CN107164839A - Formaldehyde sensitive material CdGa2O4 with hypersensitivity and selectivity and preparation method thereof - Google Patents
Formaldehyde sensitive material CdGa2O4 with hypersensitivity and selectivity and preparation method thereof Download PDFInfo
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- CN107164839A CN107164839A CN201710583457.3A CN201710583457A CN107164839A CN 107164839 A CN107164839 A CN 107164839A CN 201710583457 A CN201710583457 A CN 201710583457A CN 107164839 A CN107164839 A CN 107164839A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
A kind of novel methylene sensitive material CdGa of high sensitivity and selectivity2O4Nanofiber and preparation method thereof, belongs to inorganic functional material field.The present invention uses Cd salt and Ga salt for presoma, ethanol and N are dissolved in, the mixed solvent of N dimethylformamides adjusts solution viscosity by polyvinylpyrrolidone, nanofiber is prepared using electrostatic spinning technique, roasting obtains the rich gallium type CdGa of CdO Nanoparticle Modifieds2O4Porous nano-fibre, fiber is separated by a small amount of CdO nano-particles and modified, and causes CdGa2O4Part Ga in spinelle3+Substitute tetrahedral interstice Cd2+Position, produces free electron, is conducive to increasing absorption of the material to oxygen, improves the sensitivity of material PARA FORMALDEHYDE PRILLS(91,95).(110 DEG C) PARA FORMALDEHYDE PRILLS(91,95) gas shows high sensitivity (10ppm under relatively low operation temperature, S=60.0), to methanol, ethanol, acetone, benzene etc., other VOCs show high selectivity, while the minimum detection limit (33ppb) of PARA FORMALDEHYDE PRILLS(91,95) is less than national standard.
Description
Technical field
The invention belongs to inorganic functional material technical field, and in particular to a kind of first with hypersensitivity and selectivity
Aldehyde sensitive material CdGa2O4Porous nano-fibre and its preparation method using electrostatic spinning technique.
Background technology
Formaldehyde, with genotoxicity and carcinogenesis, seriously threatens as the primary gaseous contaminant in room air
Human health.The high sensitivity of the detection of formaldehyde, especially low concentration formaldehyde, selective enumeration method are received significant attention.China《The people
Specification is controlled with architectural engineering indoor environmental pollution》(GB50325-2010) provide, civil buildings indoor formaldehyde concentration should be less than
0.08mg/m3(about 60ppb).Metal oxide semiconductor (such as ZnO, SnO of polytype, different nanostructureds2, In2O3Deng)
The detection of the gaseous contaminants such as formaldehyde is exploited for as gas sensor.However, current domestic and international produced gas sensing
Device still can not fully meet Detection of Air Quality requirement, Monitoring lower-cut on the key indexs such as pollutant monitoring species, test limit
Mostly at ppm grades.In addition, how to improve the selectivity of formaldehyde examination, the reliability of lifting detection data is still full of challenge.
For problem above, finding and developing new has low test limit, high selectivity, highly sensitive semiconductor oxygen
Compound material is very necessary.Compared with the metal oxide of single kind, metal composite oxide can be excellent by changing component
Compound is managed and chemical property, flexible modulation crystalline phase, nanostructured, energy gap and air-sensitive property, shows huge advantage.In recent years
Come, spinel structure (such as MFe2O4, MCo2O4, MCr2O4, MGa2O4Deng) complex metal compound detection pernicious gas show it is huge
Big prospect (Sens.Actuators B, 2016,222,95~105), but CdGa2O4It is used as a kind of typical gallium spinel energy
The highly sensitive and selective enumeration method for being enough in low concentration formaldehyde is not yet cognitive.
Electrostatic spinning technique is the important means for preparing metal composite oxide nanofiber.It has equipment simple, raw
Produce the advantages of with low cost, process is easily controlled, can mass produced.Importantly, molten by regulating and controlling spinning presoma
Liquid, spinning environment and other spinning parameters, can construct the monodimension nanometer material and one-dimensional composite nano material of unique texture,
Such as solid nanofiber, middle empty nanotube, loose porous nanofiber, so as to improve materials application performance.
