CN110514700A - A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method - Google Patents
A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method Download PDFInfo
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Abstract
A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method, CuO/Co3O4Heterogeneous structural nano line is in core shell structure, wherein CuO is as core, the Co of outer layer covers3O4Nanometer sheet is as shell.The present invention prepares CuO/Co using the nanowire precursor of the synthesis of the high temperature anneal hydro-thermal method in air atmosphere in the preparation process of sensitive material3O4Nano wire.Entire synthesis process is simple, efficient, is suitable for large-scale production.Multistage core-shell structure provides more active sites for gas reaction.And the presence of p-p type hetero-junctions, further promote response of the composite material to ethylene glycol.This gas sensor has excellent sensitivity, ultrafast response speed, outstanding selectivity, reliable long-time stability and lower theoretical detection limit, is suitable for detecting ethylene glycol gas in high sensitivity.
Description
Technical field
The present invention relates to gas sensor domains, and in particular to a kind of copper oxide and cobaltosic oxide heterogeneous structural nano line
Composite sensitive material, ethylene glycol sensor and preparation method realize detection quick to ethylene glycol gas, sensitive, repeatable.
Background technique
In the industrial production, ethylene glycol is widely used in organic solvent, antifreezing agent and conjunction as a kind of important source material
In terylene.However, ethylene glycol contains hydroxyl, when working at 80 DEG C~90 DEG C for a long time, ethylene glycol can first be oxidized to second
Alkyd, then it is oxidized to oxalic acid.And oxalic acid and its by-product can first influence the central nervous system of human body, cause to have difficulty in breathing,
Cause pulmonary edema etc., if do not used appropriate ways to treat, absorbing excessive ethylene glycol will lead to death.Therefore, high-performance is manufactured
Ethylene glycol gas sensor for environmental monitoring and human health protection have important and urgent meaning.
In the gas sensor of numerous kinds, the resistor-type gas sensor based on metal oxide semiconductor has system
Standby at low cost, Monitoring lower-cut is low, and response, the advantages that resume speed is fast, are the advantageous candidates for realizing ethylene glycol gas real-time detection
Device.
Wherein, CuO and Co3O4As typical p-type oxide semiconductor sensitive material, there is high catalytic activity, Neng Gou
It works at lower temperature, is had been a great concern in monitoring poisonous gas field.However, it is many based on simple CuO and
Co3O4Gas sensitivity it is lower, selectivity it is bad.Therefore, it is necessary to by CuO and Co3O4It is compound to construct hetero-junctions,
By the synergistic effect between both ingredients, the sensing capabilities of composite material are further promoted.
Summary of the invention
It is an object of the invention to be directed to, above-mentioned gas sensitivity in the prior art is lower, selectivity is bad is asked
Topic provides a kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation side
Method, obtained core-shell structure CuO/Co3O4Nano wire, multilevel structure makes sensitive material have bigger specific surface area, for gas
Body molecule provides more adsorption sites, and it is highly sensitive, quick that the gas sensor of preparation helps to realize ethylene glycol gas
Detection.
To achieve the goals above, the present invention has the following technical solution:
A kind of CuO/Co3O4Heterogeneous structural nano line composite sensitive material, the CuO/Co having3O4Heterogeneous structural nano line
In core shell structure, wherein CuO is as core, the Co of outer layer covers3O4Nanometer sheet is greater than as shell, the length of single nano wire
10 μm, the diameter of single nano wire is 600nm-800nm, Co3O4The thickness of nanometer sheet is less than 6nm.
CuO/Co of the present invention3O4The preparation method of heterogeneous structural nano line composite sensitive material, comprising the following steps:
(1) CuO/Co is prepared3O4Nanowire precursor；
1. ethyl alcohol is mixed with deionized water, and Cu nano wire is added into this solution, ultrasound keeps the dispersion of Cu nano wire equal
It is even, then cabaltous nitrate hexahydrate, ammonium fluoride and urea are separately added into above-mentioned solution, continue to stir evenly, obtains mixed solution；
2. 1. solution that step is obtained 6~8h of hydro-thermal reaction at 80 DEG C~100 DEG C will after cooled to room temperature
Resulting brownish black precipitates eccentric cleaning, is dried later, obtains CuO/Co3O4Nanowire precursor；
(2) CuO/Co is prepared3O4Nano wire composite sensitive material；
By CuO/Co obtained3O4Nanowire precursor is made annealing treatment, and CuO/Co is obtained3O4Nano wire.
