TA-MXene composite material for acetone detection as well as preparation method and application of TA-MXene composite material
The sensor, made of tartaric acid-modified nanolayered MXene composite material, solves the problems of large size, complexity and high cost of acetone detection equipment, and realizes sensitive, low-energy-consumption room temperature acetone detection with excellent moisture resistance and long-term stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING TECH UNIV
- Filing Date
- 2026-01-26
- Publication Date
- 2026-05-12
AI Technical Summary
In existing technologies, acetone detection equipment is bulky, has complex detection procedures, is costly, and is difficult to operate at low energy consumption for a long time at room temperature. MXene materials have problems such as easy stacking of nanosheets, poor oxidation resistance, and poor long-term stability in applications.
A TA-MXene composite material was prepared by modifying MXene with a nanosheet layered structure material composed of tartaric acid and nanolayered MXene through covalent bonding. This composite material was then used to modify Au interdigitated electrodes to make sensors.
It achieves sensitive detection of acetone at room temperature, has more stable resistance and moisture resistance, short response recovery time, and low cost, and is suitable for real-time monitoring and sensing of gaseous acetone.
Smart Images
Figure CN122016949A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of MXene composite material preparation technology, specifically to a TA-MXene composite material for acetone detection, its preparation method, and the application of a modified electrode in the detection of gaseous acetone. Background Technology
[0002] Acetone is a common toxic gas in industrial environments, and its concentration in human exhaled breath is closely related to diseases. For example, as an important biomarker for diabetes detection, the acetone concentration in the exhaled breath of diabetic patients is more than twice that of healthy individuals. Current traditional methods for detecting gaseous acetone are limited by factors such as large equipment size, complex detection procedures, high cost, and susceptibility to interference (e.g., GC-MS, LPAS). Small acetone sensors based on metal-oxide-semiconductor systems often have high operating temperatures (200-300℃), making them unsuitable for long-term, low-energy-consumption operation in daily life. Therefore, designing sensitive, simple, accurate, and instantaneous sensing electrodes to achieve the sensing and detection of gaseous acetone at room temperature is crucial.
[0003] MXene is a p-type semiconductor material. Layered MXene nanosheets exhibit excellent electrical conductivity similar to metals, while their sheet-like structure enhances electron mobility and chemical stability. Furthermore, they possess advantages such as high specific surface area and low operating temperature, making them crucial for applications in reaction catalysis, sensor fabrication, and energy storage, and thus one of the most promising materials currently available. However, in practical applications, MXene materials still suffer from drawbacks such as easy nanosheet aggregation, poor oxidation resistance, and poor long-term stability. Therefore, suitable modification methods need to be designed to prepare composite materials with high gas-sensitivity to acetone.
[0004] Tartaric acid (TA), as a low-cost organic compound, can bind to the reaction sites of MXene through covalent coordination, thereby achieving the effects of anti-oxidation and improving material stability. Tartaric acid can also promote physical cross-linking in MXene composite materials and prevent MXene from decomposing due to interference from water molecules, making it one of the ideal modification materials. Summary of the Invention
[0005] The purpose of this invention is to provide a TA-MXene composite material for acetone detection, its preparation method, and its application. This material has a nanosheet layered structure with more active reaction sites, stable resistance, and better moisture resistance, thus meeting the requirements for acetone gas detection.
[0006] Technical solution: The TA-MXene composite material for acetone detection described in this invention is a nanosheet layered structure material composed of tartaric acid and nanolayered MXene.
[0007] Furthermore, the thickness of the nanosheet layered structure material is 10~15nm, and the interlayer spacing is 20~50nm.
[0008] This invention also provides a method for preparing a TA-MXene composite material for acetone detection, comprising the following steps:
[0009] Step 1: Add hydrochloric acid and lithium fluoride to a beaker for reaction, and heat and stir to obtain an initial mixture;
[0010] Step 2: Vanadium aluminum carbide is added to the initial mixture for etching, followed by centrifugation, ultrasonic cleaning and freeze drying to obtain nano-layered MXene.
