CN104777197B - A kind of molybdenum oxide nanobelt/graphene composite material and its application in terms of hydrogen sensitive element is prepared - Google Patents
A kind of molybdenum oxide nanobelt/graphene composite material and its application in terms of hydrogen sensitive element is prepared Download PDFInfo
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Abstract
The present invention relates to the preparation method of 1-dimention nano metal molybdenum oxide nanobelt/Graphene composite semiconductor material, with graphene oxide and Na2MoO4·2H2O is raw material, and molybdenum oxide nanobelt/graphene composite material, the method process is simple have been prepared using a step hydrothermal method, controllability is high, and short preparation period, yield is high, it is with low cost, overcome conventional oxidation molybdenum nanobelt/graphene composite material and prepare poor repeatability, the shortcoming of unstable properties.In addition, be coated in the molybdenum oxide nanobelt/graphene composite material after ultrasonic disperse in interdigital electrode by a kind of simple method also by the present invention, the hydrogen sensitive element of excellent performance is prepared, the hydrogen sensitive element is at room temperature to low-concentration hydrogen for 1000ppm（0.1%, volume fraction）The response time of hydrogen is only 10.6s, and sensitivity is about 95%, shows highly sensitive, quick response and turnaround time short advantage.
Description
Technical field
Preparation and gas sensitive element device arts the invention belongs to nanometer, composite semiconductor material, specifically, this hair
It is bright to be related to a kind of 1-dimention nano metal molybdenum oxide nanobelt/Graphene composite semiconductor material and preparation method thereof and the material
Application in terms of hydrogen sensitive element is prepared.
Background technology
As the fast development of economic society, the consumption of fossil fuel are more and more faster, the energy crisis and ring thus brought
Border pollution is also increasingly severe., due to its wide material sources, product is pollution-free and the advantages of automatic regeneration for hydrogen, more next by people
More concerns and research.Current hydrogen has been widely used in industrial life as a kind of protective gas and reducibility gas
The numerous areas such as product, health care and national defense and military.But because hydrogen is a kind of colourless, tasteless, odorless micro-molecular gas,
Easily leaked in production, storage, transport and use, and be difficult to discover, when its aerial content reaches 4-75%
When, run into naked light and easily explode, serious threat is caused to life and property safety.Therefore, it is necessary to use hydrogen gas sensor
It is leaked and is monitored alarm, and its aerial content is detected.
At present commercially, most hydrogen gas sensor is film-type hydrogen gas sensor.This is to study relatively more early, and
A kind of commonplace sensor of research.But the response time of this sensor can not meet requirement, turnaround time is universal
It is more long, and operating temperature is higher, needs just show the good hydrogen sensitivity energy of comparing more than 200 DEG C mostly.This is not only
The power consumption of sensor can be increased, also huge potential safety hazard can be brought because of operating temperature high.One dimension semiconductor material due to
It has than larger specific surface area, and great potential is shown in terms of device is prepared.In numerous metal oxide semiconductors,
Molybdenum trioxide as a kind of functional form semi-conducting material, in mutagens color device, gas sensor, photocatalysis, Flied emission, lithium ion
A series of fields such as battery and solar cell have shown great application value.At present it has been reported that various synthesis one
The method for tieing up molybdenum trioxide nano material, including thermal oxide, hydrothermal method and Microwave Assisted Process etc., wherein hydrothermal method has
Good product quality, the advantages of yield is high, has larger Development volue in terms of industrialized production.To be prepared into using hydro-thermal method
To nano material dispersion after for preparing a kind of method that device is commonplace use in the development of hydrogen gas sensor, but
Be because nano material size is smaller, in the sensitive layer of air-sensitive component have substantial amounts of crystal boundary, due to grain boundaries have than
Larger potential barrier, can cause scattering to the transmission of electronics, therefore directly by the nano material after dispersion for preparing gas sensing
The response time of device is still more long, still with room for promotion.For example, 2014, Manal et al. is by two-dimentional MoO3Nanometer sheet group
Hydrogen gas sensor is dressed up, the sensor is 30s to the response time of 1% hydrogen at 50 DEG C.In addition, preparing one-dimensional oxidation at present
Molybdenum carries out the repeatability of complex method, poor reliability with Graphene, needs further to be improved.Therefore one kind is found conscientiously may be used
OK, it is and simple to operate, stable preparation process, while the side that the one-dimensional molybdenum oxide for being adapted to controllable growth is combined with grapheme material
Method is necessary.
The content of the invention
In view of the deficiencies in the prior art, first purpose of the invention is to provide a kind of molybdenum oxide nanobelt/Graphene
Composite and preparation method thereof, another object of the present invention is to provide one kind comprising above-mentioned molybdenum oxide nanobelt/Graphene
The hydrogen sensitive element and the preparation method of the sensing element of composite.
To realize first purpose of the invention, a kind of molybdenum oxide nanobelt/graphene composite material of the invention is described
Composite is the molybdenum oxide nanobelt in graphenic surface homoepitaxial, and the length of the nanobelt is 7-20 microns, wide
It is 200-300nm to spend.
