CN116891250A - ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection - Google Patents

ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection Download PDF

Info

Publication number
CN116891250A
CN116891250A CN202310831657.1A CN202310831657A CN116891250A CN 116891250 A CN116891250 A CN 116891250A CN 202310831657 A CN202310831657 A CN 202310831657A CN 116891250 A CN116891250 A CN 116891250A
Authority
CN
China
Prior art keywords
zno
znsno
znsno3
hours
gas
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.)
Pending
Application number
CN202310831657.1A
Other languages
Chinese (zh)
Inventor
何利芳
李伟超
袁启明
夏章成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University of Technology AHUT
Original Assignee
Anhui University of Technology AHUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Anhui University of Technology AHUT filed Critical Anhui University of Technology AHUT
Priority to CN202310831657.1A priority Critical patent/CN116891250A/en
Publication of CN116891250A publication Critical patent/CN116891250A/en
Pending legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • Electrochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Nanotechnology (AREA)
  • Engineering & Computer Science (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

The invention discloses a ZnSnO 3 ZnO nano composite material and application thereof in formaldehyde detection. According to the preparation method, zinc acetate dihydrate is used as a raw material, a sol-gel method and a precipitation method are combined to obtain ZnO quantum dots, zinc acetate dihydrate, stannic chloride pentahydrate, potassium hydroxide and sodium fluoride are used for carrying out hydrothermal reaction and calcination to obtain ZnSnO3 nano powder, and the ZnO quantum dots are doped and compounded to obtain the ZnSnO3/ZnO nano composite material. The ZnSnO3/ZnO nanocomposite is prepared into a gas sensor, and the gas-sensitive performance of the gas sensor to formaldehyde gas is detected after high-temperature aging. The invention provides a preparation method of a ZnSnO3/ZnO nanocomposite sensor with low preparation cost and simple method. The gas sensor has high sensitivity, selectivity and short response and recovery time to formaldehyde at low temperature of 70deg.CA viable solution is provided for the development of portable gas sensors.

