CN108341425A - The preparation method and application of tin oxide/nano-ZSM-5 composite material - Google Patents
The preparation method and application of tin oxide/nano-ZSM-5 composite material Download PDFInfo
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- CN108341425A CN108341425A CN201810111331.0A CN201810111331A CN108341425A CN 108341425 A CN108341425 A CN 108341425A CN 201810111331 A CN201810111331 A CN 201810111331A CN 108341425 A CN108341425 A CN 108341425A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The present invention relates to gas sensitive technical fields, and in particular to the preparation method and application of tin oxide/5 composite materials of nanometer ZSM.The present invention has synthesized 5 type zeolites of nano level ZSM using hydro-thermal method, using infusion process by prepared zeolite and SnO2Carry out it is compound, due to spontaneous Monolayer Dispersion principle zeolite surface form grain size be 10nm SnO2Particle is prepared for gas sensor using this material as gas sensitive.One layer of 5 material of nanometer ZSM of coating makes heater-type gas sensor again outside the composite material, finds that the response of the sensor PARA FORMALDEHYDE PRILLS(91,95) improves a lot after tested, good inhibiting effect is played to acetone.
Description
Technical field
The present invention relates to gas sensitive technical fields, and in particular to the preparation method of tin oxide/nano-ZSM-5 composite material
And application.
Background technology
Formaldehyde is important industrial chemicals and organic solvent, is widely used in timber processing, the fields such as textile industry.But first
Aldehyde is also a kind of pernicious gas.The excessive formaldehyde of sucking can cause the discomfort of eyes and nose in human body, for a long time in formaldehyde ring
It can lead to the generation of cancer in border.Because content of formaldehyde present in finishing material is excessively high, therefore the monitoring of room air pollution
It is concerned with control.It is gas concentration detection to be measured to gas concentration to be measured using resistor-type semiconductor gas sensor
Common method.
Metal-oxide gas transducer often uses the detection of gas, stannic oxide conduct with its low price and high reliability
A kind of traditional semi-conducting material, have good conductive property makes it as gas with fabulous chemical stability, these characteristics
Quick material has the characteristics that high sensitivity, high stability, long-life.However SnO2The application of gas sensor also has its bottleneck,
Since it all has numerous gas the response of good air-sensitive, such as：H2、NO、NO2, methanol, ethyl alcohol, formaldehyde, acetone, chlorobenzene
Etc., therefore SnO2Gas sensor has the shortcomings that poor selectivity.For gas sensor, selectively it is not only to assess
One of an important factor for its performance, and examine the key criteria that whether has use value of gas sensor.Research and development sensitivity
The preferable gas sensing gas of selectivity is always the research hotspot of industrial monitoring and indoor environment monitoring field.
The method for improving gas sensor selectivity is a variety of, such as：Using gas sensitive to gas with various optimum temperature not
With improving its selectivity.In SnO2Middle doped precious metal nano material is improved using the catalytic effect and selectivity of noble metal
The selectivity of gas sensor.But it is usually higher that these methods use cost.
IvanP.Parkin research teams of Britain are prepared for the gas sensor of zeolite base using screen printing technique, and right
The gas-sensitive property of a variety of zeolites and metal oxide composite has done systematic research with sensitive mechanism.Prepared by cladding process
WO3Sensor is to NO2, the selectivity of CO, ethyl alcohol has been improved, zeolite base CTO, WO prepared by cladding process3Sensor to ethyl alcohol and
There has also been improvement for the selectivity of isopropanol.ZnO is mixed to prepared sensor with Y, modenite etc. respectively to low concentration
Nitrogen dioxide, acetone, ethyl alcohol, ammonia have higher response.M.Vilaseca research teams of Spain are using microtitre
Type A zeolite is coated with the SnO adulterated in Pd by method2The gas-sensitive property of the sensor of upper preparation is studied, from test result
From the point of view of the sensor there is preferable selectivity to ethyl alcohol.Ralf Moos et al. utilize Pt-MFI type Zeolite modifyings SrTi1- xFexO3-δTo improve the selectivity to propane, highly selective hydrocarbon gas is prepared for using zeolite and trivalent chromium thick film
Sensor.
But current gas sensor the problem of there are still selectivity not high, poor sensitivities, it is therefore desirable to seek new
Method further increases its sensitivity and selectivity.
Invention content
To make up the deficiencies in the prior art, first purpose of the invention is that tin oxide/nano-ZSM-5 composite wood is claimed
The preparation method of material.
