CN112903761B - Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof - Google Patents
Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material as well as a preparation method and application thereof, and belongs to the technical field of gas-sensitive materials. The composite material comprises a molybdenum disulfide-reduced graphene oxide composite nanosheet and cuprous oxide hollow nanospheres uniformly loaded on the surface of the composite nanosheet. The method combines a hydrothermal method and a soft template method to prepare the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material, has the advantages of simple process, low cost, environmental friendliness and strong operability, and is favorable for popularization in practical application. The prepared composite material has NO at room temperature 2 The gas has excellent sensitivity, selectivity and stability, and has certain practical significance in the field of the future Internet of things.
Description
Technical Field
The invention belongs to the technical field of gas-sensitive materials, and particularly relates to a molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material as well as a preparation method and application thereof.
Background
With the rapid development of industry and agriculture and the increase of automobile holding amount, the environmental pollution problem (such as haze and photochemical smog) caused by the emission of nitrogen oxides and the like becomes more and more serious. Long term exposure to NO in humans 2 The gas can cause significant damage to the respiratory system as well as to the lung tissue. World health organization enacted regarding NO 2 The air quality criterion of (a) is that the annual average concentration is 40 mu g/m 3 Average concentration at 1 hour 200. mu.g/m 3 . Therefore, development of NO suitable for environmental detection with high sensitivity and high selectivity 2 Gas sensor materials are at hand.
Material systems with nanostructures have received much attention because of their open architecture. Cu (copper) 2 O is a typical p-type semiconductor material, consisting ofHas the advantages of narrow band gap (2.1eV), simple preparation, low cost, environmental friendliness and the like, and has important application value in the gas sensitive field. The morphology of the nano material can greatly influence the property of the nano material, and researches show that the nano material with a hollow shell structure has the advantages of large specific surface area, large internal gap, good surface permeability and the like, and the material with the morphology shows good gas-sensitive performance. Cao et al prepared Cu by hydrothermal method 2 O hollow sphere and preparation of hollow Cu-based hollow sphere 2 O, which was found to be sensitive to 300ppm NO at 350 deg.C 2 Exhibit excellent sensitivity [ S, X, Cao, T, Han, L, L, Peng, C, ZHao, J, Wang, B, Yu, Ceram. int.43(2017)4721]. Zhang et al synthesized multi-layered Cu with porosity by one-pot method 2 O microspheres, with greater sensitivity to 100ppm ethanol than solid Cu at square wave voltage signal (3.5V, 0.4Hz) 2 O is greatly promoted [ H, G, Zhang, Q, S, Zhu, Y, Zhang, Y, Wang, L, ZHao, B, Yu, adv.Funct.Mater.17(2007)2766]. It can be known from observation that the improvement of the performance of the sensor device is based on the supply of external energy, which not only increases the energy consumption, but also greatly reduces the service life of the device, and severely limits the application of the device in the internet of things and wearable equipment. Therefore, development of a method for treating low concentration NO at room temperature 2 The gas sensing material with high sensitivity and high selectivity has great significance.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material; the second purpose is to provide a preparation method of the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material; the purpose is to provide an application of the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material in preparing a gas sensor.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material comprises a molybdenum disulfide-reduced graphene oxide composite nanosheet and cuprous oxide hollow nanospheres uniformly loaded on the surface of the composite nanosheet.
Preferably, the diameter of the cuprous oxide hollow nanosphere is 140-250nm, and the thickness of the shell layer of the nanosphere is 35-45 nm.
2. The preparation method of the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material comprises the following steps:
(1) adding sodium molybdate, thiourea and graphene oxide into water, uniformly dispersing, carrying out hydrothermal reaction, after the reaction is finished, centrifugally washing and drying to obtain a molybdenum disulfide-reduced graphene oxide composite nanosheet;
(2) adding the molybdenum disulfide-reduced graphene oxide composite nanosheet prepared in the step (1) and hexadecyl trimethyl ammonium bromide into water, uniformly dispersing, adding copper sulfate pentahydrate, stirring for reacting for 10-20min, standing for 5-10min, adding ascorbic acid, stirring for reacting for 20-30min at 50-60 ℃, adding NaOH solution, stirring for reacting for 20-30min, taking a solid phase, and drying.
Preferably, in the step (1), the mass ratio of the sodium molybdate, the thiourea and the graphene oxide is 235-242:305-380: 25-28.3.
Preferably, in the step (1), the ultrasonic treatment is carried out for 30-60min until the dispersion is uniform.
