CN114113238A - Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof - Google Patents
Gas sensor based on three-dimensional porous graphene @ quantum dot composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gas sensor based on a three-dimensional porous graphene @ quantum dot composite material and a preparation method thereof, wherein the prepared three-dimensional porous graphene and SnO2And mixing the quantum dots to obtain a three-dimensional porous graphene @ quantum dot composite material, and spin-coating the three-dimensional porous graphene @ quantum dot composite material on an electrode sheet to obtain the gas sensor of the three-dimensional porous graphene @ quantum dot composite material. According to the invention, the composite material is formed by the quasi-zero-dimensional material quantum dots and the three-dimensional porous graphene, and the gas sensor based on the three-dimensional graphene @ quantum dot composite material is obtained by utilizing the advantages of small size, large specific surface area and high activity of the quantum dots and the ultrahigh carrier mobility of the three-dimensional graphene. Gas sensor energy prepared by the method of the present inventionThe low concentration target gas is detected at a lower operating temperature. The preparation method is simple and controllable in process and is suitable for mass preparation of the gas sensor.
Description
Technical Field
The invention belongs to the technical field of sensors, relates to a nano gas sensor and a preparation method thereof, and particularly relates to a gas sensor based on a three-dimensional porous graphene @ quantum dot composite material and a preparation method thereof.
Background
Sigma bonds formed among carbon atoms in the graphene structure layer have super strong bond energy, so that the graphene structure layer has the characteristic of high hardness; the graphene has unique electric conduction and heat conduction characteristics due to a free electron network formed by pi electrons vertical to the plane; compared with a traditional conductor, the hole mobility on the surface of graphene is far beyond, so that the graphene has extremely high transmission performance and a free electron moving space, the traditional two-dimensional graphene has many advantages, but the single-layer graphene is only 0.34 nm thick, and is difficult to identify and operate by naked eyes, and the application of the graphene in certain macroscopic devices is greatly limited. The three-dimensional graphene refers to a porous structure material formed on the basis of the two-dimensional graphene, is formed by stacking single-layer layers of the two-dimensional graphene, inherits the excellent performance of the two-dimensional graphene, and has the advantages of larger specific surface area, higher electronic transmission speed, higher mechanical strength, visibility by naked eyes, convenience in operation and more suitability for specific application.
Tin dioxide (SnO)2) Is light yellow, white or light gray powder, and has wider band gap energy (3.6 eV) and smaller exciton binding energy (130 meV) at room temperature. Simultaneous SnO2The catalyst also has the advantages of excellent thermodynamics, mechanical stability and high catalytic activity, so that researchers make a great deal of research on the use value of the catalyst. The sensor prepared by the method is suitable for monitoring partial combustible, toxic and polluted gases. As a zero-dimensional semiconductor material, the quantum dots have excellent film-forming property at room temperature, and do not need high-temperature calcination during device manufacturing, thereby reducing manufacturing cost. In addition, the low-temperature preparation process can enable the prepared material to be more suitable for room temperature detection; secondly, the size of the quantum dot is generally within 20 nm, and the quantum dot is beneficial to the adsorption reaction process of gas molecules due to small volume, large surface area and high activity; in addition, the quantum dots can be further modified according to the adjustable band gap of the size effectEasily combined with other gas sensitive materials. Therefore, the material is an ideal gas sensitive material for preparing a low-power high-performance gas sensor. In 2004, the kanstein norworth and anderlich heimer of manchester university in the united kingdom developed the presence of graphene in the trial, from which the nobel prize was obtained in 2010. Due to its outstanding theoretical properties, researchers have invested considerable effort in the graphene material industry. For example, sigma bonds formed among carbon atoms in the graphene structure layer enable the graphene structure layer to have high hardness; the graphene has unique electric conduction and heat conduction characteristics due to a free electron network formed by pi electrons vertical to a plane; compared with a traditional conductor, the hole mobility of the graphene surface is far beyond, so that the graphene has extremely high transmittance and free space for electron movement. Thus, graphene-based materials, including reduced graphene oxide-based materials, are considered by many to be promising gas-sensitive materials. However, quantum dots and graphene also have their disadvantages. The low carrier mobility limits the application of quantum dot materials in the field of sensors, and the ultra-fast recombination, low light absorption, easy aggregation, low dispersion and the like of photo-generated carriers of graphene. These deficiencies also hinder the use of such materials in gas sensors. The existing gas sensor adopts a single graphene material and is two-dimensional, and the carrier mobility of the material is low, so that the working temperature of the gas sensor is high. The two-dimensional graphene composite material has small specific surface area and low carrier mobility, and cannot exert the advantages of a nanocrystalline material, so that the gas sensor has low responsivity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a gas sensor based on a three-dimensional porous graphene @ quantum dot composite material and a preparation method thereof, which can detect low-concentration target gas at a lower working temperature, are simple and controllable in preparation method and are suitable for mass preparation of the gas sensor.