Preferably, in one embodiment of preparation method of the present invention, in the step (1), ethyl alcohol and deionized water
Volume ratio be 1:1；The diameter of the Cu nano wire is less than 250nm, and length is greater than 10 μm.
Preferably, the cabaltous nitrate hexahydrate is mixing after being added in one embodiment of preparation method of the present invention
Concentration in solution is 0.005M~0.02M, after the ammonium fluoride is added concentration in mixed solution be 0.0025M~
0.02M, the concentration after the urea addition in mixed solution is 0.0125M~0.05M.
Preferably, the solvent of eccentric cleaning is selected from deionized water, ethyl alcohol in one embodiment of preparation method of the present invention
One of or deionized water and ethanol composition mixed solvent；The speed of the centrifugation is 5000rpm~8000rpm, described
The time of centrifugation is 5min~10min, and the temperature of the drying is 50 DEG C~80 DEG C, and drying time is 5h~12h.
Preferably, the annealing is placed in Muffle furnace and carries out in one embodiment of preparation method of the present invention,
Calcination temperature is 350 DEG C~550 DEG C, and calcination time is 2h~3h, and heating rate is 2 DEG C/min~10 DEG C/min.
The present invention gives a kind of ethylene glycol sensor, including outer surface is included that there are two annular gold electrodes separate
Al2O3Ceramic tube, Al2O3Ceramic tube inside is equipped with nickel-cadmium coil, annular gold electrode and Al2O3Ceramic tube outer surface is uniform
Coated with above-mentioned copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material.
The present invention gives a kind of preparation method of ethylene glycol sensor, comprising the following steps:
1. by CuO/Co3O4Heterogeneous structural nano line composite sensitive material powder and dehydrated alcohol are mixed for 1:10 in mass ratio
It closes, and it is made to be uniformly dispersed, above-mentioned dispersant liquid drop is then taken to come with two annular gold electrodes separate in outer surface
Al2O3Ceramic pipe surface, until ethanol evaporation forms the sensitive material film of all standing annular gold electrode；
2. nickel-cadmium coil is passed through Al2O3Ceramic tube inside is as heater strip；Finally, by above-mentioned device according to general
Heater-type gas sensor is welded and is encapsulated, and ethylene glycol sensor is then obtained.
Preferably, in the preparation method of ethylene glycol sensor of the present invention, the step 1. in by CuO/Co3O4It is heterogeneous
Structure nanometer wire composite sensitive material powder and dehydrated alcohol are uniformly dispersed by ultrasonic vibration, then take 6 μ of μ L~10 with liquid-transfering gun
The above-mentioned dispersant liquid drop of L comes with the Al of two annular gold electrodes separate in outer surface2O3Ceramic pipe surface, makes Al2O3Ceramics
The horizontal uniform rotation of pipe, until ethanol evaporation forms the sensitive material film of all standing annular gold electrode.
Compared to the prior art, composite sensitive material of the present invention is with following the utility model has the advantages that possessed CuO/Co3O4
Heterogeneous structural nano line is in core shell structure, can effectively promote the specific surface area of sensitive material, the Co of outer layer covers3O4Nanometer
Piece thickness is less than 6nm, this largely increases the active site that sensitive material is reacted under test gas.
Compared to the prior art, the preparation method of composite sensitive material of the present invention is with following the utility model has the advantages that utilizing water
Thermal method combination the high temperature anneal prepares the nuclear shell structure nano line sensitive material, and synthetic method is simple.CuO,Co3O4Both
Typical P-type material has the advantages that catalytic activity is high, detection of gas temperature is low.The present invention is by by both p-type semiconductors
It combines to construct p-p hetero-junctions, has benefited from the synergistic effect of two kinds of materials, sensitive material has greatly the sensitivity of ethylene glycol
Width is promoted, and has cracking response speed and stable test characteristic, is had in terms of ethylene glycol content in detection environment wide
Application prospect.
Compared to the prior art, ethylene glycol sensor of the invention, selects commercially available Al2O3Ceramic pipe type electrode, device technology
Simply, small in size, it is suitable for producing in enormous quantities.This gas sensor has excellent sensitivity, ultrafast response speed, outstanding
Selectivity, reliable long-time stability and low theoretical detection limit, the high sensitivity detection suitable for ethylene glycol gas.