Above-mentioned molybdenum oxide nanobelt/graphene composite material of the invention is adopted and prepared with the following method：
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
a1）The 0.5-6.0g graphite powders that to weigh respectively, 3.0-36.0g potassium permanganate are added in beaker, use glass
Rod is stirred, and after being well mixed, obtains solid mixed-powder；
a2）The 60-720ml mass fractions that will be measured respectively be 98% the concentrated sulfuric acid, 8-80ml mass fractions be 65%
SPA is added to step a1）In the beaker equipped with solid mixed-powder, after being uniformly mixed, mixing liquid is obtained；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and is incubated 12 hours
Afterwards, glutinous thick liquid mix products are obtained；
a4）The 1-20ml mass fractions that will be measured respectively are 30% hydrogen peroxide, 20-1000ml distilled water, and stirring is equal
After even, freezing forms ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, ice is treated
Block stirs product after being completely dissolved, and is then washed with the hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively
Wash, until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 2-40mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）Measure the graphene oxide dispersion prepared described in 0.5-1ml steps A, measure 26.5-36.5ml go from
Sub- water, dispersed with stirring is uniform, obtains diluting dispersion liquid；
b2）To step b1）The concentrated nitric acid that mass fraction is 65% is slowly added in the dilution dispersion liquid for obtaining, is continued
Stirring, is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 1-5 mol/L in mix acid liquor；
b3）To step b2）Sodium molybdate is added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, being slowly stirred makes molybdenum
Sour sodium fully dissolves, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.1-0.5 mol/L in mixed reaction solution；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, then naturally cool to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 5- in 60-80 DEG C of vacuum drying chamber
15h, can obtain molybdenum oxide nanobelt/graphene composite material powder.
Further, according to such scheme, step b4）The temperature of middle hydro-thermal reaction is 120-240 DEG C of temperature, hydro-thermal reaction
Time is 1-15 h.
In order to realize another object of the present invention, present invention also offers a kind of hydrogen sensitive element, the hydrogen gas sensitive element
Part is mainly made up of quartz substrate, Pt/Ti interdigital electrodes, the part of sensitive layer three, wherein, the sensitive layer is by above-mentioned system of the invention
The standby molybdenum oxide nanobelt/graphene composite material powder for obtaining is made.
In addition, present invention also offers the preparation method of above-mentioned hydrogen sensitive element, the preparation method includes following step
Suddenly：
Step 1：The preparation of electrode
11）Mask blank makes：Using L-edit Software for Design interdigital electrode predetermined patterns, wherein single interdigital electrode
Pattern dimension is 1cm × 1cm, and interdigital width of fringe is 10-50 μm, spacing is 25-200 μm, and interdigital striped quantity is 10-50
Individual, the interdigital electrode pattern equably repeats to be arranged in the square scope of length of side 70mm；
12）Substrate is cleaned：Be the twin polishing quartz plate priority acetone of 1.5cm × 1.5cm by size, absolute ethyl alcohol,
Deionized water is cleaned by ultrasonic, and is then dried, and obtains clean quartz substrate；
13）Spin coating photoresist：In step 12) one layer of photoresist of spin coating on the clean quartz substrate that obtains, then in 98-
1-3min is dried under 102 DEG C of temperature conditionss, then the spin coating photoresist substrate is placed on step 11）The mask blank of making
On, the interdigital electrode pattern and the substrate alignment；
14）Mask exposure：By step 13）The spin coating photoresist substrate for obtaining exposes in the enterprising line mask of litho machine,
Time for exposure is 2-6s, and the substrate is dried into 1-3min under 98-102 DEG C of temperature conditionss after the completion of mask exposure, then in room
The lower cooling 2-4min of temperature；Then maskless lithography 5-10s is carried out again, after the completion of double exposure, by the spin coating photoresist substrate
Develop 15 ~ 40s in developer solution, then is washed down with ultra-pure water, stand-by after drying；
15）Using standard direct current magnetron sputtering technique, successively in step under conditions of Ar atmosphere and 70W sputtering powers
14）It is described obtain clean after spin coating photoresist substrate surface sputtering Ti and Pt, formed Pt/Ti interdigital electrodes；
Step 2：Hydrogen sensitive element is constructed
21）2-10 μ l absolute ethyl alcohols are measured with liquid-transfering gun to be added in centrifuge tube, then weigh 10-100mg molybdenum oxides nanometer
Band/graphene composite material powder is added in the ethanol, ultrasonic disperse, until mixed liquor is uniformly dispersed；
22）1-3 μ l steps 21 are measured with liquid-transfering gun）Mixed liquor after the ultrasonic disperse is uniform is added drop-wise to step 15）Institute
The centre of the Pt/Ti interdigital electrodes stated, then enters the electrode under conditions of vacuum is 0.0001-0.01 Pa
Row annealing, annealing temperature is 100-300 DEG C, and annealing time is 1-3h, obtains the hydrogen sensitive element.
According to such scheme of the present invention, step 13）Described in photoresist be the classes such as AZ5214-E, A21500, A26112
Any one in type photoresist, is the product sold in the market.
According to such scheme of the present invention, step 14）Described in the development such as developer solution model AZ 400K, AZ 300
Any one in liquid, using 0.26N/2.38%TMAH (TMAH) standard recipe.
According to such scheme of the present invention, step 14）Described in ultra-pure water be construed as meeting China national use for laboratory
The pure water of water specification GB6682-92.