Preferably, in the step (1), the temperature of the hydrothermal reaction is 200-210 ℃ and the time is 20-24 h.
Preferably, in step (1), the centrifugal washing is specifically: and (3) alternately centrifuging and washing with water and absolute ethyl alcohol for 2-3 times, wherein the centrifuging speed is 8500-9500rpm and the centrifuging time is 5-10min when centrifuging and washing with water or absolute ethyl alcohol.
Preferably, in the step (1) and the step (2), the drying is carried out for 10-12h under vacuum at 60-80 ℃.
Preferably, in the step (2), the mass-to-volume ratio of the molybdenum disulfide-reduced graphene oxide composite nanosheet to the cetyltrimethylammonium bromide to the copper sulfate pentahydrate to the ascorbic acid to the NaOH solution is 0.0045-0.005:4.60-4.75:0.04-0.05:0.15-0.18:10-12, g: g: g: mL; the concentration of the NaOH solution was 0.2M.
Preferably, in the step (2), the ultrasonic treatment is carried out for 10-30min until the dispersion is uniform.
Preferably, in the step (2), the speed of the three stirring reactions is 500-700 rpm; the solid phase was obtained by centrifugation at 8500-9500rpm for 5-10 min.
3. The molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material is applied to preparation of a gas sensor.
Preferably, the gas sensor is NO 2 A gas sensor.
The invention has the beneficial effects that: the invention provides a molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and a preparation method and application thereof 2 -rGO-Cu 2 O ternary composite) is first generated in situ during hydrothermal preparation of MoS having 3D framework structure 2 The composite two-dimensional nanosheet has a large specific surface area, multiple defects and a large number of carrier transport channels, and can synergistically improve the gas-sensitive performance to the greatest extent and reduce the working temperature. In the soft-lithographic process, MoS 2 -rGO composite two-dimensional nanosheet and Cu 2 O hollow nanosphere composite, and Cu 2 The O hollow nanospheres are uniformly loaded on the surface of the composite nanosheet, a large number of heterojunctions are formed at the interface of the three materials, a two-dimensional heterojunction composite nanomaterial is constructed, and the Cu is added 2 The high gas permeability and diffusivity of the O hollow nanospheres are beneficial to improving the NO of the finally prepared composite material at room temperature 2 The sensitivity, selectivity and stability of the gas have certain practical significance in the field of the future Internet of things. The method has the advantages of simple process, low cost, environmental protection and strong operability, and is favorable for popularization in practical application.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is the MoS prepared in example 1 2 SEM images of rGO composite nanoplates;
FIG. 2 is a MoS prepared in example 1 2 -rGO-Cu 2 SEM image of the O ternary composite material;
FIG. 3 is the MoS prepared in example 1 2 -TEM images of rGO composite nanoplates;
FIG. 4 is a MoS prepared in example 1 2 -rGO-Cu 2 TEM image of O ternary composite;
FIG. 5 is the MoS prepared in example 1 2 -XRD pattern of rGO composite nanoplates;
FIG. 6 is the MoS prepared in example 1 2 -rGO-Cu 2 XRD pattern of the O ternary composite material;
FIG. 7 shows the MoS prepared in example 1 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material can detect 0.1-0.5ppm NO at room temperature 2 Gas dynamic resistance change curve;
FIG. 8 shows MoS prepared in example 1 2 -rGO-Cu 2 Gas sensor using O ternary composite material as sensitive material for 0.5ppm NO at room temperature 2 A gas repetitive response profile;
FIG. 9 shows the MoS prepared in example 1 2 -rGO-Cu 2 The O ternary composite material is used as a gas sensor of a sensitive material, and the gas sensor has a response histogram for different target gases at room temperature;
FIG. 10 is the MoS prepared in example 2 2 SEM images of rGO composite nanoplates;
FIG. 11 is the MoS prepared in example 2 2 -rGO-Cu 2 SEM image of the O ternary composite material;
FIG. 12 is the MoS prepared in example 2 2 -TEM images of rGO composite nanoplates;
FIG. 13 is the MoS prepared in example 2 2 -rGO-Cu 2 A TEM image of the O ternary composite;
FIG. 14 is the MoS prepared in example 2 2 -XRD pattern of rGO composite nanoplates;
FIG. 15 is the MoS prepared in example 2 2 -rGO-Cu 2 XRD pattern of the O ternary composite material;