In order to solve the technical problem, the invention provides a preparation method of a three-dimensional porous graphene @ quantum dot composite material, which comprises the following steps:
preparing Graphene Oxide (GO) dispersion liquid by taking natural graphite flakes as a precursor, preparing positively charged microspheres (PAS microspheres) by aminated polystyrene microspheres (PS microspheres), wrapping the negatively charged GO dispersion liquid on the surface of a three-dimensional template PAS microsphere, and finally removing the PAS microspheres to obtain three-dimensional porous graphene;
heating and stirring oleic acid, oleylamine and stannic chloride pentahydrate to prepare a precursor, adding ethanol into the prepared precursor, and heating to obtain SnO2Quantum dots, SnO prepared by ligand exchange solution pairs2Performing surface ligand exchange on the quantum dots;
exchanging the prepared three-dimensional porous graphene with surface ligands to obtain SnO2And mixing and stirring the quantum dots to obtain the three-dimensional porous graphene @ quantum dot composite material.
Preferably, the preparation method of the GO dispersion comprises the following steps: a Hummers method is adopted, natural graphite flakes are used as precursors to prepare GO, the GO powder is added into deionized water, and the mixture is subjected to ultrasonic treatment for 1-3 hours to prepare GO dispersion liquid.
Preferably, the preparation method of the positively charged PAS microspheres comprises: putting 60-70 wt% of concentrated nitric acid and 95-99 wt% of concentrated sulfuric acid into a beaker according to a volume ratio of (3: 5) - (4: 5), adding 1-10 mL of PS microsphere emulsion with the concentration of 2.5 wt% into the beaker to react for 1-4 h, adding 50-70 mL of NaOH solution with the mass fraction of 2 mol/L, and then adding Na2S2O4 And 2-4 g of the PAS microspheres serving as a reducing agent, reacting for 4-6 h, and washing the reacted mixture to reach the pH =7 by using a circulating vacuum pump to obtain the PAS microspheres with positive charges.
Preferably, the preparation method of the three-dimensional porous graphene comprises the following steps: mixing the prepared GO dispersion liquid with the PAS microspheres with positive charges according to the volume ratio of (2: 5) - (3: 5), performing ultrasonic treatment for 1-2 hours, and centrifuging at the centrifugal speed of 1000-8000 rpm for 10-30 min; taking out the supernatant, drying in a drying oven at 60-100 ℃, taking out the reaction substances, and grinding into powder to obtain a GO/PAS compound; placing the GO/PAS compound in a single-channel tube furnace, heating for 1-3 h at a constant temperature in an argon atmosphere at 400-800 ℃, wherein the heating rate is 5-10 ℃/min, heating to 400-800 ℃, removing a PAS template, and reducing GO to obtain three-dimensional porous graphene powder.
Preferably, the SnO2The preparation method of the quantum dot comprises the following steps: adding 1-5 mmol SnCl into a three-neck flask filled with 10-30 mL of oleic acid and 1-3 mL of oleylamine4·5H2Adding 10-100 umL deionized water, and then putting the mixture into a three-neck flask in a magnetic stirrer; vacuumizing, raising the temperature to 60-1000 ℃, closing a vacuum valve, and then introducing nitrogen to keep the state for 4-8 hours; taking out the solution from the three-neck flask, moving the solution into the high-pressure kettle, adding 5-30 mL of ethanol into the high-pressure kettle, then placing the high-pressure kettle into a vacuum oven, setting the heat preservation temperature to be 150-180 ℃, the heat preservation time to be 2-5 h, and the heating rate to be 5-10 ℃/min.
Preferably, the SnO2The method for performing surface ligand exchange on the quantum dots comprises the following steps: adsorbing the electrode plate on a tray, and taking 10-50 mL SnO by using a pipette2Placing the quantum dot solution on an electrode plate for 5-10 seconds, and then spin-coating at 1000-3000 rpm for 10-40 seconds to form a layer of thin film; after spin coating, the CuCl is added2Methanol solution or NaNO2Dripping a methanol solution on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, carrying out ligand exchange on the surface of the quantum dot, adjusting the rotating speed of a spin coater to be 1000-3000 rpm after 10-45 s, and adding CuCl on the surface2Methanol solution or NaNO2And (5) drying the methanol solution.
Preferably, the prepared three-dimensional porous graphene and chloroform are subjected to ultrasonic dispersion for 1-2 hours to obtain a three-dimensional porous graphene solution, wherein the concentration of the three-dimensional porous graphene in the chloroform is 10% -20%; mixing the prepared three-dimensional porous graphene solution with SnO2The quantum dot solution is mixed according to the molar ratio of (2: 5) - (3: 5), and then stirred on a magnetic stirrer for 10-30 hours.
The invention also provides the three-dimensional porous graphene @ quantum dot composite material prepared by the method.
The invention also provides a preparation method of the gas sensor based on the three-dimensional porous graphene and quantum dot composite material, and the three-dimensional porous graphene and quantum dot composite material is spin-coated on an electrode sheet by a spin coating process to obtain the gas sensor based on the three-dimensional porous graphene and quantum dot composite material.
Preferably, the method specifically comprises the following steps: the interdigital electrode plate is absorbed on a base of a spin coater, the three-dimensional porous graphene @ quantum dot composite material solution is dropped on the electrode plate, the electrode plate can completely cover the whole electrode plate, then the rotating speed of the spin coater is adjusted to be 1000-3000 rpm, and the spin coating time is 10-45 s.
The invention also provides a gas sensor made of the three-dimensional porous graphene @ quantum dot composite material and prepared by the preparation method.