According to such scheme of the present invention, step 15）Described in the deposit thickness of Ti be 20-40nm, the deposit thickness of Pt is
40-120nm。
According to such scheme of the present invention, step 21）Described in ultrasonically treated time be 2-5min, supersonic frequency is 50-
100Hz。
Compared with prior art, the present invention has following substantive distinguishing features and significant progress：（1）The present invention is aoxidizing
Graphene and Na2MoO4·2H2O is raw material, and molybdenum oxide nanobelt/Graphene composite wood has been prepared using a step hydrothermal method
Material, the method process is simple, controllability is high, and short preparation period, yield is high, with low cost, overcome conventional oxidation molybdenum nanobelt/
Graphene composite material prepares poor repeatability, the shortcoming of unstable properties；（2）The present invention by molybdenum oxide nanobelt with have it is excellent
The Graphene of electron transport ability is combined, and can not only increase the reference area of sensitive layer in air-sensitive component, can also be directly
It is transmitted by Graphene, hence helps to shorten the response time and turnaround time of hydrogen gas sensor；（3）The present invention passes through
Be coated in molybdenum oxide nanobelt/graphene composite material after ultrasonic disperse in interdigital electrode by a kind of simple method, prepares
The hydrogen sensitive element of excellent performance is gone out, few in sensitive layer weight crystal boundary because molybdenum oxide exists in the form of nanobelt, potential barrier
It is small, scattering will not be caused to the transmission of electronics, therefore, the hydrogen sensitive element shows Gao Ling to low-concentration hydrogen at room temperature
Quick, quick response and turnaround time short advantage（For 1000ppm（0.1%, volume fraction）The response time of hydrogen is only
10.6s, sensitivity is about 95%）；（4）The size of the hydrogen sensitive element prepared using the inventive method is small, power consumption is few,
Production and testing cost are effectively reduced, the requirement in the market to low-concentration hydrogen detection has been fully met.
Brief description of the drawings
Fig. 1 is the schematic diagram and pictorial diagram of hydrogen sensitive element assembling in the present invention；
Fig. 2 is the XRD of the embodiment of the present invention 1 and comparative example products therefrom, and wherein a, c is respectively step A in embodiment 1
Molybdenum oxide nanobelt/graphene composite material that the graphene oxide that obtains, step B are obtained, b is obtain in comparative example pure
Molybdenum oxide nanobelt；
Fig. 3 is the SEM figures of the embodiment of the present invention 1 and the products therefrom of embodiment 4, and wherein a, b figure is respectively the step of embodiment 1
Molybdenum oxide nanobelt/graphene composite material that graphene oxide that A is obtained, step B are obtained；C figures are that the step B of embodiment 4 is obtained
Molybdenum oxide nanobelt/the graphene composite material for arriving.
Fig. 4 is the XPS figures of the C1s of the products therefrom of the embodiment of the present invention 1, and wherein a, b figure is respectively the oxidation that step A is obtained
Molybdenum oxide nanobelt/graphene composite material that Graphene, step B are obtained；
Fig. 5 is response curve of the hydrogen sensitive element to various concentrations hydrogen obtained in the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the accompanying drawings, technical scheme is described in detail by specific embodiment.
Unless stated otherwise, the photoresist described in following examples is the type lights such as AZ5214-E, A21500, A26112
Any one in photoresist, is the product sold in the market；Described developer solution model AZ 400K, AZ 300 etc.
Any one in developer solution, using 0.26N/2.38%TMAH (TMAH) standard recipe；The ultra-pure water should be managed
Solve to meet the pure water of China national use for laboratory water specification GB6682-92.
As shown in figure 1, Fig. 1 is the schematic diagram and pictorial diagram of hydrogen sensitive element assembling in the present invention.
Embodiment 1
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
a1）3.0g graphite powders, 18.0g potassium permanganate are weighed respectively to be added in the beaker of 1000ml, are stirred with glass bar
10min, after being well mixed, obtains solid mixed-powder；
a2）The concentrated sulfuric acid, the SPA that 40ml mass fractions are 65% that 360ml mass fractions are 98% is measured respectively to be added to
Step a1）In the beaker equipped with solid mixed-powder, magnetic agitation 30min after being well mixed, obtains mixing liquid；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and is incubated 12 hours
Afterwards, glutinous thick liquid mix products are obtained；
a4）Hydrogen peroxide that 10ml mass fractions are 30%, 500ml distilled water are mixed respectively, then magnetic agitation 30min,
After uniform mixing, freezing forms ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, ice is treated
Block stirs product after being completely dissolved, and is then washed with the hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively
Wash, until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 20mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）In 50ml reaction vessels, the graphene oxide dispersion prepared described in 1.0ml steps A is measured, measured
31.75ml deionized waters, dispersed with stirring is uniform, obtains diluting dispersion liquid；
b2）To step b1）The dense nitre that 6.25ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining
Acid, continues to stir, and is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 2.5mol/L in mix acid liquor；
b3）To step b2）2.4195g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.25 in mixed reaction solution
mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, the temperature of hydro-thermal reaction is 200 DEG C of temperature, and the hydro-thermal reaction time is 12 h, then naturally cools to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 10h in 70 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
As shown in Fig. 2 the molybdenum oxide that a, c figure graphene oxide that respectively step A is prepared, step B are obtained in Fig. 2
The XRD of nanobelt/graphene composite material, by XRD spectrum we have observed that, occur the characteristic peak of graphene oxide in a figures
（About 9.8 ° of 2 θ）, illustrate that its degree of oxidation is very high.In addition, with reference to the XRD results in comparative example（B figures in Fig. 2）Understand, b, c
The XRD spectrum that figure shows is basically identical, and does not detect Graphene in molybdenum oxide nanobelt/graphene composite material
The characteristic peak of oxide, illustrates that graphene oxide has been converted into Graphene；Simultaneously because molybdenum oxide nanobelt/Graphene is compound
The XRD spectrum of material does not detect the characteristic peak of Graphene yet（2 θ are between 20 ° -30 °）, this is mainly due to Graphene
Amount is seldom and its intensity is smaller, and the peak intensity for being oxidized molybdenum is covered.As can be seen here, the oxidation that the above method of the present invention is prepared
In molybdenum nanobelt/graphene composite material molybdenum oxide be pure phase molybdenum trioxide, and Graphene presence not to molybdenum trioxide
Structure produce influence.
As shown in figure 3, a, b are respectively the molybdenum oxide that the graphene oxide, step B that step A prepares obtain and receive in Fig. 3
The SEM figures of rice band/graphene composite material, graphene oxide is can be seen that in obvious accordion from figure a, and can from b
Go out, the surface homoepitaxial of Graphene molybdenum oxide nanobelt, and the length of nanobelt is 7-20 microns, and width is about 200-
300nm, its pattern is not influenceed by the graphene oxide for adding.
As shown in figure 4, a, b are respectively the molybdenum oxide nanometer that the graphene oxide, step B that step A obtains are obtained in Fig. 4
The XPS figures of the C1s of band/graphene composite material, are schemed, the intensity highest of C-O keys in its collection of illustrative plates from a, and content is about
60%；Schemed from b, intensity highest is C-C/C=C keys in collection of illustrative plates, and its content is about 70%, and the content of C-O keys is reduced to
24.9%, illustrate that, by after hydro-thermal process, graphene oxide is changed for Graphene, it is oxidation further to demonstrate products therefrom
Molybdenum nanobelt/graphene composite material.
The present embodiment also provides molybdenum oxide nanobelt/graphene composite material that a kind of use above method prepares and exists
Application in terms of air-sensitive component, the i.e. present invention provide a kind of hydrogen sensitive element, and the hydrogen sensitive element is main by quartzy base
Bottom, Pt/Ti interdigital electrodes, the part of sensitive layer three composition, wherein, the sensitive layer is by the above-mentioned oxygen for preparing in the present embodiment
Change molybdenum nanobelt/graphene composite material powder to be made.
The hydrogen sensitive element of the present embodiment, adopts and is prepared from the following method, comprises the following steps：
Step 1：The preparation of electrode
11）Mask blank makes：Using L-edit Software for Design interdigital electrode predetermined patterns, and with the clear microelectronics in Nanjing
The customized Cr layers of photo mask board of technology Co., Ltd, wherein single interdigital electrode pattern dimension is 1cm × 1cm, interdigital bar
Line width is 10 μm, spacing is 25 μm, and interdigital striped quantity is 50, and the interdigital electrode pattern equably repeats to be arranged in side
In the square scope of 70mm long；
12）Substrate is cleaned：Be the twin polishing quartz plate priority acetone of 1.5cm × 1.5cm by size, absolute ethyl alcohol,
Deionized water carries out ultrasonic cleaning 15min, then dries 30min in the air that temperature is 40 DEG C, obtains clean quartz substrate；
13）Spin coating photoresist：The KW-4A type sol evenning machines produced using Chinese Microelectronic Institute of the Chinese Academy of Sciences, in step 12)
One layer of volume of spin coating is the photoresist of 100 μ l on the clean quartz substrate for obtaining, and is then dried under 100 DEG C of temperature conditionss
2min, then the spin coating photoresist substrate is placed on step 11）On the mask blank of making, the interdigital electrode pattern and institute
State substrate alignment；
14）Mask exposure：By step 13）The spin coating photoresist substrate for obtaining is placed on ABM.lnc（China distinguishes public
Department）The depth of production/middle ultraviolet photolithographic machine carries out mask exposure, and the time for exposure is 3s, and the substrate exists after the completion of mask exposure
1.5min is dried under 100 DEG C of temperature conditionss, then cools down 3min at room temperature；Then maskless lithography 10s is carried out again, is double exposed
After the completion of, the spin coating photoresist substrate is developed 25s in developer solution, then washed down with ultra-pure water, it is stand-by after drying；
15）It is 4 × 10 in Ar atmosphere, 70W sputtering powers, background vacuum using standard direct current magnetron sputtering technique-4
Pa, sputtering pressure be 0.5Pa, target-substrate distance be 4cm under conditions of successively in step 14）It is described obtain clean after spin coating photoetching
Glue substrate surface sputters Ti and Pt, forms Pt/Ti interdigital electrodes, wherein the deposit thickness of the Ti is 30nm, the deposition of thick of Pt
It is 100nm to spend；
Step 2：Hydrogen sensitive element is constructed
21）It is the centrifuge tube of 2.5ml to prepare 1 volume, measures 5 μ l absolute ethyl alcohols using liquid-transfering gun and is added to centrifuge tube
In, then weigh the molybdenum oxide nanobelt/graphene composite material powder prepared in 20mg steps B and be added to the ethanol
In, ultrasonically treated 5min, supersonic frequency is 100Hz, until mixed liquor is uniformly dispersed；
22）2 μ l steps 21 are measured with liquid-transfering gun）Mixed liquor after the ultrasonic disperse is uniform is added drop-wise to step 15）It is described
Pt/Ti interdigital electrodes centre, then by the electrode vacuum be 8.0 × 10-5Annealed under conditions of Pa
Treatment, annealing temperature is 200 DEG C, and annealing time is 2h, and heating rate is 5 DEG C/min.Hydrogen is obtained when it is cooled to room temperature
Air-sensitive sensing unit.
By the above-mentioned air-sensitive component for preparing of the present embodiment be placed in test cavity in, set constant operating voltage as
1.0V, weigh its air-sensitive performance, test result by testing its resistance under test gas or air as shown in figure 5,
As shown in Figure 5, air-sensitive component is respectively provided with good response to 0.5-1000ppm hydrogen at room temperature, with density of hydrogen
Improve, the response time of air-sensitive component is gradually reduced.For 1000ppm（0.1%, volume fraction）The response time of hydrogen is only
It is 10.6s, sensitivity is about 95%, and turnaround time is about 30s, compared to the sensor based on 2-D molybdenum oxide nanometer sheets, the present invention
The response time of the air-sensitive component of preparation greatly improves, but realizes the quick response to hydrogen and reply at room temperature.