The content of the invention
It is an object of the invention to provide the novel methylene sensitive material CdGa of a kind of high sensitivity and selectivity2O4It is porous
Nanofiber and preparation method thereof.A diameter of 50~100 nanometers of prepared fibrous material, a length of 1~10 μm, material of main part
For rich gallium type spinelle CdGa2O4Porous nano-fibre, CdO nano-particles are embedded in rich gallium type CdGa2O4In fiber, CdO nanoparticles
Son accounts for CdGa2O4The mole percent of porous nano-fibre is 5~20%.The material (110 DEG C) under relatively low operation temperature is right
Formaldehyde gas shows high sensitivity (10ppm, S=60.0), and to methanol, ethanol, acetone, benzene etc., other volatility are organic
Compound shows high selectivity, while the minimum detection limit (33ppb) of PARA FORMALDEHYDE PRILLS(91,95) is less than national standard.Preparing should
CdGa2O4The method of porous nano-fibre --- electrostatic spinning technique, technique is simple, facilitates controllable, short preparation period, be easy to rule
It is prepared by mould.
In order to reach the purpose, it is quick that the present invention provides a kind of one-dimensional novel methylene with hypersensitivity and selectivity
Feel material C dGa2O4The preparation method of porous nano-fibre, its step is as follows：
(1) preparation of spinning solution：Weigh gross mass and be designated as maCd (NO3)2·4H2O and Ga (NO3)2·9H2O is dissolved in
The gross mass of the in the mixed solvent of ethanol and DMF (DMF), ethanol and DMF (DMF) is
mb, it is stirred at room temperature to being completely dissolved, it is m that quality is then added theretocPolyvinylpyrrolidone (PVP), continue stirring until
It is even, obtain spinning solution, wherein ma：mb：mc=0.5~1.5：20~50：2~4；
(2) electrostatic spinning：The spinning solution that step (1) is obtained carries out electrostatic spinning, obtains nanofiber presoma；
(3) drying and calcination：The nanofiber presoma that step (2) is obtained is calcined after drying, and removes polyvinyl pyrrole
Alkanone, obtains CdGa of the present invention2O4Porous nano-fibre material.
Further, the mol ratio of the cadmium salt described in step (1) and gallium salt is 0.8~1.2：2；The mass ratio of ethanol and DMF
For 2~4：1；
Electrostatic spinning described in step (2) be temperature be 20~30 DEG C, in the environment of humidity≤35% carry out, Static Spinning
The syringe volume of silk is 5~10mL, and syringe needle internal diameter is 0.4~0.5mm, and syringe needle is connect positive source, made with aluminium foil
Power cathode is connect for receiving device, it is 15~25cm to receive distance, positive and negative voltage is 15~30kV；
Drying temperature described in step (3) is 60~80 DEG C, and the dry time is 20~30h；Calcining heat be 500~
800 DEG C, calcination time is 2~4h, and heating rate during calcining is 3~5 DEG C/min；
Present invention also offers the CdGa obtained by the above method2O4Porous nano-fibre material.
A kind of formaldehyde Sensitive Apparatus, it is to be based on CdGa2O4Porous nano-fibre prepares for sensitive material.The present invention
With advantages below：
1st, because nonstoichiometry ratio occurs for cadmium gallium spinelle, a small amount of CdO Nanoparticle Modifieds are in rich gallium type CdGa2O4
In porous nano-fibre, cause CdGa2O4Part Ga in spinelle3+Substitute tetrahedral interstice Cd2+Position, produces free electron,
Be conducive to increasing absorption of the material to oxygen, improve the sensitivity of material PARA FORMALDEHYDE PRILLS(91,95).
2nd, the present invention is prepared using electrostatic spinning technique, and technique is simple, facilitates controllable, short preparation period, it is easy to which scale is given birth to
Production.And the fibrous material prepared is CdGa2O4Nano-particle (diameter<20nm) there is provided efficient for the one-dimensional loose structure of accumulation
Formaldehyde molecule absorption and diffusion admittance.
Brief description of the drawings
Fig. 1：The CdGa obtained in embodiment 12O4X-ray diffraction (XRD) collection of illustrative plates and X-ray photoelectricity of porous nano-fibre
Sub- power spectrum (EDS)；
Fig. 2：The CdGa obtained in embodiment 12O4Porous nano-fibre ESEM (SEM) and transmission electron microscope (TEM) figure
Piece；
Fig. 3:The gas sensitive device of the material manufacture sensitivity of PARA FORMALDEHYDE PRILLS(91,95) and formaldehyde under 110 DEG C of operating temperatures in embodiment 1
Graph of a relation between gas concentration；
Fig. 4：The gas sensitive device of material manufacture is dense to ppb ranks and ppm ranks under 110 DEG C of operating temperatures in embodiment 1
Spend the dynamic response recovery curve of formaldehyde；
Fig. 5：The gas sensitive device of material manufacture is different with 100ppm for 10ppm under 110 DEG C of operating temperatures in embodiment 1
The susceptibility block diagram of gas.
