CN115684303A - Co-BDC/MXene nano composite material, preparation method and application - Google Patents
Co-BDC/MXene nano composite material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a Co-BDC/MXene nano composite material, a preparation method and application thereof, and belongs to the field of gas sensors. The invention provides a Co-BDC/MXene nano composite material and application thereof, and a Co-BDC/MXene-based sensor has good sensitivity to acetone gas, low detection limit and wide detection range. The stability of the Co-BDC/MXene composite material is also improved compared with that of a pure MXene material, so that the stability of the Co-BDC/MXene-based acetone sensor is better. Meanwhile, due to the good flexibility and plasticity of the MXene material, the Co-BDC/MXene composite material has the possibility of preparing a flexible wearable gas sensor. Finally, the conductivity of the Co-BDC/MXene composite material is significantly improved compared with the conventional MOFs.
Description
Technical Field
The invention belongs to the field of gas sensors, and particularly relates to a Co-BDC/MXene nano composite material, a preparation method and application.
Background
The gas sensor is used as an extension of human sense, and has wide application prospect in a plurality of fields such as environmental detection, food safety, industrial safety, aerospace and the like. As the most core device of a gas sensor, the development of a gas sensitive material having high sensitivity, high stability, high selectivity, low power consumption and low response time for a target gas is urgently needed.
The MXene nano material is a metal carbide and metal nitride material with a two-dimensional layered structure, and is also called graphene-like due to the structure similar to that of graphene. The material has larger specific surface area and a large number of functional groups on the surface of the material, so the material can provide abundant active sites for gas adsorption and surface reaction. Reported that Lee et al discovered Ti for the first time 3 C 2 MXene has good gas-sensitive performance, the optimal working temperature is much lower than that of common semiconductor gas-sensitive materials, and good gas-sensitive performance is shown even under room temperature conditions. However, due to the existence of functional groups on the surface of the MXene material and other reasons, the MXene material is easy to undergo an oxidation reaction in an oxidizing atmosphere, so that the two-dimensional structure is collapsed, and therefore, the MXene material used for the gas sensitive material has the defect of poor stability, which seriously limits the further development of the MXene material in the field of sensors.
At present, the common gas sensor taking a metal oxide semiconductor material as a sensitive material has the defects of low gas sensitivity, low conductivity, high working temperature, high energy consumption, long response/recovery time and the like, so that the application of the gas sensor is limited. Although the MOFs material has the advantages of large specific surface area, many active sites and the like, the defect of poor conductivity makes the MOFs material difficult to further develop in the aspect of gas sensors.
Disclosure of Invention
The invention provides a Co-BDC/MXene nanocomposite, a preparation method and application thereof, in order to further improve the performance of the conventional gas sensitive material.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a Co-BDC/MXene nanocomposite comprises the following operations:
dispersing MXene in N, N-dimethyl formylTo the amine, followed by the addition of Co (NO) 3 ) 2 ·6H 2 O, performing electrostatic adsorption self-assembly to obtain a mixed solution;
dispersing a DMF solution of terephthalic acid in the mixed solution, sequentially adding ethanol and water, and mixing to obtain a precursor;
and (3) placing the precursor in a reaction kettle, filling inert gas, reacting at 140 ℃ for 12h, and collecting precipitates after the reaction is finished to obtain the Co-BDC/MXene nano composite material.
Further, 0.035g of MXene and 0.291g of Co (NO) were dispersed in 1 ml of N, N-dimethylformamide 3 ) 2 ·6H 2 O；
In a solution of terephthalic acid in DMF, 0.166g of terephthalic acid was dispersed per 10ml of DMF.
Further, when a solution of terephthalic acid in DMF was dispersed in the mixed solution, 10ml of DMF was added to 1 ml of N, N-dimethylformamide, and mixed.
Further, when ethanol and water were added, 2ml of ethanol and 2ml of water were added per 15ml of N, N-dimethylformamide.
