CN107085020B - A kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material and preparation method and application - Google Patents
A kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material and preparation method and application Download PDFInfo
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Abstract
A kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material and preparation method and application are related to a kind of gas sensing materials and preparation method and application.The present invention is in order to solve existing detection NOxSensitive material there is a problem of that operating temperature demand is high, sensitivity is low, poor selectivity, recovery time be long.The composite air-sensitive sensing material is by MoS2It is made with indium salts.Preparation method: one, raw material is weighed；Two, dissolution of raw material will be weighed and obtains mixed liquor；Three, mixed liquor hydro-thermal reaction；Four, solid product is washed；Five, MoS is prepared2Suspension；Six, reaction solution is prepared；Seven, reaction solution hydrothermal synthesis reaction；Eight, solid product is successively subjected to washing drying.The composite air-sensitive sensing material is preparing the application in gas sensor as sensitive material；The composite air-sensitive sensing material has high sensitivity, selectivity outstanding, low cost.The present invention is suitable for preparing the application gas sensing materials and gas sensor.
Description
Technical field
The present invention relates to a kind of gas sensing materials and preparation method and application.
Background technique
With the development of science and technology with progress, the importance of sustainable development is more prominent, in the daily life of people
In work, the monitoring of toxic and harmful gas in environment is concerned.It common are malicious pernicious gas such as NO in airx、H2S、SO2、
NH3, CO etc., wherein NOxIt is one of the main gaseous pollutant in atmosphere.NOxIt is the source of environmental pollution, NOxIt can result in acid
Rain and photochemical fog cause serious disease, especially NO to the mankindxIt is easy in conjunction with the hemoglobin in human blood,
Lung is stimulated, many serious diseases are caused.A large amount of NO is exploredxGas sensor, such as SnO2, ZnO, TiO2, In2O3With
Conducting polymer.To a certain extent, these gas sensors can detect NO wellx, but they need higher work
Make temperature, sensitivity is low, poor selectivity.Therefore, there is an urgent need to develop one kind to have high sensitivity, good selectivity, quickly sound
It should be with recovery time and the NO that can be used at room temperaturexGas sensor.
Molybdenum disulfide is led due to its unique characteristic electron, the reasons such as two-dimensional layered structure and bigger specific surface area
It causes its surface to be easily absorbing gas molecule, is good gas sensing materials.Traditional metal oxide sensor is to work
At environmental requirement oddr quarter, because they are very sensitive to oxidisability and reducibility gas, and operating temperature is higher, for existing
Reported MoS2There is also many problems for gas sensor, such as: document report MoS2/ graphene gaseous mixture gel detection
NO2, the sensor is to NO2The testing result of gas is shown in more sensitive, therefore MoS when operating temperature is 200 DEG C2/ graphene
Gaseous mixture gelled sensor operating temperature is higher, can not detect at room temperature, and sensitivity is almost nil, is unfavorable for actually answering
With.Currently, the research of molybdenum-disulfide radical semiconductor gas sensor has been achieved for certain achievement, but asked there are still some
The problems such as topic, such as sensitivity is low at room temperature, response time and recovery time are slow, poor selectivity.As molybdenum sulfide and noble metal are multiple
Although the sensor for closing preparation improves sensitivity, but considerably increase cost.The sensing of single molybdenum disulfide preparation
Device is 1.83 to the sensitivity of the NOx of 100ppm, response time 7s, recovery time 6s；And do not have to nitrogen oxides and ammonia
There is good selectivity.