[0011] Step 3: Mix tartaric acid and MXene separately with deionized water and stir them evenly to obtain their respective mixtures. Then mix the two mixtures together and stir evenly to obtain a mixture of tartaric acid and MXene.
[0012] Step 4: The mixture of tartaric acid and MXene is subjected to heat treatment, centrifugation, ultrasonic washing, freeze drying and annealing in sequence to obtain TA-MXene composite material with tartaric acid covalent coordination.
[0013] Furthermore, in step 1 of the preparation method, when hydrochloric acid and lithium fluoride are mixed, the mass ratio of hydrochloric acid to lithium fluoride is 1:14 to 1:16, and the mixing reaction time is 10 to 15 minutes.
[0014] Furthermore, in step 2 of the preparation method, when vanadium aluminum carbide is added to the initial mixture, the mass ratio of vanadium aluminum carbide to hydrochloric acid is 1:23 to 1:27, and the etching reaction time is 144 to 148 h.
[0015] Furthermore, in step 3 of the preparation method, the specific steps for mixing tartaric acid and MXene with deionized water and stirring them evenly are as follows:
[0016] First, tartaric acid and MXene in a mass ratio of 45:1 to 55:1 are placed separately into deionized water, with the mass ratio of tartaric acid to deionized water being 1:2.8 to 1:3 and the mass ratio of MXene to deionized water being 1:48 to 1:50.
[0017] Then, tartaric acid and MXene are mixed with their respective deionized water and stirred for 10-15 minutes each.
[0018] Finally, nitrogen gas is introduced to seal and protect the well-stirred mixture. The nitrogen gas is introduced for 5 to 10 minutes.
[0019] Furthermore, when mixing with their respective deionized water, a magnetic stirrer is used for mixing, and the stirring speed is 300r / min~400r / min, and the temperature during mixing is 20℃~25℃.
[0020] Furthermore, in step 4 of the preparation method, the temperature of the heat treatment is 60~65℃ and the duration of the heat treatment is 48h~50h.
[0021] Furthermore, in step 4 of the preparation method, during annealing, the annealing heating rate is 5~8℃ / min, the maximum annealing temperature is 200℃, the annealing time is 1h~3h, and finally the temperature is allowed to cool naturally to room temperature.
[0022] The present invention also provides an application of TA-MXene composite material for acetone detection, wherein the TA-MXene composite material is applied to modify Au interdigitated electrodes to fabricate a sensor for detecting acetone gas.
[0023] Compared with the prior art, the beneficial effects of this invention are: (1) Tartaric acid coordinated with MXene also becomes the preferred attachment object of oxygen and water molecules, thereby making the material obtain a more stable resistance value and better moisture resistance, with better electrochemical performance than pure MXene, and enhancing the detection performance of acetone gas; (2) The preparation method has the advantages of simple operation, excellent material performance, and low implementation cost. It has great application potential in various systems involving the generation, reaction and clinical exhaled breath detection of acetone gas, as well as for real-time monitoring and sensing of acetone. Attached Figure Description
[0024] Figure 1 Here is a scanning electron microscope image of TA-MXene as an example of the present invention;
[0025] Figure 2 This is a transmission electron microscope image of TA-MXene as an example of the present invention;
[0026] Figure 3 Here is a scanning electron microscope image of MXene as an example of the present invention;
[0027] Figure 4 The response recovery curves of the MXene Au interdigitated electrode and TA-MXene Au interdigitated electrode as examples of the present invention after exposure of the electrode surface to 50 ppm acetone at 1V;
[0028] Figure 5 The continuous response recovery curves of the TA-MXene Au interdigitated electrode, as an example of the present invention, after different concentrations of acetone were exposed to the electrode surface at 1V, and the fitting curves of the response value as a function of concentration.