Description

ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection
Technical Field
The invention belongs to the technical field of gas-sensitive sensing materials, and in particular relates to ZnSnO 3 ZnO nano composite gas-sensitive material and application thereof in gas detection sensor。
Background
Formaldehyde is an important industrial raw material used in various industries such as floors, paints, composite materials, composite adhesives, disinfectants, food preservatives, and the like. However, formaldehyde is well known to react with DNA, protein, etc. of human body, and can cause canceration after long-term contact. Due to the application of formaldehyde in the generation and preparation of various indoor decoration materials, formaldehyde also becomes one of the most common pollutants in indoor environment, and has long release time and high treatment rate. The time of people working and living indoors is 60% -90%, so the concentration of formaldehyde in the room is regulated to be within 0.10 milligrams (0.07 ppm) per cubic meter. Therefore, the development of a high-performance formaldehyde sensor has important significance for detecting formaldehyde in indoor environments.
Compared with the traditional spectrum or chromatographic method which depends on large-scale equipment and technology, the semiconductor Metal Oxide (MOS) based gas sensor has the advantages of simple manufacturing method, small volume, portability, convenient operation, low cost, rapid response, capability of real-time detection and the like, and is focused on, thereby attracting extensive research. For example, ge W and the like prepare In2O3-SnO2 hybridized porous nano-structure with porous property for detecting formaldehyde. Studies have shown that hybrid nanostructures containing 3% in2o3 have a highest response value of 30.7 to 100ppm formaldehyde at 100 ℃ compared to pure SnO2, which is 14 times the original. However, the current formaldehyde gas sensor based on the MOS still has many problems such as high operation temperature dependence, high energy consumption, low response value, long recovery time and the like, and cannot effectively detect formaldehyde in a complex atmosphere.
Perovskite ABO3 (a is a rare metal and B is a transition metal ion) is a novel material that has been found to have special structural properties in recent years, wherein zinc metastanniate (ZnSnO 3) is a typical rare earth composite metal oxide having a perovskite (ABO 3) structure. The ZnSnO3 has wide application prospect in the fields of optics, catalysis, sensors and the like as a hot spot for domestic and foreign research due to various super-performance characteristics such as stable crystal structure, no toxicity, small energy band gap energy and the like. ZnSnO3 has become one of the most promising materials for the fabrication of new nanocomposite metal oxide semiconductor sensors. Previous researches show that pure ZnSnO3 has certain selectivity to formaldehyde, but the working temperature is high, and the response value can not meet the application requirement.
Disclosure of Invention
Aiming at the technical problems encountered in the prior art, the invention provides a simple novel gas sensing material capable of increasing the gas-sensitive response of ZnSnO3 to formaldehyde and reducing the working temperature of the material, and the gas sensor with higher sensitivity, selectivity and shorter response (response time of 1-3 seconds) and recovery time (recovery time of about 300 seconds) to formaldehyde is obtained, so that the portable gas sensor can be developed, and the safe and high-efficiency detection of formaldehyde in a complex gas atmosphere can be realized. Specifically, the invention is realized by adopting the following technical scheme:
ZnSnO of the invention 3 The ZnO nanocomposite is obtained by mixing, drying and grinding ZnSnO3 nanomaterial and ZnO quantum dots, wherein the ZnO quantum dots account for 1-20wt%, preferably 2-10wt%, more preferably 3-6wt%, and most preferably 5wt%.
ZnSnO according to the invention 3 The ZnO nano composite material is prepared by preserving ZnSnO3 precursor powder in air at 400-500 ℃ for 1-3 hours; the ZnSnO3 precursor powder is obtained by carrying out hydrothermal reaction on zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride in a polytetrafluoroethylene reaction kettle at 130-160 ℃ for 10-15 hours. Wherein, the effect of keeping the ZnSnO3 precursor powder in the air at 450 ℃ for 2 hours is better; preferably, the reaction materials comprise 1mmol of zinc acetate dihydrate, 1mmol of stannic chloride pentahydrate, 10mmol of potassium hydroxide and 0.1g of sodium fluoride; the hydrothermal reaction is preferably carried out at 140℃for 12 hours.
ZnSnO according to the invention 3 The ZnO nano composite material is prepared by dropwise adding lithium hydroxide solution into ethanol solution of zinc acetate dihydrate, stirring at normal temperature and normal pressure, and adding ethyl acetate to precipitate.
As a preferred oneScheme of the invention is ZnSnO 3 The ZnO nanocomposite is prepared by the following preparation method:
(1) Dropwise adding an ethanol solution of lithium hydroxide into an ethanol solution of zinc acetate dihydrate, stirring for one hour at normal temperature and normal pressure, adding excessive ethyl acetate solution until ZnO quantum dots are completely precipitated, taking out a product, washing and centrifuging, and drying at 70-90 ℃ for 20-30 hours to obtain ZnO quantum dots; molar ratio zinc acetate dihydrate: lithium hydroxide = 1:2; the ZnO quantum dots are prepared by the reaction at normal temperature and normal pressure, the higher the temperature is, the more the quantum dots are agglomerated, the quantum dots are not agglomerated when prepared at normal temperature, and the preparation condition is simple; ethyl acetate is a common precipitant used to precipitate out the quantum dots;
