CN107164839B - Formaldehyde sensitive material CdGa2O4 and preparation method thereof with hypersensitivity and selectivity - Google Patents
Formaldehyde sensitive material CdGa2O4 and preparation method thereof with hypersensitivity and selectivity Download PDFInfo
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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
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- 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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- 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
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Abstract
A kind of highly sensitive and selectivity novel methylene sensitive material CdGa2O4Nanofiber and preparation method thereof belongs to inorganic functional material field.The present invention uses Cd salt and Ga salt for presoma, it is dissolved in the mixed solvent of ethyl alcohol and n,N-Dimethylformamide, solution viscosity is adjusted by polyvinylpyrrolidone, nanofiber is prepared using electrostatic spinning technique, roasting obtains the rich gallium type CdGa of CdO Nanoparticle Modified2O4Porous nano-fibre, fiber mutually separate modification by a small amount of CdO nanoparticle, lead to CdGa2O4Part Ga in spinelle3+Substitute tetrahedral interstice Cd2+Position generates free electron, is conducive to increase 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 lower operation temperature, S=60.0), to methanol, ethyl alcohol, acetone, benzene etc., other volatile organic compounds show high selectivity, while the minimum detection limit (33ppb) of PARA FORMALDEHYDE PRILLS(91,95) is lower than national standard.
Description
Technical field
The invention belongs to inorganic functional material technical fields, and in particular to a kind of first with hypersensitivity and selectivity
Aldehyde sensitive material CdGa2O4Porous nano-fibre and its preparation method for utilizing electrostatic spinning technique.
Background technique
Formaldehyde has genotoxicity and carcinogenesis, seriously threatens as the primary gaseous pollutant in room air
Human health.The high sensitivity of the detection of formaldehyde, especially low concentration formaldehyde, selective enumeration method receive significant attention.China " people
Controlled and standardized with architectural engineering indoor environmental pollution " (GB50325-2010) regulation, civil buildings indoor formaldehyde concentration should be lower than
0.08mg/m3(about 60ppb).Metal oxide semiconductor (such as ZnO, the SnO of multiple types, different nanostructures2, In2O3Deng)
The detection of the gaseous pollutants such as formaldehyde is exploited for as gas sensor.However, current gas sensing produced both at home and abroad
Device still cannot sufficiently meet Detection of Air Quality requirement, Monitoring lower-cut on the key indexes such as pollutant monitoring type, detection limit
Mostly at ppm grades.In addition, how to improve the selectivity of formaldehyde examination, the reliability for promoting detection data is still full of challenge.
In view of the above problems, find and develop it is novel there is low detection to limit, highly selective, highly sensitive semiconductor oxygen
Compound material is very necessary.It is compared with the metal oxide of single kind, metal composite oxide can be excellent by changing component
Compound reason and chemical property, flexible modulation crystal phase, nanostructure, forbidden bandwidth and air-sensitive property show huge advantage.In recent years
Come, spinel structure (such as MFe2O4, MCo2O4, MCr2O4, MGa2O4Deng) complex metal compound detection pernicious gas show
Huge prospect (Sens.Actuators B, 2016,222,95~105), but CdGa2O4As a kind of typical gallium spinel
The highly sensitive and selective enumeration method that can be used in low concentration formaldehyde is not yet recognized.
Electrostatic spinning technique is the important means for preparing metal composite oxide nanofiber.It has equipment simple, raw
Produce the advantages that low in cost, process is easy to control, can be mass produced.Importantly, molten by regulation 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 etc., to improve material application performance.
Summary of the invention
The purpose of the present invention is to provide a kind of highly sensitive and selectivity novel methylene sensitive material CdGa2O4It is porous
Nanofiber and preparation method thereof.The diameter of prepared fibrous material be 50~100 nanometers, a length of 1~10 μm, material of main part
For rich gallium type spinelle CdGa2O4Porous nano-fibre, CdO nanoparticle are embedded in rich gallium type CdGa2O4In fiber, CdO nanoparticle
Son accounts for CdGa2O4The mole percent of porous nano-fibre is 5~20%.The material (110 DEG C) under lower operation temperature is right
Formaldehyde gas shows high sensitivity (10ppm, S=60.0), and to methanol, ethyl alcohol, acetone, benzene etc., other volatility are organic
Compound shows high selectivity, while the minimum detection limit (33ppb) of PARA FORMALDEHYDE PRILLS(91,95) is lower than national standard.Preparation should
CdGa2O4The method of porous nano-fibre --- electrostatic spinning technique, simple process, convenience is controllable, short preparation period, is easy to advise
Mould preparation.
