CN106950274A - A kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn and preparation method thereof - Google Patents
A kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn and preparation method thereof Download PDFInfo
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Abstract
A kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn and preparation method thereof, belongs to conductor oxidate gas sensor technical field.The present invention utilizes aliovalent metal ion (Sn4+) doping method p-type NiO semiconductor sensitive materials are modified, realize the relatively quantum leap of gas-sensitive property.Sensor paraxylene based on Sn NiO nanometers of bouquets of doping shows the selectivity and sensitivity (20.2~100ppm) and relatively low Monitoring lower-cut (0.3ppm) of brilliance.In addition, sensor construction of the present invention is by the commercially available Al with 2 annular gold electrodes2O3Ceramics pipe outer, it is coated in annular gold electrode and Al2O3Semiconductor sensitive material in ceramics pipe outer and through Al2O3The nichrome heating coil composition of ceramics pipe outer.Device technology is simple, small volume, suitable for producing in enormous quantities, and xylene pollution object space face has broad application prospects in detection microenvironment.
Description
Technical field
The invention belongs to conductor oxidate gas sensor technical field, and in particular to one kind is based on NiO points of Sn doping
Dimethylbenzene gas sensor of hierarchical organization nanometer bouquet sensitive material and preparation method thereof.
Background technology
Dimethylbenzene is one of representative pollutant of VOC (VOCs) in indoor environment, can be from Building wood
Discharged in material, ornament materials, wood furniture and carpet.It is well known that it not only results in environmental pollution, and directly
Threaten human health.Although dimethylbenzene has toxicity and harmfulness, but still is used in and industrially produces other as intermediate
Chemicals and used in R＆D units as solvent.Therefore, developing has good selectivity and highly sensitive diformazan
Benzene gas sensor is of great significance with realizing to the efficient detection tool of diformazan benzene gas in microenvironment.
In the gas sensor of huge number, the resistor-type gas sensing utensil by sensitive material of conductor oxidate
Have the advantages that sensitivity is high, Monitoring lower-cut is low, selectivity is good, response and resume speed are fast, preparation method is simple, cost is relatively low,
It is one of current most widely used gas sensor.With the development of nanometer science and technology, gas sensitive is regulated and controled into tool
The graduation nanostructured for having novel pattern can be greatly enhanced the specific surface area of material, increase avtive spot, can make gas
Quick characteristic is improved.Furthermore it is possible to by aliovalent metal ion mixing technology in terms of carrier concentration and absorption oxygen component
Regulating and controlling effect promote the further modification of gas-sensitive property, so as to obtain more preferable gas-sensitive property.
Nickel oxide (NiO) is a kind of important P-type mos, because it has stabilization chemically and electrically
Property, is widely used in the fields such as energy storage, lithium ion battery, catalyst and gas sensor.To NiO nanostructured sensitivities
The research of energy shows, although compared with some N-type metal-oxide semiconductor (MOS)s, its sensitivity is relatively low, but nickel oxide exists
There is outstanding catalytic activity to the oxidation aspect of VOC (VOC), this causes the modification to NiO sensitive materials
Become meaningful.Aliovalent metal ion (Sn is used in this patent4+) doping method promotes further changing for NiO gas-sensitive properties
Property, confirmed by detailed investigation of related literatures, aliovalent metal ion mixing can improve the gas-sensitive property of gas sensor really.
The content of the invention
It is an object of the invention to provide a kind of dimethylbenzene for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn
Gas sensor and preparation method thereof.
By the use of Sn doping NiO graded structure nanometer bouquets as sensitive material, on the one hand undoped with NiO nano flower balls
There is stronger oxidisability, and all there is preferable catalytic oxidation activity to a variety of VOC gases, more oxygen molecules can be caused to join
With reaction；Moreover, passing through the aliovalent metal ion (Sn to NiO4+) doping vario-property, drastically increase NiO graduation nanometer
The specific surface area of structure so that absorption oxygen ability enhancing；Further, since aliovalent metal ion mixing technology in carrier concentration and
Adsorb the regulating and controlling effect in terms of oxygen component so that carrier hole concentration is reduced in NiO materials, defect oxygen and chemically adsorbing oxygen group
Divide increase, cause the resistance variations of sensitive material more notable.Gas and sensitivity greatly improved in the collective effect of this three aspect
The reaction efficiency of material, and then improve the sensitivity of sensor.Commercially available tubular structure sensor system of the present invention
Make technique simple, small volume, beneficial to industrial batch production, therefore with important application value.
