CN106829847B - The gentle body sensor of graphene-polymer micron linear array and their preparation method and application - Google Patents
The gentle body sensor of graphene-polymer micron linear array and their preparation method and application Download PDFInfo
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Abstract
本发明公开了一种石墨烯‑聚合物微米线阵列和气体传感器以及它们的制备方法和应用。石墨烯‑聚合物微米线阵列包括石墨烯微米线阵列以及包覆在其上的聚合物薄膜层。石墨烯微米线阵列呈一维分布且相互平行，并沿一维分布的方向延伸。本发明制备的石墨烯‑聚合物微米线阵列气体传感器，克服了现有技术中单纯地利用聚合物膜制备气体传感器时成本高，工艺复杂，检测效率不高、灵敏度差、溶胀后检测通路受限及需要特殊仪器设备的缺陷，具有优良的可加工性能，并且可大面积制备，从而保证了高的检测灵敏度、选择性和性能稳定性。该方法能够在制备过程中调节石墨烯‑聚合物微米线阵列的宽度，有望在食品监测、大气污染物监测等方面展开广泛应用。
The invention discloses a graphene-polymer micro-wire array and a gas sensor, as well as a preparation method and application thereof. The graphene-polymer microwire array includes a graphene microwire array and a polymer film layer coated thereon. The graphene microwire arrays are one-dimensionally distributed and parallel to each other, and extend along the direction of the one-dimensional distribution. The graphene-polymer micro-wire array gas sensor prepared by the invention overcomes the high cost, complicated process, low detection efficiency, poor sensitivity, and limited detection path after swelling when simply using the polymer film to prepare the gas sensor in the prior art. It has excellent processability and can be prepared in a large area, thus ensuring high detection sensitivity, selectivity and performance stability. This method can adjust the width of the graphene-polymer microwire array during the preparation process, and is expected to be widely used in food monitoring, atmospheric pollutant monitoring, etc.
Description
Technical field
The invention belongs to senser element preparation technical fields, more particularly, to a kind of graphene-polymer micron linear array
With gas sensor and their preparation method and application.
Background technique
Gas sensor is highly sensitive as one kind, and the means of highly selective detection gas have obtained since the thirties in last century
Relatively broad research is arrived.But upgrading has all been arrived either in terms of industry application or basic research in the field
Crucial moment.On the one hand, as the event for influencing human health and living standard in recent years takes place frequently, such as greenhouse effects, ozone
Damage layer etc., the requirement to detectable gas type increase.From initial reducibility gas, such as hydrogen, methane etc. is extended to poison
Property atmospheric CO, nitric oxide etc. and the related gas of food.On the other hand, to the detection limit of sensor, sensitivity, repetition
Property and the requirement of stability, low cost etc. increase, unquestionably just to gas sensor, such as the gas sensing based on polymer
The preparation of device proposes new challenge.
The widely used gas sensor for being mainly based upon polymer in gas sensor, which can
To adjust detectable gas type by the type for adjusting polymer and plasticizer, gas sensor design side is substantially increased
The flexibility in face.And polymer is mainly used in the form of polymer film, but the gas based on polymer film being commonly used
Body sensor is easy to happen swelling in absorption gas post-consumer polymer film, influences detection path.Problems have obtained research institution
With extensive concern (Kim et al., the ETRI Journal, 27:585-594 (2005) of industry；Lewis et al.,
Langmuir,22:7928-7935(2006)；Suslick et al.,Chem.Soc.Rev,42:8649-8682(2013)).
To solve this problem, numerous studies turn to the gas sensor of array.But the conventional array gas based on polymer
That there are methods is cumbersome for the preparation process of sensor, needs special instruments and equipment, it is difficult to which large area preparation and poor sensitivity etc. are asked
Topic.Therefore it needs to explore a kind of novel array gas sensor based on polymer, can both guarantee high detection sensitivity,
Selectivity and stability etc., and can be with a kind of low cost, high-throughput short-cut method preparation.
