CN113984842B - Preparation method of graphene/NiZn ferrite gas-sensitive composite material - Google Patents
Preparation method of graphene/NiZn ferrite gas-sensitive composite material Download PDFInfo
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- CN113984842B CN113984842B CN202111126885.6A CN202111126885A CN113984842B CN 113984842 B CN113984842 B CN 113984842B CN 202111126885 A CN202111126885 A CN 202111126885A CN 113984842 B CN113984842 B CN 113984842B
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- 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
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- 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
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The invention discloses a preparation method of a graphene/NiZn ferrite gas-sensitive composite material, which comprises the steps of uniformly mixing nano metal oxide particles prepared by a hydrothermal method with PMMA organic carbon source, and then carrying out vacuum heat treatment technology treatment to realize graphene of PMMA and uniformly compounding with the nano metal oxide particles. The preparation method disclosed by the invention is simple in process, short in reaction time (shortened to tens of minutes), low in production equipment requirement, easy for industrial production, and capable of overcoming the defects of complex operation, high reaction temperature, uncontrollable structure and the like commonly existing in the existing preparation method of the metal oxide/graphene composite material, and the prepared graphene composite NiZn ferrite gas-sensitive material has excellent gas-sensitive performance and good application prospect in the field of gas-sensitive materials.
Description
Technical Field
The invention relates to the technical field of gas-sensitive materials, in particular to a preparation method of a graphene/NiZn ferrite gas-sensitive composite material.
Background
In recent years, with the rapid development of modern economy, the production of industrial raw materials does not generate a lot of toxic and harmful gases, such as CH 4 、NO、NO 2 、H 2 S、NH 3 CO, acetone, formaldehyde and the like, so that the atmospheric environmental pollution is more serious, and the health of people is threatened; meanwhile, toxic and harmful substances such as formaldehyde, dimethylbenzene and the like with volatility are inevitably generated in the interior decoration, and when the concentration reaches a certain amount, great threat such as organ canceration, dyspnea and the like can be generated on the health of human beings. More seriously, about 25 hundred million people in the world face the threat of indoor and outdoor double air pollution. In addition, the quality detection of products, the analysis of automobile exhaust, the inspection of drunk driving by traffic police departments, the safety detection of inflammable and explosive substances by related departments, the diagnosis of respiratory gases of patients and the like in industrial production all put forward higher requirements on gas detection equipment. Because the existing gas sensor has low sensitivity, poor stability and the like, the preparation of the gas sensor with high performance is particularly important.
Worldwide, gas sensor manufacturers are mainly focused on japan, europe and the united states, and although gas sensors and applications in China have recently developed faster, there are great differences compared with foreign countries. The performance of the gas sensor mainly depends on the gas-sensitive material, so that in the development direction of the gas-sensitive material, china has a large lifting space.
Therefore, developing a gas-sensitive material with low cost and high sensitivity is an important point for researching a gas sensor, wherein a metal oxide semiconductor (such as ZnO and the like) has been widely applied to the sensor field due to the characteristics of low cost, stable performance, abundant reserves and the like.
However, the gas-sensitive properties of single-component metal oxide semiconductors are difficult to meet the actual demands of the times development, and there are generally the following disadvantages: the working environment temperature is higher, the selectivity to gas is poor, the stability is poor, and the like, and even the sulfur oxide-containing gas easily causes the sensor poisoning.
The graphene has higher sensitivity in the aspect of gas detection, mainly because the graphene is of a single-layer structure, all atoms can adsorb gas molecules, the gas sensitivity utilization rate is higher, and the graphene has higher electron conduction speed. However, practice proves that when the prepared single-layer graphene is used as a composite material filler or is singly utilized, the single-layer graphene often exists in an agglomerated form, the theoretical advantage of the single-layer graphene cannot be reflected, and meanwhile, the preparation of pure graphene into a high-efficiency and high-sensitivity gas sensor cannot be realized at present.
Therefore, if graphene and a metal oxide semiconductor can be compounded, the respective advantages of the graphene and the metal oxide semiconductor are brought into play, development and application of a novel composite gas-sensitive material are facilitated to be expanded, and the graphene-metal oxide semiconductor composite gas-sensitive material has very important significance.
Disclosure of Invention
The invention aims to provide the graphene/NiZn ferrite gas-sensitive composite material preparation method which is simple in process, low in requirement on production equipment and easy for industrial production, and the prepared graphene composite NiZn ferrite gas-sensitive material has excellent gas-sensitive performance and good application prospect in the field of gas-sensitive materials.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention discloses a preparation method of a graphene/NiZn ferrite gas-sensitive composite material, which comprises the following steps:
(1) Nickel nitrate, zinc nitrate and ferric nitrate are dissolved in deionized water to prepare 100ml of mixed salt solution, and nickel ions in the mixed salt solution are as follows: zinc ion: the molar ratio of iron ions is 1:1:4, a step of; adding a proper amount of polyethylene glycol, titrating the NaOH solution until the pH value of the mixed salt solution is 11, stirring uniformly, heating and preserving heat for reaction; cooling to room temperature after reaction, standing, removing supernatant, and repeatedly cleaning precipitate with pure water, acetone and ethanol respectively; and (3) drying the precipitate in vacuum, and grinding to obtain the nano NiZn ferrite powder.