A kind of diformazan benzene gas biography of NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn of the present invention
Sensor, by Al of the outer surface with two parallel, ring-types and gold electrode separate2O3Earthenware substrate, it is coated in Al2O3
Sensitive material on ceramic tube outer surface and gold electrode, it is placed in Al2O3Nichrome heating coil composition in earthenware；It is special
Levy and be：Sensitive material is Sn doping NiO graded structure nanometer bouquets, and is prepared by following steps,
(1) by 0.01~0.045g SnCl4.5H2O, 0.3~0.5g NiCl2·6H2O and 0.2~0.4g HMT (six
Methenamine) it is added in 20~40mL deionized waters, and holding constantly stirring is until it all dissolves, then adds thereto
Enter 1~4mL monoethanolamines；
(2) above-mentioned solution is transferred in water heating kettle, hydro-thermal reaction is taken out after 10~14 hours at 140~200 DEG C, from
So it is cooled to the multiple eccentric cleaning of precipitation deionized water and ethanol of generation after room temperature, exists again after being then dried at room temperature for
Calcined 1~3 hour at 300~500 DEG C, so as to obtain Sn doping NiO graded structure nanometer bouquet powder.
A kind of diformazan benzene gas biography of NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn of the present invention
The preparation method of sensor, its step is as follows：
(1) Sn doping NiO graded structure nanometer bouquet powder is taken to be mixed with deionized water, and grinding forms pasty state slurry
Material, then dips a small amount of slurry and is uniformly coated on outer surface with two parallel, ring-types and gold electrode separate
Al2O3Earthenware substrate surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(2) toasted 30~45 minutes under infrared lamp, after after sensitive material drying, Al2O3Earthenware is at 300~500 DEG C
Lower calcining 1~3 hour；Then resistance value is passed through into Al for 30~40 Ω nichrome heating coil2O3Ceramic tube inside conduct
Heater strip, above-mentioned device finally welded and encapsulated according to general heater-type gas sensor, so as to obtain based on Sn doping
The dimethylbenzene gas sensor of NiO graded structures nanometer bouquet sensitive material.Wherein, Al2O3A length of the 4 of earthenware~
4.5mm, external diameter is 1.2~1.5mm, and internal diameter is 0.8~1.0mm.
Dimethylbenzene gas sensor based on Sn doping NiO graded structure nanometer bouquet sensitive materials prepared by the present invention
With advantages below：
1. successfully prepare Sn doping NiO graded structure nanometer bouquets, synthetic method using the simple hydro-thermal method of a step
Simply, it is with low cost；
2. by carrying out aliovalent metal ion (Sn to NiO sensitive materials4+) doping vario-property, improve NiO base gas sensings
The selectivity of device paraxylene and sensitivity (20.2~100ppm), reduce the gas concentration Monitoring lower-cut (1.2 of sensitive material
~0.3ppm), and with good repeatability and stability, have wide application in terms of xylene pollution in detection microenvironment
Prospect；
3. using commercially available tubular type sensor, device technology is simple, small volume, suitable for producing in enormous quantities.