(2) Zinc acetate dihydrate, stannic chloride pentahydrate, potassium hydroxide and sodium fluoride are dissolved in distilled water, stirred evenly, transferred into a 100mL polytetrafluoroethylene reaction kettle for reaction for 10-15 hours at 130-150 ℃, taken out, washed, centrifuged and dried for 20-30 hours at 70-90 ℃, and the completely dried product is ground into powder to obtain ZnSnO3 precursor powder ZnSn (OH) 6 ；
(3) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 400-500 ℃ in the air at a heating speed of 1-3 ℃/min, preserving heat for 1-3 hours, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(4) Adding the ZnSnO3 nano material into ethanol solution, adding ZnO quantum dots, stirring and carrying out ultrasonic treatment until the ZnO quantum dots are completely mixed, drying for 20-30 hours at 70-90 ℃, and grinding the completely dried product into powder to obtain the ZnSnO3/ZnO composite nano material. The mass percent of the ZnO quantum dot can be 1wt% to 20wt%, preferably 2wt% to 10wt%, more preferably 3wt% to 6wt%, and most preferably 5wt%, based on the total mass of the ZnSnO3 nanomaterial and the ZnO quantum dot.
ZnSnO according to the invention 3 The ZnO nanocomposite can be used as a gas-sensitive material in gas detection such as formaldehyde. In the application, the composite material can be made into a gas sensor or made into a gas sensor; in particular, the use is described, which makes it possible to slurry the composite material by adding solvents such as terpineol or the likeThe material is coated on an alumina ceramic tube, dried and welded on a ceramic base, and a resistance wire is added to prepare a gas sensor, and the gas sensor is obtained by heating the gas sensor to 200-300 ℃ and aging for 5-8 hours, preferably 250 ℃ and aging for 6 hours.
The ZnO quantum dot is obtained by taking zinc acetate dihydrate as a raw material and combining a sol-gel method and a precipitation method. And calcining a precursor obtained by hydrothermal reaction of zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride in air to obtain ZnSnO3 nano powder, and doping and compounding the ZnSnO3 nano powder with ZnO quantum dots prepared in advance to obtain the ZnSnO3/ZnO nano powder material. The synthesized gas-sensitive material is coated on an alumina ceramic tube loaded with a platinum electrode by terpineol to prepare the gas-sensitive sensor, and the gas-sensitive performance of the gas-sensitive sensor to formaldehyde gas is detected after high-temperature aging. The ZnSnO3/ZnO composite material is obtained by adopting a physical dispersion mixing method, the preparation process is simpler, and the preparation scheme is a preparation scheme for the gas sensitive material, which has the advantages of less equipment investment and simple process flow. According to the invention, znO prepared by a sol-gel method is nano-scale, so that the aggregation of ZnO quantum dots is reduced at normal temperature and normal pressure, the concentration of negative charges on the surface is increased by LiOH, the effect of electrostatic repulsion between the quantum dots is greatly increased, and the particle size of ZnO is better controlled.
According to the invention, the ZnSnO3/ZnO composite material is of a porous hierarchical structure, the ZnSnO3 nano material prepared by a hydrothermal method is good in chemical uniformity and fine in particles, a large number of lattice defects appear in the ZnSnO3 nano material due to annealing and sintering, a physical mixing method is simple, the ultra-microstructure such as particle size and uniformity of different doping contents is effectively controlled, more active sites are provided, the surface of the material is promoted to be additionally adsorbed with chemical oxygen, the charge transfer is effectively promoted, and the gas-sensitive performance of the material is promoted. The composite material has the advantages of large specific surface area, high sensitivity to low-concentration formaldehyde gas, good selectivity, short response/recovery time and the like. Along with the improvement of the doping amount of the ZnO quantum dots, the ZnO quantum dots show high selectivity and high response to formaldehyde gas; meanwhile, the composite material with the working temperature of 70-120 ℃ can show better detection response to formaldehyde gas; especially when the doping amount is 5wt% and the working temperature is 70 ℃, the response value of the ZSO/ZO-0.05 composite material to formaldehyde is optimal, so that the formaldehyde gas can be detected conveniently and efficiently at low temperature, and a feasible scheme is provided for developing a portable gas sensor.
Drawings
FIG. 1 is a crystal X-ray diffraction diagram of ZnSnO3/ZnO composite nanomaterial doped with ZnO quantum dots in different proportions prepared in examples 1-5 of the present invention.
FIG. 2 is a scanning electron microscope image of a ZnSnO3/ZnO (i.e., ZSO/ZO-0.05) composite nanomaterial doped with 5wt% ZnO quantum dots prepared in example 3 of the present invention.
FIG. 3 example 1 preparation of pure ZnSnO3 material sensor response to different gases at different temperatures at 100ppm concentrations.
FIG. 4 example 2 is a graph of the response of a ZSO/ZO-0.01 (i.e., znSnO3/ZnO doped with 1wt% ZnO quantum dots) composite sensor to different gases at different temperatures for 100ppm concentrations.
FIG. 5 example 3 preparation of ZSO/ZO-0.05 composite sensors response to different gases at different temperatures at 100ppm concentrations.
FIG. 6 example 4 preparation of ZSO/ZO-0.10 composite sensors response to different gases at different temperatures at 100ppm concentrations.
