CN112758918A - Preparation method and application of purple phosphorus/graphene composite material - Google Patents
Preparation method and application of purple phosphorus/graphene composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 128
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 127
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 239000008367 deionised water Substances 0.000 claims description 16
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- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
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- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
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- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a preparation method and application of a purple phosphorus/graphene composite material, which comprises the steps of stripping purple phosphorus by a physical method to obtain single-layer or few-layer purple phosphorus, compounding the purple phosphorus and graphene in a suction filtration, spin coating, heat release adhesive tape and other modes to construct a purple phosphorus/graphene heterojunction, and finally assembling to obtain a purple phosphorus/graphene composite gas-sensitive sensor; according to the invention, a heterojunction is constructed between two materials, the graphene provides electrons, and the purple phosphorus provides adsorption sites, so that the application of the purple phosphorus as a gas sensor for measurement is realized, and compared with pure graphene, the resistance change is improved by more than 30 times of the original resistance change; the preparation process of the invention is safe and pollution-free, and can be completed in an open environment at normal temperature and normal pressure.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a preparation method and application of a purple phosphorus/graphene composite material.
Background
In the industries of petroleum, chemical industry, mining and the like, potential safety hazards caused by flammable and explosive or toxic gases often exist, and once leakage or explosion is caused, serious casualty accidents and property loss can be caused. Secondly, for industries such as smart home, heating and ventilation equipment, transportation, environmental monitoring and the like, a sensor with high sensitivity, short response time and high stability is also required to be used as a detection means for the concentration and the pollution degree of the flue gas. Although many instruments based on the principle of spectroscopy, such as gas chromatography, ultraviolet-visible spectroscopy, etc., can achieve high-precision detection, they are expensive and not portable, and thus are not suitable for on-site real-time detection.
It is well known that the quality of the gas sensitive material directly determines the performance of the sensor. With the development of material science, emerging nano materials such as graphene, molybdenum disulfide, black phosphorus and the like enter the field of sensors. The materials involved in the mainstream sensor products in the market today are mostly elemental semiconductors, metal oxides and low-dimensional materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method and application of a purple phosphorus/graphene composite material aiming at the defects in the prior art, and realize the application of the purple phosphorus as a gas sensor for measurement.
The invention adopts the following technical scheme:
a preparation method of purple phosphorus/graphene composite material comprises the following steps:
s1, preparing graphene on the surface of a copper foil sample, placing the copper foil sample carrying the graphene into a corrosive liquid for etching, transferring the graphene into deionized water for cleaning after copper in the copper foil sample is completely etched, and then transferring the graphene onto a substrate;
s2, stripping the bulk purple phosphorus crystal by a physical method to obtain purple phosphorus, and transferring the purple phosphorus to the surface of the graphene on the substrate of the step S1 to form the purple phosphorus/graphene composite material.
Specifically, in step S1, the substrate is Si/SiO2Glass or organic filter membranes.
Specifically, in step S1, the etching solution is a mixed solution of ferric chloride and hydrochloric acid, and the concentration of the mixed solution is 0.1 to 1 mol/L.
Further, the volume ratio of the ferric chloride solution to the hydrochloric acid solution is 1: 1.
Specifically, in step S1, 2 to 20 graphene layers are prepared on the surface of the copper foil sample.
Specifically, in step S2, the physical method includes any one of a mechanical peeling method, an ultrasonic crushing method, and a water bath ultrasonic method.
Furthermore, the ultrasonic cell disruption power adopted by the ultrasonic disruption method is 20-30%, and the effective time is 2-4 hours; the power of the water bath ultrasound is 100-500W, and the ultrasound duration is 12-24 hours.
Specifically, in step S2, the purple phosphorus is transferred to the graphene surface of the substrate in step S1 by using thermal release tape transfer, suction filtration or spin coating.
Specifically, in step S2, the number of purple phosphorus layers obtained by peeling is 1 to 10.