Summary of the invention
The purpose of the present invention be intended to provide a kind of completely new gentle body sensor of graphene-polymer micron linear array and
Their preparation method and application.Method provided by the present invention can prepare high sensitivity, selectivity well and performance with large area
Stable graphene-polymer micron linear array, and it can be conveniently adjusted the width of micron linear array during the preparation process,
To adjust accordingly response signal.
To achieve the goals above, the present invention provides a kind of graphene-polymer micron linear arrays, comprising: graphene
Micron linear array in one-dimensional distribution and is parallel to each other, and extends along the direction of one-dimensional distribution；And it is coated on graphene micron
Polymer film layer in linear array.
Preferably, the spacing between the graphene micro wire of the coated polymer film layer be 1~15 μm, preferably 2~
10μm.The width of the graphene micro wire of the coated polymer film layer is 2~20 μm.
Preferably, the area of graphene-polymer micron linear array is up to 10 × 10cm2。
The present invention also provides a kind of graphene-polymer micron linear array gas sensors comprising substrate and cloth
Set the graphene-polymer micron linear array of the invention in substrate.
Preferably, substrate is silicon wafer or electro-conductive glass piece.
The present invention also provides a kind of preparation methods of graphene-polymer micron linear array gas sensor comprising with
Lower step:
S1, graphene micron linear array is prepared using liquid bridge revulsion；And
S2, the coated polymer film layer in the graphene micron linear array form graphene-polymer micron linear array
Column, to obtain graphene-polymer micron linear array gas sensor.
In the present invention, the step S1 includes:
S11, setting substrate, and by graphene ultrasonic disperse in the first solvent at graphene dispersing solution, by graphene point
Dispersion liquid is arranged in substrate；
S12, using the silicon column with micrometre array structure as template, be disposed at substrate is dispersed with graphene dispersing solution
Surface on, formed sandwich structure；And
After S13, the solvent volatilization wait be located in the graphene dispersion liquid layer among substrate and template, received since liquid bridge induces
Contracting is to be formed on the substrate graphene micron linear array.
In the present invention, substrate is silicon wafer or electro-conductive glass piece.First solvent is water.Optionally, graphene dispersing solution is dense
Degree is 800~1200ppm；It such as can be 900ppm, 1000ppm or 1100ppm.
In the present invention, step S2 includes:
Polymer is dissolved into the second solvent, polymer solution is formed；
Polymer solution is arranged in the substrate for foring graphene micron linear array；And after the solvent is volatilized in base
Graphene-polymer micron linear array is formd on bottom, to obtain graphene-polymer micron linear array gas sensor.
Preferably, polymer is selected from polymethylstyrene, polystyrene, polyvinyl acetate, vinyl chloride-vinyl acetate
Copolymer, ethylene-vinyl acetate copolymer, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl alcohol contracting fourth
One of aldehyde, poly-epsilon-caprolactone and polyethylene oxide are a variety of.
Preferably, the concentration of polymer solution is 0.5~1.5mol/L, such as can be 1mol/L.
Preferably, the second solvent is selected from one of water, chloroform, ethyl alcohol and acetone or a variety of.
Preferably, the area of the graphene-polymer micron linear array of the method preparation is up to 10 × 10cm2。
The present invention also provides a kind of application of graphene-polymer micron linear array gas sensor in gas detection,
Include:
Above-mentioned graphene-polymer micron line array sensor is placed in the saturation atmosphere of gas to be detected；It is molten to its
After swollen, the I-V curve variation of front and back is detected, to realize the detection to corresponding gas.
Preferably, gas can be aromatic compound (such as toluene, benzene), alcohols material (such as methanol, ethyl alcohol), alkane
One or more of hydrocarbons (such as hexane), letones (such as acetone).