FIG. 7 example 5 preparation of ZSO/ZO-0.20 composite sensors response to different gases at different temperatures at 100ppm concentrations.
FIG. 8 comparison of the response of ZnSnO3 prepared in examples 1-5 and different ZSO/ZO composite sensors to formaldehyde at 100ppm concentrations at different temperatures.
FIG. 9 is a graph of the resistance response change of a ZSO/ZO-0.05 composite sensor prepared in example 3 of the present invention for a gas-sensitive response at 70 ℃ of a) versus 0.3-100ppm acetone gas; b) And a graph of the relationship between the gas-sensitive response value and the concentration.
Detailed Description
The following examples are further illustrative of the technical content of the present invention, but the essential content of the present invention is not limited to the examples described below, and those skilled in the art can and should know that any simple changes or substitutions based on the essential spirit of the present invention should fall within the scope of the present invention as claimed.
Example 1:
the preparation method of the pure ZnSnO3 nano material (ZnO quantum dot is not added) gas sensor comprises the following steps:
(1) Zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride (zinc acetate dihydrate, tin chloride pentahydrate 1mmol, potassium hydroxide 10mmol, sodium fluoride 0.1 g) are dissolved in 80mL of distilled water, stirred uniformly, transferred into a 100mL polytetrafluoroethylene reaction kettle, reacted for 12 hours at 140 ℃, taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the completely dried product is ground into powder to obtain ZnSnO3 precursor ZnSn (OH) 6 powder.
(2) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 450 ℃ in the air, keeping the temperature for 2 hours at a heating speed of 2 ℃/min, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(3) Adding the ZnSnO3 nano material into ethanol solution, adding no ZnO quantum dot, stirring and carrying out ultrasonic treatment until the ZnO quantum dot is completely mixed, drying at 80 ℃ for 24 hours, and grinding the completely dried product into powder to obtain the pure ZnSnO3 nano material.
(4) 15mg of the product is taken and put into an agate mortar for grinding for 5-10 minutes, a proper amount of terpineol is added, grinding is continued for 5-10 minutes until the mixture is fully and uniformly mixed, the mixture is uniformly coated on an alumina ceramic tube, and the mixture is dried for 24 hours at 80 ℃. The obtained ceramic tube is welded on a ceramic base and is additionally provided with a resistance wire (providing reaction temperature) to prepare a gas sensor, and the gas sensor is heated to 250 ℃ and aged for 6 hours to obtain a stable gas sensor.
(5) And detecting the gas sensitivity of the gas sensor to different gases at different temperatures.
Example 2:
the preparation method of the gas sensor based on ZnSnO3/ZnO-0.01 nanocomposite material comprises the following steps:
(1) Zinc acetate dihydrate is dissolved in absolute ethanol solvent solution, lithium hydroxide solution is added dropwise into the solution (zinc acetate dihydrate: lithium hydroxide=1:2), and the solution is stirred for one hour at normal temperature and normal pressure, excessive ethyl acetate solution is added until ZnO quantum dots are completely precipitated, the product is taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the ZnO quantum dots are obtained.
(2) Zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride are dissolved in 80mL of distilled water (this step is the same as the step of example 1 (1)), stirred uniformly, transferred to a 100mL polytetrafluoroethylene reaction kettle, reacted for 12 hours at 140 ℃, taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the completely dried product is ground into powder to obtain ZnSnO3 precursor ZnSn (OH) 6 powder.
(3) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 450 ℃ in the air, keeping the temperature for 2 hours at a heating speed of 2 ℃/min, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(4) Adding the ZnSnO3 nano material into ethanol solution, respectively adding a certain amount of ZnO quantum dots (the mass percentage is 1 wt%) into the ethanol solution, stirring and carrying out ultrasonic treatment until the ZnO quantum dots are completely mixed, drying the mixture at 80 ℃ for 24 hours, and grinding the completely dried product into powder to obtain the ZnSnO3/ZnO composite nano material (recorded as ZSO/ZO-0.01).
(5) 15mg of the product is taken and put into an agate mortar for grinding for 5-10 minutes, a proper amount of terpineol is added, grinding is continued for 5-10 minutes until the mixture is fully and uniformly mixed, the mixture is uniformly coated on an alumina ceramic tube, and the mixture is dried for 24 hours at 80 ℃. The obtained ceramic tube is welded on a ceramic base and is additionally provided with a resistance wire (providing reaction temperature) to prepare a gas sensor, and the gas sensor is heated to 250 ℃ and aged for 6 hours to obtain a stable gas sensor.
(6) The performance of the gas sensor was measured, the resistance response of the device to 100ppm formaldehyde was 466 times that of air, and the optimum operating temperature was 70 ℃.
Example 3:
the preparation method of the gas sensor based on ZnSnO3/ZnO-0.05 nanocomposite material comprises the following steps:
(1) Zinc acetate dihydrate was dissolved in an absolute ethanol solvent solution, a lithium hydroxide solution was added dropwise to the solution (this step is the same as the step of example 2 (1)), and stirred at normal temperature and pressure for one hour, an excess of ethyl acetate solution was added until ZnO quantum dots were completely precipitated, the product was taken out, washed, centrifuged and dried at 80 ℃ for 24 hours to obtain ZnO quantum dots.