According to another technical scheme, the prepared purple phosphorus/graphene composite material is applied to a purple phosphorus/graphene composite gas-sensitive sensor.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the preparation method of the purple phosphorus/graphene composite material, the bulk purple phosphorus is stripped by adopting a physical method, and no toxic and harmful waste gas and liquid is generated in the preparation process; the purple phosphorus/graphene heterojunction is constructed by a composite method, and the graphene provides electrons for the purple phosphorus, so that the detection of the whole electrical signal of the purple phosphorus/graphene in the sensing process is realized; the purple phosphorus has a work function higher than that of graphene, an adjustable forbidden band width of 1.42-2.54 eV and more active sites, so that the purple phosphorus provides adsorption sites, and the overall adsorption capacity of the composite material is enhanced under the interaction of the purple phosphorus and the graphene.
Further, the substrate adopts Si/SiO2Glass or organic filter membrane, can not influence the test of each item characteristic of purple phosphorus/graphite alkene.
Furthermore, the corrosive liquid obtained through experiments is a mixed solution of ferric chloride and hydrochloric acid, the concentration of the mixed solution is 0.1-1 mol/L, and copper on the graphene growth substrate can be completely removed.
Furthermore, experiments show that the volume ratio of the ferric chloride solution to the hydrochloric acid solution is 1:1, so that the corrosion to copper can be accelerated.
Furthermore, 2-20 layers of graphene are prepared on the surface of the copper foil sample, so that the conductivity of the purple phosphorus can be improved.
Furthermore, the mechanical stripping method, the ultrasonic crushing method and the water bath ultrasonic method have simple procedures and low cost.
Furthermore, experiments show that the ultrasonic cell disruption power is 20-30%, and the effective time is 2-4 hours; the power of the water bath ultrasound is 100-500W, the ultrasound duration is 12-24 hours, and the purple phosphorus stripping efficiency can be improved.
Further, a continuous purple phosphorus film can be obtained by adopting a heat release adhesive tape transfer method, a suction filtration method or a spin coating method.
Furthermore, the number of the purple phosphorus layers is set to be 1-10, so that more abundant active sites can be provided.
In conclusion, the preparation process is safe and pollution-free, and can be completed in an open environment at normal temperature and normal pressure; meanwhile, the invention realizes the application of the purple phosphorus as the gas sensitive material for the first time.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a surface topography of purple phosphorus/graphene composite material;
FIG. 2 is a graph showing the sensitivity variation of pristine graphene and purple phosphorus/graphene in a carbon monoxide atmosphere of 500 ppm;
fig. 3 is a graph showing sensitivity changes of pristine graphene and purple phosphorus/graphene under a nitrogen monoxide atmosphere of 500 ppm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to and includes any and all possible combinations of one or more of the associated listed items.
The invention provides a preparation method of a purple phosphorus/graphene composite gas sensor, which is characterized in that purple phosphorus is transferred to the surface of graphene by adopting spin coating, heat release tape transfer and suction filtration methods to form a purple phosphorus/graphene heterojunction, the graphene provides electrons to realize electrical signal detection, and the purple phosphorus provides active sites with high forbidden bandwidth, dangling bonds and the like to realize adsorption. After the purple phosphorus/graphene composite material adsorbs gas molecules, charges can be transferred between the gas molecules and the composite material, so that the concentration of carriers on the surface of the composite material is changed, the resistance value is changed, an electrical signal is changed, and gas sensing is realized.
The invention relates to a preparation method of a purple phosphorus/graphene composite material, which comprises the following steps:
s1, preparing graphene on the surface of a copper foil through a chemical vapor deposition method, wherein the number of graphene layers is 2-20, placing a copper foil sample carrying the graphene into a corrosive liquid for etching for 2-4 hours, transferring the graphene into deionized water for soaking for 30-60 min for cleaning after copper in the sample is completely etched, transferring into new deionized water for soaking for 30-60 min, and finally transferring the graphene onto a substrate;
the corrosive liquid is a mixed solution of ferric chloride and hydrochloric acid, wherein the ferric chloride solution and the hydrochloric acid solution are mixed according to the volume ratio of 1:1, and the concentration is 0.1-1 mol/L.
The substrate is Si/SiO2Glass or organic filter membranes.
S2, stripping the blocky purple phosphorus crystal by a physical method to obtain a large amount of few-layer or single-layer purple phosphorus, and transferring the purple phosphorus to the surface of the graphene of the substrate in the step S1 to form a purple phosphorus/graphene composite material;
preparing bulk purple phosphorus by chemical vapor transport; physical methods include mechanical exfoliation, ultrasonication, and/or water bath ultrasonication; the transfer method includes heat release tape transfer, suction filtration or spin coating.
S3, assembling the purple phosphorus/graphene composite material obtained in the step S2 into a purple phosphorus/graphene composite gas sensor;
testing the gas-sensitive sensors in the step S3 by adopting a dynamic method and a static method, wherein the testing gases are CO and NH3、NO2、H2O、NO、N2、O2、CO2、H2、SO2Or H2S。
Referring to fig. 1, it can be seen that the purple phosphorus is uniformly distributed on the surface of the graphene film to form a heterojunction, which can improve the sensing characteristics.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performances of the purple phosphorus/graphene composite material on carbon monoxide and nitric oxide are detected. The preparation method comprises the following specific steps:
(1) graphene transfer
FeCl with the concentration of 1mol/l is prepared3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. And after etching for 2 hours, transferring the graphene into deionized water by using filter paper, soaking for 30min, transferring into new deionized water, soaking for 30min, and transferring to an organic filter membrane.
(2) Stripping of purple phosphorus
Putting 10mg of block purple phosphorus into a mortar, adding a small amount of absolute ethyl alcohol, and grinding until the powder is matte and has no obvious particles. After grinding, the powder is transferred into a colorimetric bottle through absolute ethyl alcohol, and then the colorimetric bottle is placed into an ultrasonic cleaning machine and is subjected to ultrasonic treatment for 12 hours in an ice bath in the whole process.
(3) Transfer of purple phosphorus
And (3) placing the organic filter membrane loaded with the graphene in the step (1) into a Buchner funnel, draining the purple phosphorus/ethanol solution in the step (2) through a glass rod, pouring into the Buchner funnel, and performing suction filtration to compound the purple phosphorus and the graphene.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
And (3) coating silver colloid on two ends of the graphene covered with the purple phosphorus in the step 3 to serve as electrodes, placing the sensor in an atmosphere of 500ppm of nitric oxide or carbon monoxide, and adsorbing NO and CO molecules to be detected on the surface of the purple phosphorus to generate charge transfer so as to cause resistance change. Under the atmosphere concentration, the resistance change rate of the sensor in NO atmosphere can reach 25.23%, and the obtained change rate curve is shown in figure 2; the rate of change of resistance in a CO atmosphere can reach 20.00%, and the resulting rate of change curve is shown in fig. 3.
Example 2
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performance of the purple phosphorus/graphene composite material on nitric oxide is detected. The preparation method comprises the following specific steps:
(1) graphene transfer
FeCl with the concentration of 0.1mol/l is prepared3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. After 3 hours of etching, transferring graphene into deionized water by using filter paper, soaking for 40min, transferring into new deionized water, soaking for 40min, and transferring into Si/SiO2And a glass substrate.
(2) Stripping of purple phosphorus
Putting 10mg of block purple phosphorus into a mortar, adding a small amount of absolute ethyl alcohol, and grinding until the powder is matte and has no obvious particles. And transferring the powder into a colorimetric bottle through absolute ethyl alcohol after grinding, placing the colorimetric bottle into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 24 hours in an ice bath in the whole process.
(3) Transfer of purple phosphorus
And (3) placing the graphene sample obtained in the step (1) on a spin coating instrument, and dropwise adding the purple phosphorus/ethanol solution subjected to ultrasonic treatment in the step (2) to the surface of the graphene sample through a liquid-transferring gun.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
And (3) coating silver colloid on two ends of the graphene covered with the purple phosphorus in the step 3 to serve as electrodes, placing the sensor in a nitrogen monoxide atmosphere of 500ppm, and adsorbing NO molecules to be detected on the surface of the purple phosphorus to generate charge transfer so as to cause resistance change. Under the atmosphere concentration, the resistance change rate of the sensor can reach 8.43 percent.
Example 3
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performance of the purple phosphorus/graphene composite material on nitric oxide is detected. The preparation method comprises the following specific steps:
(1) graphene transfer
Prepared at a concentration of 0.5mol/lFeCl3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. After etching for 2-4 hours, transferring graphene into deionized water by using filter paper, soaking for 50min, transferring into new deionized water, soaking for 50min, and transferring into Si/SiO2And a glass substrate.
(2) Stripping of purple phosphorus
10mg of bulk purple phosphorus was placed on the surface of a blue tape and crushed, and the purple phosphorus was mechanically peeled off by repeated tape-to-tape bonding.