Detailed description of the invention
Fig. 1 a is CuO/Co in embodiment 23O4The electron scanning micrograph of nano wire；
Fig. 1 b and Fig. 1 c are CuO/Co in embodiment 23O4The transmission electron microscope photo of nano wire；
Fig. 2 is CuO/Co in embodiment 23O4The X-ray diffractogram of nano wire hetero structure compound；
Fig. 3 is the structural schematic diagram of heater-type ethylene glycol sensor；
Fig. 4 is for the sensor based on embodiment 1, embodiment 2 and embodiment 3 to 100ppm second two at a temperature of different operating
The response curve of alcohol；
Fig. 5 is for the sensor based on embodiment 2 to the response recovery curve of various concentration ethylene glycol at 130 DEG C；
Fig. 6 is the sensor based on embodiment 2 in 130 DEG C and ethyl alcohol, formaldehyde, methanol, ammonia, third under 100ppm concentration
Ketone, normal propyl alcohol, ethylene glycol gas-selectively can scheme；
Fig. 7 is the sensor based on embodiment 2 under 130 DEG C of operating temperature, detects 100ppm concentration ethylene glycol gas
Performance figure steady in a long-term.
Specific embodiment
With reference to the accompanying drawing and specific embodiment is described in further detail technical solution of the present invention.These are provided
The purpose of explanation, which is only that, helps explain the present invention, is not the covering scope for limiting claim of the invention.
The present invention provides a kind of CuO/Co3O4Heterogeneous structural nano line, CuO/Co3O4Heterogeneous structural nano line is in nucleocapsid
Structure, wherein CuO is " core ", the Co of outer layer covers3O4Nanometer sheet is " shell ".CuO/Co3O4The length of heterogeneous structural nano line is big
In 10 μm, diameter is about 600nm, Co3O4Nanometer sheet thickness is less than 6nm.The present invention synthesizes Cu nano wire first, passes through water later
Thermal method coats Co in Cu nanowire surface3O4Nanometer sheet obtains CuO/Co3O4Nanowire precursor；Then high in air atmosphere
Temperature annealing, by above-mentioned CuO/Co3O4Nanowire precursor oxidation finally obtains CuO/Co3O4Nano wire.
The present invention is based on CuO/Co3O4The ethylene glycol sensor of heterogeneous structural nano line, by outer surface, included there are two that
The Al of this discrete annular gold electrode2O3Ceramic tube is uniformly coated on annular gold electrode and Al2O3The sensitivity of ceramic tube outer surface
Material film, Al2O3The nickel-cadmium coil of ceramic tube inside forms, and is prepared by following steps:
(1)CuO/Co3O4The preparation of nanowire precursor:
1. 20mL ethyl alcohol is mixed with 20mL deionized water, and the Cu nano wire of 20mg is added into this solution, ultrasound makes
Cu nano wire is uniformly dispersed.0.4mmol cabaltous nitrate hexahydrate, 0.2mmol~0.4mmol are separately added into above-mentioned solution later
Ammonium fluoride and 1mmol urea.Continue to stir 20min, is uniformly mixed the above solution.
2. above-mentioned reaction solution is reacted 8h at 90 DEG C.
3. to after reaction, by the mixed of a kind of in grey black precipitating deionized water, ethyl alcohol or deionized water and ethyl alcohol
Liquid eccentric cleaning is closed, dries 5~12h in an oven later, drying temperature is 50~80 DEG C, obtains CuO/Co3O4Nano wire forerunner
Body.
(2)CuO/Co3O4The preparation of nano wire composite sensitive material:
By CuO/Co3O4Nanowire precursor is placed in Muffle furnace and is made annealing treatment.It 350~550 DEG C of annealing temperature, moves back
The fiery time is 2~3h, and heating rate is 2~10 DEG C/min.Subsequent cooled to room temperature is to get arriving CuO/Co3O4Nano wire.
(3) production of ethylene glycol gas sensor:
1. by CuO/Co3O4Nanowire composite powder is mixed with dehydrated alcohol 1:10 in mass ratio, and ultrasound makes its dispersion
Uniformly, then take 6~10 above-mentioned dispersant liquid drops of μ L included there are two annular gold electrode in commercially available outer surface with liquid-transfering gun
Al2O3Ceramic pipe surface makes the horizontal uniform rotation of ceramic tube, until ethanol evaporation forms the sensitive material of all standing annular gold electrode
Expect film.