Beneficial effects of the present invention:
Graphene-polymer micron linear array gas sensor prepared by the present invention, overcomes in the prior art merely
At high cost present in gas sensor based on polymer film, complex process, detection efficiency be low, poor sensitivity, examines after swelling
The defects of access is limited and needs special instruments and equipment is surveyed, not only there is excellent processability, it is often more important that, this hair
Bright gas sensor can be prepared with large area, to ensure that high detection sensitivity, selectivity and stability, i.e.,
Make to damage by the placement up to 1 year or detection sensitivity is caused to decline.
In addition, the graphene-polymer micron linear array and corresponding gas sensor, it can be with a kind of low cost, high pass
Prepared by the short-cut method of amount, and can adjust the width of graphene micro wire by adjusting template size during the preparation process
Spacing between degree and graphene micro wire, thus the width and graphene-of final adjustment graphene-polymer micro wire
Spacing between polymer micro wire.Whole preparation process of the invention can be realized at 20~25 DEG C of room temperature, not need to mention
For complex environment.Therefore, preparation method of the invention is easy to operate, equipment is simple, easily controllable and can give birth on a large scale
It produces, which is expected to be unfolded to be widely applied in terms of Food Monitoring, atmosphere pollution.
Detailed description of the invention
Fig. 1 is the flow diagram that graphene-polymer micron linear array is prepared in the present invention；
Fig. 2 is the schematic illustration for preparing graphene micron linear array in the present invention using liquid bridge revulsion；
Fig. 3 is that the graphene-polymer micron linear array gas sensor of preparation is placed in gas to be detected in the present invention
Saturation atmosphere in carry out gas detection schematic device；
Fig. 4 be in the embodiment of the present invention 2 the graphene-polymer micron linear array gas sensor for preparing to detected
The response of toluene gas changes with time schematic diagram；And
Fig. 5 is that the graphene-polymer micron linear array gas sensor detection gas prepared in embodiment 2 are inhaled repeatedly
The schematic diagram of resistance variations when attached-desorption.
Specific embodiment
As previously mentioned, the present invention provides a kind of graphene-polymer micron linear arrays, as shown in Fig. 1 (d), including stone
Black alkene micron linear array 20 and the polymer film layer 30 being coated in graphene micron linear array 20.Wherein graphene micron
Linear array 20 is in one-dimensional distribution and is parallel to each other, and extends along the direction of one-dimensional distribution.
Specifically, due to the graphene micro wire of polymer overmold width and graphene-polymer micro wire it
Between space D1Can influence its ability for adsorbing object to be detected and detection signal, therefore, the width of above-mentioned micro wire and
Away from D1Range selection it is more crucial.Since polymer is to be uniformly coated on graphene outer layer, the present invention can prepared
The space D between width and graphene micro wire in journey by adjusting graphene micro wire0Or polymer covering layer 30
Thickness so that adjust the space D between the width and graphene-polymer micro wire of final graphene-polymer micro wire1。
Wherein, the space D between graphene micro wire0It can be by adjusting the space D in used silicon column template between silicon column2Come
It realizes.For example, the width of the graphene micro wire of the coated polymer film layer is 2~20 μm.The coated polymer is thin
The space D 1 of the graphene micro wire of film layer can be 1~15 μm, preferably 2~10 μm.
It, can be by the concentration of adjusting polymer solution, to adjust cladding in an optimal technical scheme of the invention
The thickness of polymer film layer 30 in graphene micron linear array 20.
The area of graphene-polymer micron linear array of the invention can be controlled according to actual needs, for example, its face
Product can be up to 10 × 10cm2。
As previously mentioned, the present invention also provides a kind of graphene-polymer micron linear array gas sensors, such as Fig. 1 institute
Show comprising the above-mentioned graphene-polymer micron linear array of substrate 10 and arrangement on the substrate 10.Wherein, substrate 10 can
Think electro-conductive glass piece or silicon wafer.