(3) Transfer of purple phosphorus
Cutting the thermal release adhesive tape to 10mm x 10mm, and attaching the thermal release adhesive tape to the blue film adhesive tape loaded with the mechanically stripped purple phosphorus in the step 2; cutting the thermal release adhesive tape along the edge of the blue film adhesive tape, tearing off the blue film adhesive tape, and attaching the thermal release adhesive tape carrying purple phosphorus to the substrate carrying graphene in the step 1; and (3) placing the substrate on a heating table, and heating at 60 ℃ for about 10s to volatilize the glue, so that the purple phosphorus is remained on the surface of the graphene to be compounded with the graphene.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
And (3) coating silver colloid on two ends of the graphene covered with the purple phosphorus in the step 3 to serve as electrodes, placing the sensor in a nitrogen monoxide atmosphere of 500ppm, and adsorbing NO molecules to be detected on the surface of the purple phosphorus to generate charge transfer so as to cause resistance change. Under the atmosphere concentration, the resistance change rate of the sensor can reach 1.25%.
Example 4
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performances of the purple phosphorus/graphene composite material on ammonia gas are detected. The preparation method comprises the following specific steps:
(1) graphene transfer
FeCl with the concentration of 0.6mol/l is prepared3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. After etching for 2 hours, transferring graphene into deionized water by using filter paper, soaking for 60min, transferring into new deionized water, soaking for 60min, and transferring into Si/SiO2And a glass substrate.
(2) Stripping of purple phosphorus
10mg of bulk purple phosphorus was placed on the surface of a blue tape and crushed, and the purple phosphorus was mechanically peeled off by repeated tape-to-tape bonding.
(3) Transfer of purple phosphorus
Cutting the thermal release adhesive tape to 10mm x 10mm, and attaching the thermal release adhesive tape to the blue film adhesive tape loaded with the mechanically stripped purple phosphorus in the step 2; cutting the thermal release adhesive tape along the edge of the blue film adhesive tape, tearing off the blue film adhesive tape, and attaching the thermal release adhesive tape carrying purple phosphorus to the substrate carrying graphene in the step 1; and (3) placing the substrate on a heating table, and heating at 60 ℃ for about 10s to volatilize the glue, so that the purple phosphorus is remained on the surface of the graphene to be compounded with the graphene.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
Coating silver colloid as electrodes at two ends of the purple phosphorus-covered graphene in the step 3, placing the sensor in 1000ppm nitrogen monoxide atmosphere, and measuring NH3Molecules are adsorbed on the surface of purple phosphorus, and charge transfer is generated, so that the resistance is changed. Under the atmosphere concentration, the resistance change rate of the sensor can reach 5.6%.
Example 5
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performances of the purple phosphorus/graphene composite material on nitrogen dioxide are detected. The preparation method comprises the following specific steps:
(1) graphene transfer
FeCl with the concentration of 0.3mol/l is prepared3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. After etching for 3 hours, transferring graphene into deionized water by using filter paper, soaking for 45min, transferring into new deionized water, soaking for 45min, and transferring into Si/SiO2And a glass substrate.
(2) Stripping of purple phosphorus
Putting 10mg of block purple phosphorus into a mortar, adding a small amount of absolute ethyl alcohol, and grinding until the powder is matte and has no obvious particles. After grinding, the powder is transferred into a colorimetric bottle through absolute ethyl alcohol, and then the colorimetric bottle is placed into an ultrasonic cleaning machine and is subjected to ultrasonic treatment for 12 hours in an ice bath in the whole process.
(3) Transfer of purple phosphorus
And (3) placing the graphene sample obtained in the step (1) on a spin coating instrument, and dropwise adding the purple phosphorus/ethanol solution subjected to ultrasonic treatment in the step (2) to the surface of the graphene sample through a liquid-transferring gun.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
Coating silver colloid as electrodes at two ends of the graphene covered with the purple phosphorus in the step 3, placing the sensor in a nitrogen monoxide atmosphere of 500ppm, and measuring NO2Molecules are adsorbed on the surface of purple phosphorus, and charge transfer is generated, so that the resistance is changed. Under the atmosphere concentration, the resistance change rate of the sensor can reach 2.6%.