The invention achieves the following beneficial effects: according to the invention, the composite material is formed by the quasi-zero-dimensional material quantum dots and the three-dimensional porous graphene, and the gas sensor based on the three-dimensional graphene @ quantum dot composite material, which realizes low power consumption and high sensitivity at room temperature, is obtained by utilizing the advantages of small size, large specific surface area and high activity of the quantum dots, the good gas adsorption capacity of the quantum dots at room temperature, and the ultrahigh carrier mobility and large specific surface area of the three-dimensional graphene. The gas sensor prepared by the invention can detect low-concentration target gas at lower working temperature, and the preparation method is simple and controllable, and is suitable for mass preparation of gas sensors.
Drawings
Fig. 1 is a TEM image and raman analysis of three-dimensional porous graphene;
FIG. 2 shows three-dimensional porous graphene @ SnO2A TEM image of the quantum dot composite;
FIG. 3 is SnO2Quantum dot material and three-dimensional porous graphene @ SnO2An SEM image of a gas-sensitive film of the quantum dot composite material;
fig. 4 is a gas-sensitive characteristic response curve of three-dimensional porous graphene;
FIG. 5 is SnO2The gas-sensitive characteristic response curve of the quantum dot material;
FIG. 6 is a three-dimensional porous graphene @ SnO2The gas-sensitive characteristic response curve of the quantum dot composite material.
Detailed Description
The invention is further described with reference to the following figures and examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
1. Preparing three-dimensional porous graphene:
1) GO is prepared: measuring 130 mL of H2SO4(98%) in a 800 mL beaker, 5 g of graphite and 2.5 g of NaNO were added in that order3The mixture was stirred for 2 hours in an ice bath. After the pre-oxidation treatment, 15 g of KMnO was slowly added4The ice-bath reaction was continued for 2 h. The ice bath was removed and the mixture was stirred in a water bath at 35 ℃ for 1 h. Then 230 mL of deionized water was slowly added, warmed to 98 ℃ and reacted for 30 min, 400 mL of deionized water and 10 mLH were added2O2And stirred for 1 h. After cooling, the filtered reaction product was washed with HCl until no sulfate was present, and then washed with deionized water until neutral (pH = 7) to produce a GO dispersion. This solution was dried in an oven at 80 ℃ to make GO powder. Respectively weighing 90 mg, 180 mg, 360 mg, 720 mg, 1440 mg and 2880 mg of GO powder, adding 10 mL of deionized water, and carrying out ultrasonic treatment for 2h to prepare 9 mg/mL; 18 mg/mL; 36 mg/mL; 72 mg/mL; 144 mg/mL and 288 mg/mL GO dispersions.
2) Preparing aminated polystyrene microspheres: 10 mL of PS microsphere emulsion with the concentration of 2.5 wt% is measured and added into a beaker, under the magnetic stirring of an oil bath at 47 ℃, and then 65 wt% concentrated nitric acid and 98 wt% concentrated sulfuric acid are prepared according to the proportion of 2: 3. Firstly measuring 4 mL of concentrated nitric acid and putting the concentrated nitric acid in a beaker, and then measuring 6 mL of concentrated sulfuric acid and slowly adding the concentrated nitric acid. Adding the prepared mixed acid into the PS emulsion for nitration. After reacting for 2h, repeatedly pumping and filtering the prepared reaction solution by using a circulating vacuum pump until the pH value is 7. And drying the obtained product by using a drying oven at 80 ℃, and storing the obtained product in a beaker for later use, wherein the label is PNS. Putting the PNS microsphere powder obtained in the last reaction in a beaker, putting the beaker in an oil bath kettle at 75 ℃, starting magnetic stirring, adding 60 mL of NaOH solution with the mass fraction of 2 mol/L, and then adding 3 g of Na2S2O4As a reducing agent, after reacting for 4h, the reaction mixture was washed with a circulation vacuum pump to pH =7, and the resulting product was dried with an 80 ℃ drying oven to obtain a product which was stored in a beaker for use, and labeled as PAS.
3) Preparing three-dimensional porous graphene: 0.18 g of PAS microsphere powder is weighed and added with 0.9 ml of deionized water to prepare 2 wt% PAS microsphere emulsion. Add 72 mg/mL GO solution, as per 1: 1, sonicated for 2h, and centrifuged at 8000 rpm for 30 min. And (3) taking out the supernatant, drying in a drying oven at 80 ℃, taking out the reaction substances, and grinding into powder to obtain the GO/PAS compound. Placing the GO/PAS compound in a single-channel tube furnace, heating for 1 h at a constant temperature in an argon atmosphere at 600 ℃, with a heating rate of 5 ℃/min, removing a PAS template, and reducing GO to obtain three-dimensional porous graphene, wherein the three-dimensional porous graphene is shown in a TEM (transmission electron microscope) image and Raman analysis of the three-dimensional porous graphene in figure 1. The left image is a TEM image of three-dimensional graphene, which is seen to consist of many pores, appear as transparent gauze, and with slight aggregation and wrinkling, the attractive effect between sheets is shown, indicating that the remaining part of the functional groups are not reduced. The right graph is the Raman analysis of the three-dimensional graphene, the wavelength used in the experiment is 514 nm, two peaks are respectively a peak at D =1350cm < -1 > and a peak at G =1583cm < -1 >, wherein the occurrence of the D peak is caused by vibration of a graphene ring, and the size and the purity of a graphene crystal grain determine the intensity of a peak value in a graphene Raman spectrum; the G peak appears due to the C-C bond symmetry stretch. The ratio of the D peak intensity and the G peak reflects the defects or vacancies at the edge of the graphene, and the calculated ID/IG =0.932 shows that the defects at the edge of the graphene are more, and the structure is favorable for the adsorption of gas.