FIG. 16 is a MoS prepared as in example 2 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material can detect 0.1-0.5ppm NO at room temperature 2 Gas dynamic resistance change curve;
FIG. 17 is a MoS prepared as in example 2 2 -rGO-Cu 2 Gas sensor using O ternary composite material as sensitive material for 0.5ppm NO at room temperature 2 A gas repetitive response graph;
FIG. 18 is a MoS prepared as in example 2 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as a sensitive material has a response histogram for different target gases at room temperature.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material (MoS) 2 -rGO-Cu 2 O ternary composite material)
(1) 242mg of sodium molybdate (Na) 2 MoO 4 ·2H 2 O), 380mg of thiourea (CH) 4 N 2 S) and 28.3mg of Graphene Oxide (GO) are added into 60mL of deionized water, ultrasonic treatment is carried out for 60min until the Graphene Oxide (GO) is uniformly dispersed, the mixture is poured into a reaction kettle, hydrothermal reaction is carried out for 24h at 210 ℃, centrifugal washing is carried out alternately by deionized water and absolute ethyl alcohol, and the centrifugal washing is carried out alternately for 2Centrifuging at 9500rpm for 5min each time with water or anhydrous ethanol, and vacuum drying at 60 deg.C for 12 hr to obtain molybdenum disulfide-reduced graphene oxide composite nanosheet (MoS) 2 -rGO composite nanoplates);
(2) adding 5.0mg of the molybdenum disulfide-reduced graphene oxide composite nanosheet prepared in the step (1) and 4.75g of cetyltrimethylammonium bromide (CTAB) into 100mL of deionized water, performing ultrasonic treatment for 30min until the mixture is uniformly dispersed, and adding 0.05g of copper sulfate pentahydrate (CuSO) 4 ·5H 2 O), stirring and reacting at the speed of 700rpm for 20min, standing for 5min, adding 0.18g of Ascorbic Acid (AA), stirring and reacting at the speed of 500rpm for 20min at 60 ℃, adding 12mL of 0.2M NaOH solution, stirring and reacting at the speed of 500rpm for 30min, centrifuging at the speed of 9500rpm for 5min, taking a solid phase, and finally vacuum drying at the temperature of 60 ℃ for 12h to prepare MoS 2 -rGO-Cu 2 And (3) an O ternary composite material.
FIG. 1 is a MoS prepared in example 1 2 SEM picture of-rGO composite nano-sheet, and the flaky self-assembled flower-like MoS in the material can be known 2 Inlay in the rGO nanometer piece, present 3D skeleton structure, this structure has great specific surface area, can provide a large amount of adsorption sites, and then improve gas sensitive performance.
FIG. 2 is a MoS prepared in example 1 2 -rGO-Cu 2 SEM image of O ternary composite material, it can be seen that Cu is present 2 O nanospheres in MoS 2 The surface of rGO is uniformly dispersed, and the close contact among the three materials constructs a large number of heterojunctions to improve the performance.
FIG. 3 is the MoS prepared in example 1 2 TEM image of-rGO composite nanosheet, showing MoS 2 rGO exhibits a typical nanosheet structure.
FIG. 4 is a MoS prepared in example 1 2 -rGO-Cu 2 TEM image of O ternary composite material, Cu is known 2 The O nanosphere has a hollow shell structure of Cu 2 The particle size distribution range of the O hollow nanospheres is 140-250nm, the average particle size is 180nm, the thickness of the shell layer of the nanospheres is 35-45nm, and the structural morphology has large specific surface area and high gas permeability and is beneficial to gas adsorption and diffusion.
FIG. 5 is the MoS prepared in example 1 2 XRD pattern of-rGO composite nanosheet, showing MoS 2 Corresponds to standard PDF card No. 37-1492.
FIG. 6 is the MoS prepared in example 1 2 -rGO-Cu 2 XRD pattern of O ternary composite material, Cu is known 2 The peak position of O corresponds to the standard PDF card No. 05-0667.
MoS prepared in example 1 2 -rGO-Cu 2 The O-ternary composite material as a sensitive material was coated on the interdigital electrode by a drop coating method, and the change in the sensor resistance was monitored by using a Keithley2700 semiconductor parameter analyzer, and the results are shown in fig. 7, 8 and 9.
FIG. 7 shows the MoS prepared in example 1 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material can detect 0.1-0.5ppm NO at room temperature 2 MoS can be known from gas dynamic resistance change curve chart 2 -rGO-Cu 2 0.1-0.5ppm NO of O ternary composite nano material film 2 The gas has high sensitivity and NO 2 The reduction in gas concentration reduces the responsiveness of the gas sensor.