[0029] Figure 6 Resistance variation curves of MXene Au interdigitated electrodes and TA-MXene Au interdigitated electrodes stored at room temperature at 1V for one month as examples of the present invention.
[0030] Figure 7 The following are scanning electron microscope images of MXene and TA-MXene stored at room temperature for one month before and after, respectively, as examples of the present invention, where (a) and (b) are MXene, and (c) and (d) are TA-MXene. Detailed Implementation
[0031] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings, but the scope of protection of the present invention is not limited to the embodiments described.
[0032] like Figure 1 As shown, the TA-MXene composite material for acetone detection disclosed in this invention is a nanosheet layered structure material composed of tartaric acid and nanolayered MXene.
[0033] Furthermore, the thickness of the nanosheet layered structure material is 10~15nm, and the interlayer spacing is 20~50nm.
[0034] This invention also provides a method for preparing a TA-MXene composite material for acetone detection, comprising the following steps:
[0035] Step 1: Add hydrochloric acid (HCl) and lithium fluoride (LiF) to a beaker and react for a period of time. Then, heat and stir the mixture in a magnetic stirrer to obtain an initial mixture.
[0036] Step 2: Vanadium aluminum carbide (V4AlC3) is added to the initial mixture for etching, followed by centrifugation, ultrasonic cleaning and freeze drying to obtain nano-layered MXene.
[0037] Step 3: Mix tartaric acid and MXene separately with deionized water and stir them evenly to obtain their respective mixtures. Then mix the two mixtures together and stir evenly to obtain a mixture of tartaric acid and MXene.
[0038] Step 4: The mixture of tartaric acid and MXene is subjected to heat treatment, centrifugation, ultrasonic washing, freeze drying and annealing in sequence to obtain TA-MXene composite material with a nanosheet layered structure covalently coordinated with tartaric acid.
[0039] Furthermore, in step 1 of the preparation method, when hydrochloric acid and lithium fluoride are mixed, the mass ratio of hydrochloric acid to lithium fluoride is 1:14 to 1:16, preferably 1:15, and the mixing reaction time is 10 to 15 minutes.
[0040] Furthermore, in step 2 of the preparation method, when vanadium aluminum carbide is added to the initial mixture, the mass ratio of vanadium aluminum carbide to hydrochloric acid is 1:23 to 1:27, preferably 1:25, and the etching reaction time is 144 to 148 h, preferably 144 h.
[0041] Furthermore, in step 3 of the preparation method, the specific steps for mixing tartaric acid and MXene with deionized water and stirring them evenly are as follows:
[0042] First, tartaric acid and MXene in a mass ratio of 45:1 to 55:1 are placed separately in deionized water, with the preferred mass ratio being 50:1; the mass ratio of tartaric acid to deionized water is 1:2.8 to 1:3, preferably 1:3; the mass ratio of MXene to deionized water is 1:48 to 1:50, preferably 1:50.
[0043] Then, tartaric acid and MXene are mixed with their respective deionized water and stirred for 10-15 minutes each.
[0044] Finally, nitrogen gas is introduced to seal and protect the well-stirred mixture. The nitrogen gas is introduced for 5 to 10 minutes.
[0045] Furthermore, when mixing with their respective deionized water, a magnetic stirrer is used for mixing, and the stirring speed is 300r / min~400r / min, and the temperature during mixing is 20℃~25℃.
[0046] Furthermore, in step 4 of the preparation method, when performing heat treatment, the temperature of the heat treatment is 60~65℃, preferably 60℃, and the duration of the heat treatment is 48h~50h, preferably 48h.
[0047] Furthermore, in step 4 of the preparation method, during centrifugal separation, the bottom precipitate obtained from the heat treatment is first collected and washed 3-5 times with 1M dilute hydrochloric acid at a speed of 3500 r / min to 6000 r / min, preferably 3500 r / min, for a centrifugation time of 5 min; then washed 3-5 times with deionized water at a speed of 3500 r / min to 6000 r / min, preferably 3500 r / min, for a centrifugation time of 5 min, until the pH is approximately 7, at which point the precipitate is collected.