Embodiment
Below by embodiment and the invention will be further described with reference to accompanying drawing, but protection scope of the present invention is not limited to
Following embodiments.It will be apparent to those skilled in the art that can be to the present invention in the case of without departing from spirit and scope of the present invention
Make change or adjust, these changes or adjustment are also included in protection scope of the present invention.
Embodiment 1：CdGa2O4The preparation of porous nano-fibre material
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 600 DEG C in atmosphere is driven, the rich gallium type of CdO Nanoparticle Modifieds is obtained
CdGa2O4Porous nano-fibre.
The CdGa prepared to the above method2O4Material has carried out some phase structures and morphology characterization.Fig. 1 is acquisition
CdGa2O4Porous nano-fibre X-ray diffraction (XRD) collection of illustrative plates and X-ray energy spectrum (EDS).Figure 1A shows cadmium gallium spinelle
Metering is learned than deviateing, a small amount of CdO nano-particles are separated out；Crystallite dimension is calculated by Scherrer formula and finds CdO nano-particles about
60nm, CdGa2O4Particle about 15nm.Even if Figure 1B is shown containing part CdO phases, n (Cd):N (Ga) is still 1:2, show
CdGa2O4Spinelle is rich gallium type.Fig. 2 is the CdGa obtained2O4Porous nano-fibre ESEM (SEM) and transmission electron microscope
(TEM) picture, Fig. 2A shows nanofiber average diameter about 50~100nm, and length is more than 10 μm；Fig. 2 B show CdO nanometers
Particle (about 10~20nm) is embedded in CdGa after being separated2O4In porous nano-fibre, its particle size is consistent with XRD analysis result.
Embodiment 2：CdGa2O4The manufacture of material gas sensitive device
The main body of gas sensor be diameter 1mm, length 4mm corundum ceramic pipe, the both sides of ceramic tube outer surface respectively have one
Enclose on Au electrodes, each Au electrodes and connect two platinum filaments respectively as wire.Tube core is the heater strip of a nichrome, effect
It is heater element to provide operating temperature.The preparation method of gas sensitive device is as follows：(1) appropriate CdGa is taken2O4Sensitive material is placed in clean
In net agate mortar, a small amount of ethanol and then firmly grinding 5 minutes is added dropwise, thick slurry is modulated into.(2) will be upper with sensitive brush
State slurry to be uniformly coated on the outer surface of corundum ceramic pipe, and all cover gold electrode, dry at room temperature standby；
CdGa2O4The thickness of sensitive thin film is about 0.1mm.(3) Ni-Cr heater strips are penetrated in earthenware, by the above-mentioned pottery for scribbling sample
Porcelain tube and heater strip are welded on the base of element, check whether welding is firm after completing.(4) ready-made device is placed on
On agingtable at 200 DEG C aging 24 hours, you can for testing.
Embodiment 3：CdGa2O4The air-sensitive property test of gas sensitive device
The air-sensitive property of material is that material is made into intelligent air-sensitive analysis system (Beijing Ai Li of gas sensitive device CGS-8 types
Special Science and Technology Ltd.) come what is assessed.The system is a static analysis system, by gas tank, gas tank base and three, main frame
It is grouped into, actual test is carried out with the gas cylinder for the 2.5 liters of volumes provided for oneself.First, experimental situation condition (relative humidity 20%,
20 DEG C of room temperature) under, device has a resistance after reaching stabilization in atmosphere, is designated as Ra, then with syringe or micro-sampling
Tolerance takes a certain amount of under test gas, is injected into test gas cylinder, by certain time after gas is mixed thoroughly, by device
Part is put into test bottle, and now the resistance of device can change because of the interaction of material and under test gas, until resistance
Value is stablized again, and resistance now is designated as into Rg, then take out device carried out in fresh air desorption be allowed to return to it is initial
Near value.Sensitivity S is designated as Ra/Rg。
Some performance studies have been carried out to the gas sensitive device of material manufacture in embodiment 1.Fig. 3 is CdGa2O4Gas sensitive device exists
Graph of a relation under 110 DEG C of operating temperatures between the sensitivity of PARA FORMALDEHYDE PRILLS(91,95) and formaldehyde gas concentration.The response of device PARA FORMALDEHYDE PRILLS(91,95) is equal
Increase with the increase of concentration of formaldehyde；Good linear relationship is presented in (≤2ppm) at low concentrations between concentration and response,
Minimum detection limit as little as 33ppb.Fig. 4 is CdGa2O4Gas sensitive device is dense to ppb ranks and ppm ranks under 110 DEG C of operating temperatures
The dynamic response recovery curve of formaldehyde is spent, shows that device has excellent response to recover feature to the formaldehyde of wide range of concentrations,
Sensitivity to 10ppm formaldehyde wherein under 110 DEG C of operating temperatures is 60.0.Fig. 5 is CdGa2O4Gas sensitive device is in 110 DEG C of work
At a temperature of compare for the susceptibility of 10ppm and 100ppm gas with various, show that device has very outstanding selection for formaldehyde
Property, its sensitivity common are malicious pernicious gas far above some other.