The technical solution adopted by the present invention is specific as follows：
By concentration 150mg/mLSnCl2·2H2O is mixed with nanoscale ZSM-5 type zeolite solutions, SnCl2·2H2O and ZSM-
5 mass ratio is 12:5, then mixed liquor is placed in baking oven and is evaporated at 100 DEG C to obtain SnCl2- ZSM-5 compounds.
By the SnCl of synthesis2- ZSM-5 composite materials are calcined 5 hours at 600 DEG C, and atmosphere temperature rising rate is 5 DEG C/min, is then cooled down
Composite material SnO is obtained to environment temperature2-ZSM-5。
Application of the above-mentioned composite material on gas sensor is claimed in another object of the present invention.
The preparation method of gas sensor is：
First by SnO2- ZSM-5 composite materials are added deionized water and form paste, by the paste coated in clean ceramics
On pipe and cover top electrode and electric wire, then in air 400 DEG C annealing two hours, Ni-Cr resistance wires are worn after annealing
Enter and be used as heater strip in ceramic tube, electrode and heater strip are finally welded on to the gas sensor that heater-type is made on pedestal.
The gas sensor can also be prepared with the following method：First by SnO2Deionized water is added in-ZSM-5 composite materials
Paste is formed, which is coated on clean ceramic tube and covers top electrode and electric wire, in air 400 DEG C of annealing
Two hours after annealing, coat one layer of nano-ZSM-5 in ceramic pipe outer wall again, then the lower 500 DEG C of annealing two of aerobic environment
Ni-Cr resistance wires are penetrated after annealing and are used as heater strip in ceramic tube, electrode and heater strip are finally welded on pedestal by a hour
Upper obtained Z-SnO2The gas sensor of-ZSM-5 heater-types.
Advantageous effect：
The present invention has synthesized nano level ZSM-5 types zeolite using hydro-thermal method, using infusion process by prepared zeolite with
SnO2Carry out it is compound, due to spontaneous Monolayer Dispersion principle zeolite surface form grain size be 10nm SnO2Particle, with this material
It is prepared for gas sensor as gas sensitive.One layer of nano-ZSM-5 material of coating makes heater-type again outside the composite material
Gas sensor finds that the response of the sensor PARA FORMALDEHYDE PRILLS(91,95) improves a lot after tested, is played to acetone and inhibits to make well
With.
Description of the drawings
Fig. 1 is SnO2- ZSM-5 composite materials TEM figures, wherein a：SnO2- ZSM-5 composite material crystal grain TEM figures, b：SnO2-
110 crystal face TEM figures of stannic oxide in ZSM-5 composite materials；
Fig. 2 is pure SnO2With SnO2- ZSM-5 compounds PARA FORMALDEHYDE PRILLS(91,95) response curve under different operating temperatures；
Fig. 3 is tin oxide and SnO2- ZSM-5 composite material selectivity comparison diagrams；
Fig. 4 is SnO2Gas sensor, SnO2- ZSM-5 composite materials gas sensor and Z-SnO2- ZSM-5 sensors pair
The response comparison diagram of formaldehyde and acetone；
Fig. 5 is SnO2The response curve of-ZSM-5 sensors PARA FORMALDEHYDE PRILLS(91,95) under different humidity；
Fig. 6 is stannic oxide sensor, SnO2- ZSM-5 composite materials gas sensor and Z-SnO2- ZSM-5 sensors pair
The response recovery curve of formaldehyde；
Fig. 7 is stannic oxide sensor, SnO2- ZSM-5 composite materials gas sensor and Z-SnO2- ZSM-5 sensors pair
The response recovery curve of acetone；
Specific implementation mode
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method is conventional method used by invention, and experiment equipment used, material, reagent etc. can chemically company be bought.
For convenience of understanding, SnO is referred to as to stannic oxide sensor involved in following embodiments2Sensor, SnO2-ZSM-5
Sensor prepared by composite material is referred to as SnO2- ZSM-5 sensors, to SnO2One layer of coating is received again outside-ZSM-5 composite materials
The sensor of rice ZSM-5 is referred to as Z-SnO2- ZSM-5 sensors.
ZSM-5 used in following embodiments is prepared by hydrothermal synthesis method.
