CN209707429U - Graphene composite gas sensitive material, gas sensor - Google Patents
Graphene composite gas sensitive material, gas sensor Download PDFInfo
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- CN209707429U CN209707429U CN201822231845.8U CN201822231845U CN209707429U CN 209707429 U CN209707429 U CN 209707429U CN 201822231845 U CN201822231845 U CN 201822231845U CN 209707429 U CN209707429 U CN 209707429U
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Abstract
The utility model discloses a kind of graphene composite gas sensitive material and gas sensors.The graphene composite gas sensitive material includes metal catalytic layer, multiple graphene layers and multiple metal oxides and/or metal-modified layer, wherein a graphene layer is directly folded is located on metal catalytic layer, and the multiple graphene layer and the multiple metal oxide and/or the alternately laminated setting of metal-modified layer, make the graphene composite gas sensitive material that there is 3-dimensional multi-layered composite construction.Graphene composite gas sensitive material provided by the utility model has good gas-sensitive property; it can work at a lower temperature; and there is good selectivity, repeatability; it can be widely applied in a variety of gas sensors; its preparation process is simply easily implemented simultaneously; controllability is good, is suitable for large-scale production.
Description
Technical field
The utility model relates to a kind of gas sensitive material and preparation method thereof, in particular to a kind of graphene composite gas
Sensitive material, gas sensor and preparation method thereof.
Background technique
Gas sensor mainly has semiconductor-type, electric chemical formula, catalytic combustion type etc. several at this stage.Wherein, semiconductor
The most practical a kind of gas sensor of formula gas sensor, it have it is low in cost, be simple to manufacture, high sensitivity, response speed
Fastly, the advantages that service life is long, and circuit low to humidity sensitive is simple.One of semiconductor-type gas sensor core is sensitive material
Quality, determine the core parameters such as sensitivity, the response time of gas sensor.
Current Semiconductor gas sensors material is mainly based on oxide, such as tin oxide, zinc oxide, copper oxide.These gas
Quick material needs could work at a certain temperature, usually be more than 250 degree.It can also make there are also some carbon nano-tube materials
It for gas sensitive, and can work at a lower temperature, but its selectivity and desorption row are poor, influence the production of device
Energy.On the other hand, graphene is expected to become novel air-sensitive because having the specific surface area of superelevation and ultralow Johnson noise
Material.However, many experiments and calculation shows that, intrinsic graphene only to NH3、NO2Etc. a few gases have higher sensitivity, and
And the adsorption desorption time is longer, gas-selectively is poor.In order to improve the air-sensitive performance of grapheme material, researcher is proposed to stone
The method that black alkene material carries out functionalization.For example, the method for having researcher to use composite reduction, loads SnO on graphene2
Particle improves the selectivity of graphene-based material and restorative, but the material of such method preparation is easy to reunite, and influences its gas
Quick characteristic.There are also researchers to prepare graphene using CVD method, is modified by Pt, Pd metal it.Although this method exists
The preparation of graphene composite material also may be implemented to a certain extent, but the uniformity of its metal-modified particle and consistency are difficult to
It is protected.
Summary of the invention
The main purpose of the utility model is to provide a kind of graphene composite gas sensitive materials, can be compared with low temperature
The lower work of degree, and there is good selectivity, repeatability, to overcome the deficiencies in the prior art.
The another object of the utility model is to provide a kind of method for making the graphene composite gas sensitive material.
The further object of the utility model is to provide the application of the graphene composite gas sensitive material.
For realization aforementioned invention purpose, the technical solution adopted in the utility model includes:
The utility model embodiment provides a kind of graphene composite gas sensitive material, it is characterised in that urges including metal
Change layer, multiple graphene layers and multiple metal oxides and/or metal-modified layer, wherein a graphene layer is directly folded to be located at metal
In Catalytic Layer, and the multiple graphene layer and the multiple metal oxide and/or the alternately laminated setting of metal-modified layer, make
The graphene composite gas sensitive material has 3-dimensional multi-layered composite construction.
The utility model embodiment additionally provides a kind of production method of graphene composite gas sensitive material comprising:
The first step of metal catalytic layer is formed on the substrate；
The second step of graphene layer is formed on the metal catalytic layer；
The third step of metal oxide and/or metal-modified layer is formed on the graphene layer；
The four steps of graphene layer is formed on the metal oxide and/or metal-modified layer；
Wherein, the third step and four steps repeat more than twice, to form multiple graphene layers and more
A metal oxide and/or the alternately stacked structure of metal-modified layer.
The utility model embodiment additionally provides the purposes of the graphene composite gas sensitive material.For example, this is practical
New embodiment additionally provides a kind of gas sensor comprising the graphene composite gas sensitive material.