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 are as follows:
(1) it the preparation of spinning solution: weighs gross mass and is denoted as maCd (NO3)2·4H2O and Ga (NO3)2·9H2O is dissolved in
The gross mass of the in the mixed solvent of ethyl alcohol and n,N-Dimethylformamide (DMF), ethyl alcohol and n,N-Dimethylformamide (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, spinning solution is obtained, 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) it drying and calcination: is calcined after the nanofiber presoma that step (2) obtains is dried, removes polyvinyl pyrrole
Alkanone obtains CdGa of the present invention2O4Porous nano-fibre material.
Further, the molar ratio of cadmium salt described in step (1) and gallium salt is 0.8~1.2:2;The mass ratio of ethyl alcohol and DMF
For 2~4:1;
It is 20~30 DEG C that electrostatic spinning described in step (2), which is in temperature, is carried out in the environment of humidity≤35%, 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 pole, made with aluminium foil
Power cathode is connect for receiving device, receiving distance is 15~25cm, and 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;Calcination temperature be 500~
800 DEG C, calcination time is 2~4h, and heating rate when calcining is 3~5 DEG C/min;
The present invention also provides the CdGa obtained by the above method2O4Porous nano-fibre material.
A kind of formaldehyde Sensitive Apparatus is based on CdGa2O4Porous nano-fibre is prepared for sensitive material.The present invention
It has the advantage that
1, since nonstoichiometry ratio occurs for cadmium gallium spinelle, a small amount of CdO Nanoparticle Modified is in rich gallium type CdGa2O4
In porous nano-fibre, lead to CdGa2O4Part Ga in spinelle3+Substitute tetrahedral interstice Cd2+Position generates free electron,
Be conducive to increase absorption of the material to oxygen, improve the sensitivity of material PARA FORMALDEHYDE PRILLS(91,95).
2, the present invention is prepared using electrostatic spinning technique, simple process, convenient controllable, and it is raw to be easy to scale for short preparation period
It produces.And the fibrous material of preparation is CdGa2O4The one-dimensional porous structure of nanoparticle (diameter < 20nm) accumulation, provides efficiently
Formaldehyde molecule absorption and diffusion admittance.
Detailed description of the invention
Fig. 1: the CdGa obtained in embodiment 12O4X-ray diffraction (XRD) map and X-ray photoelectricity of porous nano-fibre
Sub- power spectrum (EDS);
Fig. 2: the CdGa obtained in embodiment 12O4Porous nano-fibre scanning electron microscope (SEM) and transmission electron microscope (TEM) figure
Piece;
Fig. 3: the gas sensitive device that material manufactures in embodiment 1 sensitivity of PARA FORMALDEHYDE PRILLS(91,95) and formaldehyde under 110 DEG C of operating temperatures
Relational graph between gas concentration;
Fig. 4: the gas sensitive device that material manufactures in embodiment 1 is dense to ppb rank and ppm rank under 110 DEG C of operating temperatures
Spend the dynamic response recovery curve of formaldehyde;
Fig. 5: in embodiment 1 material manufacture gas sensitive device under 110 DEG C of operating temperatures for 10ppm and 100ppm not
With the susceptibility histogram of gas.
Specific embodiment
The invention will be further described by way of example and in conjunction with the accompanying drawings, 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 without departing from spirit and scope of the present invention
Variation or adjustment are made, these variations 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 (0.412 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 600 DEG C in air, obtain the rich gallium type of CdO Nanoparticle Modified
CdGa2O4Porous nano-fibre.