Synthesis step is as follows：The deionized water of predetermined amount is added in 25%TPAOH aqueous solutions, is made 15.7%
TPAOH aqueous solutions, are added 16g deionized waters and 1.12g sodium hydroxides are added in 50g15.7%TPAOH aqueous solutions, and stirring is mixed
It closes object 10 minutes, 0.07g aluminium isopropoxides is added, then stir the mixture for 5 hours to obtain clear solution, then will
32mlTEOS is added in mixture.Beaker is covered with sealed membrane, and is stirred at room temperature 12 hours, is then transferred into poly- four
It in the stainless steel autoclave of vinyl fluoride lining, is heated 12 hours in 100 DEG C, then heats to 180 DEG C, continue crystallization 12 hours.
Obtained solid product is detached with mother liquor by centrifuging.After cooling, mixture 4000rpm is centrifuged 30 minutes, discards supernatant liquid.It will
The deionized water of predetermined amount is added in centrifuge tube, makes within 10 minutes solid dispersion in deionized water by ultrasonic activation.It is above-mentioned
Process is repeated twice.Then, ethyl alcohol washing sample is used again.Later, sample is 2 hours dry at 100 DEG C, then 550
It is calcined 6 hours at DEG C, heating rate is 2 DEG C/min, obtains nanoscale ZSM-5.
1 infusion process of embodiment prepares SnO2- ZSM-5 composite materials
Building-up process is as follows：1.2gSnCl2·2H2O (Sinopharm Chemical Reagent Co., Ltd.) is dissolved in 8.0mL deionizations
In water, SnCl is obtained2Solution adds 0.5gZSM-5 solution, and then aqueous solvent is placed in baking oven and is evaporated at 100 DEG C
To obtain SnCl2- ZSM-5 compounds.By the SnCl of synthesis2- ZSM-5 composite materials are calcined 5 hours at 600 DEG C, atmosphere temperature rising
Rate is 5 DEG C/min, is subsequently cooled to environment temperature and obtains composite material SnO2-ZSM-5。
As shown in Figure 1, when nanoscale ZSM-5 type zeolites are impregnated in SnCl2When in solution, SnCl2Solution diffuses to zeolite
Surface.After calcining, since it is acted on by spontaneous Monolayer Dispersion principle, the two of high degree of dispersion is formed in the outer surface portion of zeolite
Tin oxide grain.It can be seen from the figure that SnO2Show uniform Nanoparticulate, and be grown in zeolite outer surface and
It is internal.Its grain size is 10nm, these cause it with larger specific surface area, to further improve the spirit of gas sensor
Sensitivity.Simultaneously using nano-sized ZSM-5 zeolite to the suction-operated of polar molecule also further increase under test gas formaldehyde with it is quick
The contact for feeling material silica tin, to play certain effect to the raising of sensitivity.
Embodiment 2
First by SnO2- ZSM-5 composite materials are added deionized water and form paste, by the paste coated in clean ceramics
On pipe and cover top electrode and electric wire, then in air 400 DEG C annealing two hours, Ni-Cr resistance wires are worn after annealing
Enter and be used as heater strip in ceramic tube, finally electrode and heater strip are welded on pedestal and are prepared into a SnO2- ZSM-5 heater-types
Gas sensor.
Embodiment 3
First by SnO2- ZSM-5 composite materials are added deionized water and form paste, by the paste coated in clean ceramics
On pipe and top electrode and electric wire are covered, in air 400 DEG C of two hours of annealing, after annealing, again in ceramic pipe outer wall
Then the nano-ZSM-5 of one layer of preparation of coating, is worn Ni-Cr resistance wires after annealing at aerobic environment lower 500 DEG C of two hours of annealing
Enter and be used as heater strip in ceramic tube, finally electrode and heater strip are welded on pedestal and are prepared into an outer layer covers nanometer ZSM-
The SnO of 5 zeolite layers2Gas sensor (the Z-SnO of-ZSM-5 heater-types2- ZSM-5 sensors).
Comparative example 1
Prepare nano SnO2Sensor, preparation method is the same as embodiment 2, wherein nano SnO2Purchased from Chinese medicines group chemical reagent
Co., Ltd, particle are more about uniformly 10nm.
Embodiment 4
SnO2The gas-sensitive property of-ZSM-5 composite materials is tested by static test system.Sensor is placed in volume
For the static test intracavitary portion of 50L.The target liq that certain volume is extracted using microsyringe, injects closed static test
On the crucible of intracavitary, in the case where two fans drive, object gas is evenly distributed in entire test chamber.It opens and surveys when desorbing gas
Examination chamber makes element exposure in air.The output voltage of gas sensor is measured by a bleeder circuit, partial pressure electricity
Routing series connection divider resistance RL connects with gas sensor, test voltage 10V.The response S of sensor is defined as S=Ra/Rg,
Ra=RL (10-Vair)/Vair, Rg=RL (10-Vgas)/Vgas, Vair are the aerial voltage of gas sensor, and Vgas is
Voltage of the gas sensor in object gas, Ra are the aerial resistance of sensor, and Rg is sensor in object gas
Resistance.