Embodiment 4
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 600 DEG C in atmosphere is driven, the rich gallium type CdGa of CdO modifications is obtained2O4It is porous to receive
Rice fiber.CdO nano-particles, gained richness gallium type CdGa are removed with 1M HCl2O4The device of porous nano-fibre material manufacture exists
It is 37.6 to the sensitivity of 10ppm formaldehyde under 110 DEG C of operating temperatures.
Embodiment 5
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 500 DEG C in atmosphere is driven, obtained cadmium gallium composite fibre is not crystallized.Gained material
Expect that sensitivity of the device of manufacture to 10ppm formaldehyde under 110 DEG C of operating temperatures is 1.2.
Embodiment 6
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 700 DEG C in atmosphere is driven, the CdGa of pure phase is obtained2O4Nanofiber.Gained material
Expect that sensitivity of the device of manufacture to 10ppm formaldehyde under 110 DEG C of operating temperatures is 15.3.
Embodiment 7
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 800 DEG C in atmosphere is driven, the CdGa of pure phase is obtained2O4Nanofiber.Gained material
Expect that sensitivity of the device of manufacture to 10ppm formaldehyde under 110 DEG C of operating temperatures is 7.4.
Embodiment 8
By 0.059g Cd (NO3)2·4H2O (0.193mmol) and 0.178g Ga (NO3)3·9H2O (0.426mmol) according to
It is secondary to be added to 6.6g ethanol and 2.2g DMF in the mixed solvents, it is stirred at room temperature to dissolving completely, is colourless transparent solution.In stirring
Under state, 0.8g polyvinylpyrrolidones (PVP) are added, 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL notes
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as negative electrode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, humidity is 20%, then carries out connecing after electrostatic spinning, 24h
Receive and nanofiber presoma is obtained on plate.Nanofiber presoma is placed in before 70 DEG C of dry 24h, the drying nano fiber of gained
Body calcining 3h (heating rate is 3 DEG C/min) at 700 DEG C in atmosphere is driven, rich gallium type CdGa is obtained2O4Porous nano-fibre.Institute
It is 28.3 to obtain sensitivity of the device of material manufacture to 10ppm formaldehyde under 110 DEG C of operating temperatures.
Claims (6)
1. a kind of formaldehyde sensitive material CdGa with hypersensitivity and selectivity2O4The preparation method of porous nano-fibre, its
Step is as follows：
(1) preparation of spinning solution：Weigh gross mass and be designated as maCd (NO3)2·4H2O and Ga (NO3)2·9H2O be dissolved in ethanol and
The gross mass of the in the mixed solvent of DMF, ethanol and DMF is mb, it is stirred at room temperature to complete
Fully dissolved, it is m that quality is then added theretocPolyvinylpyrrolidone, continue stirring until uniform, obtain spinning solution, its
Middle ma：mb：mc=0.5~1.5：20~50：2~4；
(2) electrostatic spinning：The spinning solution that step (1) is obtained carries out electrostatic spinning, obtains nanofiber presoma；
(3) drying and calcination：The nanofiber presoma that step (2) is obtained is calcined after drying, and removes polyvinylpyrrolidone,
Obtain CdGa2O4Porous nano-fibre material.
2. a kind of formaldehyde sensitive material CdGa with hypersensitivity and selectivity as claimed in claim 12O4Porous nano
The preparation method of fiber, it is characterised in that：The mol ratio of cadmium salt and gallium salt described in step (1) is 0.8~1.2：2；Ethanol and
The mass ratio of DMF is 2~4：1.
3. a kind of formaldehyde sensitive material CdGa with hypersensitivity and selectivity as claimed in claim 12O4Porous nano
The preparation method of fiber, it is characterised in that：Electrostatic spinning described in step (2) be temperature be 20~30 DEG C, humidity≤35%
In the environment of carry out, the syringe volume of electrostatic spinning is 5~10mL, and syringe needle internal diameter is 0.4~0.5mm, and syringe needle connects
Positive source, connects power cathode using aluminium foil as receiving device, and it is 15~25cm to receive distance, and positive and negative voltage is 15~
30kV。
4. a kind of formaldehyde sensitive material CdGa as claimed in claim 12O4The preparation method of porous nano-fibre, its feature exists
In：Drying temperature described in step (3) is 60~80 DEG C, and the dry time is 20~30h；Calcining heat is 500~800 DEG C,
Calcination time is 2~4h, and the heating rate of calcining is 3~5 DEG C/min.