In of the invention one preferred technical solution, the polymer in polymer film layer has the following conditions: 1)
Polymer is soluble high-molecular, and easily formation lotion, molecular weight are no more than 100000；2) polymer easily occurs in atmosphere
Swelling；3) fine solvent of polymer will not damage graphene micron cable architecture.Preferably, polymer, which can be, is selected from
Polymethylstyrene, polystyrene, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate are total
Polymers, polyvinylpyrrolidone, polymethyl methacrylate, polyvinyl butyral, poly-epsilon-caprolactone and polyethylene oxide
One of or it is a variety of.
As depicted in figs. 1 and 2, the present invention also provides a kind of graphene-polymer micron linear array gas sensors
It is poly- can quickly and easily to prepare highly sensitive, highly selective and stability graphene-using this method for preparation method
Close object micron linear array gas sensor.Itself the following steps are included:
S1, graphene micron linear array 20 is prepared using liquid bridge revulsion, specifically include:
S11, setting substrate 10, and graphene ultrasonic disperse is formed into graphene dispersing solution in the first solvent, later will
Graphene dispersing solution is arranged on the substrate 10；
S12, using the silicon column with micrometre array structure as template 40, graphene dispersing solution is added dropwise in template 40, thus
Form sandwich structure.Wherein, template 40 is the silicon column with patterning micrometre array structure.Such as the template 40 can pass through
The method of lithography process obtains.
After S13, the solvent volatilization wait be located in the graphene dispersing solution among substrate 10 and template 40, since liquid bridge induces
It shrinks to form the graphene micron linear array 20 on the substrate 10；
S2, the coated polymer film layer 30 in graphene micron linear array 20 form graphene-polymer micron linear array
Column, to obtain graphene-polymer micron linear array gas sensor.Wherein step S2 is specifically included: first that polymer is molten
Solution forms polymer solution into the second solvent；Polymer solution setting is being formd into graphene micron linear array 20 later
Substrate 10 on；The graphene-polymer micro wire is formd on the substrate 10 after solvent volatilization in object solution to be polymerized
Array, to obtain graphene-polymer micron linear array gas sensor.
In a preferred embodiment of the invention, the second solvent for example be can be in water, chloroform, ethyl alcohol and acetone
It is one or more.The present invention is not limited thereto the selection of the second solvent, as long as polymer and shape can preferably be dissolved
At homogeneous solution.Preferably, the concentration of polymer solution for example can be 0.5~1.5mol/L.It can be poly- by adjusting
The concentration of polymer solution and then the thickness for adjusting polymer film layer.The concentration of polymer solution is preferably limited to by the present invention
0.5~1.5mol/L, available performance more preferably polymer film layer thickness, otherwise the concentration of polymer solution is too high or too
The low cladding for being unfavorable for subsequent polymer.
From (b) in Fig. 1-(d) as can be seen that obvious orderly graphene micron linear array 20 has been formed on the substrate.
Fig. 2 gives the schematic illustration that liquid bridge revulsion prepares graphene micron linear array.From figure 2 it can be seen that liquid graphite
Alkene dispersion liquid starts to carry out regular separation, and the liquid bridge formed later starts to shrink self assembly under the action of surface tension,
One-dimensional graphene micro wire is eventually formed.Specifically, due to substrate and template be all it is hydrophilic, graphene dispersing solution is first
It can enter among silicon column, form one layer of liquid film；As the solvent evaporates, silicon column is formed as supporting point control liquid film fracture
One-dimensional liquid bridge.Liquid bridge is further shunk, and is completed confinement assembling, is ultimately formed one-dimensional graphene micro wire.