One of an important factor for operating temperature is measurement gas sensor performance, Fig. 2 gives pure SnO2With SnO2- ZSM-5 is multiple
Close object PARA FORMALDEHYDE PRILLS(91,95) response curve under different operating temperatures, concentration of formaldehyde 10ppm, humidity 30%RH.Pass through curve
It can be found that SnO2When-ZSM-5 compound peak responses appear in 420 DEG C, the peak response of stannic oxide also appears in 420
DEG C, maximum response is respectively 5.1 and 4.5.With the raising of temperature, pure SnO2With SnO2- ZSM-5 compound PARA FORMALDEHYDE PRILLS(91,95)s
Response decreases, this is because under high temperature, bulk gas molecule collides with hole wall, Michel Knuysen of the gas molecule in zeolite
Spread it is slack-off, so as to cause gas-sensitive perception decline.Therefore 420 DEG C are selected for its optimum working temperature, and as rear
The operating temperature of continuous air-sensitive test.
Fig. 3 gives SnO2With prepared SnO2- ZSM-5 composite material selectivity comparison diagrams.At 420 DEG C, respectively to
It is passed through formaldehyde, ethyl alcohol, toluene, acetone, methanol, ammonia and the benzene of 10ppm in test box, is found by comparing response, wherein
Responding higher gas has ethyl alcohol, formaldehyde and acetone.SnO2The response of-ZSM-5 composite material PARA FORMALDEHYDE PRILLS(91,95)s compared with pure zirconia tin have compared with
Big raising then has certain reduction to the response of acetone, ethyl alcohol.
Fig. 4 gives SnO2Gas sensor, SnO2- ZSM-5 composite materials gas sensor and Z-SnO2- ZSM-5 is sensed
The response comparison diagram of device PARA FORMALDEHYDE PRILLS(91,95) and acetone.Under test gas is respectively the formaldehyde and acetone of a concentration of 30ppm, can from figure
Go out, SnO2- ZSM-5 sensors are compared with SnO2The response of sensor PARA FORMALDEHYDE PRILLS(91,95) is greatly improved, in contrast be in figure
SnO2- ZSM-5 sensors are compared with SnO2Sensing but has apparent inhibition, further Z-SnO for the response of acetone2- ZSM-5 is passed
The promotion of sensor PARA FORMALDEHYDE PRILLS(91,95) response and to the inhibition of acetone compared with SnO2- ZSM-5 sensors have further improvement.
Fig. 5 is SnO2The response return curve of-ZSM-5 sensors PARA FORMALDEHYDE PRILLS(91,95) under different humidity, gas concentration is from 10-
50ppm, test temperature are 420 DEG C, relative humidity 30%RH.SnO when 10ppm from figure2- MFI sensor response responses
It is 5.1.Its response reaches 11.1 when 50ppm.With the increase of humidity, the response of PARA FORMALDEHYDE PRILLS(91,95) continuously decreases, test result table
PARA FORMALDEHYDE PRILLS(91,95) has preferable response sensitivity to the bright sensor under low moisture conditions.
Humidity is usually constructed with certain influence to zeolite base gas sensor, and Fig. 5 gives different sensors in DIFFERENT WET
The response curve of the lower PARA FORMALDEHYDE PRILLS(91,95) of degree.It should be apparent that aqueous vapor has large effect to the response of sensor from figure.
Under the conditions of 10ppm formaldehyde, when relative humidity is 30%RH, SnO2The response of-MFI sensors reaches 5.0.With this formation pair
Ratio, under the conditions of 90%RH, response only has 1.8.Under the conditions of same concentrations, with the increase of humidity, the sound of PARA FORMALDEHYDE PRILLS(91,95)
It should decline instead.With the raising of concentration of formaldehyde, the gap between response is more apparent.Under the conditions of humidity is 90%RH, with
The raising of concentration of formaldehyde, SnO2Too big change does not occur for the response of-ZSM-5 sensor PARA FORMALDEHYDE PRILLS(91,95)s.This shows high humidity feelings
The response of condition lower sensor depends primarily on aqueous vapor, and formaldehyde influences it to ignore.