2. The specific preparation and synthesis process steps of the quantum dots comprise the following seven steps:
1) seed preparation: to a three-necked flask containing 20 ml of oleic acid and 2.5 ml of amine was added 1.7 mmol of SnCl4·5H2O, 80. mu.l of deionized water was added, and then placed in a three-necked flask in a magnetic stirrer. Vacuumizing, raising the temperature to 80 ℃, closing a vacuum valve, and then introducing nitrogen to keep the state for 6 hours;
2) and (3) quantum dot synthesis: taking out the solution from the three-neck flask, moving the solution into an autoclave, adding 10 ml of ethanol into the autoclave, then placing the autoclave into a vacuum oven, setting the heat preservation temperature to be 180 ℃, the heat preservation time to be 3 h, and the heating rate to be 10 ℃/min;
3) and (3) cleaning the quantum dots: after the temperature of the oven is naturally cooled to room temperature, adding ethanol into the solution obtained in the step 2), centrifuging, taking out the centrifuge tube, removing the supernatant, leaving the bottom precipitate, uniformly dispersing the obtained precipitate with toluene, then adding ethanol again, centrifuging and dispersing in a plurality of centrifuge tubes, and repeating the steps of precipitating and centrifuging three times. Finally, dispersing the obtained precipitate in toluene for later use;
4) spin coating of quantum dots: placing the electrode slice on a tray of a spin coater, and opening an air pump to suck the electrode slice onto the tray; then, 50 ml of the tin dioxide quantum dot solution was pipetted and placed on the electrode plate for 10 seconds, followed by spin coating at 1000 rpm for 30 seconds to form a thin film.
5) Repeating spin coating: repeating the steps in 4) once;
6) ligand exchange: after 30 seconds of spin coating, CuCl was added2Dripping methanol solution (10 mg/mL) on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, and performing ligand exchange on the surface of the quantum dot for 45 s; adjusting the rotating speed of a spin coater to 1000 rpm, and adding CuCl on the surface2Drying the methanol solution; repeating the above operations three times to ensure that the ligand exchange is fully completed;
7) removing impurities: after 45s of spin coating, dripping ethanol solution on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, so as to remove the residual CuCl in the step 62Methanol solution, after 15 s; adjusting the rotating speed of the spin coater to 1100 rpm; this operation was repeated three times to ensure complete removal of impurities.
3. The preparation method of the gas sensor based on the three-dimensional porous graphene @ quantum dot composite material comprises the following steps:
1) preparing a three-dimensional porous graphene solution: weighing 10 mg of prepared three-dimensional porous graphene on an analytical balance, weighing 10 ml of chloroform by using a measuring cylinder, then putting the two substances into a beaker, and carrying out ultrasonic cleaning for half an hour to uniformly disperse the solution;
2) preparing a three-dimensional porous graphene @ quantum dot composite material: mixing the three-dimensional porous graphene solution prepared in the step 1 with SnO2The ratio of the quantum dot solution according to the molar ratio of 1:2Mixing, and stirring for 24 hours on a magnetic stirrer to obtain the three-dimensional porous graphene @ quantum dot composite material, which is three-dimensional porous graphene @ SnO shown in figure 22TEM images of quantum dot composites. FIG. 2 (a) at a scale of 500 nm, transparent gauze-like graphene can be seen, and graphene agglomeration is not seen, indicating SnO2There is sufficient interfacial contact with graphene, and fig. 2(b) at a scale of 20 nm, a dotted SnO can be seen2The graphene is uniformly distributed on the surface of the graphene, and SnO does not appear in the graph2Agglomeration, taken together, indicates SnO2the/3D rGO composite material is successfully prepared. FIG. 2(c) SnO is visible within the blue circle at a scale of 10 nm2An obvious interface exists between the quantum dots and the graphene, and the lattice stripes have coherence, so that a P-N heterojunction is formed between the quantum dots and the graphene, the transmission speed of electrons is increased due to the existence of the P-N heterojunction, and the detection of the gas-sensitive performance is facilitated.
3) Spin coating preparation at room temperature: firstly, turning on a spin coater and a vacuum pump, then sucking an interdigital electrode plate on a base, measuring 150 uL of three-dimensional porous graphene @ quantum dot solution through a liquid-transferring gun, uniformly dripping the solution on the electrode plate to enable the solution to completely cover the whole electrode plate, then adjusting the rotating speed of the spin coater to enable the rotating speed to reach 1000 rpm, setting the spin coating time to be 30 s, and finally repeating the step twice to ensure that a composite material film exists on the surface of the electrode plate, as shown in fig. 3, fig. 3 is SnO2Quantum dot material and three-dimensional porous graphene @ SnO2And (3) an SEM image of a gas-sensitive film of the quantum dot composite material. FIG. 3 shows SEM images of gas-sensitive films before and after recombination, and FIG. 3(a) shows monomer SnO2Quantum dot material thin film, FIG. 3(b) is SnO2the/3D rGO composite material film is shown in the figure, after composite treatment, the surface appearance of the composite material is changed from dense to loose porous structure, and according to the analysis, the three-dimensional porous graphene can provide larger specific surface area, so that a plurality of fine holes are formed on the surface of the film, and the porous crack structure of the film is beneficial to gas adsorption and diffusion.