Invention further provides any of the above-described kind of graphene-polymer micron linear array gas sensors in gas detection
Application, be using any of the above-described kind graphene-polymer micron linear array gas sensor or any of the above-described kind of method
The graphene-polymer micron linear array gas sensor of preparation, by the graphene-polymer micron linear array gas sensor
It is placed in the saturation atmosphere of gas to be detected, as detection gas are adsorbed in micron linear array, swelling action is adjoint to be occurred,
The I-V curve for the graphene-polymer micron linear array that detection front and back measures changes, i.e. graphene-polymer micro wire
Array has sensing effect to gas, to realize the detection to corresponding gas.Fig. 3 is in the present invention that the graphene-of preparation is poly-
It closes object micron linear array gas sensor and is placed in the saturation atmosphere of gas to be detected the schematic device for carrying out gas detection,
Including graphene-polymer micron linear array gas sensor of the invention.Line among the bottom of device of Fig. 3 represents the stone
Black alkene-polymer micron linear array) and the coupled probe for detecting signal (it is two that the line both ends in Fig. 3, which pick out,
A probe).It is under test gas in described device.Detected gas in the present invention can be aromatic compound (such as toluene, benzene
Deng), alcohols material (such as methanol, ethyl alcohol), alkanes substance (such as hexane), one of letones (such as acetone) or several
Kind.The gas sensor has a wide range of applications in terms of Food Monitoring, atmosphere pollution.
Technical solution of the present invention is described in detail below by way of illustrative specific embodiment.But it should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on above content of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, documented raw material and reagent are commercial product in embodiment.
Embodiment 1
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and silicon column size (width) is 2 μm, and spacing is 2 μ between silicon column
m.Graphene ultrasonic disperse is formed to the graphene dispersing solution that concentration is 800ppm in water, dispersant liquid drop is added in ito glass
In substrate.Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located in substrate and template
Between graphene dispersion liquid layer in solvent volatilization after, take silicon column template away, due to liquid bridge induction shrink in substrate shape
At the black alkene micron linear array of large area, for preparing the gas sensor of polymer overmold in next step.It is specifically shown in Fig. 1
Step (a) and step (b).
(2) graphene-polymer micron linear array gas sensor is prepared
At 25 DEG C of room temperature, polyvinyl butyral is dissolved in the second etoh solvent, obtaining concentration is the poly- of 1mol/L
Polymer solution.Polymer solution is added drop-wise in the graphene micron linear array formed in step (1).It volatilizees completely to solvent
Afterwards, the graphene micron linear array of polyvinyl butyral cladding is formed to get graphene-polymer micron linear array gas has been arrived
Body sensor.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
Fig. 3 is the detection device schematic diagram for detection gas.It is that the gas prepared in preceding step passes used in Fig. 3
Sensor is the saturation atmosphere of methanol gas in device.In detection process, detection gas are adsorbed in micron linear array, discovery
Detection path is not limited after it is swollen, and detection sensitivity 2.50ppm, theoretical lowest detection is limited to 0.59ppm.
In order to detect the stability of the gas sensor, the gas sensor in embodiment 1 is placed and is up to one-year age,
It is placed in the saturation atmosphere of methanol gas to be detected and detects under the same conditions again, it is found that its detection sensitivity is
2.495ppm illustrates that placing the sensor for a long time will not damage, and its detection sensitivity will not decline, which passes
The stability of sensor is very strong.
Embodiment 2
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and silicon column size (width) is 3 μm, and spacing is 3 μ between silicon column
m.Graphene ultrasonic disperse is formed to the graphene dispersing solution that concentration is 1200ppm in water, dispersant liquid drop is added in silicon wafer base
On bottom.Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located among substrate and template
Graphene dispersion liquid layer in solvent volatilization after, silicon column template is taken away, since liquid bridge induction is shunk to being formed on the substrate
Graphene micron linear array, for preparing the gas sensor of polymer overmold in next step.The step being specifically shown in flow chart 1
(a) and step (b).
(2) graphene-polymer micron linear array gas sensor is prepared
At 25 DEG C of room temperature, polyethylene oxide is dissolved in the second solvent chloroform, obtains the polymer that concentration is 1mol/L
Solution.Polymer solution solution is added drop-wise in the graphene micron linear array formed in step (1).It volatilizees completely to solvent
Afterwards, the graphene micron linear array for forming polyethylene oxide cladding, can be prepared into required gas sensor.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
Detection of the gas sensor prepared in embodiment 2 to toluene gas is carried out using mode same in embodiment 1,
Detection gas are adsorbed in micron linear array, and detection path is not limited after finding its swelling, and detection sensitivity is
2.00ppm, theoretical lowest detection are limited to 0.49ppm.
