CN114674903B - MXene/SnS-based 2 Method for detecting Cr (VI) in water body by using functional composite material - Google Patents
MXene/SnS-based 2 Method for detecting Cr (VI) in water body by using functional composite material Download PDFInfo
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- 229910052724 xenon Inorganic materials 0.000 claims description 4
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The inventionBelongs to the field of functional materials and photoelectric sensing, and adopts two-dimensional MXene materials and SnS 2 The combined composite material is used as a photosensitizer for constructing a photoelectric sensor and detecting Cr (VI) in a water body. The invention adopts a hydrothermal method to prepare MXene/SnS 2 Functional composite material and using MXene/SnS 2 The photoelectric sensor is a sensing device which is based on photosensitive materials and converts optical signals into electric signals through a signal converter to be output. The composite material of the invention is based on MXene with large specific surface area as SnS with visible light response 2 The nano material provides an attachment site, and the two materials are combined, so that the problem of MXene accumulation can be avoided, and the SnS can be improved 2 The electron transfer efficiency of the material can be used in the field of photoelectric sensors, the concentration of Cr (VI) in wastewater can be sensitively detected, and the sensor has the advantages of low cost, simplicity in operation and high sensitivity.
Description
Technical Field
The invention belongs to the field of nano materials and photoelectrochemical sensing, and relates to an MXene/SnS 2 The functional composite material is used for constructing a photoelectrochemical sensor and is used for a method for detecting Cr (VI) in a water body.
Background
MXene was reported from 2012 as an emerging two-dimensional layered material 2 X、M 3 X 2 And M 4 X 3 (M is a transition metal element, such as Ti, zr, V, mo, X represents C or N), and the application thereof has been widely paid attention to scientific researchers in different fields. The MXene material is composed of transition metal carbide, nitride or carbonitride with a thickness of several atomic layers, is generally obtained by acid etching, has a plurality of hydroxyl groups or terminal oxygen groups and the like on the surface, so that the MXene material has the metal conductivity of transition metal, and simultaneously has large specific surface area, good mechanical properties and the like due to the special element composition and the layered structure, and has excellent properties such as chemical stability, biocompatibility and conductivity of 2000S/cm and the likeThe Xene material has wide application in the fields of electrical devices, catalysts, energy storage, sensors and the like. However, the MXene material itself does not have the visible light response property, and has a problem of interlayer collapse.
SnS 2 Belongs to two-dimensional transition metal chalcogenide, has the characteristics of proper band gap, low cost, unique ion diffusion channel and visible light response, can be used as an excellent photocatalyst, has wider interlayer spacing and can promote the transfer and attachment of electrons, but SnS 2 There is a problem in that the electron conductivity and the utilization rate are low due to the rapid recombination and slow transfer of the photo-induced electron-hole pairs.
MXene material and SnS 2 In combination, can utilize the large specific surface area of MXene and excellent adsorption performance, is SnS 2 The nanoparticles provide attachment sites, improve the electron utilization rate, improve the performance of the nanoparticles in electrochemical application, and effectively relieve the problem of MXene interlayer collapse, and the combination of the nanoparticles and the MXene interlayer can lead the composite material to show more excellent photoelectrochemical performance.
Cr (VI) is a swallow poison or an inhalant poison, because hexavalent chromium is easily absorbed by human body, it can invade human body through digestive tract, respiratory tract, skin and mucous membrane, and causes harm to human health, and skin contact of human body may cause allergy; severe cases may cause genetic defects. In addition, cr (VI) is mostly present in the wastewater discharged by industry, and has serious harm to the water environment and water organisms. Because Cr (VI) has strong toxicity and has strong threat to the health of human bodies and the survival of other organisms, hexavalent chromium compounds are listed in the name of toxic and harmful water pollutants in 2019, and the world health organization has corresponding limit on the content of Cr (VI) in discharged water and drinking water to the highest allowable concentration. Therefore, the method has great significance in sensitive detection of Cr (VI) in the water body, and has great application significance and practical value in protecting the environment and the health of human bodies.
Disclosure of Invention
The invention aims to invent a simple and easy-to-operate method for preparing a nano functional composite material which is applied to Cr (VI) in water body) Is used in the detection application field. The photoelectrochemical sensor constructed by the invention has the advantages of low cost, reusability and simple preparation. To expand the optoelectronic applications of the MXene materials described above, the present invention incorporates SnS 2 The preparation and application of the composite material of the nano material and the two-dimensional MXene can extend the field. MXene/SnS is prepared by a simple hydrothermal method 2 The functional composite material is used as a photosensitizer to construct a photoelectric sensing platform, so that the sensitive detection of Cr (VI) in the water body is realized.
The invention adopts the technical proposal that crystalline stannic chloride and thioacetamide are dissolved at room temperature, MXene aqueous solution with certain mass ratio is added into the mixed solution to be completely and uniformly ultrasonically treated, and MXene/SnS with different mass ratio is obtained through continuous reaction under high temperature condition, cooling, centrifugation and washing 2 Functional composite materials. The composite material is modified on an indium tin oxide electrode which is cut into uniform sizes and covered by a pretreated insulating adhesive tape, the electrode is fully reacted with an aqueous solution containing Cr (VI) as a working electrode, the change of a current signal is displayed through the conversion of a photoelectric signal, the detection effect of Cr (VI) with different concentrations is realized through the change of the current signal, and the detection of a linear curve and an actual sample is completed.