FIGS. 4-6 show three-dimensional porous graphene and SnO2Quantum dot material and three-dimensional porous graphene @ SnO2The gas-sensitive characteristic response curve of the quantum dot composite material. FIG. 4 is a gas-sensitive response curve of a three-dimensional graphene material at 25 ℃, and the result shows that the three-dimensional graphene material has NO2The response values at concentrations of 50 ppm, 25 ppm, 10 ppm and 5 ppm are approximately 7.9, 6, 4.2 and 3.9.
FIG. 5 is SnO2The gas-sensitive response curve of the quantum dot material at 25 ℃ shows that along with NO2The lower the concentration and the lower the gas sensitive response value of the material, in NO2The response values at concentrations of 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm and 5 ppm were 12.02, 8.23, 6.91, 5.03, 4.68 and 3.1.
FIG. 6 is SnO2The gas-sensitive response curve of the/3D rGO composite material at 25 ℃ shows that along with NO2The lower the concentration and the lower the gas sensitive response value of the material, in NO2Response values at concentrations of 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, and 5 ppm were 66.03, 45.32, 32.41, 24.07, 11.72, and 7.1.
As can be seen from the figure, the responsivity of the composite material is greatly improved compared with that of two single materials.
Example 2
1. Preparing three-dimensional porous graphene:
1) GO is prepared: measuring 130 mL of H2SO4(98%) in a 800 mL beaker, 5 g of graphite and 2.5 g of NaNO were added in that order3The mixture was stirred for 2 hours in an ice bath. After the pre-oxidation treatment, 15 g of KMnO was slowly added4The ice-bath reaction was continued for 2 h. The ice bath was removed and the mixture was stirred in a water bath at 35 ℃ for 1 h. Then 230 mL of deionized water was slowly added, warmed to 98 ℃ and reacted for 30 min, 400 mL of deionized water and 10 mLH were added2O2And stirred for 1 h. After cooling, the filtered reaction product was washed with HCl until no sulfate was present, and then washed with deionized water until neutral (pH = 7) to produce a GO dispersion. This solution was dried in an oven at 80 ℃ to make GO powder. Respectively weighing 90 mg, 180 mg, 360 mg, 720 mg, 1440 mg and 2880 mg of GO powder, adding 10 mL of deionized water, and carrying out ultrasonic treatment for 2h to prepare 9 mg/mL; 18 mg/mL; 36 mg/mL;72 mg/mL; 144 mg/mL and 288 mg/mL GO dispersions.
2) Preparing aminated polystyrene microspheres: 10 mL of PS microsphere emulsion with the concentration of 2.5 wt% is measured and added into a beaker, under the magnetic stirring of an oil bath at 47 ℃, and then 65 wt% concentrated nitric acid and 98 wt% concentrated sulfuric acid are prepared according to the proportion of 1: 3. Firstly measuring 4 mL of concentrated nitric acid and putting the concentrated nitric acid in a beaker, and then measuring 6 mL of concentrated sulfuric acid and slowly adding the concentrated nitric acid. Adding the prepared mixed acid into the PS emulsion for nitration. After reacting for 2h, repeatedly pumping and filtering the prepared reaction solution by using a circulating vacuum pump until the pH value is 7. And drying the obtained product by using a drying oven at 80 ℃, and storing the obtained product in a beaker for later use, wherein the label is PNS. Putting the PNS microsphere powder obtained in the last reaction in a beaker, putting the beaker in an oil bath kettle at 75 ℃, starting magnetic stirring, adding 60 mL of NaOH solution with the mass fraction of 2 mol/L, and then adding 3 g of Na2S2O4As a reducing agent, after reacting for 4h, the reaction mixture was washed with a circulation vacuum pump to pH =7, and the resulting product was dried with an 80 ℃ drying oven to obtain a product which was stored in a beaker for use, and labeled as PAS.
3) Preparing three-dimensional porous graphene: 0.18 g of PAS microsphere powder is weighed and added with 0.9 ml of deionized water to prepare 2 wt% PAS microsphere emulsion. Add 72 mg/mL GO solution as per 2:3, sonicated for 2h, and centrifuged at 8000 rpm for 30 min. And (3) taking out the supernatant, drying in a drying oven at 80 ℃, taking out the reaction substances, and grinding into powder to obtain the GO/PAS compound. And (3) placing the GO/PAS compound in a single-channel tube furnace, heating for 1 h at a constant temperature in an argon atmosphere at 600 ℃, removing a PAS template at a heating rate of 5 ℃/min, and reducing GO to obtain the three-dimensional porous graphene.