Summary of the invention
The present invention is in order to solve existing detection NOxSensitive material that there are operating temperature demands is high, sensitivity is low, selection
Property poor, recovery time long problem, propose a kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material and preparation method and
Using；
Molybdenum disulfide of the present invention/indium hydroxide composite air-sensitive sensing material is by MoS2It is made with indium salts；
The MoS2Molar ratio with indium salts is (1~4): (0.5~3)；The molybdenum disulfide/indium hydroxide composite air-sensitive
The partial size of indium hydroxide is 5~10nm in sensing material；
The molybdenum disulfide/indium hydroxide composite air-sensitive sensing material pattern is three-dimensional petal-shaped；
Above-mentioned molybdenum disulfide/indium hydroxide composite air-sensitive sensing material preparation method sequentially includes the following steps:
One, it weighs containing molybdenum material and sulphurous materials as raw material；The molybdenum material that contains is Na2MoO4·2H2O or (NH4)2MoO4·2H2O；The sulphurous materials are CH4N2S；
The mass ratio containing molybdenum material and sulphurous materials is (0.5~1.45): (0.3~1.90)；
Two, by the weighed dissolution of raw material deionized water of step 1, it is then ultrasonically treated 0.5~1h, finally stirring 0.5~
3h obtains mixed liquor；
The quality of the weighed raw material of step 1 and the volume ratio of deionized water are (0.85~3.35) g:(50~70)
ml；
Three, the mixed liquor for obtaining step 2 is placed in water heating kettle, at 150~200 DEG C carry out hydro-thermal reaction 10~
Solid product is obtained by filtration in 30h；
Four, the solid product successively obtained with ionized water and ethanol washing step 3, consolidating after then vacuum drying is washed
Body product is to obtain the MoS that length is 100~200nm2Nanometer sheet；
The vacuum drying temperature is 50~70 DEG C, and the vacuum drying time is 5~15h；
Five, the MoS that step 4 obtains is weighed2Nanometer sheet is placed in 0.5~1h of ultrasonic disperse in deionized water and obtains MoS2
Suspension；
The MoS that the weighed step 4 obtains2The quality of nanometer and the volume ratio of deionized water are (0.01~0.5) g:
(50~100) mL；
Six, the MoS obtained to step 52Indium salts and aqueous slkali are sequentially added in suspension, and stir 10~60min, are obtained
To reaction solution；
The mass ratio of the indium salts and aqueous slkali is (0.01~1.90): (0.05~1)；
The indium salts are InCl3Or In (NO3)3；
The aqueous slkali is NaOH solution or ammonium hydroxide；The concentration of the NaOH solution is 0.001~0.05mol/L；It is described
The concentration of ammonium hydroxide is 0.001~0.05mol/L；
Seven, it places reaction liquid into reaction kettle, hydrothermal synthesis reaction 10h~48h is carried out at 120~250 DEG C, then mistake
Filter obtains solid product；
Eight, the solid product for obtaining step 7 successively carries out carrying out washing treatment and drying process, obtains molybdenum disulfide/hydrogen-oxygen
Change indium composite air-sensitive sensing material；
Cleaning solution used in the carrying out washing treatment is the ethanol solution of mass fraction 10~50%；
The technique of the drying are as follows: dry 6 at 50~70 DEG C~for 24 hours；
Above-mentioned molybdenum disulfide/indium hydroxide composite air-sensitive sensing material is preparing answering in gas sensor as sensitive material
With；
The method for preparing gas sensor are as follows: by molybdenum disulfide/indium hydroxide composite air-sensitive sensing material ultrasonic disperse
In the ethanol solution of 5~7 times of volumes, finely dispersed suspension is obtained, then suspension is spin-coated in Au interdigital electrode,
It is dried at room temperature to get gas sensor is arrived；
Prepared using molybdenum disulfide/indium hydroxide composite air-sensitive sensing material as sensitive material gas sensor in temperature be 20
~35 DEG C and humidity be 20~40% under conditions of to NOxIt is detected.
The present invention have it is following the utility model has the advantages that
1, MoS prepared by the present invention2/In(OH)3Composite material, MoS2For lamellar structure, In (OH)3For thin crystal particles
Polycrystalline material, MoS2Itself is in lamellar structure, can not only be effectively prevented aggregation, also adds more contact sites,
And In (OH)3Nano particle is scattered in nanometer sheet, increases the catalytic site of gas, facilitates the adsorption desorption of gas, is improved
The sensitivity of composite material；
2, using MoS prepared by the present invention2/In(OH)3The gas sensor that composite material is prepared as sensitive material is to air
Middle NOxIt carries out not needing to heat in detection process, can be 25 DEG C in room temperature, carry out under conditions of humidity is 25%, it can be with
The NO of detectionxThe minimum 0.1ppm of molar concentration, responding when detection and restoring the response time is only 0.7s and 0.8s.
3, at room temperature with NH3It is compared with CO, unified implantation concentration is 100ppm, MoS prepared by the present invention2/In(OH)3
Composite material reaches 14~16 to the sensitivity of NOx as gas sensor prepared by sensitive material, and for NH3It is sensitive with CO
Degree is less than 2, therefore MoS prepared by the present invention2/In(OH)3Composite material has NOx as gas sensor prepared by sensitive material
There is selectivity very outstanding.