To the CdGa of above method preparation2O4Material has carried out some phase structures and morphology characterization.Fig. 1 is to obtain
CdGa2O4Porous nano-fibre X-ray diffraction (XRD) map and X-ray energy spectrum (EDS).Figure 1A shows cadmium gallium spinelle
Metering is learned than deviateing, a small amount of CdO nanoparticle is precipitated;Crystallite dimension discovery CdO nanoparticle is calculated about by Scherrer formula
60nm, CdGa2O4About 15 nm of particle.Figure 1B is shown even if being still 1:2 containing part CdO phase, n (Cd): n (Ga), is shown
CdGa2O4Spinelle is rich gallium type.Fig. 2 is the CdGa obtained2O4Porous nano-fibre scanning electron microscope (SEM) and transmission electron microscope
(TEM) picture, Fig. 2A show nanofiber average diameter about 50~100nm, and length is at 10 μm or more;Fig. 2 B shows CdO nanometers
Particle (about 10~20nm) is embedded in CdGa after mutually separating2O4In porous nano-fibre, particle size is consistent with XRD analysis result.
Embodiment 2:CdGa2O4The manufacture of material gas sensitive device
The main body of gas sensor is diameter 1mm, and the corundum ceramic pipe of length 4mm, the both sides of ceramic tube outer surface respectively have one
Au electrode is enclosed, connects two platinum filaments respectively as conducting wire on each Au electrode.Tube core is the heater strip of a nichrome, effect
It is heating device to provide operating temperature.Gas sensitive device the production method is as follows: (1) take appropriate CdGa2O4Sensitive material is placed in clean
In net agate mortar, a small amount of ethyl alcohol is added dropwise and then firmly grinds 5 minutes, is modulated into thick slurry.It (2) will be upper with sensitive brush
It states slurry to be uniformly coated on the outer surface of corundum ceramic pipe, and all covers gold electrode, dry at room temperature spare;
CdGa2O4The thickness of sensitive thin film is about 0.1mm.(3) Ni-Cr heater strip is penetrated in ceramic tube, by the above-mentioned pottery for being coated with sample
Porcelain tube and heater strip are welded on the pedestal of element, check whether welding is secured after completing.(4) ready-made device is placed
On agingtable at 200 DEG C aging 24 hours, can be used to test.
Embodiment 3:CdGa2O4The air-sensitive property of gas sensitive device is tested
The air-sensitive property of material is that material is made to gas sensitive device CGS-8 type intelligence air-sensitive analysis system (Beijing Ai Li
Special Science and Technology Ltd.) come what is assessed.The system is a static analysis system, by gas tank, gas tank pedestal and three, host
It is grouped as, actual test is carried out with the gas cylinder for the 2.5 liters of volumes provided for oneself.Firstly, experimental situation condition (relative humidity 20%,
20 DEG C of room temperature) under, device has a resistance after reaching stable in air, is denoted 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 the resistance of device can change because of the interaction of material and under test gas at this time, until resistance
Value is stable again, and resistance at this time is denoted as Rg, then take out device carried out in fresh air desorption be allowed to be restored to it is initial
Near value.Sensitivity S is denoted as Ra/Rg。
The gas sensitive device manufactured to material in embodiment 1 has carried out some performance studies.Fig. 3 is CdGa2O4Gas sensitive device exists
Relational graph under 110 DEG C of operating temperatures between the sensitivity and formaldehyde gas concentration of PARA FORMALDEHYDE PRILLS(91,95).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 is down to 33ppb.Fig. 4 is CdGa2O4Gas sensitive device is dense to ppb rank and ppm rank under 110 DEG C of operating temperatures
The dynamic response recovery curve for spending formaldehyde shows that device has excellent response to restore feature in the formaldehyde of wide range of concentrations,
It is wherein 60.0 to the sensitivity of 10ppm formaldehyde under 110 DEG C of operating temperatures.Fig. 5 is CdGa2O4Gas sensitive device works at 110 DEG C
At a temperature of the susceptibility of 10ppm and 100ppm gas with various is compared, show that device has formaldehyde very outstanding selection
Property, sensitivity common are malicious pernicious gas much higher than some other.
Embodiment 4
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 600 DEG C in air, obtain the rich gallium type CdGa of CdO modification2O4It is porous to receive
Rice fiber.CdO nanoparticle, gained richness gallium type CdGa are removed with the HCl of 1M2O4The 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 (0.412 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 500 DEG C in air, obtained cadmium gallium composite fibre does not crystallize.Gained material
The device for expecting manufacture is 1.2 to the sensitivity of 10 ppm formaldehyde under 110 DEG C of operating temperatures.