Compared with prior art, graphene composite gas sensitive material provided by the utility model has good air-sensitive special
Property, it can work at a lower temperature, and there is good selectivity, repeatability, it can be in a variety of gas sensors extensively
Using, while its preparation process is simply easily implemented, controllability is good, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is a kind of structural schematic diagram of graphene composite gas sensitive material in one exemplary embodiments of the utility model；
Fig. 2 is a kind of preparation process flow of graphene composite gas sensitive material in one exemplary embodiments of the utility model
Figure.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of many defects of the existing technology, obtain
To propose the technical solution of the utility model.The technical solution, its implementation process and principle etc. will further be solved as follows
Release explanation.A kind of graphene composite gas sensitive material that the one aspect of the utility model provides includes metal catalytic layer, more
A graphene layer and multiple metal oxides and/or metal-modified layer, wherein a graphene layer is directly folded to be located at metal catalytic layer
On, and the multiple graphene layer and the multiple metal oxide and/or the alternately laminated setting of metal-modified layer, make the stone
Black alkene composite gas sensitive material has 3-dimensional multi-layered composite construction.
Preferably, the aperture of hole contained by the graphene composite gas sensitive material is 0.1-500nm, and specific surface area is
100-5000m2/g。
A kind of production method for graphene composite gas sensitive material that the other side of the utility model provides includes:
The first step of metal catalytic layer is formed on the substrate；
The second step of graphene layer is formed on the metal catalytic layer；
The third step of metal oxide and/or metal-modified layer is formed on the graphene layer；
The four steps of graphene layer is formed on the metal oxide and/or metal-modified layer；
Wherein, the third step and four steps repeat more than twice, to form multiple graphene layers and more
A metal oxide and/or the alternately stacked structure of metal-modified layer.
In some embodiments, the first step includes: that metal catalytic is formed on the substrate using magnetron sputtering
Layer.
In some embodiments, the second step or four steps include: to grow to form graphite in the way of CVD
Alkene layer.
In some embodiments, the third step includes: raw on graphene layer in the way of atomic layer deposition
Length forms metal oxide and/or metal-modified layer.
In some embodiments, the first step further include: substrate is pre-processed, is given birth on substrate later
Length forms metal catalytic layer；The pretreatment includes cleaning, is dried.
Further, the graphene composite gas sensitive material has 3-dimensional multi-layered composite construction.
Further, the graphene layer is single-layer graphene.
Further, the graphene layer with a thickness of 0.1-500nm.
Further, the material of the metal catalytic layer includes Ni and/or Cu, but not limited to this.For example, the metal is urged
Changing layer is Ni metal layer and/or Cu metal layer.
Further, the metal catalytic layer with a thickness of 0.1-500nm.
Further, the metal oxide and/or metal-modified layer are by multiple metal oxides and/or metallic particles shape
At.
Preferably, the metal oxide and/or metallic particles are discrete distributions, and particle size range is in 0.1nm-100nm.
Further, the metal oxide and/or metal-modified layer with a thickness of 0.1-500nm.
In the utility model embodiment, preferably pass through atomic layer deposition mode alternating deposit multilayer single-layer graphene and metal
Oxide and/or metal-modified layer, make wherein each graphene layer there is the uniformly modified effect of metal, compared with existing skill
In art by chemical modification on the surface of the material deposited particles decorative material in the way of, can make to be formed by gas sensitive material tool
There is good air-sensitive selectivity.
The utility model embodiment additionally provides a kind of gas sensor comprising the graphene composite gas is sensitive
Material.The gas sensor may also include the components such as necessary electrode, data collection module, data analysis unit, to
With with the sensing unit that the graphene composite gas sensitive material forms.
Clear, complete description is carried out to the technical solution of the utility model below in conjunction with attached drawing and typical case.
Embodiment: refering to Figure 1, in an exemplary embodiments of the utility model, a kind of compound gas of graphene
Body sensitive material includes the metal catalytic layer 2 being formed on substrate 1, multiple graphene layers 3 and multiple metal oxides and/or gold
Belong to decorative layer 4, be located on metal catalytic layer 2 wherein a graphene layer 3 is directly folded, and the multiple graphene layer with it is the multiple
Metal oxide and/or the alternately laminated setting of metal-modified layer have the graphene composite gas sensitive material three-dimensional more
Layer composite construction.
Further, the graphene layer can be single-layer graphene.
Further, the thickness of the graphene layer can be 0.1nm-500nm.
Further, the material of the metal catalytic layer can be Ni, Cu or its alloy.
Further, the thickness of the metal catalytic layer can be 0.1nm-500nm.
Further, the metal oxide and/or metal-modified layer can be by multiple metal oxides of discrete distribution
And/or metallic particles is formed.
Wherein, the material of metal oxide and/or metallic particles can be Pt, Pd, Au, SnO2、ZnO2Equal metals, metal
The combination of any one or more in oxide.
Further, the thickness of the metal oxide and/or metal-modified layer can be 0.1nm-100nm.