Example 6
The purple phosphorus is peeled off by a physical method, transferred to the surface of graphene to be compounded with the graphene, and the adsorption and desorption performances of the purple phosphorus/graphene composite material on carbon dioxide are detected. The preparation method comprises the following specific steps:
(1) graphene transfer
FeCl with the concentration of 0.1mol/l is prepared3And the/HCl solution is used for etching copper, and graphene/copper foil with the area of 10mm x 10mm is cut and placed on the surface of the etching solution. After etching for 4 hours, transferring graphene into deionized water by using filter paper, soaking for 55min, transferring into new deionized water, soaking for 55min, and transferring into Si/SiO2And a glass substrate.
(2) Stripping of purple phosphorus
10mg of bulk purple phosphorus was placed on the surface of a blue tape and crushed, and the purple phosphorus was mechanically peeled off by repeated tape-to-tape bonding.
(3) Transfer of purple phosphorus
Cutting the thermal release adhesive tape to 10mm x 10mm, and attaching the thermal release adhesive tape to the blue film adhesive tape loaded with the mechanically stripped purple phosphorus in the step 2; cutting the thermal release adhesive tape along the edge of the blue film adhesive tape, tearing off the blue film adhesive tape, and attaching the thermal release adhesive tape carrying purple phosphorus to the substrate carrying graphene in the step 1; and (3) placing the substrate on a heating table, and heating at 60 ℃ for about 10s to volatilize the glue, so that the purple phosphorus is remained on the surface of the graphene to be compounded with the graphene.
(4) Purple phosphorus/graphene composite gas sensor assembly and test
Coating silver colloid as electrodes at two ends of the purple phosphorus-covered graphene in the step 3, placing the sensor in a nitrogen monoxide atmosphere of 500ppm, and measuring CO2Molecules are adsorbed on the surface of purple phosphorus, and charge transfer is generated, so that the resistance is changed. Under the atmosphere concentration, the resistance change rate of the sensor can reach 0.79 percent.
In summary, according to the preparation method of the purple phosphorus/graphene composite gas sensor, the heterojunction is constructed between the two materials, the graphene provides electrons, and the purple phosphorus provides adsorption sites, so that the application of the purple phosphorus as the gas sensor for measurement is realized, and compared with pure graphene, the resistance change is improved by more than 30 times of the original resistance change; the preparation process of the invention is safe and pollution-free, and can be completed in an open environment at normal temperature and normal pressure.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the purple phosphorus/graphene composite material is characterized by comprising the following steps:
s1, preparing graphene on the surface of a copper foil sample, placing the copper foil sample carrying the graphene into a corrosive liquid for etching, transferring the graphene into deionized water for cleaning after copper in the copper foil sample is completely etched, and then transferring the graphene onto a substrate;
s2, stripping the bulk purple phosphorus crystal by a physical method to obtain purple phosphorus, and transferring the purple phosphorus to the surface of the graphene on the substrate of the step S1 to form the purple phosphorus/graphene composite material.
2. The method of claim 1, wherein in step S1, the substrate is Si/SiO2Glass or organic filter membranes.
3. The method according to claim 1, wherein in step S1, the etching solution is a mixed solution of ferric chloride and hydrochloric acid, and the concentration of the mixed solution is 0.1-1 mol/L.
4. The method of claim 3, wherein the volume ratio of the ferric chloride solution to the hydrochloric acid solution is 1: 1.
5. The method according to claim 1, wherein in step S1, 2-20 layers of graphene are prepared on the surface of the copper foil sample.
6. The method according to claim 1, wherein in step S2, the physical method includes any one of a mechanical peeling method, an ultrasonic crushing method, and a water bath ultrasonic method.
7. The method according to claim 6, wherein the ultrasonic cell disruption method adopts the ultrasonic cell disruption power of 20-30% and the effective time of 2-4 hours; the power of the water bath ultrasound is 100-500W, and the ultrasound duration is 12-24 hours.
8. The method of claim 1, wherein in step S2, the purple phosphorus is transferred to the graphene surface of the substrate in step S1 by thermal release tape transfer, suction filtration or spin coating.
9. The method according to claim 1, wherein in step S2, the number of purple phosphorus layers obtained by peeling is 1-10.
10. The purple phosphorus/graphene composite material prepared by the method according to claim 1 is applied to a purple phosphorus/graphene composite gas sensor.
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