |
| CN112844363A (en) * | 2021-01-12 | 2021-05-28 | 山东科技大学 | Preparation of tubular ZnO-SnO by biological template method2Composite nanomaterial |
| CN112844363B (en) * | 2021-01-12 | 2022-09-20 | 山东科技大学 | Preparation of tubular ZnO-SnO by biological template method 2 Composite nanomaterial |
| CN115385372A (en) * | 2022-08-16 | 2022-11-25 | 中科检测技术服务(广州)股份有限公司 | Moisture-proof high-selectivity response triethylamine gas-sensitive material constructed based on bimetallic MOF route and preparation method and application thereof |
| CN115385372B (en) * | 2022-08-16 | 2024-01-26 | 中科检测技术服务(广州)股份有限公司 | Moisture-resistant high-selective response triethylamine gas-sensitive material constructed based on bimetallic MOF route and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111579600B (en) | 2022-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111579600B (en) | Camellia flower-shaped ZnO/SnO-SnO 2 Composite material and preparation method and application thereof | |
| Kou et al. | Beet juice utilization: Expeditious green synthesis of noble metal nanoparticles (Ag, Au, Pt, and Pd) using microwaves | |
| KR101235873B1 (en) | A process for the preparation of silver nano particles | |
| CN114106276B (en) | Preparation method of shape-controllable covalent organic framework material | |
| CN108251108A (en) | A kind of preparation of iron ion doping carbon quantum dot and obtained carbon quantum dot and application | |
| CN109761275B (en) | Bismuth silver sulfide hollow nanospheres and preparation method thereof | |
| CN108311712A (en) | A kind of preparation method of high catalytic performance polyhedral gold-palldium alloy nano material | |
| Zhao et al. | Gallol‐Tethered Injectable AuNP Hydrogel with Desirable Self‐Healing and Catalytic Properties | |
| CN101905328B (en) | Method for preparing water-soluble Au10 nano-cluster molecules | |
| CN101740191B (en) | Composite particles whose nano magnetic iron oxide particles are assembled on surfaces of gold particles and method for preparing same | |
| CN108997383A (en) | Metal organic framework compound and its preparation method and application | |
| CN109534306A (en) | The method for preparing spherical hexagonal boron nitride powder based on urea nitrogen source | |
| KR20150008661A (en) | Gold nanocluster and its preparation method | |
| CN111484084A (en) | Acetone gas-sensitive material and preparation method thereof | |
| Li et al. | Gold nanocrystals: Optical properties, fine-tuning of the shape, and biomedical applications | |
| Fard et al. | Synthesis and characterization of a new nano lead (II) 0-D coordination supramolecular compound: A precursor to produce pure phase nano-sized lead (II) oxide | |
| CN106395804A (en) | Silkworm-chrysalis-shaped PbS quantum dot/graphene composite material and preparation method thereof | |
| CN108568519A (en) | A kind of preparation method and application of argentum nano composite material | |
| CN102275966A (en) | Preparation method of calcium carbonate particulates | |
| CN110724519A (en) | Preparation method and application of fluorescence-enhanced gold nanocluster composite material based on supermolecule macrocycle | |
| EP2505558B1 (en) | Process for preparing magnetic (Fe3O4) and derivatives thereof | |
| CN103933973A (en) | Preparation method of supported nano palladium/carbon catalyst | |
| CN106279009B (en) | Ytterbium complex and preparation method thereof as lead ion fluorescence probe | |
| JiáYoon et al. | First direct-formation and properties of microspherical superstructure. Morphology of diamineplatinum (ii) complexes with isonicotinate | |
| CN107043096A (en) | A kind of nanometer spherical Ag3PO4And its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |