CN104792830B - The preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide - Google Patents
The preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide Download PDFInfo
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- CN104792830B CN104792830B CN201510249413.8A CN201510249413A CN104792830B CN 104792830 B CN104792830 B CN 104792830B CN 201510249413 A CN201510249413 A CN 201510249413A CN 104792830 B CN104792830 B CN 104792830B
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Abstract
The preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide, it is related to a kind of preparation method of gas sensitive material.The present invention is that only have the technical problem of sensitivity high to a few gases to solve intrinsic Graphene gas sensitive nanoparticle.Molybdenum bisuphide is wrapped in Graphene outer surface in material.Preparation method：First, the concentrated sulfuric acid is cooled down, adds natural flake graphite, potassium permanganate, stirring adds the mixed solution being made up of hydrogen peroxide and distilled water, is centrifuged and washs, precipitation is dissolved in deionized water, obtains solution；2nd, sodium molybdate, cysteine and cetyl benzenesulfonic acid sodium are dissolved in deionized water, add step one resulting solution, be put into reactor, eccentric cleaning, freeze-drying is obtained final product.Composite of the invention has selectivity and sensitiveness higher.The invention belongs to the preparation field of gas sensitive material.
Description
Technical field
The present invention relates to a kind of preparation method of gas sensitive material.
Background technology
With the continuous improvement that people are required quality of life, people for problem of environmental pollution growing interest, especially
The atmosphere pollution constituted a threat to human survival.Wherein, NO2Gas is extremely serious to environment and human health risk in air
One of pollutant, especially NO in recent years2The major sources of gas --- vehicle exhaust is surprising per annual growth rate so that right
NO2Monitoring become particularly important, therefore timely and accurately know in environment and about the NO of pollution sources2The concentration of gas, to ring
Border is monitored and environmental protection is significant.
Because although traditional semiconductor gas sensor is widely used, but because its operating temperature higher (is more than 300
DEG C), usually limit the use of this type sensor.Therefore, researcher proposes the microcosmic chi by reducing semi-conducting material
Degree, can reduce operating temperature, and the less energy of consumption and operation are safer, therefore may be widely used for making gas biography
Sensor.Research in recent years finds that some characteristics of Graphene cause that it turns into a kind of very promising gas sensitive.Due to stone
Black alkene be two-dimensional structure each carbon atom exposed to surface, while having electron mobility very high, its electronics at room temperature
Transmission can reach 0.3um, and its electron transfer rate has apparent change when its binding molecule, so Graphene
It can be a kind of sensor sensing material having good prospects to be proved to.But, it has now been found that intrinsic Graphene gas is passed
Dissolubility is poor in itself for sensor nano particle, only has sensitivity high to a few gases and often needs to be desorbed by heating, one
Determine to be limited in degree the extensive use of this kind of gas sensor.
The content of the invention
Only have high to a few gases the invention aims to solve intrinsic Graphene gas sensitive nanoparticle
A kind of technical problem of sensitivity, there is provided gas sensitive material being combined based on Graphene/molybdenum bisuphide and preparation method thereof.
In the gas sensitive material being combined based on Graphene/molybdenum bisuphide the mol ratio of molybdenum atom and carbon atom for 1 ﹕ 1~
5, molybdenum bisuphide is wrapped in Graphene outer surface, and the number of plies of molybdenum bisuphide is 5~20 layers, is 0.62~0.65nm per interlamellar spacing.
The preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide is followed the steps below：
First, 15~25ml concentrated sulfuric acids are cooled to -1~1 DEG C, add 0.5~1.5g natural flake graphites stirring 30~
50min, 5~8g KMnO are added under conditions of being less than 5 DEG C in temperature by several times in 25min4, 1~3h is stirred, obtain mixture；
2nd, the 30~60min of stirred in water bath by mixture at 40 DEG C, the temperature to water-bath is 45 DEG C, stops stirring, is obtained
Slurries；
3rd, slurries are gone into the stirring of 80 DEG C of thermostat water baths, treat slurries be warmed up in 80 DEG C, gradation 20min add 60~
It is 90 DEG C that 80ml distilled water is stirred to reacting liquid temperature, and reaction solution then is removed into water-bath stirring 15min, adds 40~70ml
Distilled water diluting, adds 10~15ml by the hydrogen peroxide that mass percent concentration is 30% and the mixing that 60ml distilled water is constituted
To there is golden yellow, it is 5~6 to be centrifuged and wash to washing lotion pH value to solution, and then the precipitation after centrifugation is dissolved in deionized water,
Obtain the solution that concentration is 1~3mg/ml；
4th, 0.5g sodium molybdates, 1g cysteines and 0.3g cetyl benzenesulfonic acid sodiums are dissolved in 60ml deionized waters, so
20mL step 3 resulting solutions being added afterwards, then mixed solution being put into 100ml reactors, 18~24h is kept at 240 DEG C, from
The heart is cleaned, freeze-drying, obtains final product the gas sensitive material being combined based on Graphene/molybdenum bisuphide.
Advantages of the present invention：
First, the gas sensitive based on Graphene/molybdenum bisuphide composite of the invention, relative to metal oxide air-sensitive
Material operating temperature is lower, saves more multiple-energy-source；
2nd, the gas sensitive based on Graphene/molybdenum bisuphide composite of the invention, preparation process is simple, easy to operate；
3rd, the gas sensitive based on Graphene/molybdenum bisuphide composite of the invention, by loading molybdenum disulfide nano
Particle, has selectivity and sensitiveness higher relative to pure Graphene；
4th, the preparation method of the gas sensitive based on Graphene/molybdenum bisuphide composite of the invention, prepares
Electronics conduction path is used as by Graphene in composite, the shortcoming of molybdenum bisuphide poorly conductive in itself is overcome.By two
Molybdenum sulfide drastically increases gas sensitization performance as gas sensor.
Brief description of the drawings
Fig. 1 is to test a gas sensitive material being combined based on Graphene/molybdenum bisuphide for preparing to be scanned electronic display
Micro mirror photo；
Fig. 2 is the air-sensitive performance curve for testing a gas sensitive material being combined based on Graphene/molybdenum bisuphide for preparing,
1 represents the air-sensitive performance curve of Graphene in figure, and 2 represent the air-sensitive performance curve of molybdenum bisuphide, and 3 represent based on Graphene/bis-
The air-sensitive performance curve of the compound gas sensitive material of molybdenum sulfide.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment
Any combination.
Specific embodiment one：Molybdenum is former during present embodiment is based on the gas sensitive material that Graphene/molybdenum bisuphide is combined
Son is 1 ﹕ 1~5 with the mol ratio of carbon atom, and molybdenum bisuphide is wrapped in Graphene outer surface, and the number of plies of molybdenum bisuphide is 5~20
Layer, is 0.62~0.65nm per interlamellar spacing.
Specific embodiment two：Present embodiment is described from unlike specific embodiment one to be based on Graphene/bis- sulphur
The mol ratio for changing molybdenum atom and carbon atom in the compound gas sensitive material of molybdenum is 1 ﹕ 3.Other are identical with specific embodiment one.
Specific embodiment three：It is described per interlamellar spacing unlike one of present embodiment and specific embodiment one or two
It is 0.64nm.Other are identical with one of specific embodiment one or two.
Specific embodiment four：The gas sensitization material being combined based on Graphene/molybdenum bisuphide described in specific embodiment one
The preparation method of material is followed the steps below：
First, 15~25ml concentrated sulfuric acids are cooled to -1~1 DEG C, add 0.5~1.5g natural flake graphites stirring 30~
50min, 5~8g KMnO are added under conditions of being less than 5 DEG C in temperature by several times in 25min4, 1~3h is stirred, obtain mixture；
2nd, the 30~60min of stirred in water bath by mixture at 40 DEG C, the temperature to water-bath is 45 DEG C, stops stirring, is obtained
Slurries；
3rd, slurries are gone into the stirring of 80 DEG C of thermostat water baths, treat slurries be warmed up in 80 DEG C, gradation 20min add 60~
It is 90 DEG C that 80ml distilled water is stirred to reacting liquid temperature, and reaction solution then is removed into water-bath stirring 15min, adds 40~70ml
Distilled water diluting, adds 10~15ml by the hydrogen peroxide that mass percent concentration is 30% and the mixing that 60ml distilled water is constituted
To there is golden yellow, it is 5~6 to be centrifuged and wash to washing lotion pH value to solution, and then the precipitation after centrifugation is dissolved in deionized water,
Obtain the solution that concentration is 1~3mg/ml；
4th, 0.5g sodium molybdates, 1g cysteines and 0.3g cetyl benzenesulfonic acid sodiums are dissolved in 60ml deionized waters, so
20mL step 3 resulting solutions being added afterwards, then mixed solution being put into 100ml reactors, 18~24h is kept at 240 DEG C, from
The heart is cleaned, freeze-drying, obtains final product the gas sensitive material being combined based on Graphene/molybdenum bisuphide.
Specific embodiment five：Present embodiment and the concentrated sulfuric acid described in step one unlike specific embodiment four
Mass percent concentration is 95%~98%.Other are identical with specific embodiment four.
Specific embodiment six：Present embodiment from step one unlike specific embodiment four or five by the concentrated sulfuric acid
It is cooled to 0 DEG C.Other are identical with specific embodiment four or five.
Specific embodiment seven：Added in step one unlike one of present embodiment and specific embodiment four to six
1g natural flake graphites stir 40min.Other are identical with one of specific embodiment one to six.
Specific embodiment eight：In temperature in step one unlike one of present embodiment and specific embodiment four to six
Spend to add 6g KMnO by several times in 25min under conditions of less than 5 DEG C4.Other phases one of with specific embodiment one to six
Together.
Specific embodiment nine：Will be mixed in step 2 unlike one of present embodiment and specific embodiment four to six
Stirred in water bath 30~60min of the compound at 40 DEG C.Other are identical with one of specific embodiment one to six.
Specific embodiment ten：In step 4 unlike one of present embodiment and specific embodiment four to six
240 DEG C of holding 20h.Other are identical with one of specific embodiment one to six.
Using following experimental verifications effect of the present invention：
Experiment one：
The preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide is followed the steps below：
First, by 20ml mass percent concentrations for 98% concentrated sulfuric acid is cooled to -1 DEG C, the stirring of 1g natural flake graphites is added
30min, divides 3 times in 25min under conditions of being less than 2 DEG C in temperature and adds 6g KMnO4, 2h is stirred, obtain mixture；
2nd, the stirred in water bath 60min by mixture at 40 DEG C, the temperature to water-bath is 45 DEG C, stops stirring, must be starched
Liquid；
3rd, slurries are gone into 80 DEG C of thermostat water bath stirrings, treats that slurries are warmed up to and 80ml is added in 80 DEG C, gradation 20min
(first few, rear cumulative) distilled water (now reactant and its sticky, quick stirring radiating as far as possible, if temperature is raised to 90 DEG C, then
15min is stirred during reaction solution removal water-bath is gone into air, is gradually added water), 50ml distilled water dilutings are added, add 15ml
By the hydrogen peroxide that mass percent concentration is 30% and the mixed solution that 60ml distilled water is constituted to there is golden yellow, it is centrifuged and washes
It is 5 to wash to washing lotion pH value, and then the precipitation after centrifugation is dissolved in deionized water, obtains the solution that concentration is 2mg/ml；
4th, 0.5g sodium molybdates, 1g cysteines and 0.3g cetyl benzenesulfonic acid sodiums are dissolved in 60ml deionized waters, so
20mL step 3 resulting solutions being added afterwards, then mixed solution being put into 100ml reactors, 18h is kept at 240 DEG C, centrifugation is clear
Wash, freeze-drying, obtain final product the gas sensitive material being combined based on Graphene/molybdenum bisuphide.