Embodiment 6
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 700 DEG C in air, obtain the CdGa of pure phase2O4Nanofiber.Gained material
The device for expecting manufacture is 15.3 to the sensitivity of 10 ppm formaldehyde under 110 DEG C of operating temperatures.
Embodiment 7
By 0.063g Cd (NO3)2·4H2O (0.206mmol) and 0.172g Ga (NO3)3·9H2O (0.412 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 800 DEG C in air, obtain the CdGa of pure phase2O4Nanofiber.Gained material
The device for expecting manufacture is 7.4 to the sensitivity of 10 ppm formaldehyde under 110 DEG C of operating temperatures.
Embodiment 8
By 0.059g Cd (NO3)2·4H2O (0.193mmol) and 0.178g Ga (NO3)3·9H2O (0.426 mmol) according to
It is secondary to be added to 6.6g ethyl alcohol and 2.2g DMF in the mixed solvent, it is stirred at room temperature to dissolution completely, is colourless transparent solution.It is stirring
Under state, it is added 0.8g polyvinylpyrrolidone (PVP), 12h is stirred at room temperature and obtains homogeneous solution.Pour this solution into 5mL note
In emitter, syringe needle internal diameter is 0.41mm, and aluminium foil collects nano-fiber product, aluminium foil and syringe needle two-plate as cathode receiver board
Between distance be 20cm, applications voltage be 22kV, temperature be 25 DEG C, then humidity 20% carries out electrostatic spinning, for 24 hours after connecing
It receives and obtains nanofiber presoma on plate.Nanofiber presoma is placed in 70 DEG C of dryings for 24 hours, before resulting drying nano fiber
It drives body and calcines 3h (heating rate is 3 DEG C/min) at 700 DEG C in air, obtain rich gallium type CdGa2O4Porous nano-fibre.Institute
The device for obtaining material manufacture is 28.3 to the sensitivity of 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,
Steps are as follows:
(1) it the preparation of spinning solution: weighs gross mass and is denoted as maCd (NO3)2·4H2O and Ga (NO3)2·9H2O be dissolved in ethyl alcohol and
The gross mass of the in the mixed solvent of n,N-Dimethylformamide, ethyl alcohol and n,N-Dimethylformamide is mb, it is stirred at room temperature to complete
Fully dissolved, it is m that quality is then added theretocPolyvinylpyrrolidone, continue stirring until uniformly, obtain spinning solution,
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: calcining after the nanofiber presoma that step (2) obtains is dried, remove polyvinylpyrrolidone,
Obtain CdGa2O4Porous nano-fibre material.
2. a kind of formaldehyde sensitive material CdGa with hypersensitivity and selectivity as described in claim 12O4Porous nano
The preparation method of fiber, it is characterised in that: the molar ratio of cadmium salt described in step (1) and gallium salt is 0.8~1.2:2;Ethyl alcohol and
The mass ratio of n,N-Dimethylformamide is 2~4:1.
3. a kind of formaldehyde sensitive material CdGa with hypersensitivity and selectivity as described in claim 12O4Porous nano
The preparation method of fiber, it is characterised in that: it is 20~30 DEG C that electrostatic spinning described in step (2), which is in temperature, 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 pole, connects power cathode using aluminium foil as receiving device, and receiving distance is 15~25cm, and positive and negative voltage is 15~
30kV。
4. a kind of formaldehyde sensitive material CdGa as described in claim 12O4The preparation method of porous nano-fibre, feature exist
In: drying temperature described in step (3) is 60~80 DEG C, and the dry time is 20~30h;Calcination temperature 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: appointed as described in Claims 1 to 4
What method is prepared.
6. a kind of formaldehyde Sensitive Apparatus, it is characterised in that: be based on the formaldehyde sensitive material CdGa described in claim 52O4It is porous
Nanofiber is prepared.
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CN101021544B (en) * | 2007-03-14 | 2010-07-28 | 黑龙江大学 | Formaldehyde sensitive component and method for producing sensitive component |
CN103901081B (en) * | 2014-03-19 | 2016-03-30 | 中国矿业大学 | ZnO-In 2o 3nano semiconductor crystal gas sensitive preparation method |
CN104677950B (en) * | 2015-02-15 | 2018-03-06 | 南京益得冠电子科技有限公司 | Formaldehyde sensitive material and semiconductor formaldehyde sensor for 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 |
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