[0048] Furthermore, in step 4 of the preparation method, the freeze-drying temperature is -40℃ to -60℃, the freeze-drying vacuum degree is 1.0 Pa, and the freeze-drying time is 48h to 60h.
[0049] Furthermore, in step 4 of the preparation method, during annealing, the annealing heating rate is 5~8℃ / min, preferably 5℃ / min, the maximum annealing temperature is 200℃, the annealing time is 1h~3h, preferably 2h, and finally the temperature is allowed to cool naturally to room temperature.
[0050] The present invention also provides an application of TA-MXene composite material for acetone detection, wherein the TA-MXene composite material is applied to modify Au interdigitated electrodes to create a sensor for detecting acetone gas.
[0051] The specific steps for modifying Au interdigitated electrodes are as follows:
[0052] First, the Au interdigitated electrodes are pretreated: the Au interdigitated electrodes are polished with magnesium oxide powder with particle sizes of 0.4μm and 0.02μm, respectively. The polished electrodes are then ultrasonically cleaned in anhydrous ethanol for 6-10 minutes to remove organic dirt. Next, they are ultrasonically cleaned in ultrapure water for 10-15 minutes to remove residual ethanol and magnesium oxide particles. Finally, the electrode surface is dried with high-purity nitrogen.
[0053] Then, the Au interdigitated electrode was constructed: 2-5 mg of TA-MXene composite material was weighed and mixed with 0.1 mL-0.25 mL of anhydrous ethanol and ultrasonically homogenized to obtain a uniform TA-MXene anhydrous ethanol composite dispersion. 10-15 µL of the TA-MXene anhydrous ethanol composite dispersion was pipetted onto the surface of the Au interdigitated electrode. The modification was repeated 3-5 times and then heated and dried on a heating stage for 2-3 h.
[0054] Furthermore, after the Au interdigitated electrode was modified, the surface of the Au interdigitated electrode was exposed to acetone gas of different concentrations, and the sensor resistance over time was tested under different concentrations of acetone gas. The test voltage was 1V.
[0055] The following examples illustrate the above preparation process and the prepared TA-MXene Au interdigitated electrodes through experimental testing:
[0056] Example 1: Preparation of MXene.
[0057] 20 ml of HCl and 1.6 g of LiF were mixed and added to a beaker, and the mixture was reacted for 10 min. 1 g of V4AlC3 was added to the resulting mixture, and the mixture was continuously stirred in a magnetic stirrer for 144 h at a speed of 400 r / min and a temperature of 20℃~25℃. The resulting solution was centrifuged, sonicated, and freeze-dried for 60 h to obtain layered MXene.
[0058] Example 2: Preparation of TA-MXene composite material and construction of TA-MXene Au interdigitated electrode.
[0059] First, MXene was synthesized through etching and other operations: 3g of tartaric acid (C4H6O6) and 60mg of MXene were mixed with 9mL and 3mL of deionized water, respectively, and stirred for 10min. Nitrogen gas was continuously introduced into the stirred solution and then sealed for 10min. The nitrogen-protected mixture was placed in an oil bath magnetic stirrer and stirred continuously for 48h at a speed of 300r / min and a temperature of 60℃ to obtain a tartaric acid-loaded MXene composite material. The obtained material was then annealed at a heating rate of 5℃ / min to 200℃ for 2h, followed by natural cooling to room temperature. The TA-MXene composite material was obtained.
[0060] from Figure 1 and Figure 2 It can be seen that the TA-MXene composite material is a nanosheet layered material, and a tartaric acid film layer of about 5 nm is attached to the surface of the nanosheet.
[0061] Figure 3 The SEM image of MXene shows that the layered MXene material was successfully prepared, laying the foundation for the successful loading of pure material.