The gas sensitive material being combined based on Graphene/molybdenum bisuphide prepared by this experiment is scanned electron microscope
Test, obtains Fig. 1.From Fig. 1, the number of plies that can clearly observe molybdenum bisuphide in compound is about 5~20 layers or so, lamella
It is spaced about 0.64nm.
It is quick based on the gas that Graphene/molybdenum bisuphide is combined to gained using CGS-1PT vapor sensitivities test system
Sense material carries out the NO under room temperature condition2Vapor sensitivity is tested, as shown in Fig. 2 vapor sensitivity is defined asResistance when wherein Rg is in gas, R0It is first under nitrogen exposure
Beginning resistance.The NO of the gas sensitive material being wherein combined based on Graphene/molybdenum bisuphide2Vapor sensitivity is 200%, is far above
Pure Graphene and pure molybdenum bisuphide.
Claims (6)
1. the preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide, it is characterised in that based on Graphene/bis-
The preparation method of the compound gas sensitive material of molybdenum sulfide is followed the steps below：
First, 15~25ml concentrated sulfuric acids are cooled to -1~1 DEG C, add 0.5~1.5g natural flake graphites to stir 30~50min,
5~8g KMnO are added by several times in 25min under conditions of being less than 5 DEG C in temperature4, 1~3h is stirred, obtain mixture；
2nd, the 30~60min of stirred in water bath by mixture at 40 DEG C, the temperature to water-bath is 45 DEG C, stops stirring, must be starched
Liquid；
3rd, slurries are gone into 80 DEG C of thermostat water bath stirrings, treats that slurries are warmed up to and 60~80ml is added in 80 DEG C, gradation 20min
It is 90 DEG C that distilled water is stirred to reacting liquid temperature, and reaction solution then is removed into water-bath stirring 15min, adds 40~70ml distillations
Water dilutes, and adds 10~15ml by the hydrogen peroxide that mass percent concentration is 30% and the mixed solution that 60ml distilled water is constituted
Golden yellow to occurring, it is 5~6 to be centrifuged and wash to washing lotion pH value, and then the precipitation after centrifugation is dissolved in deionized water, is obtained
Concentration is the solution of 1~3mg/ml；
4th, 0.5g sodium molybdates, 1g cysteines and 0.3g cetyl benzenesulfonic acid sodiums are dissolved in 60ml deionized waters, Ran Houjia
Enter 20mL step 3 resulting solutions, then mixed solution is put into 100ml reactors, 18~24h is kept at 240 DEG C, centrifugation is clear
Wash, freeze-drying, obtain final product the gas sensitive material being combined based on Graphene/molybdenum bisuphide.
2. the preparation method of the gas sensitive material being combined based on Graphene/molybdenum bisuphide according to claim 1, its feature
The mass percent concentration for being the concentrated sulfuric acid described in step one is 95%~98%.
3. it is according to claim 1 or claim 2 based on Graphene/molybdenum bisuphide be combined gas sensitive material preparation method, its
It is characterised by that the concentrated sulfuric acid is cooled into 0 DEG C in step one.
4. it is according to claim 1 or claim 2 based on Graphene/molybdenum bisuphide be combined gas sensitive material preparation method, its
It is characterised by adding 1g natural flake graphites stirring 40min in step one.
5. it is according to claim 1 or claim 2 based on Graphene/molybdenum bisuphide be combined gas sensitive material preparation method, its
It is characterised by adding 6g KMnO by several times in 25min under conditions of temperature is for less than 5 DEG C in step one4。
6. it is according to claim 1 or claim 2 based on Graphene/molybdenum bisuphide be combined gas sensitive material preparation method, its
It is characterised by keeping 20h at 240 DEG C in step 4.