Embodiment 2
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
The graphene oxide that graphene oxide is prepared using embodiment 1；
Step B：Prepare molybdenum oxide nanobelt/graphene composite material
b1）In 50ml reaction vessels, the graphene oxide dispersion prepared described in 0.75ml steps A is measured, measured
33ml deionized waters are taken, dispersed with stirring is uniform, obtain diluting dispersion liquid；
b2）To step b1）The dense nitre that 6.25ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining
Acid, continues to stir, and is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 2.5mol/L in mix acid liquor；
b3）To step b2）2.4195g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.25 in mixed reaction solution
mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, the temperature of hydro-thermal reaction is 200 DEG C of temperature, and the hydro-thermal reaction time is 12 h, then naturally cools to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 10h in 70 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
The present embodiment also provides molybdenum oxide nanobelt/graphene composite material that a kind of use above method prepares and exists
Application in terms of air-sensitive component, the i.e. present invention provide a kind of hydrogen sensitive element, and the hydrogen sensitive element is main by quartzy base
Bottom, Pt/Ti interdigital electrodes, the part of sensitive layer three composition, wherein, the sensitive layer is by the above-mentioned oxygen for preparing in the present embodiment
Change molybdenum nanobelt/graphene composite material powder to be made.
The hydrogen sensitive element of the present embodiment, adopts and is prepared from the following method, comprises the following steps：
Step 1：The preparation of electrode
11）Mask blank makes：Using L-edit Software for Design interdigital electrode predetermined patterns, wherein single interdigital electrode
Pattern dimension is 1cm × 1cm, and interdigital width of fringe is 50 μm, spacing is 200 μm, and interdigital striped quantity is 10, described interdigital
Electrode pattern equably repeats to be arranged in the square scope of length of side 70mm；
12）Substrate is cleaned：Be the twin polishing quartz plate priority acetone of 1.5cm × 1.5cm by size, absolute ethyl alcohol,
Deionized water is cleaned by ultrasonic, and is then dried, and obtains clean quartz substrate；
13）Spin coating photoresist：In step 12) one layer of photoresist of spin coating on the clean quartz substrate that obtains, then at 98 DEG C
Temperature conditionss under dry 3min, then the spin coating photoresist substrate is placed on step 11）On the mask blank of making, the fork
Refer to electrode pattern and the substrate alignment；
14）Mask exposure：By step 13）The spin coating photoresist substrate for obtaining exposes in the enterprising line mask of litho machine,
Time for exposure is 2s, the substrate is dried into 3min under 98 DEG C of temperature conditionss after the completion of mask exposure, then cool down at room temperature
2min；Then maskless lithography 5s is carried out again, after the completion of double exposure, the spin coating photoresist substrate is developed in developer solution
15s, then washed down with ultra-pure water, it is stand-by after drying；
15）Using standard direct current magnetron sputtering technique, successively in step under conditions of Ar atmosphere and 70W sputtering powers
14）It is described obtain clean after spin coating photoresist substrate surface sputtering Ti and Pt, formed Pt/Ti interdigital electrodes, the Ti's
Deposit thickness is 20nm, and the deposit thickness of Pt is 40nm；
Step 2：Hydrogen sensitive element is constructed
21）2 μ l absolute ethyl alcohols are measured with liquid-transfering gun to be added in centrifuge tube, then weigh and be prepared into described in 10mg steps B
To molybdenum oxide nanobelt/graphene composite material powder be added in the ethanol, ultrasonic disperse, when described ultrasonically treated
Between be 2min, supersonic frequency is 100Hz, until mixed liquor is uniformly dispersed；
22）1 μ l steps 21 are measured with liquid-transfering gun）Mixed liquor after the ultrasonic disperse is uniform is added drop-wise to step 15）It is described
Pt/Ti interdigital electrodes centre, then by the electrode vacuum be 0.0001 Pa under conditions of carry out at annealing
Reason, annealing temperature is 100 DEG C, and annealing time is 3h, obtains the hydrogen sensitive element.
Embodiment 3
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
The graphene oxide that graphene oxide is prepared using embodiment 1.
Step B：Prepare molybdenum oxide nanobelt/graphene composite material
b1）In 50ml reaction vessels, the graphene oxide dispersion prepared described in 0.5ml steps A is measured, measured
33.25ml deionized waters are taken, dispersed with stirring is uniform, obtain diluting dispersion liquid；
b2）To step b1）The dense nitre that 6.25ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining
Acid, continues to stir, and is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 2.5mol/L in mix acid liquor；
b3）To step b2）2.4195g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.25 in mixed reaction solution
mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, the temperature of hydro-thermal reaction is 200 DEG C of temperature, and the hydro-thermal reaction time is 12 h, then naturally cools to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 10h in 70 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
The present embodiment also provides molybdenum oxide nanobelt/graphene composite material that a kind of use above method prepares and exists
Application in terms of air-sensitive component, the i.e. present invention provide a kind of hydrogen sensitive element, and the hydrogen sensitive element is main by quartzy base
Bottom, Pt/Ti interdigital electrodes, the part of sensitive layer three composition, wherein, the sensitive layer is by the above-mentioned oxygen for preparing in the present embodiment
Change molybdenum nanobelt/graphene composite material powder to be made.