Brief description of the drawings
Fig. 1：(a, b) is respectively undoped with (comparative example 1) and Sn doping NiO (embodiment 1) graded structure nanometer bouquets
SEM shape appearance figures；
Fig. 2：(a1,a2, b, c) and it is respectively that the SEM undoped with NiO (comparative example 1), TEM, high-resolution TEM, Selected area electron spread out
Penetrate figure；(d1,d2, e, f) be respectively Sn doping NiO (embodiment 1) SEM, TEM, high-resolution TEM, SEAD figure；
Fig. 3：XRD undoped with (comparative example 1) and Sn doping NiO (embodiment 1) graded structure nanometer bouquets；
Fig. 4：In (illustration in a) comparative example 1 and embodiment 1 sensor at a temperature of different operating to 100ppm dimethylbenzene gas
The sensitivity curve of body；(a) selection of the sensor at 225 DEG C to 8 kinds of 100ppm under test gas in comparative example 1 and embodiment 1
Linearity curve；Selectivity of the sensor at different temperatures to the different under test gas of 6 kinds of 100ppm is bent in (illustration in b) embodiment 1
Line；(b) sensitivity curve that sensor is worked under different temperatures respectively in 6 kinds of gas with various in embodiment 1；
Fig. 5：Sensitivity-dimethylbenzene of the sensor under optimum working temperature (225 DEG C) is dense in comparative example 1 and embodiment 1
Characteristic curve is spent, wherein interior illustration is the enlarged drawing of relatively low xylene concentration (1~10ppm) place response characteristic；
Fig. 6：(a) sensor is dense on dimethylbenzene under optimum working temperature (225 DEG C) in comparative example 1 and embodiment 1
Spend the response recovery curve of gradient (10~100ppm)；(b) sensor in embodiment 1 at 225 DEG C for low concentration (1~
8ppm) the response recovery curve of dimethylbenzene；(c) sensor in embodiment 1 at 225 DEG C for low concentration (0.1~
0.8ppm) the response recovery curve of dimethylbenzene；(d) sensor in embodiment 1 at 225 DEG C for low concentration (0.1~
8ppm) the sensitivity of dimethylbenzene；
Fig. 7：Response of the sensor under optimum working temperature (225 DEG C) for 100ppm diformazan benzene gas in embodiment 1
Recovery curve (5 circulations)；
Fig. 8：Working sensor resistance in (225 DEG C) air in optimum working temperature in (draw above) embodiment 1
Linearity curve steady in a long-term；In (following figure) embodiment 1 working sensor in optimum working temperature (225 DEG C) in 100ppm bis-
The linearity curve steady in a long-term of toluene gas medium sensitivity；
As shown in figure 1, be graduation nano flower spherical structure undoped with (comparative example 1) and Sn doping NiO (embodiment 1), point
Dissipating that property is good, single nanometer bouquet is made up of the two-dimensional nano piece of many flexural deformations, the diameter of nanometer bouquet is about 2.5~
4.5μm。
As shown in Fig. 2 the TEM figures undoped with NiO (comparative example 1) scheme shown pattern unification with SEM, it is by many bendings
The graduation nano flower spherical structure that the two-dimensional nano piece of deformation is constituted, high-resolution TEM figures are shown between the wide lattices of 0.241nm
Away from (111) crystal face with pure NiO is identical, and what SEAD showed synthesis is polycrystalline undoped with NiO nanometers of bouquets；Sn mixes
TEM figures and the SEM of miscellaneous NiO (embodiment 1) scheme shown pattern unification, are to be made up of the two-dimensional nano piece of many flexural deformations
Graduation nano flower spherical structure, high-resolution TEM figures show the wide spacings of lattice of 0.241nm and 0.205nm, (111) with NiO
(200) crystal face coincide, and SEAD shows that the Sn of synthesis adulterates NiO nanometers of bouquets for polycrystalline.
As shown in figure 3, Sn doping NiO (embodiment 1) nanometer bouquet XRD spectra with undoped with NiO (comparative example 1) nanometer
The XRD spectra of bouquet is compared, and NiO characteristic peaks coincide, and the miscellaneous peak of other phases do not occur, show Sn4+Successfully it is incorporated into NiO brilliant
In lattice.
As shown in figure 4, comparative example 1 and the optimum working temperature of the sensor in embodiment 1 are 225 DEG C, now device
Be respectively 1.7 and 20.2 to the sensitivity of 100ppm dimethylbenzene, 12 times of sensitivity enhancement, and paraxylene selectivity most
Good, for sensor in comparative example 1, the sensor air-sensitive performance lifting in embodiment 1 is larger.
As shown in figure 5, for sensor in comparative example 1, with the increase of dimethylbenzene gas concentration, embodiment 1
In sensor sensitivity enhancement substantially, and preferable linear increase relation is shown between sensitivity and concentration.