2. nickel-cadmium coil is passed through Al2O3Ceramic tube inside is as heater strip, finally by above-mentioned device according to general side
Hot type gas sensor is welded and is encapsulated, to obtain CuO/Co3O4Nanowire composite ethylene glycol sensor.
Embodiment 1:
CuO/Co3O4The preparation of heterogeneous structural nano line, the specific method is as follows:
(1) 20mL ethyl alcohol is mixed with 20mL deionized water, and the Cu nano wire of 20mg is added into this solution, ultrasound makes
Cu nano wire is uniformly dispersed.Be separately added into 0.4mmol cabaltous nitrate hexahydrate into above-mentioned solution later, 0.2mmol ammonium fluoride with
And 1mmol urea.Continue to stir 20min, is uniformly mixed the above solution.Above-mentioned reaction solution is reacted into 8h at 90 DEG C, this
Magnetic agitation is kept in the process.To which after reaction, resulting grey black precipitating deionized water, ethyl alcohol alternating centrifugal are cleaned
6 times, in 60 DEG C of dry 12h, obtain CuO/Co3O4Nanowire precursor.
(2) sample is made annealing treatment in Muffle furnace.Annealing conditions are as follows: by room temperature with the heating rate of 5 DEG C/min
450 DEG C are risen to, 2h is kept the temperature, subsequent cooled to room temperature obtains CuO/Co3O4Heterogeneous structural nano line.
Embodiment 2:
CuO/Co3O4The preparation of heterogeneous structural nano line, the specific method is as follows:
(1) 20mL ethyl alcohol is mixed with 20mL deionized water, and the Cu nano wire of 20mg is added into this solution, ultrasound makes
Cu nano wire is uniformly dispersed.Be separately added into 0.4mmol cabaltous nitrate hexahydrate into above-mentioned solution later, 0.3mmol ammonium fluoride with
And 1mmol urea.Continue to stir 20min, is uniformly mixed the above solution.Above-mentioned reaction solution is reacted into 8h at 90 DEG C, this
Magnetic agitation is kept in the process.It is to after reaction, resulting grey black precipitating deionized water, ethyl alcohol alternating centrifugal is clear
It washes, in 60 DEG C of dry 12h, obtains CuO/Co3O4Nanowire precursor.
(2) sample is made annealing treatment in Muffle furnace.Annealing conditions are as follows: by room temperature with the heating rate of 5 DEG C/min
450 DEG C are risen to, 2h is kept the temperature, subsequent cooled to room temperature obtains CuO/Co3O4Heterogeneous structural nano line.
Embodiment 3:
CuO/Co3O4The preparation of heterogeneous structural nano line, the specific method is as follows:
(1) 20mL ethyl alcohol is mixed with 20mL deionized water, and the Cu nano wire of 20mg is added into this solution, ultrasound makes
Cu nano wire is uniformly dispersed.Be separately added into 0.4mmol cabaltous nitrate hexahydrate into above-mentioned solution later, 0.4mmol ammonium fluoride with
And 1mmol urea.Continue to stir 20min, is uniformly mixed the above solution.Above-mentioned reaction solution is reacted into 8h at 90 DEG C, this
Magnetic agitation is kept in the process.It is to after reaction, resulting grey black precipitating deionized water, ethyl alcohol alternating centrifugal is clear
It washes, in 60 DEG C of dry 12h, obtains CuO/Co3O4Nanowire precursor.
(2) sample is made annealing treatment in Muffle furnace.Annealing conditions are as follows: by room temperature with the heating rate of 5 DEG C/min
450 DEG C are risen to, 2h is kept the temperature, subsequent cooled to room temperature obtains CuO/Co3O4Heterogeneous structural nano line.
Embodiment 4:
The preparation of ethylene glycol gas sensor, the specific method is as follows:
(1) nano material that embodiment 1-3 is obtained is mixed with dehydrated alcohol 1:10 in mass ratio respectively, and ultrasound makes it
It is uniformly dispersed, then takes the 6 above-mentioned dispersant liquid drops of μ L included there are two annular gold electrode in commercially available outer surface with liquid-transfering gun
Al2O3Ceramic pipe surface makes the horizontal uniform rotation of ceramic tube, until ethanol evaporation forms the sensitive material of all standing annular gold electrode
Expect film.