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| CN105126876B (en) * | 2015-09-07 | 2017-06-06 | 复旦大学 | A kind of flower-shaped carbon load MoS2Composite of nano particle and preparation method thereof |
| CN106248735A (en) * | 2016-07-12 | 2016-12-21 | 电子科技大学 | A kind of humidity sensor based on ultra-thin sulfide film and preparation method thereof |
| CN107085020B (en) * | 2017-05-26 | 2019-03-26 | 黑龙江大学 | A kind of molybdenum disulfide/indium hydroxide composite air-sensitive sensing material and preparation method and application |
| CN107393721B (en) * | 2017-07-28 | 2019-01-29 | 浙江理工大学 | A kind of graphene-zinc oxide nano tube array sensing material preparation method of molybdenum disulfide quantum dot modification |
| CN108680610B (en) * | 2018-06-13 | 2021-04-20 | 湘潭大学 | Based on MoS2Room temperature NO of PbS composite2Gas sensor and preparation method thereof |
| CN111307876B (en) * | 2018-12-11 | 2023-04-14 | 有研工程技术研究院有限公司 | Gas sensor for detecting nitrogen dioxide and preparation method thereof |
| CN110208337B (en) * | 2019-06-28 | 2022-02-08 | 西南交通大学 | Molybdenum disulfide/nano diamond composite humidity sensor and preparation method thereof |
| CN112903761B (en) * | 2021-01-19 | 2022-09-23 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
| WO2023272664A1 (en) * | 2021-06-30 | 2023-01-05 | 苏州大学 | Graphene composite material, sensor and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101303322A (en) * | 2008-07-08 | 2008-11-12 | 清华大学 | Surface modification method of WO3 thick film gas-sensitive sensor |
| CN104049022A (en) * | 2014-06-10 | 2014-09-17 | 中国石油大学(华东) | Molybdenum disulfide/silicon heterogeneous film component with hydrogen sensitivity effect as well as preparation method and application thereof |
| CN104122305A (en) * | 2014-07-28 | 2014-10-29 | 黑龙江大学 | Rare-earth doped modified graphene composite material gas sensitive element for detecting NOx and preparation method of gas sensitive element |
| CN104402056A (en) * | 2014-10-30 | 2015-03-11 | 郑州轻工业学院 | Semitubular nanometer WO3/graphene composite gas-sensitive material and its preparation method and use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9063063B2 (en) * | 2013-03-15 | 2015-06-23 | The United States Of America, As Represented By The Secretary Of The Navy | Low-dimensional material chemical vapor sensors |
| WO2014178016A2 (en) * | 2013-05-01 | 2014-11-06 | Indian Institute Of Science | Non-volatile opto-electronic device |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101303322A (en) * | 2008-07-08 | 2008-11-12 | 清华大学 | Surface modification method of WO3 thick film gas-sensitive sensor |
| CN104049022A (en) * | 2014-06-10 | 2014-09-17 | 中国石油大学(华东) | Molybdenum disulfide/silicon heterogeneous film component with hydrogen sensitivity effect as well as preparation method and application thereof |
| CN104122305A (en) * | 2014-07-28 | 2014-10-29 | 黑龙江大学 | Rare-earth doped modified graphene composite material gas sensitive element for detecting NOx and preparation method of gas sensitive element |
| CN104402056A (en) * | 2014-10-30 | 2015-03-11 | 郑州轻工业学院 | Semitubular nanometer WO3/graphene composite gas-sensitive material and its preparation method and use |
Non-Patent Citations (1)
| Title |
|---|
| 类石墨烯二硫化钼及其在光电子器件上的应用;汤鹏等;《物理化学学报》;20131231;第29卷(第4期);667-677 * |
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