5. a kind of formaldehyde sensitive material CdGa2O4Porous nano-fibre, it is characterised in that：It is as appointing described in Claims 1 to 4
What method is prepared.
6. a kind of formaldehyde Sensitive Apparatus, it is characterised in that：It is based on the formaldehyde sensitive material CdGa described in claim 52O4It is porous
Nanofiber is prepared.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517583A (en) * | 2018-04-27 | 2018-09-11 | 浙江大学 | A kind of preparation method of gallic acid zinc nano-fiber material |
| CN109342521A (en) * | 2018-10-15 | 2019-02-15 | 吉林大学 | The In of alkaline earth metal doping2O3Formaldehyde sensitive material and its application in formaldehyde examination |
| CN110171841A (en) * | 2019-05-30 | 2019-08-27 | 安徽工业大学 | A kind of La doped gallium oxide-cadmium oxide composite material of pair of ethyl alcohol high sensitivity, quick response |
| CN113358710A (en) * | 2021-06-03 | 2021-09-07 | 吉林大学 | Olivine structure gas-sensitive material for detecting formaldehyde and preparation method thereof |
| CN113564812A (en) * | 2021-07-20 | 2021-10-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof |
| CN114703659A (en) * | 2022-03-14 | 2022-07-05 | 陕西师范大学 | Pt/In2O3-xComposite nanofiber material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101021544A (en) * | 2007-03-14 | 2007-08-22 | 黑龙江大学 | Sensitive material and formaldehyde sensitive component produced with sensitive material and method for producing sensitive component |
| CN103901081A (en) * | 2014-03-19 | 2014-07-02 | 中国矿业大学 | Preparation method for ZnO-In2O3 nano semiconductor crystal gas sensitive material |
| CN104677950A (en) * | 2015-02-15 | 2015-06-03 | 南京益得冠电子科技有限公司 | Formaldehyde-sensitive material used for semiconductor formaldehyde sensor and semiconductor formaldehyde sensor |
| CN106290728A (en) * | 2016-08-08 | 2017-01-04 | 三峡大学 | A kind of gas sensitive detecting formaldehyde and preparation method thereof |
-
2017
- 2017-07-18 CN CN201710583457.3A patent/CN107164839B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101021544A (en) * | 2007-03-14 | 2007-08-22 | 黑龙江大学 | Sensitive material and formaldehyde sensitive component produced with sensitive material and method for producing sensitive component |
| CN103901081A (en) * | 2014-03-19 | 2014-07-02 | 中国矿业大学 | Preparation method for ZnO-In2O3 nano semiconductor crystal gas sensitive material |
| CN104677950A (en) * | 2015-02-15 | 2015-06-03 | 南京益得冠电子科技有限公司 | Formaldehyde-sensitive material used for semiconductor formaldehyde sensor and semiconductor formaldehyde sensor |
| CN106290728A (en) * | 2016-08-08 | 2017-01-04 | 三峡大学 | A kind of gas sensitive detecting formaldehyde and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHU XIANGFENG 等: "Preparation and gas-sensing properties of CdGa2O4 semiconductors", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| HUI CHEN 等: "Electrospinning preparation of mesoporous spinel gallate (MGa2O4;M=Ni, Cu, Co) nanofibers and their M(II) ions-dependent gas sensingproperties", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (6)
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| CN108517583A (en) * | 2018-04-27 | 2018-09-11 | 浙江大学 | A kind of preparation method of gallic acid zinc nano-fiber material |
| CN109342521A (en) * | 2018-10-15 | 2019-02-15 | 吉林大学 | The In of alkaline earth metal doping2O3Formaldehyde sensitive material and its application in formaldehyde examination |
| CN110171841A (en) * | 2019-05-30 | 2019-08-27 | 安徽工业大学 | A kind of La doped gallium oxide-cadmium oxide composite material of pair of ethyl alcohol high sensitivity, quick response |
| CN113358710A (en) * | 2021-06-03 | 2021-09-07 | 吉林大学 | Olivine structure gas-sensitive material for detecting formaldehyde and preparation method thereof |
| CN113564812A (en) * | 2021-07-20 | 2021-10-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof |
| CN114703659A (en) * | 2022-03-14 | 2022-07-05 | 陕西师范大学 | Pt/In2O3-xComposite nanofiber material and preparation method and application thereof |
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