(2) Zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride are dissolved in 80mL of distilled water (the step is the same as that of the step of the example 1 (1)), stirred uniformly, transferred into a 100mL polytetrafluoroethylene reaction kettle, reacted for 12 hours at 140 ℃, taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the completely dried product is ground into powder to obtain ZnSn (OH) 6 powder as ZnSnO3 precursor.
(3) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 450 ℃ in the air, keeping the temperature for 2 hours at a heating speed of 2 ℃/min, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(4) Adding the ZnSnO3 nano material into ethanol solution, respectively adding a certain amount of ZnO quantum dots (the mass percentage is 5 wt%) into the ethanol solution, stirring and carrying out ultrasonic treatment until the ZnO quantum dots are completely mixed, drying the mixture at 80 ℃ for 24 hours, and grinding the completely dried product into powder to obtain the ZnSnO3/ZnO composite hierarchical nano material (recorded as ZSO/ZO-0.05).
(5) 15mg of the product is taken and put into an agate mortar for grinding for 5-10 minutes, a proper amount of terpineol is added, grinding is continued for 5-10 minutes until the mixture is fully and uniformly mixed, the mixture is uniformly coated on an alumina ceramic tube, and the mixture is dried for 24 hours at 80 ℃. The obtained ceramic tube is welded on a ceramic base and is additionally provided with a resistance wire (providing reaction temperature) to prepare a gas sensor, and the gas sensor is heated to 250 ℃ and aged for 6 hours to obtain a stable gas sensor.
(6) The performance of the gas sensor was measured, the resistance response of the device to 100ppm formaldehyde was 613 times that of air, and the optimum operating temperature was 70 ℃.
Example 4:
the preparation method of the gas sensor based on ZnSnO3/ZnO-0.10 nanocomposite material comprises the following steps:
(1) Zinc acetate dihydrate was dissolved in an absolute ethanol solvent solution, a lithium hydroxide solution was added dropwise to the solution (this step is the same as the step of example 2 (1)), and stirring was carried out at normal temperature and pressure for one hour, an excess of ethyl acetate solution was added until ZnO quantum dots were completely precipitated, the product was taken out, washed, centrifuged and dried at 80 ℃ for 24 hours to obtain ZnO quantum dots.
(2) Zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride are dissolved in 80mL of distilled water (this step is the same as the step of example 1 (1)), stirred uniformly, transferred to a 100mL polytetrafluoroethylene reaction kettle, reacted for 12 hours at 140 ℃, taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the completely dried product is ground into powder to obtain ZnSn (OH) 6 powder as ZnSnO3 precursor.
(3) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 450 ℃ in the air, keeping the temperature for 2 hours at a heating speed of 2 ℃/min, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(4) Adding the ZnSnO3 nano material into ethanol solution, respectively adding a certain amount of ZnO quantum dots (the mass percentage is 10 wt%) into the ethanol solution, stirring and carrying out ultrasonic treatment until the ZnO quantum dots are completely mixed, drying the mixture at 80 ℃ for 24 hours, and grinding the completely dried product into powder to obtain the ZnSnO3/ZnO composite nano material (recorded as ZSO/ZO-0.10).
(5) 15mg of the product is taken and put into an agate mortar for grinding for 5-10 minutes, a proper amount of terpineol is added, grinding is continued for 5-10 minutes until the mixture is fully and uniformly mixed, the mixture is uniformly coated on an alumina ceramic tube, and the mixture is dried for 24 hours at 80 ℃. The obtained ceramic tube is welded on a ceramic base and is additionally provided with a resistance wire (providing reaction temperature) to prepare a gas sensor, and the gas sensor is heated to 250 ℃ and aged for 6 hours to obtain a stable gas sensor.
(6) The performance of the gas sensor was measured, the resistance response of the device to 100ppm formaldehyde was 417 times that of air, and the optimum operating temperature was 70 ℃.
Example 5:
the preparation method of the gas sensor based on ZnSnO3/ZnO-0.20 nanocomposite material comprises the following steps:
(1) Zinc acetate dihydrate was dissolved in an absolute ethanol solvent solution, a lithium hydroxide solution was added dropwise to the solution (this step is the same as the step of example 2 (1)), and stirred at normal temperature and pressure for one hour, an excess of ethyl acetate solution was added until ZnO quantum dots were completely precipitated, the product was taken out, washed, centrifuged and dried at 80 ℃ for 24 hours to obtain ZnO quantum dots.
(2) Zinc acetate dihydrate, tin chloride pentahydrate, potassium hydroxide and sodium fluoride are dissolved in 80mL of distilled water (this step is the same as the step of example 1 (1)), stirred uniformly, transferred to a 100mL polytetrafluoroethylene reaction kettle, reacted for 12 hours at 140 ℃, taken out, washed, centrifuged and dried at 80 ℃ for 24 hours, and the completely dried product is ground into powder to obtain ZnSn (OH) 6 powder as ZnSnO3 precursor.
(3) And (3) placing the ZnSnO3 precursor powder into a muffle furnace, heating to 450 ℃ in the air, keeping the temperature for 2 hours at a heating speed of 2 ℃/min, naturally cooling to room temperature, and taking out a target product to obtain the ZnSnO3 nanomaterial.
(4) And adding the ZnSnO3 nano material into an ethanol solution, respectively adding a certain amount of ZnO quantum dots (the mass percentage is 20 wt%) into the ethanol solution, stirring and carrying out ultrasonic treatment until the ZnO quantum dots are completely mixed, drying the mixture at 80 ℃ for 24 hours, and grinding the completely dried product into powder to obtain the ZnSnO3/ZnO nano composite material (recorded as ZSO/ZO-0.20).