[0062] The Au interdigitated electrode was polished with magnesium oxide powder with particle sizes of 0.4 μm and 0.02 μm. The polished electrode was then ultrasonically cleaned in anhydrous ethanol for 6–10 minutes to remove organic contaminants. Next, it was ultrasonically cleaned in ultrapure water for 10–15 minutes to remove residual ethanol and magnesium oxide particles. Finally, the electrode surface was dried with high-purity nitrogen. 2–5 mg of TA-MXene composite material was weighed and mixed with 0.1 mL–0.25 mL of anhydrous ethanol, then ultrasonically homogenized to obtain a homogeneous TA-MXene anhydrous ethanol composite dispersion. 10–15 µL of this dispersion was drop-cast onto the surface of the Au interdigitated electrode using a pipette. This modification was repeated 3–5 times, and the electrode was then heated and dried on a heating stage for 2–3 hours to obtain the TA-MXene Au interdigitated electrode.
[0063] Example 3: Au interdigitated electrode comparison experiment.
[0064] The MXene and TA-MXene obtained by the methods in Examples 1 and 2 were used to modify Au interdigitated electrodes, which were then used as gas-sensitive substrates to construct MXene Au interdigitated electrodes and TA-MXene Au interdigitated electrodes. 50 ppm acetone was exposed to the surface of the Au interdigitated electrodes, and the sensor resistance over time was tested. The resistance of both electrodes to 50 ppm acetone over time was tested at a test voltage of 1V. Figure 4As shown, when the MXene Au interdigitated electrode is used as the gas-sensitive substrate, the response time is 22s and the recovery time is 12s. However, when the TA-MXene Au interdigitated electrode is used as the gas-sensitive substrate, the response time is 15s and the recovery time is 5s, both significantly shorter than the response and recovery times of pure MXene. This demonstrates the superior sensing performance of the composite material.
[0065] Example 4: Experiment on the response value of TA-MXene Au interdigitated electrode.
[0066] Using the TA-MXene Au interdigitated electrode obtained according to the method in Example 2 as a gas-sensitive substrate, different concentrations of gaseous acetone were continuously exposed to the surface of the Au interdigitated electrode. The sensor response value over time was tested. The gas-sensing performance of the TA-MXene Au interdigitated electrode to acetone was demonstrated by detecting the change in response value over time. The change in response value over time is shown in the figure below. Figure 5 As shown in the figure. The results indicate that as the acetone concentration gradually increases, the sensor's response value gradually increases, and there is a good linear relationship between the material's response value and the acetone concentration.
[0067] As can be seen from the above, the TA-MXene composite material synthesized in this invention is highly sensitive to the detection of gaseous acetone and has a short response recovery time. It has excellent performance in acetone detection and therefore has great application potential in various systems involving the generation, reaction and clinical exhaled breath detection of gaseous acetone, as well as in the real-time monitoring and sensing of acetone.
[0068] Example 5: Long-term stability test.
[0069] The MXene Au interdigitated electrode and TA-MXene Au interdigitated electrode obtained according to the method in Example 2 were used as gas-sensitive substrates. Both sensors were placed at room temperature for 30 days, during which the resistance characteristics of the sensors over time were tested. The resistance stability of the TA-MXene Au interdigitated electrode was demonstrated by detecting the change in resistance over time. The change in resistance over time is shown in the figure. Figure 6 As shown in the figure, the resistivity of TA-MXene remained essentially consistent with the initial value compared to pure MXene over a period of one month; a comparison of SEM images of the two materials before and after one month is shown. Figure 7 As shown in the figure, (a) and (b) are MXene, and (c) and (d) are TA-MXene. This shows that after one month, the interlayer spacing of pure MXene increased significantly and the structure collapsed. Different degrees of fracture and dislocation appeared in each layer of the cross section. The morphology and structure of TA-MXene remained almost unchanged, which strongly proves that the material has excellent long-term stability.