It please refers to shown in Fig. 2, a kind of method making the graphene composite gas sensitive material may include walking as follows
It is rapid:
(1) monocrystalline substrate 1 is sufficiently cleaned, comprising: a, with the concentrated sulfuric acid, 85 DEG C are boiled 15min；B, it then uses
50wt% potassium hydroxide solution impregnates 10min；C, with acetone soln ultrasound 15min, deionized water solution ultrasound 15min.
(2) cleaned monocrystalline substrate is sufficiently dry (120 DEG C of heating 1h) in vacuum drying oven or nitrogen drying；
(3) metal catalytic layers such as Cu, Ni 2, thickness about 10- are formed on a monocrystaline silicon substrate using magnetron sputtering technique
500nm；
(4) single-layer graphene 3, thickness about 0.1-500nm are grown on metal catalytic layer in the way of CVD；
(5) in the way of atomic layer deposition on single-layer graphene the metal of depositing discrete or metal oxide particle (grain
Diameter about 0.1nm-100nm) it is modified, that is, form metal oxide or metal-modified layer 4, thickness about 0.1-500nm；
(6) single-layer graphene 5, thickness about 0.1- are grown on metal or metal oxide layer in the way of CVD again
500nm；
(7) again in the way of atomic layer deposition on single-layer graphene deposited metal or modified metal oxide layer 6,
Thickness about 0.1-500nm.
The process conditions of the magnetron sputtering, CVD, the atomic layer deposition that use in aforementioned production method etc. may each be industry
Know.After repeating abovementioned steps (5)-(7), three-dimensional graphene composite material, the graphene composite gas sensitivity material are formed
Material has 3-dimensional multi-layered composite construction, and the aperture of hole contained therein is 0.1-500nm, specific surface area 100-5000m2/g。
Reference examples 1: the production method and embodiment of a kind of graphene composite gas sensitive material provided in the reference examples
It is essentially identical, but do not include step (6)-step (7).
Reference examples 2: the mode recorded referring to documents such as CN 106219537B, it is compound that production forms stannic oxide/graphene
Gas sensitive material.
By multiple batches of graphene made from multiple batches of graphene composite gas sensitive material made from embodiment 1, reference examples 1
Multiple batches of graphene composite gas sensitive material made from composite gas sensitive material, reference examples 2 respectively Direct precipitation, slurry is made
The form for expecting coating implements the superposition of sensitive material in measuring electrode, prepares semiconductor-type gas sensor, recycles
NH3And NO2Gas is tested as object gas, tests the gas-sensitive property of these graphene composite gas sensitive materials, test
The results show that the graphene composite gas sensitive material, reference examples 1, the graphene of reference examples 2 of the utility model embodiment are compound
The response sensitivity (average value of multiple batches of sample) of gas sensitive material is respectively 50%, 52%, 55%, is recycled through 500 times
Rear response time and detection limit (average value of multiple batches of sample) are respectively 40 seconds, 55 seconds, 48 seconds, detection limit 5ppm,
10ppm、8ppm。
In addition, the graphene of the graphene composite gas sensitive material of the utility model embodiment, reference examples 1, reference examples 2
The operating temperature of composite gas sensitive material is respectively 28 DEG C, 30 DEG C, 30 DEG C or so.
The technology contents and technical characteristic of the utility model have revealed that as above, however those skilled in the art still may be used
Can teaching based on the utility model and announcement and make various replacements and modification without departing substantially from the spirit of the present invention, therefore, this
Utility model protection range should be not limited to the revealed content of embodiment, and should include the various replacements without departing substantially from the utility model
And modification, and covered by present patent application claim.
Claims (8)
1. a kind of graphene composite gas sensitive material, it is characterised in that including metal catalytic layer, multiple graphene layers and multiple
Metal oxide and/or metal-modified layer are located on metal catalytic layer wherein a graphene layer is directly folded, and the multiple graphite
Alkene layer and the multiple metal oxide and/or the alternately laminated setting of metal-modified layer keep the graphene composite gas sensitive
Material has 3-dimensional multi-layered composite construction.
2. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the graphene composite gas is quick
The aperture for feeling hole contained by material is 0.1-500nm, specific surface area 100-5000m2/g。
3. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the graphene layer is single layer stone
Black alkene.
4. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the graphene layer with a thickness of
0.1-500nm。
5. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the metal catalytic layer is Ni gold
Belong to layer and/or Cu metal layer.
6. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the thickness of the metal catalytic layer
For 0.1-500nm.
7. graphene composite gas sensitive material as described in claim 1, it is characterised in that: the metal oxide and/or
Metal-modified layer with a thickness of 0.1-500nm.
8. a kind of gas sensor, it is characterised in that quick including graphene composite gas of any of claims 1-7
Feel material.
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| CN111474214A (en) * | 2020-04-29 | 2020-07-31 | 青岛菲灿新材料科技服务有限责任公司 | Graphene-based high-sensitivity hydrogen sensor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111474214A (en) * | 2020-04-29 | 2020-07-31 | 青岛菲灿新材料科技服务有限责任公司 | Graphene-based high-sensitivity hydrogen sensor and preparation method thereof |
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