4, MoS prepared by the present invention2/In(OH)3The gas sensor that composite material is prepared as sensitive material is in NOx concentration
For within the scope of 0.1~100ppm, the corresponding time is 0.2~0.8s, recovery time is 0.8~2.8s；
5, MoS prepared by the present invention2/In(OH)3The gas sensor and molybdenum disulfide that composite material is prepared as sensitive material
Cost can be reduced compared with the sensor of the compound preparation of noble metal；
Detailed description of the invention:
Fig. 1 is gas sensor detection NO prepared by testing example 1xSensitivity curve figure；Wherein curve 1~7 is successively
Corresponding is the Nox that concentration is 100ppm, 50ppm, 30ppm, 10ppm, 5ppm, 3ppm and 1ppm；
Fig. 2 is molybdenum disulfide/indium hydroxide composite air-sensitive sensing material X-ray diffractogram that embodiment 1 obtains；
Fig. 3 is molybdenum disulfide/indium hydroxide composite air-sensitive sensing material transmission electron microscope picture that embodiment 1 obtains；
Fig. 4 is that embodiment 1 obtains molybdenum disulfide/indium hydroxide composite air-sensitive sensing material specific surface area test chart；Figure
Middle curve 1 is desorption curve, and curve 2 is desorption curve；
Fig. 5 is the gas-selectively test chart carried out at room temperature to gas sensor prepared by embodiment 1, wherein testing
Gas includes: NH3, NOx and CO.
Specific embodiment:
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any reasonable combination.
Specific embodiment 1: a kind of molybdenum disulfide of present embodiment/indium hydroxide composite air-sensitive sensing material, this is compound
Gas sensing materials are by MoS2It is made with indium salts；The MoS2Molar ratio with indium salts is (1~4): (0.5~3).
Present embodiment have it is following the utility model has the advantages that
1, the MoS of present embodiment preparation2/In(OH)3Composite material, MoS2For lamellar structure, In (OH)3For Bao Jingti
The polycrystalline material of particle, MoS2Itself is in lamellar structure, can not only be effectively prevented aggregation, also adds more contact positions
Point, and In (OH)3Nano particle is scattered in nanometer sheet, increases the catalytic site of gas, is facilitated the adsorption desorption of gas, is mentioned
The high sensitivity of composite material；
2, the MoS prepared using present embodiment2/In(OH)3The gas sensor pair that composite material is prepared as sensitive material
NO in airxIt carries out not needing to heat in detection process, can be 25 DEG C in room temperature, carry out under conditions of humidity is 25%,
The NO that can be detectedxThe minimum 0.1ppm of molar concentration, responding when detection and restoring the response time is only 0.7s and 0.8s.
3, at room temperature with NH3It is compared with CO, unified implantation concentration is 100ppm, the MoS of present embodiment preparation2/In
(OH)3Composite material reaches 14~16 to the sensitivity of NOx as gas sensor prepared by sensitive material, and for NH3With CO's
Sensitivity is less than 2, therefore the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material
There is selectivity very outstanding to NOx.
4, the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material is in NOx
Concentration is within the scope of 0.1~100ppm, and the corresponding time is 0.2~0.8s, and recovery time is 0.8~2.8s；
5, the MoS of present embodiment preparation2/In(OH)3The gas sensor and two sulphur that composite material is prepared as sensitive material
Cost can be reduced compared with the sensor of the compound preparation of noble metal by changing molybdenum；
Specific embodiment 2: the present embodiment is different from the first embodiment in that: the molybdenum disulfide/hydroxide
The partial size of indium hydroxide is 5~10nm in indium composite air-sensitive sensing material.Other steps and parameter and one phase of specific embodiment
Together.