The hydrogen sensitive element of the present embodiment, adopts and is prepared from the following method, comprises the following steps：
Step 1：The preparation of electrode
11）Mask blank makes：Using L-edit Software for Design interdigital electrode predetermined patterns, wherein single interdigital electrode
Pattern dimension is 1cm × 1cm, and interdigital width of fringe is 30 μm, spacing is 100 μm, and interdigital striped quantity is 40, described interdigital
Electrode pattern equably repeats to be arranged in the square scope of length of side 70mm；
12）Substrate is cleaned：Be the twin polishing quartz plate priority acetone of 1.5cm × 1.5cm by size, absolute ethyl alcohol,
Deionized water is cleaned by ultrasonic, and is then dried, and obtains clean quartz substrate；
13）Spin coating photoresist：In step 12) one layer of photoresist of spin coating on the clean quartz substrate that obtains, then at 102 DEG C
Temperature conditionss under dry 1min, then the spin coating photoresist substrate is placed on step 11）On the mask blank of making, the fork
Refer to electrode pattern and the substrate alignment；
14）Mask exposure：By step 13）The spin coating photoresist substrate for obtaining exposes in the enterprising line mask of litho machine,
Time for exposure is 6s, the substrate is dried into 1min under 102 DEG C of temperature conditionss after the completion of mask exposure, then cool down at room temperature
4min；Then maskless lithography 10s is carried out again, after the completion of double exposure, the spin coating photoresist substrate is shown in developer solution
Shadow 40s, then washed down with ultra-pure water, it is stand-by after drying；
15）Using standard direct current magnetron sputtering technique, successively in step under conditions of Ar atmosphere and 70W sputtering powers
14）It is described obtain clean after spin coating photoresist substrate surface sputtering Ti and Pt, formed Pt/Ti interdigital electrodes, the Ti's
Deposit thickness is 40nm, and the deposit thickness of Pt is 120nm；
Step 2：Hydrogen sensitive element is constructed
21）10 μ l absolute ethyl alcohols are measured with liquid-transfering gun to be added in centrifuge tube, then weigh and be prepared into described in 100mg steps B
To molybdenum oxide nanobelt/graphene composite material powder be added in the ethanol, ultrasonic disperse, when described ultrasonically treated
Between be 5min, supersonic frequency is 50Hz, until mixed liquor is uniformly dispersed；
22）3 μ l steps 21 are measured with liquid-transfering gun）Mixed liquor after the ultrasonic disperse is uniform is added drop-wise to step 15）It is described
Pt/Ti interdigital electrodes centre, then by the electrode vacuum be 0.01 Pa under conditions of carry out at annealing
Reason, annealing temperature is 300 DEG C, and annealing time is 1h, obtains the hydrogen sensitive element.
Embodiment 4
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
a1）The 0.5g graphite powders that to weigh respectively, 3.0g potassium permanganate are added in beaker, are stirred with glass bar, are mixed
After closing uniformly, solid mixed-powder is obtained；
a2）The 60ml mass fractions that will be measured respectively are 98% concentrated sulfuric acid, the SPA that 8ml mass fractions are 65% adds
Enter to step a1）In the beaker equipped with solid mixed-powder, after being uniformly mixed, mixing liquid is obtained；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and is incubated 12 hours
Afterwards, glutinous thick liquid mix products are obtained；
a4）The 1ml mass fractions that will be measured respectively are 30% hydrogen peroxide, 20ml distilled water, cold after stirring
Freeze, form ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, ice is treated
Block stirs product after being completely dissolved, and is then washed with the hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively
Wash, until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 2mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）The graphene oxide dispersion prepared described in 1ml steps A is measured, 36.5ml deionized waters are measured, stirred
It is uniformly dispersed, obtains diluting dispersion liquid；
b2）To step b1）The concentrated nitric acid that 2.5ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining,
Continue to stir, be well mixed, obtain mix acid liquor, the concentration of nitric acid is 1mol/L in mix acid liquor；
b3）To step b2）0.9678g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is in mixed reaction solution
0.1mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, the temperature of hydro-thermal reaction is 120 DEG C of temperature, and the hydro-thermal reaction time is 15 h, then naturally cools to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 15h in 60 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
Embodiment 5
A kind of preparation method of molybdenum oxide nanobelt/graphene composite material, comprises the following steps：
Step A：The preparation of graphene oxide
a1）The 6.0g graphite powders that to weigh respectively, 36.0g potassium permanganate are added in beaker, are stirred with glass bar, are mixed
After closing uniformly, solid mixed-powder is obtained；
a2）The 720ml mass fractions that will be measured respectively are 98% concentrated sulfuric acid, the SPA that 80ml mass fractions are 65%
It is added to step a1）In the beaker equipped with solid mixed-powder, after being uniformly mixed, mixing liquid is obtained；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and is incubated 12 hours
Afterwards, glutinous thick liquid mix products are obtained；
a4）The 20ml mass fractions that will be measured respectively are 30% hydrogen peroxide, 1000ml distilled water, after stirring,
Freezing, forms ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, ice is treated
Block stirs product after being completely dissolved, and is then washed with the hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively
Wash, until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 40mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）The graphene oxide dispersion prepared described in 1ml steps A is measured, 26.5ml deionized waters are measured, stirred
It is uniformly dispersed, obtains diluting dispersion liquid；
b2）To step b1）The dense nitre that 12.5ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining
Acid, continues to stir, and is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 5mol/L in mix acid liquor；
b3）To step b2）4.8390g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.5 in mixed reaction solution
mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, then naturally cool to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 5h in 80 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
Further, according to such scheme, step b4）The temperature of middle hydro-thermal reaction is 240 DEG C of temperature, the hydro-thermal reaction time
It is 1h.