As shown in fig. 6, for the sensor of embodiment 1 in dimethylbenzene, the resistance of semiconductor becomes big, this characteristic
It is consistent with the gas-sensitive property of p-type oxide semiconductor, and sensor shows excellent response to the dimethylbenzene of various concentrations
And recovery characteristics.When embodiment device operating temperature be 225 DEG C at, the sensitivity of device is with the increase of xylene concentration
Increase, sensitivity of the sensor of embodiment 1 to 10,30,50,80 and 100ppm dimethylbenzene is respectively 3.2,5.8,7.7,12.7 and
20.2, and sensitivity of the device of comparative example 1 to 10~100ppm dimethylbenzene is only 1.1~1.7.In addition, the sensor of embodiment 1
Monitoring lower-cut is relatively low, can reach ppb ranks, also has preferable response to low concentration dimethylbenzene, from Fig. 6 c, can be seen in Fig. 6 d
Arrive, be 1.2 to the sensitivity of 300ppb dimethylbenzene, show in embodiment 1 Sn adulterate NiO sensors can be used for it is micro- in microenvironment
Measure the detection of xylene pollution thing.
As shown in fig. 7, response of the sensor for 100ppm dimethylbenzene under 225 DEG C of operating temperatures in embodiment 1 is extensive
Compound curve is not fluctuated significantly, and sensitivity is higher, shows its good repeatability.
As shown in figure 8, in 20 days of follow-on test, being operated in the sensor in the embodiment 1 at a temperature of 225 DEG C in sky
Initial resistance and its corresponding sensitivity curve fluctuation in 100ppm diformazan benzene gas in gas is smaller, shows that its is good
Long-time stability.
Note：Found during actual test, the gas-sensitive property of sensor is best in embodiment 1, hence it is evident that better than embodiment 2 and implementation
Gas sensor in example 3, it is more representative.So as shown in Figures 1 to 8, emphasis is to embodiment 1 and contrast in this patent
The gas-sensitive property of sensor carries out comparative study in example 1, hence it is evident that and representative show the Sn doping synthesized by hydro-thermal method
NiO graded structures nanometer bouquet sensitive material is relative to the remarkable dimethylbenzene gas shown undoped with NiO sensitive materials
Body sensing characteristicses.In addition, the sensitivity (P-type semiconductor) for device is defined as it tested in test reducibility gas
Resistance value (R in gasg) with resistance value (R in atmosphereaThe ratio between) size, as S=Rg/Ra.In test process, using quiet
State test system is tested, and device is placed in 50~80L gas tank, inwardly injects a certain amount of under test gas, observation is simultaneously
Its change in resistance is recorded, corresponding sensitivity number is obtained by calculating.
Embodiment
Comparative example 1：
Dimethylbenzene sensor is made as sensitive material with undoped with NiO graded structures nanometer bouquet, its specific system
Make process：
(1) 30mL deionized waters are measured first, are poured into beaker, and are constantly stirred；
(2) by 0.47g NiCl2·6H2O and 0.28g HMT (hexa) are added to equipped with deionized water
In beaker, and constantly stirring is kept until it all dissolves, then adds 2mL monoethanolamines to it；
(3) above-mentioned solution is transferred in water heating kettle, is taken out after being kept for 12 hours at 160 DEG C, naturally cool to room temperature
Afterwards by the multiple eccentric cleaning of precipitation deionized water and ethanol of generation, 2 are calcined at 400 DEG C again after being then dried at room temperature for
Hour, so as to obtain undoped with NiO graded structures nanometer bouquet powder, the specific surface area of material is 45.9m2g-1；
(4) take what is prepared in right amount with hydro-thermal method to be mixed undoped with NiO graded structures nanometer bouquet powder with deionized water,
And grind and form pasty slurry, then dip a small amount of slurry and be uniformly coated on outer surface and come with 2 annular gold electrodes
Al2O3Ceramic pipe surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(5) toasted 30 minutes under infrared lamp, after after sensitive material drying, Al2O3It is small that earthenware calcines 2 at 400 DEG C
When；Then resistance value is passed through into Al for 32 Ω nichrome heating coil2O3Ceramic tube inside, finally will be upper as heater strip
State device to be welded and encapsulated according to general heater-type gas sensor, so as to obtain being based on receiving undoped with NiO graded structures
The dimethylbenzene gas sensor of popped rice ball sensitive material.