Specific embodiment 3: a kind of preparation of molybdenum disulfide of present embodiment/indium hydroxide composite air-sensitive sensing material
Method, the preparation method sequentially include the following steps:
One, it weighs containing molybdenum material and sulphurous materials as raw material；The molybdenum material that contains is Na2MoO4·2H2O or (NH4)2MoO4·2H2O；The sulphurous materials are CH4N2S；
The mass ratio containing molybdenum material and sulphurous materials is (0.5~1.45): (0.3~1.90)；
Two, by the weighed dissolution of raw material deionized water of step 1, it is then ultrasonically treated 0.5~1h, finally stirring 0.5~
3h obtains mixed liquor；
The quality of the weighed raw material of step 1 and the volume ratio of deionized water are (0.85~3.35) g:(50~70)
ml；
Three, the mixed liquor for obtaining step 2 is placed in water heating kettle, at 150~200 DEG C carry out hydro-thermal reaction 10~
Solid product is obtained by filtration in 30h；
Four, the solid product successively obtained with ionized water and ethanol washing step 3, consolidating after then vacuum drying is washed
Body product is to obtain the MoS that length is 100~200nm2Nanometer sheet；
The vacuum drying temperature is 50~70 DEG C, and the vacuum drying time is 5~15h；
Five, the MoS that step 4 obtains is weighed2Nanometer sheet is placed in 0.5~1h of ultrasonic disperse in deionized water and obtains MoS2
Suspension；
The MoS that the weighed step 4 obtains2The quality of nanometer and the volume ratio of deionized water are (0.01~0.5) g:
(50~100) mL；
Six, the MoS obtained to step 52Indium salts and aqueous slkali are sequentially added in suspension, and stir 10~60min, are obtained
To reaction solution；
The mass ratio of the indium salts and aqueous slkali is (0.01~1.90): (0.05~1)；
Seven, it places reaction liquid into reaction kettle, hydrothermal synthesis reaction 10h~48h is carried out at 120~250 DEG C, then mistake
Filter obtains solid product；
Eight, the solid product for obtaining step 7 successively carries out carrying out washing treatment and drying process, obtains molybdenum disulfide/hydrogen-oxygen
Change indium composite air-sensitive sensing material.
Present embodiment have it is following the utility model has the advantages that
1, the MoS of present embodiment preparation2/In(OH)3Composite material, MoS2For lamellar structure, In (OH)3For Bao Jingti
The polycrystalline material of particle, MoS2Itself is in lamellar structure, can not only be effectively prevented aggregation, also adds more contact positions
Point, and In (OH)3Nano particle is scattered in nanometer sheet, increases the catalytic site of gas, is facilitated the adsorption desorption of gas, is mentioned
The high sensitivity of composite material；
2, the MoS prepared using present embodiment2/In(OH)3The gas sensor pair that composite material is prepared as sensitive material
NO in airxIt carries out not needing to heat in detection process, can be 25 DEG C in room temperature, carry out under conditions of humidity is 25%,
The NO that can be detectedxThe minimum 0.1ppm of molar concentration, responding when detection and restoring the response time is only 0.7s and 0.8s.
3, at room temperature with NH3It is compared with CO, unified implantation concentration is 100ppm, the MoS of present embodiment preparation2/In
(OH)3Composite material reaches 14~16 to the sensitivity of NOx as gas sensor prepared by sensitive material, and for NH3With CO's
Sensitivity is less than 2, therefore the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material
There is selectivity very outstanding to NOx.
4, the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material is in NOx
Concentration is within the scope of 0.1~100ppm, and the corresponding time is 0.2~0.8s, and recovery time is 0.8~2.8s；
5, the MoS of present embodiment preparation2/In(OH)3The gas sensor and two sulphur that composite material is prepared as sensitive material
Cost can be reduced compared with the sensor of the compound preparation of noble metal by changing molybdenum；
Specific embodiment 4: present embodiment is unlike specific embodiment three: carrying out washing treatment described in step 8
Cleaning solution used is the ethanol solution of mass fraction 10~50%.Other steps and parameter are the same as the specific implementation mode 3.
Specific embodiment 5: present embodiment is unlike specific embodiment three or four: dry described in step 8
Technique are as follows: dry 6 at 50~70 DEG C~for 24 hours.Other steps and parameter are identical as specific embodiment three or four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment three to five: described in step 6
Indium salts are InCl3Or In (NO3)3.Other steps and parameter are identical as one of specific embodiment three to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment three to six: described in step 6
Aqueous slkali is NaOH solution or ammonium hydroxide；The concentration of the NaOH solution is 0.001~0.05mol/L；The concentration of the ammonium hydroxide is
0.001~0.05mol/L.Other steps and parameter are identical as one of specific embodiment three to six.