The Co-BDC/MXene nanocomposite is characterized by being prepared according to the preparation method provided by the invention.
Further, the gas sensitive material is used for detecting the concentration of VOCs gas.
Further, putting the Co-BDC/MXen nano composite material into a mortar, adding ethanol, and then grinding into pasty liquid;
and (3) coating the pasty liquid on a counter electrode, and obtaining the Co-BDC/MXene gas sensor after the ethanol volatilizes.
Further, the detection was carried out at an operating temperature of 110 ℃.
Further, the method is used for detecting the concentrations of acetone, methanol, n-propanol, toluene, ethanol and formaldehyde.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a Co-BDC/MXene nano composite material and application thereof, and a Co-BDC/MXene-based sensor has good sensitivity to acetone gas, low detection limit and wide detection range. The stability of the Co-BDC/MXene composite material is also improved compared with that of a pure MXene material, so that the stability of the Co-BDC/MXene-based acetone sensor is better. Meanwhile, due to the good flexibility and plasticity of the MXene material, the Co-BDC/MXene composite material has the possibility of preparing a flexible wearable gas sensor. Finally, the conductivity of the Co-BDC/MXene composite material is significantly improved compared with the conventional MOFs.
The invention provides a preparation method of a Co-BDC/MXene nano composite material, which has simple steps and controllable reaction.
Drawings
FIG. 1 is a graph showing the relationship between the sensitivity of a Co-BDC/MXene gas sensor to 100ppm acetone gas and the operating temperature;
FIG. 2 is a graph of the response of a Co-BDC/MXene gas sensor to six different VOC gases, namely acetone, methanol, n-propanol, toluene, ethanol and formaldehyde, at a working temperature of 110 ℃;
FIG. 3 is a graph showing the dynamic response of a Co-BDC/MXene gas sensor to different concentrations of acetone gas at a working temperature of 110 ℃.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
the application of MXene material in the field of gas sensors is still in the beginning, and a plurality of problems in the aspects of reaction mechanism research and practical application still need to be researched. However, the MXene material has the advantages of large specific surface area, high electron mobility, good plasticity and the like, so the MXene material has wide prospect when being applied to a gas sensor. To promote the further application of the MXene material to the gas sensor, the problems of how to improve the stability of the MXene material, how to promote the adsorption reaction of the gas and the like need to be solved. The MXene material and the MOFs material are compounded to form the composite nano material Co-BDC/MXene material, so that the performance of the MXene material is improved, and the gas sensitive material with better performance is prepared.
The invention provides a method for manufacturing a VOC gas sensor based on a Co-BDC/MXene composite material. Firstly, synthesizing a Co-BDC/MXene material by the following method, then uniformly coating the obtained material on an electrode of an indirectly heated gas-sensitive element, and finally testing a series of performances of the sensor on acetone gas. The final experimental result shows that the Co-BDC/MXene-based acetone gas transmission has good sensitivity, detection limit and detection range.