(2) nickel-cadmium coil is passed through into Al2O3Ceramic tube inside is as heater strip, finally by above-mentioned device according to general
Heater-type gas sensor is welded and is encapsulated, to obtain ethylene glycol sensor.
It can see CuO/Co from Fig. 1 a3O4The length of nano wire is greater than 10 μm, and Fig. 1 b can see CuO/Co3O4Nanometer
The diameter of line is about 600nm, and Fig. 1 c can see composition CuO/Co3O4The Co of nano wire3O4Nanometer sheet thickness is less than 6 μm.
As shown in Fig. 2, all diffraction maximums can all correspond to CuO and Co in X-ray diffraction spectrogram3O4Base peak, card
CuO/Co obtained after making annealing treatment is illustrated3O4Nano wire has good crystallinity.
As shown in figure 3, ethylene glycol sensor produced by the present invention is by Al2O3Ceramic tube, annular gold electrode, is welded on annular
Platinum line on gold electrode, semiconductor sensitive material and nickel-cadmium coil and binding post pedestal composition.
As shown in figure 4, the optimum working temperature of embodiment 1 is 110 DEG C, the optimum working temperature of embodiment 2 is 130 DEG C,
The optimum working temperature of embodiment 3 is 120 DEG C.The sensitivity definition of gas sensor is its resistance value R in glycol steamgWith
Aerial resistance value RaRatio, the spirit of embodiment 1, embodiment 2 and embodiment 3 to 100ppm ethylene glycol under Optimal Temperature
Sensitivity is respectively 2.81,6.27 and 2.53.Using high sensitivity as starting point, selection example 2 is optimal sample.
As shown in figure 5, device is in 5- when the working sensor in embodiment 2 is under optimal operating temperature (130 DEG C)
Excellent response-recovery performance is all had in the concentration range of 200ppm, and sensitivity increases with the increase of glycol concentration
Greatly.
As shown in fig. 6, when the working sensor in embodiment 2 is when under optimal operating temperature (130 DEG C), to second two
The response sensitivity of alcohol is much higher than the response sensitivity to his gas, shows 2 core-shell structure CuO/Co of the embodiment of the present invention3O4It receives
The ethylene glycol gas sensor of rice noodles preparation has excellent gas-selectively to ethylene glycol gas.
As shown in fig. 7,2 core-shell structure CuO/Co of embodiment3O4The ethylene glycol gas sensor of nano wire preparation, 30
In it, still there is the response greater than 6 to the ethylene glycol under 100ppm concentration under 130 DEG C of operating temperature, show this hair
Core-shell structure CuO/Co in bright embodiment 23O4Detection long-time stability of the gas sensor of nano wire preparation to ethylene glycol gas
Well, can suitable for actual environment ethylene glycol monitoring, have broad application prospects.
Claims (9)
1. a kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, it is characterised in that: the sensitive material
With CuO/Co3O4Heterogeneous structural nano line, the CuO/Co3O4Heterogeneous structural nano line is in core shell structure, wherein CuO
As core, the Co of outer layer covers3O4Nanometer sheet is greater than 10 μm as shell, the length of single nano wire, the diameter of single nano wire
For 600nm-800nm, Co3O4The thickness of nanometer sheet is less than 6nm.
2. the preparation side of a kind of copper oxide as described in claim 1 and cobaltosic oxide heterogeneous structural nano line composite sensitive material
Method, which comprises the following steps:
(1) CuO/Co is prepared3O4Nanowire precursor；
1. ethyl alcohol is mixed with deionized water, and Cu nano wire being added into this solution, ultrasound makes Cu nano wire be uniformly dispersed, then
It is separately added into cabaltous nitrate hexahydrate, ammonium fluoride and urea into above-mentioned solution, continues to stir evenly, obtains mixed solution；
2. 1. solution that step is obtained 6~8h of hydro-thermal reaction at 80 DEG C~100 DEG C, after cooled to room temperature, by gained
Brownish black precipitate eccentric cleaning, be dried later, obtain CuO/Co3O4Nanowire precursor；
(2) CuO/Co is prepared3O4Nano wire composite sensitive material；
By CuO/Co obtained3O4Nanowire precursor is made annealing treatment, and CuO/Co is obtained3O4Nano wire.