Embodiment 1：
Dimethylbenzene sensor is made as sensitive material with Sn doping NiO graded structure nanometer bouquets, its specific system
Make process：
(1) 30mL deionized waters are measured first, are poured into beaker, and are constantly stirred；
(2) by 0.021g SnCl4.5H2O, 0.47g NiCl2·6H2O and 0.28g HMT (hexa) add
Enter into the beaker equipped with deionized water, and keep constantly stirring until it all dissolves, then adds 2mL monoethanolamines to it；
(3) above-mentioned solution is transferred in water heating kettle, is taken out after being kept for 12 hours at 160 DEG C, naturally cool to room temperature
Afterwards by the multiple eccentric cleaning of precipitation deionized water and ethanol of generation, 2 are calcined at 400 DEG C again after being then dried at room temperature for
Hour, so as to obtain Sn doping NiO graded structure nanometer bouquet powder, the specific surface area of material is 90.2m2g-1；
(4) the appropriate Sn doping NiO graded structure nanometer bouquet powder prepared with hydro-thermal method is taken to be mixed with deionized water,
And grind and form pasty slurry, then dip a small amount of slurry and be uniformly coated on outer surface and come with 2 annular gold electrodes
Al2O3Ceramic pipe surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(5) toasted 30 minutes under infrared lamp, after after sensitive material drying, Al2O3It is small that earthenware calcines 2 at 400 DEG C
When；Then resistance value is passed through into Al for 32 Ω nichrome heating coil2O3Ceramic tube inside, finally will be upper as heater strip
State device to be welded and encapsulated according to general heater-type gas sensor, so as to obtain receiving based on Sn doping NiO graded structures
The dimethylbenzene gas sensor of popped rice ball sensitive material.
Embodiment 2：
Dimethylbenzene sensor is made as sensitive material with Sn doping NiO graded structure nanometer bouquets, its specific system
Make process：
(1) 20mL deionized waters are measured first, are poured into beaker, and are constantly stirred；
(2) by 0.01g SnCl4.5H2O, 0.32g NiCl2·6H2O and 0.23g HMT (hexa) are added
Into the beaker equipped with deionized water, and constantly stirring is kept until it all dissolves, then adds 4mL monoethanolamines to it；
(3) above-mentioned solution is transferred in water heating kettle, is taken out after being kept for 10 hours at 200 DEG C, naturally cool to room temperature
Afterwards by the multiple eccentric cleaning of precipitation deionized water and ethanol of generation, 3 are calcined at 300 DEG C again after being then dried at room temperature for
Hour, so as to obtain Sn doping NiO graded structure nanometer bouquet powder, the specific surface area of material is 70.8m2g-1；
(4) the appropriate Sn doping NiO graded structure nanometer bouquet powder prepared with hydro-thermal method is taken to be mixed with deionized water,
And grind and form pasty slurry, then dip a small amount of slurry and be uniformly coated on outer surface and come with 2 annular gold electrodes
Al2O3Ceramic pipe surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(5) toasted 45 minutes under infrared lamp, after after sensitive material drying, Al2O3It is small that earthenware calcines 2 at 300 DEG C
When；Then resistance value is passed through into Al for 40 Ω nichrome heating coil2O3Ceramic tube inside, finally will be upper as heater strip
State device to be welded and encapsulated according to general heater-type gas sensor, so as to obtain receiving based on Sn doping NiO graded structures
The dimethylbenzene gas sensor of popped rice ball sensitive material.
Embodiment 3：
Dimethylbenzene sensor is made as sensitive material with Sn doping NiO graded structure nanometer bouquets, its specific system
Make process：
(1) 40mL deionized waters are measured first, are poured into beaker, and are constantly stirred；
(2) by 0.045g SnCl4.5H2O, 0.5g NiCl2·6H2O and 0.38g HMT (hexa) are added
Into the beaker equipped with deionized water, and constantly stirring is kept until it all dissolves, then adds 3mL monoethanolamines to it；
(3) above-mentioned solution is transferred in water heating kettle, is taken out after being kept for 14 hours at 140 DEG C, naturally cool to room temperature
Afterwards by the multiple eccentric cleaning of precipitation deionized water and ethanol of generation, 1 is calcined at 500 DEG C again after being then dried at room temperature for
Hour, so as to obtain Sn doping NiO graded structure nanometer bouquet powder, the specific surface area of material is 77.8m2g-1；
(4) the appropriate Sn doping NiO graded structure nanometer bouquet powder prepared with hydro-thermal method is taken to be mixed with deionized water,
And grind and form pasty slurry, then dip a small amount of slurry and be uniformly coated on outer surface and come with 2 annular gold electrodes
Al2O3Ceramic pipe surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(5) toasted 40 minutes under infrared lamp, after after sensitive material drying, Al2O3It is small that earthenware calcines 1 at 500 DEG C
When；Then resistance value is passed through into Al for 31 Ω nichrome heating coil2O3Ceramic tube inside, finally will be upper as heater strip
State device to be welded and encapsulated according to general heater-type gas sensor, so as to obtain receiving based on Sn doping NiO graded structures
The dimethylbenzene gas sensor of popped rice ball sensitive material.