[0070] As can be seen from the above, the TA-MXene composite material synthesized in this invention is highly sensitive to the detection of acetone as a gas-sensitive material for sensors, with a short response recovery time. It has excellent performance in the detection of gaseous acetone and has great application potential in various systems involving the generation, reaction, and clinical exhaled breath detection of gaseous acetone, as well as in the real-time monitoring and sensing of acetone.
[0071] As described above, although the invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims
1. A TA-MXene composite material for acetone detection, characterized in that, The TA-MXene composite material is a nanosheet layered structure material composed of tartaric acid and nanolayered MXene.
2. The TA-MXene composite material for acetone detection according to claim 1, characterized in that, The thickness of the nanosheet layered structure material is 10~15nm, and the interlayer spacing is 20~50nm.
3. A method for preparing a TA-MXene composite material for acetone detection, characterized in that, Includes the following steps: Step 1: Add hydrochloric acid and lithium fluoride to a beaker for reaction, and heat and stir to obtain an initial mixture; Step 2: Vanadium aluminum carbide is added to the initial mixture for etching, followed by centrifugation, ultrasonic cleaning and freeze drying to obtain nano-layered MXene. Step 3: Mix tartaric acid and MXene separately with deionized water and stir them evenly to obtain their respective mixtures. Then mix the two mixtures together and stir evenly to obtain a mixture of tartaric acid and MXene. Step 4: The mixture of tartaric acid and MXene is subjected to heat treatment, centrifugation, ultrasonic washing, freeze drying and annealing in sequence to obtain TA-MXene composite material with tartaric acid covalent coordination.
4. The method for preparing the TA-MXene composite material for acetone detection according to claim 3, characterized in that, In step 1, when hydrochloric acid and lithium fluoride are mixed, the mass ratio of hydrochloric acid to lithium fluoride is 1:14 to 1:16, and the mixing reaction time is 10 to 15 minutes.
5. The method for preparing the TA-MXene composite material for acetone detection according to claim 3, characterized in that, In step 2, when vanadium aluminum carbide is added to the initial mixture, the mass ratio of vanadium aluminum carbide to hydrochloric acid is 1:23 to 1:27, and the etching reaction time is 144 to 148 h.
6. The method for preparing the TA-MXene composite material for acetone detection according to claim 3, characterized in that, In step 3, the specific steps for mixing tartaric acid and MXene with deionized water separately and stirring them evenly are as follows: First, tartaric acid and MXene in a mass ratio of 45:1 to 55:1 are placed separately into deionized water, with the mass ratio of tartaric acid to deionized water being 1:2.8 to 1:3 and the mass ratio of MXene to deionized water being 1:48 to 1:
50. Then, tartaric acid and MXene are mixed with their respective deionized water and stirred for 10-15 minutes each. Finally, nitrogen gas is introduced to seal and protect the well-stirred mixture. The nitrogen gas is introduced for 5 to 10 minutes.
7. The method for preparing the TA-MXene composite material for acetone detection according to claim 6, characterized in that, When mixing with their respective deionized water, a magnetic stirrer is used for mixing, and the stirring speed is 300r / min~400r / min, and the temperature during mixing is 20℃~25℃.
8. The method for preparing the TA-MXene composite material for acetone detection according to claim 3, characterized in that, In step 4, the heat treatment temperature is 60~65℃ and the heat treatment duration is 48h~50h.
9. The method for preparing the TA-MXene composite material for acetone detection according to claim 3, characterized in that, In step 4, during the annealing process, the annealing heating rate is 5~8℃ / min, the maximum annealing temperature is 200℃, the annealing time is 1h~3h, and finally the temperature is allowed to cool naturally to room temperature.
10. The application of the TA-MXene composite material for acetone detection according to claim 1, characterized in that, The TA-MXene composite material was used to modify Au interdigitated electrodes to fabricate a sensor for detecting acetone gas.