Specific embodiment 8: molybdenum disulfide described in present embodiment/indium hydroxide composite air-sensitive sensing material conduct
Sensitive material is preparing the application in gas sensor.
A kind of application of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material, by the compound gas of molybdenum disulfide/indium hydroxide
Sensitive sensing material prepares gas sensor as sensitive material, and it is for 20~35 DEG C and wet that the gas sensor of preparation is then placed in temperature
Degree under conditions of 20~40% to NOxIt is detected.
Present embodiment have it is following the utility model has the advantages that
1, the MoS prepared using present embodiment2/In(OH)3The gas sensor pair that composite material is prepared as sensitive material
NO in airxIt carries out not needing to heat in detection process, can be 25 DEG C in room temperature, carry out under conditions of humidity is 25%,
The NO that can be detectedxThe minimum 0.1ppm of molar concentration, responding when detection and restoring the response time is only 0.7s and 0.8s.
2, at room temperature with NH3It is compared with CO, unified implantation concentration is 100ppm, the MoS of present embodiment preparation2/In
(OH)3Composite material reaches 14~16 to the sensitivity of NOx as gas sensor prepared by sensitive material, and for NH3With CO's
Sensitivity is less than 2, therefore the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material
There is selectivity very outstanding to NOx.
3, the MoS of present embodiment preparation2/In(OH)3The gas sensor that composite material is prepared as sensitive material is in NOx
Concentration is within the scope of 0.1~100ppm, and the corresponding time is 0.2~0.8s, and recovery time is 0.8~2.8s；
5, the MoS of present embodiment preparation2/In(OH)3The gas sensor and two sulphur that composite material is prepared as sensitive material
Cost can be reduced compared with the sensor of the compound preparation of noble metal by changing molybdenum；
Specific embodiment 9: present embodiment is unlike specific embodiment eight: the gas sensor for preparing
Method are as follows: by molybdenum disulfide/indium hydroxide composite air-sensitive sensing material ultrasonic disperse in the ethanol solution of 5~7 times of volumes, obtain
To finely dispersed suspension, then suspension is spin-coated in Au interdigital electrode, is dried at room temperature to get gas sensitive element is arrived
Part.Other steps and parameter are identical as specific embodiment eight.
Specific embodiment 10: present embodiment is unlike specific embodiment eight or nine: with molybdenum disulfide/hydrogen-oxygen
Change indium composite air-sensitive sensing material as sensitive material prepare gas sensor in temperature be 20~35 DEG C with humidity be 20~40%
Under conditions of to NOxIt is detected.Other steps and parameter are identical as specific embodiment eight or nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment 1:
A kind of molybdenum disulfide of the present embodiment/indium hydroxide composite air-sensitive sensing material preparation method according to the following steps into
Row:
One, 1.45g is weighed containing molybdenum material and 1.90g sulphurous materials as raw material；The molybdenum material that contains is Na2MoO4·
2H2O；The sulphurous materials are CH4N2S；
Two, by the weighed dissolution of raw material 70ml deionized water of step 1, it is then ultrasonically treated 1h, 3h is finally stirred and obtains
Mixed liquor；
Three, the mixed liquor for obtaining step 2 is placed in water heating kettle, and hydro-thermal reaction 30h is carried out at 200 DEG C, is obtained by filtration
Solid product；
Four, the solid product successively obtained with ionized water and ethanol washing step 3, is then dried in vacuo at 70 DEG C and washes
Solid product 15h after washing is to get the MoS for being 200nm to length2Nanometer sheet；
Five, the MoS that 0.5g step 4 obtains is weighed2Nanometer sheet is placed in ultrasonic disperse 1h in 100mL deionized water and obtains
MoS2Suspension；
Six, the MoS obtained to step 521.90g indium salts and 1g aqueous slkali are sequentially added in suspension, and stir 60min,
Obtain reaction solution；
The indium salts are InCl3；The aqueous slkali is NaOH solution；The concentration of the NaOH solution be 0.001~
0.05mol/L；
Seven, it places reaction liquid into reaction kettle, hydrothermal synthesis reaction 48h is carried out at 250 DEG C, that then filters arrives solid
Product；
Eight, the solid product for obtaining step 7 successively carries out carrying out washing treatment and drying process, obtains molybdenum disulfide/hydrogen-oxygen
Change indium composite air-sensitive sensing material；Cleaning solution used in the carrying out washing treatment is the ethanol solution of mass fraction 50%；It is described dry
Dry technique are as follows: dried for 24 hours at 70 DEG C；
The application of above-mentioned molybdenum disulfide/indium hydroxide composite air-sensitive sensing material sequentially includes the following steps:
Gas sensor is prepared using molybdenum disulfide/indium hydroxide composite air-sensitive sensing material as sensitive material, it then will system
Standby gas sensor be placed in temperature be 35 DEG C and humidity be 40% under conditions of to NOxIt is detected；
The method for preparing gas sensor are as follows: by molybdenum disulfide/indium hydroxide composite air-sensitive sensing material ultrasonic disperse
In the ethanol solution of 5~7 times of volumes, finely dispersed suspension is obtained, then suspension is spin-coated in Au interdigital electrode,
It is dried at room temperature to get gas sensor is arrived.