Examples
(1) Synthesis of MXene materials
Firstly, measuring 20ml of HCl with the concentration of 12mol/L by using a measuring cylinder, and transferring the HCl into a centrifugal tube for later use; 1.2g LiF (99%) are weighed in a weighing balance, transferred into HCl, the solution is placed in an oil bath until the liquid temperature reaches 40 ℃ and stirred for 20min (18 r). Weighing 1.0g MAX (Ti) with balance 3 AlC 2 ) Solid, added to the above system in small portions over ten minutes. After the raw material is addedAnd then, filling Ar gas into the centrifugal tube, sealing the centrifugal tube by using a preservative film, tightly covering the centrifugal tube, putting the centrifugal tube into a water bath kettle at the temperature of 40 ℃, and stirring and reacting for 48 hours at the rotating speed of 18 r. After the reaction is finished, taking out the centrifugal tube, averagely transferring the liquid in the centrifugal tube into two new centrifugal tubes, respectively adding a small amount of water, putting the centrifugal tubes into a centrifugal machine, setting the rotating speed of the centrifugal machine to 3000r, centrifuging the liquid for 2min to make the liquid sticky, pouring out the upper layer liquid, adding water to 45ml, then putting the centrifugal machine into the centrifugal machine again, centrifuging the centrifugal machine for 5min at the rotating speed of 3500r, centrifuging for four times to precipitate sticky, and testing that the pH value of the upper layer liquid is close to neutral. Stirring and shaking the clay-like precipitate uniformly, adding water to mix into uniform liquid, transferring into a round-bottom flask, and carrying out ice bath ultrasound for 4 hours while stirring. After the ultrasonic treatment, the mixture was centrifuged at 3500r for 1 hour in a centrifuge, and the supernatant liquid was collected. Pre-freezing the collected liquid, freeze-drying, and collecting MXene (Ti) 3 C 2 ) And (5) performing vacuum freezing storage.
(2) Synthesis of Co-BDC/MXene nano composite material
0.035g of MXene solid was weighed, transferred to 15ml of N, N-Dimethylformamide (DMF) solution, and subjected to ultrasonic treatment in ice bath for 20min to disperse the solid uniformly. Then 0.291g Co (NO) 3 ) 2 ·6H 2 And adding O into the MXene dispersion liquid, performing ultrasonic treatment for 15min, and performing electrostatic adsorption self-assembly. 0.166g of terephthalic acid (BDC) was transferred into 10ml of DMF solution and was thoroughly dissolved by sonication for 15 min. The BDC solution is poured into MXene dispersion liquid dissolved with cobalt ions while stirring, then 2ml ethanol and 2ml water are rapidly added in sequence, and stirring is carried out for 30min at room temperature. Then transferring the solution into a polytetrafluoroethylene reaction kettle with the volume of 100ml, filling inert gas Ar, putting the reaction kettle into a muffle furnace, maintaining the temperature at 140 ℃, and keeping for 12 hours. After the reaction is finished, the solution cooled to room temperature is put into a centrifuge tube, and is alternately centrifuged three times by DMF and ethanol in a centrifuge at the rotating speed of 7500r, and the final precipitate is collected. And pre-freezing the obtained precipitate, freeze-drying, and collecting the product for later use.
(3) Preparation of Co-BDC/MXene gas-sensitive element
The frozen Co-BDC/MXen sample is scraped from the bottom of a glass dish, the scraped solid particles are collected into a sealed bag and put into a mortar, a binder ethanol solution is added to uniformly disperse the solid in the solution, and then the mixture is ground and prepared into uniform pasty liquid. The adjusted paste sample was carefully applied to the two pairs of gold electrodes with a brush pen, the application ensuring uniform and complete coverage of the electrodes. And after the adhesive is completely volatilized, obtaining the Co-BDC/MXene gas sensor.
The performance of the Co-BDC/MXene gas sensors was tested as follows:
the properties of the Co-BDC/MXene composite nanomaterial were tested for acetone gas using a related instrument under experimental conditions of 27 ℃ temperature and 33% humidity. The response of the Co-BDC/MXene material to acetone gas at 100ppm concentration at five different temperatures (80 deg.C, 100 deg.C, 110 deg.C, 120 deg.C and 140 deg.C) was measured by an instrument and the data obtained is shown in FIG. 1, where it can be seen that the optimum working temperature of the material is 110 deg.C.