Fig. 4 is that the gas sensor prepared in embodiment 2 shows what the response of toluene gas detected changed over time
It is intended to, it can be seen that with increasing for detected toluene gas, sensor is responded, and resistance value rises.It consequently reaches full
With.As the time further elapses, desorbing gas, resistance value decline.
Fig. 5 is that the graphene-polymer micron linear array gas sensor detection gas prepared in embodiment 2 are inhaled repeatedly
The schematic diagram of resistance variations in attached-desorption process, it can be seen that using the gas sensor prepared in embodiment 2 to gas
During carrying out adsorption-desorption repeatedly, resistance value remains stable, illustrates the gas sensing prepared using method of the invention
Device stability with higher.
In order to further detect the stability of the gas sensor prepared in embodiment 2, by the gas sensing in embodiment 2
Device, which is placed, is up to one-year age, is placed in the saturation atmosphere of toluene gas to be detected and is examined under the same conditions again
It surveys, it is found that its detection sensitivity is 1.99ppm, illustrate that the stability of the gas sensor is very strong, placed even across long-time
It will not damage or detection sensitivity is caused to decline.
Embodiment 3
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and silicon column size (width) is 4 μm, and spacing is 4 μ between silicon column
m.Graphene ultrasonic disperse is formed to the graphene dispersing solution that concentration is 1000ppm in water, graphene dispersing solution is added dropwise
In ito glass substrate.Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located at substrate and
After solvent volatilization in graphene dispersion liquid layer among template, silicon column template is taken away, since liquid bridge induction is shunk in base
The graphene micron linear array that large area is formd on bottom, the step (a) and step (b) being specifically shown in flow chart 1.The large area
Graphene micron linear array be used to prepare the gas sensor of polymer overmold in next step.
(2) graphene-polymer micron linear array gas sensor is prepared
At 23 DEG C of room temperature, polyethylene oxide is dissolved in the second solvent chloroform, obtains the polymerization that concentration is 0.5mol/L
Object solution.Polymer solution is added drop-wise in the graphene micron linear array formed in step (1).After solvent volatilizees completely,
The graphene-polymer micron linear array for forming polyethylene oxide cladding, can be prepared into required gas sensor.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
The detection of toluene gas is carried out to the gas sensor prepared in embodiment 3 using mode same in embodiment 1,
Detection gas are adsorbed in micron linear array, and detection path is not limited after finding its swelling, and detection sensitivity is
1.50ppm, theoretical lowest detection are limited to 0.40ppm.
In order to detect the stability of the gas sensor, the gas sensor prepared in embodiment 3 is placed and is up to 1 year
Time is placed in the saturation atmosphere of toluene gas to be detected under the same conditions again and is detected, and finds its detection spirit
Sensitivity is 1.495ppm, with sensitivity technique result the year before almost without difference, illustrates to place even across long-time
It will not damage or detection sensitivity is caused to decline, gas sensor stability with higher prepared by the present invention.
Embodiment 4
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and for silicon column having a size of 5 μm, the spacing between silicon column is 5 μm.It will
Graphene ultrasonic disperse forms the graphene dispersing solution that concentration is 900ppm in water, and dispersant liquid drop is added in ito glass substrate
On.Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located among substrate and template
After solvent volatilization in graphene dispersion liquid layer, silicon column template is taken away, since liquid bridge induction shrinks to be formed on the substrate
The graphene micron linear array of large area, for preparing the gas sensor of polymer overmold in next step.It is specifically shown in flow chart 1
The step of (a) and step (b).