As shown in fig. 6-7, to SnO2The sensor of one layer of nano-ZSM-5 of coating carries out formaldehyde again outside-ZSM-5 composite materials
The experiment of response is found, the response higher of PARA FORMALDEHYDE PRILLS(91,95), equally and SnO by test2Sensor and SnO2- ZSM-5 is sensed
Device has done the comparison of formaldehyde response, and when test concentrations 2-100ppm, wherein 30ppm, the response of PARA FORMALDEHYDE PRILLS(91,95) reaches 11.1, and
SnO2- ZSM-5 sensors and SnO2Sensor response only 8.6 and 6.5, while acetone is also shown and preferably inhibits to make
With 30ppmZ-SnO2The response of-ZSM-5 sensors only has 5.5, and SnO2Sensor and SnO2The response of-ZSM-5 sensors point
It Wei 9.1 and 5.6.
The preferable specific implementation mode of the above, only the invention, but the protection domain of the invention is not
It is confined to this, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (4)
1. the preparation method of tin oxide/nano-ZSM-5 composite material, which is characterized in that by concentration 150mg/mLSnCl2·2H2O
It is mixed with nanoscale ZSM-5 type zeolite solutions, SnCl2·2H2The mass ratio of O and ZSM-5 is 12:5, then mixed liquor is placed in
It is evaporated in baking oven and at 100 DEG C to obtain SnCl2- ZSM-5 compounds, by the SnCl of synthesis2- ZSM-5 composite materials are 600
It is calcined 5 hours at DEG C, atmosphere temperature rising rate is 5 DEG C/min, is subsequently cooled to environment temperature and obtains composite material SnO2-ZSM-5。
2. a kind of tin oxide as described in claim 1/application of the nano-ZSM-5 composite material on gas sensor.
3. application according to claim 2, which is characterized in that the preparation method of the gas sensor is：First by SnO2-
ZSM-5 composite materials are added deionized water and form paste, which are coated on clean ceramic tube and covering powers on
Pole and electric wire, then in air 400 DEG C annealing two hours, after annealing by Ni-Cr resistance wires penetrate in ceramic tube as plus
Electrode and heater strip are finally welded on the gas sensor that heater-type is made on pedestal by heated filament.
4. application according to claim 2, which is characterized in that the preparation method of the gas sensor is：First by SnO2-
ZSM-5 composite materials are added deionized water and form paste, which are coated on clean ceramic tube and covering powers on
Pole and electric wire in air 400 DEG C of two hours of annealing, after annealing, coat one layer of nanometer ZSM- in ceramic pipe outer wall again
5, then aerobic environment lower 500 DEG C of two hours of annealing, Ni-Cr resistance wires are penetrated after annealing and are used as heater strip in ceramic tube,
Finally electrode and heater strip are welded on pedestal, Z-SnO is made2The gas sensor of-ZSM-5 heater-types.
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| CN109115842A (en) * | 2018-08-28 | 2019-01-01 | 大连理工大学 | Stannic oxide/ZSM-5 type zeolite composite nano fiber method and application are prepared using method of electrostatic spinning |
| CN110395761A (en) * | 2019-07-26 | 2019-11-01 | 北京化工大学 | A kind of surface Co-doped ZnO composite material and preparation method and application |
| CN113092543A (en) * | 2021-04-09 | 2021-07-09 | 中国科学院上海微***与信息技术研究所 | Gas sensing material and preparation method and application thereof |
| CN113325042A (en) * | 2021-06-11 | 2021-08-31 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109115842A (en) * | 2018-08-28 | 2019-01-01 | 大连理工大学 | Stannic oxide/ZSM-5 type zeolite composite nano fiber method and application are prepared using method of electrostatic spinning |
| CN109115842B (en) * | 2018-08-28 | 2020-07-24 | 大连理工大学 | Method for preparing stannic oxide/ZSM-5 type zeolite composite nano-fiber and application |
| CN110395761A (en) * | 2019-07-26 | 2019-11-01 | 北京化工大学 | A kind of surface Co-doped ZnO composite material and preparation method and application |
| CN110395761B (en) * | 2019-07-26 | 2020-09-04 | 北京化工大学 | Surface cobalt-doped zinc oxide composite material and preparation method and application thereof |
| CN113092543A (en) * | 2021-04-09 | 2021-07-09 | 中国科学院上海微***与信息技术研究所 | Gas sensing material and preparation method and application thereof |
| CN113325042A (en) * | 2021-06-11 | 2021-08-31 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
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Application publication date: 20180731 |