Comparative example
The preparation of pure molybdenum oxide nanobelt：
b1）In 50ml reaction vessels, 31.75ml deionized waters are measured, dispersed with stirring is uniform, obtain diluting dispersion liquid；
b2）To step b1）The dense nitre that 6.25ml mass fractions are 65% is slowly added in the dilution dispersion liquid for obtaining
Acid, continues to stir, and is well mixed, and obtains mix acid liquor, and the concentration of nitric acid is 2.5mol/L in mix acid liquor；
b3）To step b2）2.4195g sodium molybdates are added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, slowly
Stirring makes sodium molybdate fully dissolve, and is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.25 in mixed reaction solution
mol/L；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal is carried out in insulating box anti-
Should, the temperature of hydro-thermal reaction is 200 DEG C of temperature, and the hydro-thermal reaction time is 12 h, then naturally cools to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 10h in 70 DEG C of vacuum drying chamber, can
Obtain molybdenum oxide nanobelt/graphene composite material powder.
As shown in Fig. 2 b is the XRD of the pure molybdenum oxide nanobelt that this comparative example is prepared in Fig. 2.
It should be noted that it will be understood by those within the art that, technical scheme can be carried out
Modification or equivalent, without deviating from the objective and scope of technical solution of the present invention, it all should cover will in right of the invention
Ask in the middle of scope.
Claims (9)
1. a kind of molybdenum oxide nanobelt/graphene composite material, it is characterised in that the composite is equal in graphenic surface
The even molybdenum oxide nanobelt for growing, the length of the nanobelt is 7-20 microns, and width is 200-300nm, is using following
Product obtained in method, comprises the following steps：
Step A：The preparation of graphene oxide
a1）The 0.5-6.0g graphite powders that to weigh respectively, 3.0-36.0g potassium permanganate are added in beaker, are stirred with glass bar
Mix, after being well mixed, obtain solid mixed-powder；
a2）The dense phosphorus that the concentrated sulfuric acid that the 60-720ml mass fractions that will be measured respectively are 98%, 8-80ml mass fractions are 65%
Acid is added to step a1）In the beaker equipped with solid mixed-powder, after being uniformly mixed, mixing liquid is obtained；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and after being incubated 12 hours, is obtained
To glutinous thick liquid mix products；
a4）The 1-20ml mass fractions that will be measured respectively are 30% hydrogen peroxide, 20-1000ml distilled water, after stirring,
Freezing, forms ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, treat that ice cube is complete
Product is stirred after CL, is then washed with hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively,
Until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 2-40mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）The graphene oxide dispersion prepared described in 0.5-1ml steps A is measured, 26.5-36.5ml deionizations are measured
Water, dispersed with stirring is uniform, obtains diluting dispersion liquid；
b2）To step b1）The concentrated nitric acid that mass fraction is 65% is slowly added in the dilution dispersion liquid for obtaining, continues to stir,
It is well mixed, mix acid liquor is obtained, the concentration of nitric acid is 1-5 mol/L in mix acid liquor；
b3）To step b2）Sodium molybdate is added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, being slowly stirred makes sodium molybdate
Fully dissolving, is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.1-0.5 mol/L in mixed reaction solution；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal reaction is carried out in insulating box, so
After naturally cool to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 5-15h in 60-80 DEG C of vacuum drying chamber,
Can obtain molybdenum oxide nanobelt/graphene composite material powder.
2. a kind of molybdenum oxide nanobelt/graphene composite material according to claim 1, it is characterised in that：The step
b4）The temperature of middle hydro-thermal reaction is 120-240 DEG C of temperature, and the hydro-thermal reaction time is 1-15 h.
3. a kind of molybdenum oxide nanobelt/graphene composite material according to claim 1, it is characterised in that：The step
a5）Obtained product graphene oxide is accordion.
4. a kind of preparation method of the molybdenum oxide nanobelt/graphene composite material described in claim 1, methods described is included such as
Lower step：
Step A：The preparation of graphene oxide
a1）The 0.5-6.0g graphite powders that to weigh respectively, 3.0-36.0g potassium permanganate are added in beaker, are stirred with glass bar
Mix, after being well mixed, obtain solid mixed-powder；
a2）The dense phosphorus that the concentrated sulfuric acid that the 60-720ml mass fractions that will be measured respectively are 98%, 8-80ml mass fractions are 65%
Acid is added to step a1）In the beaker equipped with solid mixed-powder, after being uniformly mixed, mixing liquid is obtained；
a3）By step a2）The beaker for filling mixing liquid is put into 50 DEG C of water-baths, continues to stir, and after being incubated 12 hours, is obtained
To glutinous thick liquid mix products；
a4）The 1-20ml mass fractions that will be measured respectively are 30% hydrogen peroxide, 20-1000ml distilled water, after stirring,
Freezing, forms ice cube；
a5）By step a3）The glutinous thick liquid mix products for obtaining are added to step a4）In the ice cube, treat that ice cube is complete
Product is stirred after CL, is then washed with hydrochloric acid, distilled water, ethanol alternating centrifugal that mass fraction is 5% respectively,
Until product is in neutrality, products therefrom is graphene oxide dispersion, and concentration is 2-40mg/ml；
Step B：The preparation of molybdenum oxide nanobelt/graphene composite material
b1）The graphene oxide dispersion prepared described in 0.5-10ml steps A is measured, 26.5-36.5ml deionizations are measured
Water, dispersed with stirring is uniform, obtains diluting dispersion liquid；
b2）To step b1）The concentrated nitric acid that mass fraction is 65% is slowly added in the dilution dispersion liquid for obtaining, continues to stir,
It is well mixed, mix acid liquor is obtained, the concentration of nitric acid is 1-5 mol/L in mix acid liquor；
b3）To step b2）Sodium molybdate is added in the mix acid liquor for obtaining（Na2MoO4·2H2O）, being slowly stirred makes sodium molybdate
Fully dissolving, is well mixed, and obtains mixed reaction solution, and the concentration of molybdenum element is 0.1-0.5 mol/L in mixed reaction solution；
b4）By step b3）The mixed reaction solution for obtaining is transferred in reactor, hydro-thermal reaction is carried out in insulating box, so
After naturally cool to room temperature；
b5）By step b4）The product for obtaining is separated by filtration, and is then placed in drying 5-15h in 60-80 DEG C of vacuum drying chamber,
Can obtain molybdenum oxide nanobelt/graphene composite material powder.