FIG. 8 shows MoS prepared in example 1 2 -rGO-Cu 2 Gas sensor using O ternary composite material as sensitive material and capable of detecting 0.5ppm NO at room temperature 2 Gas repeated response curve chart, namely MoS 2 -rGO-Cu 2 O ternary composite nano material film pair NO 2 The gas has good repetitive response characteristics.
FIG. 9 shows the MoS prepared in example 1 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material has a histogram of responsivity to different target gases at room temperature, and MoS can be known 2 -rGO-Cu 2 O ternary composite nano material film pair NO 2 The gas has good selectivity.
Example 2
Preparation of molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material (MoS) 2 -rGO-Cu 2 O ternary composite material)
(1) Mixing 235mg of molybdic acidSodium (Na) 2 MoO 4 ·2H 2 O), 305mg of thiourea (CH) 4 N 2 S) and 25mg of Graphene Oxide (GO) are added into 50mL of deionized water, the mixture is subjected to ultrasonic treatment for 30min until the mixture is uniformly dispersed, the mixture is poured into a reaction kettle, hydrothermal reaction is performed for 20h at 200 ℃, the deionized water and absolute ethyl alcohol are used for alternative centrifugal washing for 3 times, the centrifugal speed is 8500rpm when water or absolute ethyl alcohol is used for centrifugal washing each time, the centrifugal time is 10min, and finally vacuum drying is performed for 10h at 80 ℃ to obtain the molybdenum disulfide-reduced graphene oxide composite nanosheet (MoS) 2 -rGO composite nanoplates);
(2) adding 4.5mg of the molybdenum disulfide-reduced graphene oxide composite nanosheet prepared in the step (1) and 4.60g of cetyltrimethylammonium bromide (CTAB) into 90mL of deionized water, performing ultrasonic treatment for 10min until the mixture is uniformly dispersed, and adding 0.04g of copper sulfate pentahydrate (CuSO) 4 ·5H 2 O), stirring and reacting at the speed of 500rpm for 10min, standing for 10min, adding 0.15g of Ascorbic Acid (AA), stirring and reacting at the speed of 700rpm for 30min at 50 ℃, adding 10mL of 0.2M NaOH solution, stirring and reacting at the speed of 700rpm for 20min, centrifuging at the speed of 8500rpm for 10min, taking a solid phase, and finally vacuum drying at the temperature of 80 ℃ for 10h to prepare MoS 2 -rGO-Cu 2 And (3) an O ternary composite material.
FIG. 10 is the MoS prepared in example 2 2 SEM picture of-rGO composite nano sheet, and the flaky self-assembled flower-like MoS in the material can be known 2 The gas sensitive membrane is embedded in the rGO nano sheet and has a 3D framework structure, and the structure has a large specific surface area and can provide a large number of adsorption sites, so that the gas sensitive performance is improved.
FIG. 11 is the MoS prepared in example 2 2 -rGO-Cu 2 As a result of SEM photograph of the O ternary composite material, Cu was observed 2 O nanospheres in MoS 2 The surface of rGO is uniformly dispersed, and the close contact among the three materials constructs a large number of heterojunctions to improve the performance.
FIG. 12 is the MoS prepared in example 2 2 TEM image of-rGO composite nanosheet, showing MoS 2 rGO exhibits a typical nanosheet structure.
FIG. 13 is the MoS prepared in example 2 2 -rGO-Cu 2 Of ternary O composite materialsTEM image showing Cu 2 The O nanosphere has a hollow shell structure of Cu 2 The particle size distribution range of the O hollow nanospheres is 140-250nm, the average particle size is 180nm, the thickness of the shell layer of the nanospheres is 35-45nm, and the structure has large specific surface area and high gas permeability, thereby being beneficial to the adsorption and diffusion of gas.
FIG. 14 is the MoS prepared in example 2 2 XRD pattern of-rGO composite nanosheet, known as MoS 2 Corresponds to standard PDF card No. 37-1492.
FIG. 15 is the MoS prepared in example 2 2 -rGO-Cu 2 XRD pattern of O ternary composite material, Cu is known 2 The peak position of O corresponds to the standard PDF card No. 05-0667.
MoS prepared in example 2 2 -rGO-Cu 2 The O-ternary composite material as a sensitive material was coated on the interdigital electrode by a drop coating method, and the change in the sensor resistance was monitored by using a Keithley2700 semiconductor parameter analyzer, and the results are shown in fig. 16, 17 and 18.