(2) Mixing the nano NiZn ferrite powder with PMMA solution, performing ultrasonic treatment, and drying to obtain a drying mixture. The mobility of PMMA solution can realize the uniform coating of the nano NiZn ferrite powder.
(3) And placing the dried mixture in a crucible, filling the crucible into a microwave vacuum tube furnace, opening vacuum, introducing nitrogen, and performing microwave heating reaction to obtain a reaction product, namely the graphene/NiZn ferrite gas-sensitive composite material. The uniform coating of graphene and NiZn ferrite particles is realized by utilizing the heat treatment technology of a microwave vacuum tube furnace, and the defects of easy aggregation and poor compounding of graphene caused by the fact that graphene is firstly generated and then coated with ferrite particles in the traditional method are avoided.
Preferably, in the step (1), the concentration of the NaOH solution is 2mol/L.
Preferably, in the step (1), the temperature of the heating and heat-preserving reaction is 180 ℃ and the heat-preserving time is 12 hours.
Preferably, in the step (1), the precipitate is repeatedly washed 3 to 4 times with pure water, acetone, and ethanol.
Preferably, in step (1), the vacuum drying temperature is 60℃and the drying time is 10 hours.
Preferably, in the step (2), the concentration of the PMMA solution is 250mg/mL.
Preferably, in step (2), 0.05g of nano NiZn ferrite powder is mixed with 1mL of PMMA solution.
Preferably, in step (2), the ultrasound time is 1h.
Preferably, in step (3), the microwave vacuum tube furnace is evacuated to 5×10 -3 Pa, the reaction temperature is 1000 ℃, and the reaction time is 30min. The reaction temperature has a larger influence on the growth of the graphene, the higher the reaction temperature is, the better the crystallinity of the graphene is, but the sp is generated when the reaction temperature is too high 3 Hybrid defects.
Therefore, the invention has the following beneficial effects: according to the invention, nano metal oxide particles prepared by a hydrothermal method and PMMA organic carbon source are uniformly mixed and then treated by a vacuum heat treatment technology, so that graphene of PMMA is realized, and the graphene composite material is uniformly compounded with the nano metal oxide particles.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the nano-NiZn ferrite powder obtained in example 1.
FIG. 2 is a Raman spectrum of the graphene/NiZn ferrite gas-sensitive composite material obtained in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the graphene/NiZn ferrite gas-sensitive composite material obtained in example 1.
Fig. 4 is a gas-sensitive performance test result of the graphene/NiZn ferrite gas-sensitive composite material obtained in example 1 on ethanol gas.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
Example 1
(1) Nickel nitrate, zinc nitrate and ferric nitrate are dissolved in deionized water to prepare 100ml of mixed salt solution, and nickel ions in the mixed salt solution are as follows: zinc ion: the molar ratio of iron ions is 1:1:4, a step of; adding 2g of polyethylene glycol, titrating 2mol/L NaOH solution until the pH value of the mixed salt solution is 11, stirring and uniformly mixing, heating to 180 ℃, and carrying out heat preservation reaction for 12h; cooling to room temperature after reaction, standing, removing supernatant, and repeatedly cleaning precipitate with pure water, acetone and ethanol for 3 times respectively; and (3) drying the precipitate in vacuum, and grinding to obtain nano NiZn ferrite powder, wherein the X-ray diffraction (XRD) pattern of the nano NiZn ferrite powder is shown in figure 1. As can be seen from the XRD pattern of FIG. 1, the product is NiZn ferrite, and the peak is sharp, and the crystal growth is good.
(2) Mixing 0.05g of nano NiZn ferrite powder with 250mg/mL of 1mL of PMMA solution, performing ultrasonic treatment for 1h, and drying to obtain a drying mixture. The mobility of PMMA solution can realize the uniform coating of the nano NiZn ferrite powder.
(3) Placing the dried mixture in a crucible, filling the crucible into a microwave vacuum tube furnace, and starting vacuum pumping until the vacuum is 5 x 10 - 3 And (3) Pa, introducing nitrogen, and performing microwave heating reaction at 1000 ℃ for 30min to obtain a reaction product, namely the graphene/NiZn ferrite gas-sensitive composite material.
The raman spectrum diagram of the graphene/NiZn ferrite gas-sensitive composite material is shown in figure 2. The apparent graphene peaks can be seen in fig. 2, which illustrates that PMMA has been converted to graphene via vacuum high temperature processing techniques.