Claims (3)
1. a kind of dimethylbenzene gas sensor for the NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn, by outer surface
Al with two parallel, ring-types and gold electrode separate2O3Earthenware substrate, it is coated in Al2O3Ceramic tube outer surface and
Sensitive material on gold electrode, it is placed in Al2O3Nichrome heating coil composition in earthenware；It is characterized in that：Sensitive material
Adulterate NiO graded structure nano flower ball materials, and prepared by following steps for Sn,
(1) by 0.01~0.045g SnCl4.5H2O, 0.3~0.5g NiCl2·6H2O and 0.2~0.4g HMT are added to 20
In~40mL deionized waters, and constantly stirring is kept until it all dissolves, then adds 1~4mL monoethanolamines thereto；
(2) above-mentioned solution, hydro-thermal reaction is taken out after 10~14 hours at 140~200 DEG C, and naturally cooling to after room temperature will be raw
Into precipitation deionized water and the multiple eccentric cleaning of ethanol, calcine 1 at 300~500 DEG C again after being then dried at room temperature for
~3 hours, so as to obtain Sn doping NiO graded structure nanometer bouquet powder.
2. a kind of diformazan benzene gas of NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn described in claim 1
The preparation method of sensor, its step is as follows：
(1) Sn doping NiO graded structure nanometer bouquet powder is taken to be mixed with deionized water, and grinding forms pasty slurry, so
A small amount of slurry is dipped afterwards is uniformly coated on Al of the outer surface with two parallel, ring-types and gold electrode separate2O3Ceramics
Tube lining basal surface, forms sensitive material film, and make sensitive material that annular gold electrode is completely covered；
(2) toasted 30~45 minutes under infrared lamp, after after sensitive material drying, Al2O3Earthenware is forged at 300~500 DEG C
Burn 1~3 hour；Then resistance value is passed through into Al for 30~40 Ω nichrome heating coil2O3Ceramic tube inside is used as heating
Silk, above-mentioned device finally welded and encapsulated according to general heater-type gas sensor, so as to obtain based on NiO points of Sn doping
The dimethylbenzene gas sensor of hierarchical organization nanometer bouquet sensitive material.
3. a kind of dimethylbenzene gas of NiO graded structures nanometer bouquet sensitive material that adulterated based on Sn as claimed in claim 2
The preparation method of body sensor, it is characterised in that：Al2O3A length of 4~4.5mm of earthenware, external diameter is 1.2~1.5mm, internal diameter
For 0.8~1.0mm.
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| CN108152338A (en) * | 2017-12-26 | 2018-06-12 | 吉林大学 | Based on Sn of equal value2+Dimethylbenzene gas sensor of NiO nano flower-like microballoons of gap doping and preparation method thereof |
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| CN109768259A (en) * | 2019-01-23 | 2019-05-17 | 福州大学 | A kind of graded structure germanium dioxide of Fe2O3 doping |
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| CN108872324A (en) * | 2018-05-16 | 2018-11-23 | 吉林大学 | One kind being based on NiO/NiCr2O4Dimethylbenzene gas sensor of nano combined sensitive material and preparation method thereof |
| CN109768259A (en) * | 2019-01-23 | 2019-05-17 | 福州大学 | A kind of graded structure germanium dioxide of Fe2O3 doping |
| CN110082398A (en) * | 2019-06-03 | 2019-08-02 | 海南大学 | NiO oxide semiconductor dimethylbenzene sensor and the preparation method and application thereof |
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