FIG. 16 is a MoS prepared as in example 2 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material can detect 0.1-0.5ppm NO at room temperature 2 MoS can be known from the gas dynamic resistance change curve chart 2 -rGO-Cu 2 0.1-0.5ppm NO of O ternary composite nano material film 2 The gas has high sensitivity and NO 2 The gas sensor responsivity decreases with a decrease in gas concentration.
FIG. 17 is a MoS prepared as in example 2 2 -rGO-Cu 2 Gas sensor using O ternary composite material as sensitive material and capable of detecting 0.5ppm NO at room temperature 2 Gas repeated response curve chart, namely MoS 2 -rGO-Cu 2 O ternary composite nano material film pair NO 2 The gas has good repetitive response characteristics.
FIG. 18 is a MoS prepared as in example 2 2 -rGO-Cu 2 The gas sensor using the O ternary composite material as the sensitive material has a response histogram of different target gases at room temperature, and MoS can be known 2 -rGO-Cu 2 O ternary composite nano material film pair NO 2 The gas has good selectivity.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material is characterized by comprising molybdenum disulfide-reduced graphene oxide composite nanosheets and cuprous oxide hollow nanospheres uniformly loaded on the surfaces of the composite nanosheets;
the composite material is prepared according to the following method:
(1) adding sodium molybdate, thiourea and graphene oxide into water, uniformly dispersing, carrying out hydrothermal reaction, after the reaction is finished, centrifugally washing and drying to obtain a molybdenum disulfide-reduced graphene oxide composite nanosheet;
(2) adding the molybdenum disulfide-reduced graphene oxide composite nanosheet prepared in the step (1) and hexadecyl trimethyl ammonium bromide into water, uniformly dispersing, adding copper sulfate pentahydrate, stirring for reacting for 10-20min, standing for 5-10min, adding ascorbic acid, stirring for reacting for 20-30min at 50-60 ℃, adding NaOH solution, stirring for reacting for 20-30min, taking a solid phase, and drying.
2. The molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material as claimed in claim 1, wherein the diameter of the cuprous oxide hollow nanosphere is 140-250nm, and the thickness of the nanosphere shell layer is 35-45 nm.
3. The preparation method of the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material according to claim 1 or 2, characterized by comprising the following steps:
(1) adding sodium molybdate, thiourea and graphene oxide into water, uniformly dispersing, carrying out hydrothermal reaction, after the reaction is finished, centrifugally washing and drying to obtain a molybdenum disulfide-reduced graphene oxide composite nanosheet;
(2) adding the molybdenum disulfide-reduced graphene oxide composite nanosheet prepared in the step (1) and hexadecyl trimethyl ammonium bromide into water, uniformly dispersing, adding copper sulfate pentahydrate, stirring for reacting for 10-20min, standing for 5-10min, adding ascorbic acid, stirring for reacting for 20-30min at 50-60 ℃, adding NaOH solution, stirring for reacting for 20-30min, taking a solid phase, and drying.
4. The method as claimed in claim 3, wherein in the step (1), the mass ratio of the sodium molybdate, the thiourea and the graphene oxide is 235-242:305-380: 25-28.3.
5. The method as claimed in claim 3, wherein the hydrothermal reaction in step (1) is carried out at a temperature of 200 ℃ and 210 ℃ for a period of 20-24 h.
6. The method according to claim 3, wherein in step (1), the centrifugal washing is specifically: and (3) alternately centrifuging and washing with water and absolute ethyl alcohol for 2-3 times, wherein the centrifuging speed is 8500-9500rpm and the centrifuging time is 5-10min when centrifuging and washing with water or absolute ethyl alcohol.
7. The method of claim 3, wherein in step (1) and step (2), the drying is performed under vacuum at 60-80 ℃ for 10-12 h.
8. The method of claim 3, wherein in step (2), the mass-to-volume ratio of the molybdenum disulfide-reduced graphene oxide composite nanosheets, cetyltrimethylammonium bromide, copper sulfate pentahydrate, ascorbic acid, and NaOH solution is 0.0045-0.005:4.60-4.75:0.04-0.05:0.15-0.18:10-12, g: g: g: mL; the concentration of the NaOH solution was 0.2M.
9. The method as claimed in claim 3, wherein in the step (2), the three stirring reactions are performed at a speed of 500-700 rpm; the solid phase was obtained by centrifugation at 8500-9500rpm for 5-10 min.
10. The use of the molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material of claim 1 or 2 in the preparation of a gas sensor.
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