3. preparation method according to claim 2, it is characterised in that: the volume ratio of the ethyl alcohol and deionized water is 1:
1；The diameter of the Cu nano wire is less than 250nm, and length is greater than 10 μm.
4. preparation method according to claim 2, it is characterised in that: the cabaltous nitrate hexahydrate is molten in mixing after being added
Concentration in liquid is 0.005M~0.02M, after the ammonium fluoride is added concentration in mixed solution be 0.0025M~
0.02M, the concentration after the urea addition in mixed solution is 0.0125M~0.05M.
5. preparation method according to claim 2, it is characterised in that: the solvent of eccentric cleaning is selected from deionized water, ethyl alcohol
One of or deionized water and ethanol composition mixed solvent；The speed of the centrifugation is 5000rpm~8000rpm, described
The time of centrifugation is 5min~10min, and the temperature of the drying is 50 DEG C~80 DEG C, and drying time is 5h~12h.
6. preparation method according to claim 2, it is characterised in that: the annealing is placed in Muffle furnace and carries out,
Calcination temperature is 350 DEG C~550 DEG C, and calcination time is 2h~3h, and heating rate is 2 DEG C/min~10 DEG C/min.
7. a kind of ethylene glycol sensor, it is characterised in that: included there are two annular gold electrode separate including outer surface
Al2O3Ceramic tube, Al2O3Ceramic tube inside is equipped with nickel-cadmium coil, annular gold electrode and Al2O3Ceramic tube outer surface uniformly applies
It is covered with copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material as described in claim 1.
8. a kind of preparation method of ethylene glycol sensor as claimed in claim 7, which comprises the following steps:
1. by CuO/Co3O4Heterogeneous structural nano line composite sensitive material powder with dehydrated alcohol is that 1:10 is mixed in mass ratio, and
So that it is uniformly dispersed, above-mentioned dispersant liquid drop is then taken to come with the Al of two annular gold electrodes separate in outer surface2O3Ceramics
Pipe surface, until ethanol evaporation forms the sensitive material film of all standing annular gold electrode；
2. nickel-cadmium coil is passed through Al2O3Ceramic tube inside is as heater strip；Finally, by above-mentioned device according to general indirect heat
Formula gas sensor is welded and is encapsulated, and ethylene glycol sensor is then obtained.
9. preparation method according to claim 8, it is characterised in that: the step 1. in by CuO/Co3O4Heterojunction structure
Nano wire composite sensitive material powder and dehydrated alcohol are uniformly dispersed by ultrasonic vibration, then are taken on 6 μ of μ L~10 L with liquid-transfering gun
It states dispersant liquid drop and comes with the Al of two annular gold electrodes separate in outer surface2O3Ceramic pipe surface, makes Al2O3Ceramic tube
Horizontal uniform rotation, until ethanol evaporation forms the sensitive material film of all standing annular gold electrode.
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Cited By (4)
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|---|---|---|---|---|
| CN113358710A (en) * | 2021-06-03 | 2021-09-07 | 吉林大学 | Olivine structure gas-sensitive material for detecting formaldehyde and preparation method thereof |
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| CN113358710A (en) * | 2021-06-03 | 2021-09-07 | 吉林大学 | Olivine structure gas-sensitive material for detecting formaldehyde and preparation method thereof |
| CN113387397A (en) * | 2021-06-15 | 2021-09-14 | 河北工业大学 | Based on O2Plasma treated two-dimensional Co3O4Preparation method of nanosheet material and ethanol gas sensor |
| CN113387397B (en) * | 2021-06-15 | 2022-05-20 | 河北工业大学 | Based on O2Two-dimensional Co plasma treated3O4Preparation method of nanosheet material and ethanol gas sensor |
| CN113948690A (en) * | 2021-10-12 | 2022-01-18 | 西安交通大学 | Hollow spherical CuO/Co3O4Composite material and preparation method and application thereof |
| CN113960122A (en) * | 2021-10-29 | 2022-01-21 | 上海理工大学 | Three-dimensional SnO2/Co3O4Core-shell nano composite material and humidity-resistant acetone gas-sensitive element prepared from same |
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