2. The specific preparation and synthesis process steps of the quantum dots comprise the following seven steps:
1) seed preparation: to a three-necked flask containing 20 ml of oleic acid and 2.5 ml of amine was added 1.7 mmol of SnCl4·5H2O, 80. mu.l of deionized water was added, and then placed in a three-necked flask in a magnetic stirrer. Vacuumizing, raising the temperature to 80 ℃, closing a vacuum valve, and then introducing nitrogen to keep the state for 6 hours;
2) and (3) quantum dot synthesis: taking out the solution from the three-neck flask, moving the solution into an autoclave, adding 10 ml of ethanol into the autoclave, then placing the autoclave into a vacuum oven, setting the heat preservation temperature to be 180 ℃, the heat preservation time to be 3 h, and the heating rate to be 10 ℃/min;
3) and (3) cleaning the quantum dots: after the temperature of the oven is naturally cooled to room temperature, adding ethanol into the solution obtained in the step 2), centrifuging, taking out the centrifuge tube, removing the supernatant, leaving the bottom precipitate, uniformly dispersing the obtained precipitate with toluene, then adding ethanol again, centrifuging and dispersing in a plurality of centrifuge tubes, and repeating the steps of precipitating and centrifuging three times. Finally, dispersing the obtained precipitate in toluene for later use;
4) spin coating of quantum dots: placing the electrode slice on a tray of a spin coater, and opening an air pump to suck the electrode slice onto the tray; then, 50 ml of the tin dioxide quantum dot solution was pipetted and placed on the electrode plate for 10 seconds, followed by spin coating at 1000 rpm for 30 seconds to form a thin film.
5) Repeating spin coating: repeating the steps in 4) once;
6) ligand exchange: after 30 seconds of spin coating, NaNO was added2Dripping methanol solution (10 mg/mL) on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, and performing ligand exchange on the surface of the quantum dot for 45 s; adjusting the rotating speed of a spin coater to 1000 rpm, and adding NaNO on the surface2Drying the methanol solution; repeating the above operations three times to ensure that the ligand exchange is fully completed;
7) removing impurities: after 45s of spin coating, dripping ethanol solution on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, so as to remove the residual NaNO in the step 62Methanol solution, after 15 s; adjusting the rotating speed of the spin coater to 1100 rpm; this operation was repeated three times to ensure complete removal of impurities.
3. The preparation method of the gas sensor based on the three-dimensional porous graphene @ quantum dot composite material comprises the following steps:
1) preparing a three-dimensional porous graphene solution: weighing 10 mg of prepared three-dimensional porous graphene on an analytical balance, weighing 10 ml of chloroform by using a measuring cylinder, then putting the two substances into a beaker, and carrying out ultrasonic cleaning for half an hour to uniformly disperse the solution;
2) preparing a three-dimensional porous graphene @ quantum dot composite material: mixing the three-dimensional porous graphene solution prepared in the step 1 with SnO2And mixing the quantum dot solution according to the molar ratio of 2:3, and stirring for 24 hours on a magnetic stirrer to obtain the three-dimensional porous graphene @ quantum dot composite material.
3) Spin coating preparation at room temperature: firstly, opening a spin coater and a vacuum pump, then sucking an interdigital electrode plate on a base, measuring 150 uL of three-dimensional porous graphene @ quantum dot solution through a liquid-transferring gun, uniformly dripping the solution on the electrode plate to enable the electrode plate to completely cover the whole electrode plate, then adjusting the rotating speed of the spin coater to enable the rotating speed to reach 1000 rpm, setting the spin coating time to be 30 s, and finally repeating the step twice to ensure that a composite material film exists on the surface of the electrode plate.
Example 3
1. Preparing three-dimensional porous graphene:
1) GO is prepared: measuring 130 mL of H2SO4(98%) in a 800 mL beaker, 5 g of graphite and 2.5 g of NaNO were added in that order3The mixture was stirred for 2 hours in an ice bath. After the pre-oxidation treatment, 15 g of KMnO was slowly added4The ice-bath reaction was continued for 2 h. The ice bath was removed and the mixture was stirred in a water bath at 35 ℃ for 1 h. Then 230 mL of deionized water was slowly added, warmed to 98 ℃ and reacted for 30 min, 400 mL of deionized water and 10 mLH were added2O2And stirred for 1 h. After cooling, the filtered reaction product was washed with HCl until no sulfate was present, and then washed with deionized water until neutral (pH = 7) to produce a GO dispersion. This solution was dried in an oven at 80 ℃ to make GO powder. Respectively weighing 90 mg, 180 mg, 360 mg, 720 mg, 1440 mg and 2880 mg of GO powder, adding 10 mL of deionized water, and carrying out ultrasonic treatment for 2h to prepare 9 mg/mL; 18 mg/mL; 36 mg/mL; 72 mg/mL; 144 mg/mL and 288 mg/mL GO dispersions.
2) Preparing aminated polystyrene microspheres: 10 mL of PS microsphere emulsion with the concentration of 2.5 wt% is measured and added into a beaker, under the magnetic stirring of an oil bath at 47 ℃, and then 65 wt% concentrated nitric acid and 98 wt% concentrated sulfuric acid are prepared according to the proportion of 2: 3. First measuring 4And putting the mL of concentrated nitric acid into a beaker, measuring 6 mL of concentrated sulfuric acid, and slowly adding the concentrated nitric acid into the beaker. Adding the prepared mixed acid into the PS emulsion for nitration. After reacting for 2h, repeatedly pumping and filtering the prepared reaction solution by using a circulating vacuum pump until the pH value is 7. And drying the obtained product by using a drying oven at 80 ℃, and storing the obtained product in a beaker for later use, wherein the label is PNS. Putting the PNS microsphere powder obtained in the last reaction in a beaker, putting the beaker in an oil bath kettle at 75 ℃, starting magnetic stirring, adding 60 mL of NaOH solution with the mass fraction of 2 mol/L, and then adding 3 g of Na2S2O4As a reducing agent, after reacting for 4h, the reaction mixture was washed with a circulation vacuum pump to pH =7, and the resulting product was dried with an 80 ℃ drying oven to obtain a product which was stored in a beaker for use, and labeled as PAS.