Fig. 1 is gas sensor detection NO prepared by testing example 1xSensitivity curve figure；Wherein curve 1~7 is successively
Corresponding is the Nox that concentration is 100ppm, 50ppm, 30ppm, 10ppm, 5ppm, 3ppm and 1ppm；From fig. 1, it can be seen that can from figure
To find out, the high sensitivity for the gas sensor that when the concentration of Nox is 100ppm prepared by embodiment 1 is dense as Nox up to 15.39
The sensitivity for the gas sensor that when degree is 0.1ppm prepared by embodiment 1 is greater than 1.38, and the gas sensor after injecting NOx gas
Resistance start to change to the time used in complete stability less than 1 second, illustrate embodiment 1 prepare gas sensor response speed
Fastly, reversibility of adsorption is good；
Fig. 2 is molybdenum disulfide/indium hydroxide composite air-sensitive sensing material X-ray diffractogram that embodiment 1 obtains；From figure
In 2 as can be seen that figure in 2 θ angle value be 14.3 °, 30.3 °, 33.3 °, 39.4 ° of MoSs corresponding with 58.7 °2(002),(004),
(101), (102), (103), (110) crystal face.(200), (220), (310), (222) and (420) corresponding cubic system In
(OH)3；
Fig. 3 is molybdenum disulfide/indium hydroxide composite air-sensitive sensing material transmission electron microscope picture that embodiment 1 obtains；From Fig. 2
As can be seen that molybdenum disulfide/indium hydroxide composite air-sensitive sensing material is by sheet MoS2 and granular In (OH)3Composition
, In (OH)3Nano particle is scattered in MoS2 nanometer sheet, increases the catalytic site of MoS2, improves molybdenum disulfide/hydrogen-oxygen
Change the sensitivity of indium composite air-sensitive sensing material；And from figure it can be seen that the length of molybdenum disulfide nano sheet be 100~
200nm, the partial size of indium hydroxide nano particle are 5-10nm；
Fig. 4 is that embodiment 1 obtains molybdenum disulfide/indium hydroxide composite air-sensitive sensing material specific surface area test chart；Figure
Middle curve 1 is desorption curve, and curve 2 is desorption curve, and molybdenum disulfide/indium hydroxide composite material has it is known from figures that
Biggish specific surface area, specific surface area 54.684m2/ g, big specific surface area facilitate the quick adsorption desorption of gas, Jin Erneng
Enough improve its air-sensitive performance；
Fig. 5 is the gas-selectively test chart carried out at room temperature to gas sensor prepared by embodiment 1, wherein testing
Gas includes NH3, NOx and CO, unified implantation concentration is 100ppm.From Fig. 5 result it is found that gas sensor prepared by embodiment 1
There is selectivity very outstanding to NOx at room temperature.