(2) graphene-polymer micron linear array gas sensor is prepared
At 25 DEG C of room temperature, ethylene-vinyl acetate copolymer is dissolved in the second solvent acetone, obtaining concentration is
The polymer solution of 1.5mol/L.Polymer solution is added drop-wise in the graphene micron linear array formed in step (1).To molten
After agent is volatilized completely, the graphene micron linear array of polyvinyl butyral cladding is formed, required gas can be prepared into and passed
Sensor.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
Detection of the gas sensor for carrying out preparing in embodiment 4 by the way of same as Example 1 to hexane gas,
Gas is adsorbed in micron linear array, and detection path is not limited after finding its swelling, detection sensitivity 1.50ppm,
Theoretical lowest detection is limited to 0.40ppm.
In order to detect the stability of the gas sensor, the gas sensor in embodiment 4 is placed and is up to one-year age,
It is placed in the saturation atmosphere of hexane gas to be detected and is detected under the same conditions again, it is found that its detection sensitivity is
1.49ppm, illustrating to place even across long-time will not damage or detection sensitivity is caused to decline, gas sensor it is steady
It is qualitative very strong.
Embodiment 5
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and silicon column size (width) is 10 μm, and spacing is between silicon column
10μm.Graphene ultrasonic disperse is formed to the graphene dispersing solution that concentration is 1200ppm in water, dispersant liquid drop is added in silicon wafer
In substrate.Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located in substrate and template
Between graphene dispersion liquid layer in solvent volatilization after, take silicon column template away, due to liquid bridge induction shrink in substrate shape
At the graphene micron linear array of large area, the step (a) and step (b) that are specifically shown in flow chart 1.The graphite of the large area
Alkene micron linear array is used to prepare the gas sensor of polymer overmold in next step.
(2) graphene-polymer micron linear array gas sensor is prepared
At 25 DEG C of room temperature, polyvinylpyrrolidone is dissolved in the second aqueous solvent, obtaining concentration is the poly- of 1mol/L
Polymer solution.Polymer solution solution is added drop-wise in the graphene micron linear array formed in step (1).It is waved completely to solvent
After hair, the graphene micron linear array of polyethylene oxide cladding is formed, required gas sensor can be prepared into.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
Inspection by the way of similarly to Example 1, using the gas sensor prepared in embodiment 5 to alcohol gas
It surveys, detection gas are adsorbed in micron linear array, and detection path is not limited after finding its swelling, and detection sensitivity is
1.00ppm, theoretical lowest detection are limited to 0.39ppm.
In order to detect the stability of the gas sensor, the gas sensor in embodiment 5 is placed and is up to one-year age,
It is placed in the saturation atmosphere of alcohol gas to be detected and is detected under the same conditions again, it is found that its detection sensitivity is
0.985ppm, with sensitivity technique result the year before almost without difference, illustrating to place even across long-time will not be by
It damages or detection sensitivity is caused to decline, the stability of the gas sensor is very strong.
Embodiment 6
(1) large-area graphene micron linear array is prepared using liquid bridge revulsion
Selecting the silicon column with micron-scale pattern is template, and silicon column size (width) is 2 μm, and spacing is 2 μ between silicon column
m.Graphene ultrasonic disperse is formed to the dispersion liquid that concentration is 1100ppm in water, dispersant liquid drop is added in silicon wafer substrate.It will
Silicon column template is placed in top, forms sandwich structure.After being placed at room temperature for 24 hours, wait be located at the graphene among substrate and template
After dispersing the solvent volatilization in liquid layer, silicon column template is taken away, since liquid bridge induction shrinks that large area has been formed on the substrate
Graphene micron linear array, for preparing the gas sensor of polymer overmold in next step.The step being specifically shown in flow chart 1
(a) and step (b).
(2) graphene-polymer micron linear array gas sensor is prepared
It is at 25 DEG C of room temperature, polyvinylpyrrolidone is soluble in water, obtain the polymer solution that concentration is 1mol/L.
Polymer solution solution is added drop-wise in the graphene micron linear array formed in step (1).After solvent volatilizees completely, formed
The graphene micron linear array of polyvinyl butyral cladding, can be prepared into required gas sensor.