(5) 15mg of the product is taken and put into an agate mortar for grinding for 5-10 minutes, a proper amount of terpineol is added, grinding is continued for 5-10 minutes until the mixture is fully and uniformly mixed, the mixture is uniformly coated on an alumina ceramic tube, and the mixture is dried for 24 hours at 80 ℃. The obtained ceramic tube is welded on a ceramic base and is additionally provided with a resistance wire (providing reaction temperature) to prepare a gas sensor, and the gas sensor is heated to 250 ℃ and aged for 6 hours to obtain a stable gas sensor.
(6) The performance of the gas sensor was measured, the resistive response of the device to 100ppm formaldehyde was 309.4 times that of air, and the optimum operating temperature was 70 ℃.
FIG. 1 is a crystal X-ray diffraction diagram of ZnSnO3/ZnO nanocomposite doped with ZnO quantum dots in different proportions prepared in examples 1-5 of the present invention. According to the graph, znSnO3 is of an amorphous structure, a diffraction peak appears on the ZnO quantum dot along with the increase of doping amount, and the result shows that the ZnSnO3/ZnO composite material is successfully synthesized.
FIG. 2 is a scanning electron microscope image of a ZnSnO3/ZnO (ZSO/ZO-0.05) nanocomposite doped with 5wt% ZnO quantum dots prepared in example 3 of the present invention. The composite material consists of cubic blocks with the size of 100-200 nanometers.
FIG. 3 example 1 preparation of pure ZnSnO3 material sensor response to different gases at different temperatures at 100ppm concentrations. The results show that the pure ZnSnO3 material sensor has certain response to various gases, can reach the maximum at 170 ℃ for formaldehyde, can only reach 32 for 100ppm of formaldehyde, and also has the response to formic acid gas approaching 20, and lacks the response to certain gases.
FIG. 4 example 2 is a graph of the response of ZSO/ZO-0.01 nanocomposite sensors to different gases at different temperatures for 100ppm concentrations. The results show that the ZSO/ZO-0.01 composite material only has a significant response to formaldehyde compared with other gases, and reaches a maximum at 70 ℃, and the response to 100ppm formaldehyde reaches 450, and the response value decreases with increasing temperature. Indicating 70 c as its optimal operating temperature.
FIG. 5 example 3 preparation of ZSO/ZO-0.05 nanocomposite sensors response to different gases at 100ppm concentrations at different temperatures. The results show that the ZSO/ZO-0.05 composite material only has a significant response to formaldehyde compared to other gases, and reaches a maximum at 70 ℃, 600 for 100ppm formaldehyde, and a decrease in response with increasing temperature. Indicating an optimum operating temperature of 70 ℃.
FIG. 6 example 4 preparation of ZSO/ZO-0.10 nanocomposite sensors response to different gases at 100ppm concentrations at different temperatures. The results show that the ZSO/ZO-0.10 composite material only has a significant response to formaldehyde compared to other gases, and reaches a maximum at 70 ℃, 400 for 100ppm formaldehyde, and a decrease in response with increasing temperature. Indicating that the optimum working temperature is 70 DEG C
FIG. 7 example 5 preparation of ZSO/ZO-0.20 nanocomposite sensors response to different gases at 100ppm concentrations at different temperatures. The results show that the ZSO/ZO-0.20 composite material only has a significant response to formaldehyde compared with other gases, and reaches a maximum at 70 ℃, reaches 350 for 100ppm formaldehyde, and decreases with increasing temperature. Indicating an optimum operating temperature of 70 ℃.
FIG. 8 comparison of the response of ZnSnO3 prepared in examples 1-5 and different ZSO/ZO nanocomposite sensors to formaldehyde at 100ppm concentrations at different temperatures. As a result, it was found that the ZnSnO3 gas sensor of undoped ZnO quantum dots had no high response to formaldehyde, and as the ZnO quantum dots were doped, it exhibited high selectivity and high response to formaldehyde gas, and when the doping amount was 5wt%, the ZSO/ZO-0.05 composite had a maximum formaldehyde response value, and the optimum operating temperature was 70 ℃.
FIG. 9 is a graph of the resistance response of a ZSO/ZO-0.05 nanocomposite sensor prepared in example 3 of the present invention with respect to 0.3-100ppm formaldehyde gas in response to a graph of a) gas-sensitive response at 70 ℃; b) And a graph of the relationship between the gas-sensitive response value and the concentration. It can be seen from the graph that the response value of the gas sensor increases with increasing formaldehyde concentration and can be completely and quickly recovered in one test period, which shows that the gas sensor has good cycle performance and stability performance. The high response of the gas sensor to formaldehyde can be seen through the linear relation diagram between the response and the concentration, and the high-selectivity detection of the gas sensor to formaldehyde in a complex gas atmosphere is facilitated.
It should be noted that the foregoing technical disclosure is only for explanation and illustration to enable one skilled in the art to know the technical spirit of the present invention, and the technical disclosure is not intended to limit the scope of the present invention. The essential scope of the invention is as defined in the appended claims. Those skilled in the art should understand that any modification, equivalent substitution, improvement, etc. made based on the spirit of the present invention should fall within the spirit and scope of the present invention.