3) Preparing three-dimensional porous graphene: 0.18 g of PAS microsphere powder is weighed and added with 0.9 ml of deionized water to prepare 2 wt% PAS microsphere emulsion. Add 72 mg/mL GO solution, as per 1:3, sonicated for 2h, and centrifuged at 8000 rpm for 30 min. And (3) taking out the supernatant, drying in a drying oven at 80 ℃, taking out the reaction substances, and grinding into powder to obtain the GO/PAS compound. And (3) placing the GO/PAS compound in a single-channel tube furnace, heating for 1 h at a constant temperature in an argon atmosphere at 600 ℃, removing a PAS template at a heating rate of 5 ℃/min, and reducing GO to obtain the three-dimensional porous graphene.
2. The specific preparation and synthesis process steps of the quantum dots comprise the following seven steps:
1) seed preparation: to a three-necked flask containing 20 ml of oleic acid and 2.5 ml of amine was added 1.7 mmol of SnCl4·5H2O, 80. mu.l of deionized water was added, and then placed in a three-necked flask in a magnetic stirrer. Vacuumizing, raising the temperature to 80 ℃, closing a vacuum valve, and then introducing nitrogen to keep the state for 6 hours;
2) and (3) quantum dot synthesis: taking out the solution from the three-neck flask, moving the solution into an autoclave, adding 10 ml of ethanol into the autoclave, then placing the autoclave into a vacuum oven, setting the heat preservation temperature to be 180 ℃, the heat preservation time to be 3 h, and the heating rate to be 10 ℃/min;
3) and (3) cleaning the quantum dots: after the temperature of the oven is naturally cooled to room temperature, adding ethanol into the solution obtained in the step 2), centrifuging, taking out the centrifuge tube, removing the supernatant, leaving the bottom precipitate, uniformly dispersing the obtained precipitate with toluene, then adding ethanol again, centrifuging and dispersing in a plurality of centrifuge tubes, and repeating the steps of precipitating and centrifuging three times. Finally, dispersing the obtained precipitate in toluene for later use;
4) spin coating of quantum dots: placing the electrode slice on a tray of a spin coater, and opening an air pump to suck the electrode slice onto the tray; then, 50 ml of the tin dioxide quantum dot solution was pipetted and placed on the electrode plate for 10 seconds, followed by spin coating at 1000 rpm for 30 seconds to form a thin film.
5) Repeating spin coating: repeating the steps in 4) once;
6) ligand exchange: after 30 seconds of spin coating, CuCl was added2Dripping methanol solution (10 mg/mL) on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, and performing ligand exchange on the surface of the quantum dot for 45 s; adjusting the rotating speed of a spin coater to 1000 rpm, and adding CuCl on the surface2Drying the methanol solution; repeating the above operations three times to ensure that the ligand exchange is fully completed;
7) removing impurities: after 45s of spin coating, dripping ethanol solution on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, so as to remove the residual CuCl in the step 62Methanol solution, after 15 s; adjusting the rotating speed of the spin coater to 1100 rpm; this operation was repeated three times to ensure complete removal of impurities.
3. The preparation method of the gas sensor based on the three-dimensional porous graphene @ quantum dot composite material comprises the following steps:
1) preparing a three-dimensional porous graphene solution: weighing 10 mg of prepared three-dimensional porous graphene on an analytical balance, weighing 10 ml of chloroform by using a measuring cylinder, then putting the two substances into a beaker, and carrying out ultrasonic cleaning for half an hour to uniformly disperse the solution;
2) preparing a three-dimensional porous graphene @ quantum dot composite material: mixing the three-dimensional porous graphene solution prepared in the step 1 with SnO2The quantum dot solution is mixed according to the molar ratio of 1:3, and then magnetic force is appliedStirring the mixture for 24 hours on a stirrer to obtain the three-dimensional porous graphene @ quantum dot composite material.
3) Spin coating preparation at room temperature: firstly, opening a spin coater and a vacuum pump, then sucking an interdigital electrode plate on a base, measuring 150 uL of three-dimensional porous graphene @ quantum dot solution through a liquid-transferring gun, uniformly dripping the solution on the electrode plate to enable the electrode plate to completely cover the whole electrode plate, then adjusting the rotating speed of the spin coater to enable the rotating speed to reach 1000 rpm, setting the spin coating time to be 30 s, and finally repeating the step twice to ensure that a composite material film exists on the surface of the electrode plate.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (11)
1. A preparation method of a three-dimensional porous graphene @ quantum dot composite material is characterized by comprising the following steps:
preparing Graphene Oxide (GO) dispersion liquid by taking natural graphite flakes as a precursor, preparing positively charged microspheres (PAS microspheres) by aminated polystyrene microspheres (PS microspheres), wrapping the negatively charged GO dispersion liquid on the surface of a three-dimensional template PAS microsphere, and finally removing the PAS microspheres to obtain three-dimensional porous graphene;
heating and stirring oleic acid, oleylamine and stannic chloride pentahydrate to prepare a precursor, adding ethanol into the prepared precursor, and heating to obtain SnO2Quantum dots, SnO prepared by ligand exchange solution pairs2Performing surface ligand exchange on the quantum dots;
exchanging the prepared three-dimensional porous graphene with surface ligands to obtain SnO2And mixing and stirring the quantum dots to obtain the three-dimensional porous graphene @ quantum dot composite material.
2. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the preparation method of the GO dispersion liquid is as follows: a Hummers method is adopted, natural graphite flakes are used as precursors to prepare GO, the GO powder is added into deionized water, and the mixture is subjected to ultrasonic treatment for 1-3 hours to prepare GO dispersion liquid.
3. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the preparation method of the positively charged PAS microspheres is as follows: putting 60-70 wt% of concentrated nitric acid and 95-99 wt% of concentrated sulfuric acid into a beaker according to a volume ratio of (3: 5) - (4: 5), adding 1-10 mL of PS microsphere emulsion with the concentration of 2.5 wt% into the beaker to react for 1-4 h, adding 50-70 mL of NaOH solution with the mass fraction of 2 mol/L, and then adding Na2S2O4 And 2-4 g of the PAS microspheres serving as a reducing agent, reacting for 4-6 h, and washing the reacted mixture to reach the pH =7 by using a circulating vacuum pump to obtain the PAS microspheres with positive charges.
4. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the preparation method of the three-dimensional porous graphene is as follows: mixing the prepared GO dispersion liquid with the PAS microspheres with positive charges according to the volume ratio of (2: 5) - (3: 5), performing ultrasonic treatment for 1-2 hours, and centrifuging at the centrifugal speed of 1000-8000 rpm for 10-30 min; taking out the supernatant, drying in a drying oven at 60-100 ℃, taking out the reaction substances, and grinding into powder to obtain a GO/PAS compound; placing the GO/PAS compound in a single-channel tube furnace, heating for 1-3 h at a constant temperature in an argon atmosphere at 400-800 ℃, wherein the heating rate is 5-10 ℃/min, heating to 400-800 ℃, removing a PAS template, and reducing GO to obtain three-dimensional porous graphene powder.
5. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the SnO is2The preparation method of the quantum dot comprises the following steps: adding 1-5 mmol SnCl into a three-neck flask filled with 10-30 mL of oleic acid and 1-3 mL of oleylamine4·5H2Adding 10-100 umL deionized water, and then putting the mixture into a three-neck flask in a magnetic stirrer; vacuumizing, raising the temperature to 60-1000 ℃, closing a vacuum valve, and then introducing nitrogen to maintainIn this state, 4-8 h; taking out the solution from the three-neck flask, moving the solution into the high-pressure kettle, adding 5-30 mL of ethanol into the high-pressure kettle, then placing the high-pressure kettle into a vacuum oven, setting the heat preservation temperature to be 150-180 ℃, the heat preservation time to be 2-5 h, and the heating rate to be 5-10 ℃/min.
6. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the SnO is2The method for performing surface ligand exchange on the quantum dots comprises the following steps: adsorbing the electrode plate on a tray, and taking 10-50 mL SnO by using a pipette2Placing the quantum dot solution on an electrode plate for 5-10 seconds, and then spin-coating at 1000-3000 rpm for 10-40 seconds to form a layer of thin film; after spin coating, the CuCl is added2Methanol solution or NaNO2Dripping a methanol solution on the surface of the electrode plate by using a rubber head dropper to enable the electrode plate to cover the whole film, carrying out ligand exchange on the surface of the quantum dot, adjusting the rotating speed of a spin coater to be 1000-3000 rpm after 10-45 s, and adding CuCl on the surface2Methanol solution or NaNO2And (5) drying the methanol solution.
7. The preparation method of the three-dimensional porous graphene @ quantum dot composite material according to claim 1, wherein the prepared three-dimensional porous graphene and chloroform are subjected to ultrasonic dispersion for 1-2 hours to obtain a three-dimensional porous graphene solution, and the concentration of the three-dimensional porous graphene in the chloroform is 10% -20%; mixing the prepared three-dimensional porous graphene solution with SnO2The quantum dot solution is mixed according to the molar ratio of (2: 5) - (3: 5), and then stirred on a magnetic stirrer for 10-30 hours.
8. The three-dimensional porous graphene @ quantum dot composite material prepared by the method according to any one of claims 1 to 7.
9. The preparation method of the gas sensor based on the three-dimensional porous graphene @ quantum dot composite material as claimed in claim 8, wherein the three-dimensional porous graphene @ quantum dot composite material is spin-coated on an electrode sheet by a spin coating process, so that the gas sensor based on the three-dimensional porous graphene @ quantum dot composite material is obtained.
10. The preparation method according to claim 9, which specifically comprises: the interdigital electrode plate is absorbed on a base of a spin coater, the three-dimensional porous graphene @ quantum dot composite material solution is dropped on the electrode plate, the electrode plate can completely cover the whole electrode plate, then the rotating speed of the spin coater is adjusted to be 1000-3000 rpm, and the spin coating time is 10-45 s.
11. The gas sensor made of the three-dimensional porous graphene @ quantum dot composite material obtained by the preparation method according to claim 9 or 10.
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