5. a kind of molybdenum oxide nanobelt/graphene composite material according to claim 4, it is characterised in that：The step
b4）The temperature of middle hydro-thermal reaction is 120-240 DEG C of temperature, and the hydro-thermal reaction time is 1-15 h.
6. a kind of hydrogen sensitive element, it is characterised in that：The hydrogen sensitive element it is main by quartz substrate, Pt/Ti interdigital electrodes,
The part of sensitive layer three constitutes, wherein, molybdenum oxide nanobelt/Graphene of the sensitive layer as described in claim any one of 1-3
Composite powder is made.
7. hydrogen sensitive element according to claim 6, it is characterised in that：The hydrogen sensitive element is made by the following method
It is standby to form, comprise the following steps：
Step 1：The preparation of electrode
11）Mask blank makes：Using L-edit Software for Design interdigital electrode predetermined patterns, wherein single interdigital electrode pattern
Size is 1cm × 1cm, and interdigital width of fringe is 10-50 μm, spacing is 25-200 μm, and interdigital striped quantity is 10-50, institute
Interdigital electrode pattern is stated equably to repeat to be arranged in the square scope of length of side 70mm；
12）Substrate is cleaned：Be the twin polishing quartz plate priority acetone of 1.5cm × 1.5cm by size, absolute ethyl alcohol, go from
Sub- water is cleaned by ultrasonic, and is then dried, and obtains clean quartz substrate；
13）Spin coating photoresist：In step 12) one layer of photoresist of spin coating on the clean quartz substrate that obtains, then at 98-102 DEG C
Temperature conditionss under dry 1-3min, then the spin coating photoresist substrate is placed on step 11）It is described on the mask blank of making
Interdigital electrode pattern and the substrate alignment；
14）Mask exposure：By step 13）The spin coating photoresist substrate for obtaining is in the enterprising line mask exposure of litho machine, exposure
Time is 2-6s, and the substrate is dried into 1-3min under 98-102 DEG C of temperature conditionss after the completion of mask exposure, then at room temperature
Cooling 2-4min；Then maskless lithography 5-10s is carried out again, after the completion of double exposure, by the spin coating photoresist substrate aobvious
Develop 15 ~ 40s in shadow liquid, then is washed down with ultra-pure water, stand-by after drying；
15）Using standard direct current magnetron sputtering technique, successively in step 14 under conditions of Ar atmosphere and 70W sputtering powers）Institute
State obtain clean after spin coating photoresist substrate surface sputtering Ti and Pt, formed Pt/Ti interdigital electrodes；
Step 2：Hydrogen sensitive element is constructed
21）2-10 μ l absolute ethyl alcohols are measured with liquid-transfering gun to be added in centrifuge tube, then to weigh 10-100mg claims 1-3 any
Molybdenum oxide nanobelt/graphene composite material powder described in is added in the ethanol, ultrasonic disperse, until mixed liquor point
Dissipate uniform；
22）1-3 μ l steps 21 are measured with liquid-transfering gun）Mixed liquor after the ultrasonic disperse is uniform is added drop-wise to step 15）Described
The centre of Pt/Ti interdigital electrodes, is then moved back the electrode under conditions of vacuum is 0.0001-0.01 Pa
Fire treatment, annealing temperature is 100-300 DEG C, and annealing time is 1-3h, obtains the hydrogen sensitive element.
8. hydrogen sensitive element according to claim 7, it is characterised in that：Step 15）Described in the deposit thickness of Ti be
The deposit thickness of 20-40nm, Pt is 40-120nm.
9. the hydrogen sensitive element according to claim 7 or 8, it is characterised in that：Step 21）Described in it is ultrasonically treated when
Between be 2-5min, supersonic frequency is 50-100Hz.
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| CN107367905B (en) * | 2017-07-14 | 2019-04-12 | 北京师范大学 | The method for preparing photoresist-grapheme material compound system of high-specific surface area |
| CN108007976A (en) * | 2017-11-08 | 2018-05-08 | 东北电力大学 | MoS2The preparation of/graphene composite material and structure elemental mercury from vapor sensor |
| CN108398155A (en) * | 2018-02-08 | 2018-08-14 | 深圳森阳环保材料科技有限公司 | A kind of highly sensitive environmental quality monitoring system |
| CN110441380B (en) * | 2019-08-07 | 2021-07-23 | 暨南大学 | Electrochemical sensor based on molecular imprinting electrode technology and preparation method and application thereof |
| CN111122661A (en) * | 2020-01-08 | 2020-05-08 | 湖北大学 | Based on MoO3Preparation method and application of room-temperature FET type hydrogen sensitive element with nano-belt modified graphene |
| CN111735856B (en) * | 2020-06-29 | 2024-01-26 | 黄冈师范学院 | Doped MoO 3 Nanobelt, preparation method and application thereof |
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