Between being depended in used silicon column template between silicon column due to the spacing between the graphene micro wire of preparation
Away from can the graphene micron of required spacing be prepared by adjusting the spacing in silicon column template between silicon column during the preparation process
Linear array.The size of replacement silicon column template, then executes step (2) such as in step (1), forms the polymerization with different spacing
Object-graphene micron linear array gas sensor.
Detection by the way of similarly to Example 1 using the gas sensor prepared in embodiment 6 to acetone gas,
Detection gas are adsorbed in micron linear array, and detection path is not limited after finding its swelling, and detection sensitivity is
2.50ppm, theoretical lowest detection are limited to 0.59ppm.
In order to detect the stability of the gas sensor, the gas sensor in embodiment 6 is placed and is up to one-year age,
It is placed in the saturation atmosphere of acetone gas to be detected and is detected under the same conditions again, it is found that its detection sensitivity is
2.495ppm, with sensitivity technique result the year before almost without difference, illustrating to place for a long time will not damage or examine
Sensitivity decline is surveyed, the stability of the gas sensor is very strong.
Claims (16)
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847838A (en) * | 2006-04-07 | 2006-10-18 | 福建师范大学 | A gas sensor based on nanowire array and its preparation method |
| JP2008180529A (en) * | 2007-01-23 | 2008-08-07 | Furukawa Electric Co Ltd:The | Gas sensor |
| CN102016126A (en) * | 2008-03-20 | 2011-04-13 | Gsi重离子研究亥姆霍茨中心有限公司 | Nanowire structural element |
| CN102358610A (en) * | 2011-07-09 | 2012-02-22 | 电子科技大学 | Preparation method of conductive polymer one-dimensional nanostructured array |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN102664104A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing one-dimensional graphene/semiconductor nano wire compound photo anode by adopting electric spinning method |
| CN103399085A (en) * | 2013-08-19 | 2013-11-20 | 上海理工大学 | Langasite bulk acoustic wave high temperature gas sensor based on zinc oxide nanowire array |
| CN103714972A (en) * | 2013-11-25 | 2014-04-09 | 浙江大学 | Linear secure high-energy-density supercapacitor and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281154B (en) * | 2008-05-21 | 2011-03-30 | 中国科学院合肥物质科学研究院 | Capacitive gas sensor based on carbon nanotube array and its preparation method |
| CN103641061B (en) * | 2013-12-03 | 2015-08-19 | 电子科技大学 | A kind of have micro-nano gas sensor of air-sensitive reconstruct effect and preparation method thereof |
-
2015
- 2015-12-03 CN CN201510883063.0A patent/CN106829847B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847838A (en) * | 2006-04-07 | 2006-10-18 | 福建师范大学 | A gas sensor based on nanowire array and its preparation method |
| JP2008180529A (en) * | 2007-01-23 | 2008-08-07 | Furukawa Electric Co Ltd:The | Gas sensor |
| CN102016126A (en) * | 2008-03-20 | 2011-04-13 | Gsi重离子研究亥姆霍茨中心有限公司 | Nanowire structural element |
| CN102358610A (en) * | 2011-07-09 | 2012-02-22 | 电子科技大学 | Preparation method of conductive polymer one-dimensional nanostructured array |
| CN102447113A (en) * | 2011-12-12 | 2012-05-09 | 南开大学 | Lithium battery with polymer-coated sulfur/carbon composite material as anode |
| CN102664104A (en) * | 2012-05-04 | 2012-09-12 | 东南大学 | Method for preparing one-dimensional graphene/semiconductor nano wire compound photo anode by adopting electric spinning method |
| CN103399085A (en) * | 2013-08-19 | 2013-11-20 | 上海理工大学 | Langasite bulk acoustic wave high temperature gas sensor based on zinc oxide nanowire array |
| CN103714972A (en) * | 2013-11-25 | 2014-04-09 | 浙江大学 | Linear secure high-energy-density supercapacitor and preparation method thereof |
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