Table 1 is sensitivity and response recovery time of the gas sensor of the preparation of testing example 1 under different NOx concentrations,
As it can be seen from table 1 high sensitivity possesses quickly response and restores up to 15.39 when nitrous oxides concentration is 100ppm
Time is 0.3s and 2.8s；I.e. the gas sensor possesses response and recovery characteristics well to nitrogen oxides, and sensitivity is higher,
Medium sensitivity S=Ra/Rg, middle Ra are the initial resistance of gas sensor, and Rg is the resistance of gas sensor under NOx atmosphere；
Table 1
| NOx concentration (ppm) | 100 | 50 | 30 | 10 | 5 | 3 | 1 | 0.5 | 0.2 | 0.1 |
| Sensitivity (Ra/Rg) | 15.39 | 8.82 | 8.19 | 4.99 | 3.74 | 3.37 | 2.86 | 2.49 | 1.5 | 1.38 |
| Response time (s) | 0.3 | 0.4 | 0.2 | 0.13 | 0.6 | 0.6 | 0.7 | 0.8 | 0.4 | 0.7 |
| Restore response time (s) | 2.8 | 1.8 | 2.8 | 2.2 | 1.8 | 1.6 | 1 | 1 | 1.2 | 0.8 |
Claims (5)
1. a kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material preparation method, the composite air-sensitive sensing material is by MoS2
It is made with indium salts；The MoS2Molar ratio with indium salts is (1~4): (0.5~3), the molybdenum disulfide/indium hydroxide are compound
The partial size of indium hydroxide is 5~10nm in gas sensing materials, it is characterised in that: the preparation method sequentially includes the following steps:
One, it weighs containing molybdenum material and sulphurous materials as raw material；The molybdenum material that contains is Na2MoO4·2H2O or (NH4)2MoO4·
2H2O；The sulphurous materials are CH4N2S；
The mass ratio containing molybdenum material and sulphurous materials is (0.5~1.45): (0.3~1.90)；
Two, by the weighed dissolution of raw material deionized water of step 1, it is then ultrasonically treated 0.5~1h, 0.5~3h is finally stirred and obtains
To mixed liquor；
The quality of the weighed raw material of step 1 and the volume ratio of deionized water are (0.85~3.35) g:(50~70) ml；
Three, the mixed liquor for obtaining step 2 is placed in water heating kettle, and 10~30h of hydro-thermal reaction, mistake are carried out at 150~200 DEG C
Filter obtains solid product；
Four, the solid product successively obtained with ionized water and ethanol washing step 3, then the solid after vacuum drying washing produces
Object is to obtain the MoS that length is 100~200nm2Nanometer sheet；
The vacuum drying temperature is 50~70 DEG C, and the vacuum drying time is 5~15h；
Five, the MoS that step 4 obtains is weighed2Nanometer sheet is placed in 0.5~1h of ultrasonic disperse in deionized water and obtains MoS2It suspends
Liquid；
The MoS that the weighed step 4 obtains2Nanometer quality and deionized water volume ratio be (0.01~0.5) g:(50~
100)mL；
Six, the MoS obtained to step 52Indium salts and aqueous slkali are sequentially added in suspension, and stir 10~60min, are reacted
Liquid；
The mass ratio of the indium salts and aqueous slkali is (0.01~1.90): (0.05~1)；
Seven, it places reaction liquid into reaction kettle, hydrothermal synthesis reaction 10h~48h is carried out at 120~250 DEG C, is then filtered
To solid product；
Eight, the solid product for obtaining step 7 successively carries out carrying out washing treatment and drying process, obtains molybdenum disulfide/indium hydroxide
Composite air-sensitive sensing material.
2. molybdenum disulfide according to claim 1/indium hydroxide composite air-sensitive sensing material preparation method, feature exist
In: cleaning solution used in carrying out washing treatment described in step 8 is the ethanol solution of mass fraction 10~50%.
3. molybdenum disulfide according to claim 1/indium hydroxide composite air-sensitive sensing material preparation method, feature exist
In: dry technique described in step 8 are as follows: dry 6 at 50~70 DEG C~for 24 hours.
4. molybdenum disulfide according to claim 1/indium hydroxide composite air-sensitive sensing material preparation method, feature exist
In: indium salts described in step 6 are InCl3Or In (NO3)3。
5. molybdenum disulfide according to claim 1/indium hydroxide composite air-sensitive sensing material preparation method, feature exist
In: aqueous slkali described in step 6 is NaOH solution or ammonium hydroxide；The concentration of the NaOH solution is 0.001~0.05mol/L；It is described
The concentration of ammonium hydroxide is 0.001~0.05mol/L.
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| CN109781800B (en) * | 2019-01-25 | 2021-06-04 | 青岛大学 | Gas sensor based on metal molybdate nano composite material and preparation method thereof |
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| CN112345599B (en) * | 2020-10-28 | 2022-10-11 | 微纳感知(合肥)技术有限公司 | Preparation method of zinc oxide-based gas-sensitive material, prepared gas-sensitive material and application thereof |
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