A Scanning Electron Microscope (SEM) image of the graphene/NiZn ferrite gas-sensitive composite material is shown in fig. 3. As can be seen from fig. 4, the ferrite has a lamellar graphene structure and irregular particle shapes coated by the graphene structure, and the specific surface area of the ferrite particles compounded with graphene is large.
12mg of the obtained graphene/NiZn ferrite gas-sensitive composite material is weighed into a small test tube, 1ml of distilled water is added, then the ultrasonic treatment is carried out for 40min, a pipette gun is adjusted to the suction amount of 45ml, a sample is dripped on an interdigital electrode, then the interdigital electrode is placed into an oven to be dried, the gas-sensitive characteristic of the graphene/NiZn ferrite gas-sensitive composite material to ethanol is detected, and the detection result is shown in figure 4. From FIG. 4, it can be seen that the response recovery curve is smoother, the sensitivity to 80ppm ethanol gas reaches 5.2, and the response recovery time is shorter.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (8)
1. The preparation method of the graphene/NiZn ferrite gas-sensitive composite material is characterized by comprising the following steps of:
(1) Nickel nitrate, zinc nitrate and ferric nitrate are dissolved in deionized water to prepare 100ml of mixed salt solution, and nickel ions in the mixed salt solution are as follows: zinc ion: the molar ratio of iron ions is 1:1:4, a step of; adding a proper amount of polyethylene glycol, titrating the NaOH solution until the pH value of the mixed salt solution is 11, stirring uniformly, heating and preserving heat for reaction; cooling to room temperature after reaction, standing, removing supernatant, and repeatedly cleaning precipitate with pure water, acetone and ethanol respectively; vacuum drying the precipitate, and grinding to obtain nano NiZn ferrite powder;
(2) Mixing nano NiZn ferrite powder with PMMA solution, performing ultrasonic treatment, and drying to obtain a dried mixture;
(3) Placing the dried mixture in a crucible, filling the crucible into a microwave vacuum tube furnace, opening vacuum, introducing nitrogen, and performing microwave heating reaction to obtain a reaction product, namely the graphene/NiZn ferrite gas-sensitive composite material;
in the step (3), the microwave vacuum tube furnace is vacuumized to 5 x 10 -3 Pa, heating temperature is 1000 ℃, and reaction time is 30min.
2. The method for preparing the graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (1), the concentration of the NaOH solution is 2mol/L.
3. The preparation method of the graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (1), the temperature of the heating and heat-preserving reaction is 180 ℃, and the heat-preserving time is 12 hours.
4. The method for preparing the graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (1), the precipitate is repeatedly washed 3-4 times with pure water, acetone and ethanol.
5. The preparation method of the graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (1), the vacuum drying temperature is 60 ℃, and the drying time is 10 hours.
6. The method for preparing a graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (2), the concentration of the PMMA solution is 250mg/mL.
7. The method for preparing a graphene/NiZn ferrite gas-sensitive composite material according to claim 6, wherein in the step (2), 0.05g of nano NiZn ferrite powder is mixed with 1mL of PMMA solution.
8. The method for preparing the graphene/NiZn ferrite gas-sensitive composite material according to claim 1, wherein in the step (2), the ultrasonic time is 1h.
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| CN108587159A (en) * | 2018-05-11 | 2018-09-28 | 东南大学 | One type graphene carbonitride/ferroso-ferric oxide/polyaniline nano composite wave-suction material and preparation method thereof |
| CN110554072A (en) * | 2019-08-30 | 2019-12-10 | 郑州大学 | Preparation method and application of composite material and gas sensor |
| CN111945138A (en) * | 2020-08-17 | 2020-11-17 | 南京信息工程大学 | Graphene quantum dot-based functionalized titanium dioxide/chlorella nanocomposite and preparation method and application thereof |
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| CN102683697B (en) * | 2012-05-14 | 2014-12-17 | 国光电器股份有限公司 | Preparation method of graphene-based LiFePO4/C composite material |
| KR102311971B1 (en) * | 2017-05-24 | 2021-10-12 | 엘지디스플레이 주식회사 | Mehtod for manufacturing graphene-tin oxide nanocomposites and graphene-tin oxide nanocomposites |
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| CN108587159A (en) * | 2018-05-11 | 2018-09-28 | 东南大学 | One type graphene carbonitride/ferroso-ferric oxide/polyaniline nano composite wave-suction material and preparation method thereof |
| CN110554072A (en) * | 2019-08-30 | 2019-12-10 | 郑州大学 | Preparation method and application of composite material and gas sensor |
| CN111945138A (en) * | 2020-08-17 | 2020-11-17 | 南京信息工程大学 | Graphene quantum dot-based functionalized titanium dioxide/chlorella nanocomposite and preparation method and application thereof |
Non-Patent Citations (1)
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| 关于石墨烯与金属氧化物复合材料应用于气敏材料的研究;冯秋霞;王兢;李晓干;;功能材料(第10期);全文 * |
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