Claims (9)

1.ZnSnO 3 ZnO nanocomposite material, which is ZnSnO 3 The nano material is obtained by mixing, drying and grinding ZnO quantum dots, wherein the ZnO quantum dots account for 1-20wt%.
2. The composite material of claim 1, wherein the ZnSnO 3 The nanomaterial is prepared by mixing ZnSnO 3 The precursor powder is obtained by heat preservation for 1-3 hours at 400-500 ℃ in the air; by a means ofZnSnO (ZnSnO) 3 The precursor powder is obtained by hydrothermal reaction of 1mmol of zinc acetate dihydrate, 1mmol of stannic chloride pentahydrate, 10mmol of potassium hydroxide and 0.1g of sodium fluoride in a polytetrafluoroethylene reaction kettle at 130-160 ℃ for 10-15 hours.
3. The composite material according to claim 1, wherein the ZnO quantum dot is obtained by adding a lithium hydroxide solution dropwise to an ethanol solution of zinc acetate dihydrate, stirring at normal temperature and normal pressure, and adding ethyl acetate to precipitate.
4. A composite material according to any one of claims 1 to 3, obtained by the following preparation method:
(1) Dropwise adding an ethanol solution of lithium hydroxide into an ethanol solution of zinc acetate dihydrate, stirring for one hour at normal temperature and normal pressure, adding excessive ethyl acetate until ZnO quantum dots are completely precipitated, taking out a product, washing and centrifuging, and drying at 70-90 ℃ for 20-30 hours to obtain ZnO quantum dots; molar ratio of zinc acetate dihydrate to lithium hydroxide = 1:2;
(2) Dissolving zinc acetate dihydrate, stannic chloride pentahydrate, potassium hydroxide and sodium fluoride in distilled water, stirring uniformly, transferring into a polytetrafluoroethylene reaction kettle, reacting for 10-15 hours at 130-150 ℃, taking out the product, washing and centrifuging, drying for 20-30 hours at 70-90 ℃, grinding the completely dried product into powder, and obtaining ZnSnO 3 Precursor powder ZnSn (OH) 6 ；
(3) The ZnSnO is prepared 3 Placing the precursor powder into a muffle furnace, heating to 400-500 ℃ in air at a heating speed of 1-3 ℃/min, preserving heat for 1-3 hours, naturally cooling to room temperature, and taking out the target product to obtain ZnSnO 3 A nanomaterial.
(4) The ZnSnO is prepared 3 Adding nano material into ethanol solution, adding ZnO quantum dot, stirring, ultrasonic treating to completely mix, drying at 70-90deg.C for 20-30 hr, grinding completely dried product into powder to obtain ZnSnO 3 ZnO composite nano material.
5. Use of the composite material according to any one of claims 1-4 as a gas sensitive material in gas detection.
6. Use according to claim 5, wherein the composite material is made into a gas sensor.
7. Use according to claim 5, wherein the composite material is made into a gas sensor.
8. The method according to claim 5, wherein the composite material is prepared into slurry, the slurry is coated on an alumina ceramic tube, the slurry is dried and welded on a ceramic base, a resistance wire is added to prepare a gas sensor, and the gas sensor is obtained by heating the gas sensor to 200-300 ℃ and aging for 5-8 hours.
9. The use according to claim 5, wherein the gas is formaldehyde.
CN202310831657.1A 2023-07-07 2023-07-07 ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection Pending CN116891250A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310831657.1A CN116891250A (en) 2023-07-07 2023-07-07 ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310831657.1A CN116891250A (en) 2023-07-07 2023-07-07 ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection

Publications (1)

Publication Number Publication Date
CN116891250A true CN116891250A (en) 2023-10-17

Family

ID=88309626

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310831657.1A Pending CN116891250A (en) 2023-07-07 2023-07-07 ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection

Country Status (1)

Country Link
CN (1) CN116891250A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105565372A (en) * 2016-03-10 2016-05-11 天津师范大学 Preparation method and application of graded zinc stannate sub/micro-sphere material
CN110117025A (en) * 2019-06-05 2019-08-13 河南理工大学 A kind of ZnO/Zn2SnO4Heterojunction structure composite air-sensitive material and preparation method and application
CN111257376A (en) * 2020-02-10 2020-06-09 天津大学 Preparation method of composite modified spherical zinc metastannate low-temperature gas-sensitive material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105565372A (en) * 2016-03-10 2016-05-11 天津师范大学 Preparation method and application of graded zinc stannate sub/micro-sphere material
CN110117025A (en) * 2019-06-05 2019-08-13 河南理工大学 A kind of ZnO/Zn2SnO4Heterojunction structure composite air-sensitive material and preparation method and application
CN111257376A (en) * 2020-02-10 2020-06-09 天津大学 Preparation method of composite modified spherical zinc metastannate low-temperature gas-sensitive material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SONG LI, ET AL.: "Dual role of the reactant MOH (M=Li, Na or K) in the growth of ZnO quantum dots under a sol-gel process: promoter and inhibitor", <RSC ADVANCES>, 31 December 2016 (2016-12-31), pages 50173 - 50179 *
WEIWEI GUO，ET AL.: "One pot synthesis of hierarchical and porous ZnSnO3 nanocubes and gas sensing properties to formaldehyde", 《RESULTS IN PHYSICS》, 22 August 2019 (2019-08-22), pages 1 - 6 *
王炳山;袁建军;韩文华;刘建华;吴翠;: "ZnO/ZnSnO_3纳米复合物的制备及其HCHO气敏性研究", 材料导报, no. 20, 25 October 2015 (2015-10-25), pages 48 *

Similar Documents

Publication Publication Date Title
CN108663417B (en) One kind being directed to low concentration of NO2The novel I n of gas2O3/Sb2O3Composite hollow nanotube gas sensitive
Zhang et al. Facile synthesis of highly ethanol-sensitive SnO2 nanoparticles
CN101182197B (en) W-Sn nano composite metal oxide gas-sensing material and preparation method thereof
WO2018082585A1 (en) Synthesis method for composite gas sensitive material of porous zinc oxide nanosheet loaded with a high-dispersion nano precious metal
CN110217759B (en) For low-concentration NO at low temperature2Oxygen vacancy modified metal oxide gas-sensitive material for gas detection and preparation method thereof
CN104990961A (en) Ethanol gas sensor based on Al-doped NiO nano rod-flower material and preparation method thereof
CN102539487A (en) Air-sensitive material compounded by titanium dioxide nanometer lines and stannic oxide nanometer particles and preparation method thereof
CN108918633A (en) Pd-SnO2Nanocomposite preparation and the application in hydrogen gas sensor
CN108715457A (en) Based on MOF template controlledly synthesis nano structure of zinc oxide gas sensors
KR20160014134A (en) Metal/oxide core-shell structure nanoparticle mixed sensing materials for semiconductor gas sensor
CN107966480A (en) One kind is based on graphene coated α-Fe2O3The room temperature NO of compound2Sensor and preparation method thereof
JPH11258193A (en) Antimonic anhydride zinc semiconductor gas sensor and its manufacture
CN110412086B (en) ZnSnO based on perovskite structure3Nano-sphere isopropanol gas sensor and preparation method thereof
CN116891250A (en) ZnSnO 3 ZnO nanocomposite and application thereof in formaldehyde detection
CN109632894B (en) Noble metal in-situ co-doped CuO-based NO2Preparation and application of gas-sensitive material
CN109626425B (en) Nano linear Na1.1V3O7.9Material, method for the production thereof and use thereof
CN104445376B (en) The olive shape porous oxidation tin of hydrogen sulfide sensitivity and Synthesis and applications
CN105806893A (en) High-sensitivity formaldehyde gas sensor and production method thereof
CN112362701B (en) N-amyl alcohol sensor of Au-loaded ZnO nano composite material synthesized based on one-step solvothermal method and preparation method thereof
JP2007526865A (en) Mixed metal oxides and their use in CO2 sensors
CN112225245B (en) Rare earth element doped SnO 2 Basic high response SO 2 Method for preparing sensitive material
CN108439455B (en) Method for preparing superfine cuprous oxide with high yield
CN113277551A (en) Composite lithium lanthanum titanate material, preparation method and application
CN110208331B (en) SrO-doped SnO2Radical NH3Method for preparing sensitive material
CN110108758B (en) Formaldehyde sensitive material, sensitive element and preparation method thereof

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