The response value of the sensor to acetone gas with the concentration of 100ppm at different temperatures is tested, and the experimental result shows (as shown in figure 1) that the response value of the sensor reaches the maximum of 30.8 at 110 ℃ by adjusting the temperatures (80 ℃,100 ℃,110 ℃,120 ℃ and 140 ℃) of the Co-BDC/MXene-based sensor, and the response value of the sensor is reduced when the temperature is increased or reduced from the node. The optimum operating temperature of the acetone sensor is 110 c, which is much lower than that of the commercially available metal oxide based gas sensors. Secondly, the dynamic response of the sensor to different concentrations of acetone at 110 ℃ is tested, and through experimental results (fig. 3), it can be seen that in the range of 30ppm to 300ppm, a good linear relationship exists between the response value of the sensor and the concentration of acetone gas, and it is noted that the response value of the sensor to 10ppm of acetone gas still has a response value greater than 2, so that the sensor has a good detection limit and a good detection range. Finally, the response values of the VOCs sensor to various gases were tested by testing the response values of the sensor to six different gases (acetone, methanol, n-propanol, toluene, ethanol and formaldehyde) (the target analyte concentration was 100 ppm) at 110 ℃, and the test results (fig. 2) showed that the sensor response values were 31, 4, 28, 19, 24 and 4 in this order. The response value of the sensor to acetone gas is up to 31, and the response values to n-propanol and ethanol reach more than 20, so that the material shows good response values to various gases.
By combining the experimental results, the Co-BDC/MXene-based sensor has good sensitivity to acetone gas, low detection limit and wide detection range. The stability of the Co-BDC/MXene composite material is also improved compared with that of a pure MXene material, so that the stability of the Co-BDC/MXene-based VOCs gas sensor is better. Meanwhile, due to the good flexibility and plasticity of the MXene material, the Co-BDC/MXene composite material has the possibility of preparing a flexible wearable gas sensor. Finally, the conductivity of the Co-BDC/MXene composite material is significantly improved compared with the conventional MOFs.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a Co-BDC/MXene nanocomposite is characterized by comprising the following operations:
MXene was dispersed in N, N-dimethylformamide, after which Co (NO) was added 3 ) 2 ·6H 2 O, performing electrostatic adsorption self-assembly to obtain a mixed solution;
dispersing a DMF solution of terephthalic acid in the mixed solution, sequentially adding ethanol and water, and mixing to obtain a precursor;
and (3) placing the precursor in a reaction kettle, filling inert gas, reacting at 140 ℃ for 12h, and collecting precipitates after the reaction is finished to obtain the Co-BDC/MXene nano composite material.
2. The method for preparing Co-BDC/MXene nanocomposite as claimed in claim 1, wherein 0.035g MXene and 0.291g Co (NO) are dispersed in 15ml N, N-dimethylformamide in the mixed solution 3 ) 2 ·6H 2 O；
0.166g of terephthalic acid was dispersed in 10ml of DMF.
3. The method of preparing a Co-BDC/MXene nanocomposite of claim 1, wherein a DMF solution of terephthalic acid is dispersed in the mixed solution, and mixed with 10ml DMF per 15ml n, n-dimethylformamide.
4. The method for preparing Co-BDC/MXene nanocomposite as claimed in claim 3, wherein adding ethanol and water is adding 2ml ethanol and 2ml water per 15ml N, N-dimethylformamide.
5. A Co-BDC/MXene nanocomposite characterized by being prepared according to the preparation method of any one of claims 1-4.
6. Use of the Co-BDC/MXene nanocomposite material according to claim 5 as a gas sensitive material for detecting the concentration of VOCs gases.
7. The use of the Co-BDC/MXene nanocomposite according to claim 6, wherein the Co-BDC/MXen nanocomposite is placed in a mortar, ethanol is added, followed by grinding to a pasty liquid;
and (3) coating the pasty liquid on a counter electrode, and obtaining the Co-BDC/MXene gas sensor after the ethanol volatilizes.
8. Use of a Co-BDC/MXene nanocomposite according to claim 7, characterized in that the detection is carried out at a working temperature of 110 ℃.
9. Use of the Co-BDC/MXene nanocomposite according to claim 8 for detecting the concentration of acetone, methanol, n-propanol, toluene, ethanol and formaldehyde.
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