MXene/SnS-based 2 The method for detecting Cr (VI) in the water body by using the functional composite material comprises the following steps:
step 1, preparation of MXene/SnS 2 A functional composite material;
slowly adding the crystallized tin tetrachloride and thioacetamide into the mixed solution of water and ethanol in sequence according to the proportion, and performing ultrasonic dispersion at room temperature; then adding a certain amount of uniformly dispersed MXene aqueous solution into the mixed solution, and carrying out ultrasonic treatment until the solution is uniformly dispersed; transferring to a polytetrafluoroethylene reaction kettle, and heating in a constant-temperature oven for reaction; cooling to room temperature, centrifuging the brown yellow precipitate, washing with deionized water and anhydrous ethanol for several times, and drying at constant temperature to obtain MXene/SnS 2 The functional composite material is ground for standby.
In addition, under the same conditions, the preparation of undoped MXene SnS of 2 Nano material is used as a contrast material;
wherein, the mol mass ratio of the crystalline stannic chloride to the thioacetamide is 1:3, in the mixed solution of water and ethanol, the volume ratio of water to ethanol is 2:1;
the mass concentration of the MXene aqueous solution is 5mg/mL;
the temperature of the heating reaction is 150 ℃, and the heat preservation time is 2 hours;
centrifugal washing is carried out for about 10 times, the centrifugal rotating speed is 5000rpm, and the time is 3min;
the constant temperature drying temperature is 60 ℃ and the holding time is 5h.
Step 2, constructing a photoelectric signal sensing platform:
weighing MXene/SnS in the step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain MXene/SnS 2 A functional composite dispersion;
the indium tin oxide glass electrode is stuck and covered by an insulating adhesive tape which is subjected to pre-punching treatment; then MXene/SnS is carried out 2 The functional composite material dispersion liquid is modified in small holes on the surface of the electrode for a plurality of times, and is dried under the illumination of an infrared lamp in sequence; drying to obtain MXene/SnS 2 A photoelectric signal sensing platform modified by a functional composite material;
step 3, preparing a working electrode, and detecting Cr (VI):
diluting the potassium dichromate standard solution to obtain a series of Cr (VI) solutions with different concentrations; respectively modifying potassium dichromate solutions with different concentrations into small holes on the photoelectric signal sensing platform in the step 2, enabling the potassium dichromate solutions to fully react under illumination of an infrared lamp, finally adding a naphthol solution into the small hole range, and continuously drying under illumination of the infrared lamp to obtain working electrodes modified by Cr (VI) ions with different concentrations;
the electrochemical working station is used for photoelectric performance test, under the irradiation of a xenon lamp, the working electrode shows the change of photocurrent signals with different degrees, and the change of the photocurrent signals is compared to detect Cr (VI) aqueous solutions with different concentrations, so that a linear curve for detecting Cr (VI) is obtained.
In step 2, MXene/SnS 2 The concentration of the functional composite material dispersion liquid is 2mg/mL, and the dosage is 100 mu L; the modification mode is as follows: 100. Mu.L MXene/SnS 2 The functional composite dispersion is modified for 3 times.
In step 2, the size of the indium tin oxide electrode is 1X 2cm 2 The size of the pretreated insulating tape is 1X 1cm 2 The aperture of the upper hole of the insulating tape is 6mm.
In the step 3, the modification amount of the potassium dichromate solution is 10 mu L, and the concentration is 10 -4 ～10 5 nmol/L, the time of the illumination reaction under an infrared lamp is 30min.
In the step 3, the addition amount of the naphthol solution is 10 mu L, and the mass percentage concentration of the naphthol solution is 1%.
In step 3, in the photoelectrochemical detection process, a three-electrode system is used, a calomel electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a Phosphate Buffer Solution (PBS) with ph=7.4 is used as an electrolyte.
The invention has the beneficial effects that:
(1) MXene/SnS utilized by the invention 2 The functional composite material has the advantages of larger specific surface area and excellent biocompatibility, can provide more attachment sites for photoelectron release, is environment-friendly, and in addition, the MXene/SnS related by the invention 2 The preparation method of the functional composite material is simple and has low cost.
(2) The built photoelectrochemical sensor takes the indium tin oxide electrode as a substrate, has the advantage of reusability, has small dosage for materials and targets in the preparation process, and uses detection instruments including an electrochemical workstation, a xenon lamp and an ultraviolet-visible spectrophotometer, and has the advantages of simple operation, high analysis speed and low cost.
Drawings
FIG. 1 is a graph (a-j: 10) of photocurrent signals of the present invention for detecting Cr (VI) aqueous solutions of different concentrations -4 nmol/L,10 -3 nmol/L,10 -2 nmol/L,0.1nmol/L,1nmol/L,10nmol/L,10 2 nmol/L,10 3 nmol/L,10 4 nmol/L,10 5 nmol/L)；
FIG. 2 is a linear fit of the composite material to detect Cr (VI) aqueous solutions of different concentrations.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
step 1, (0.1 wt%) MXene/SnS 2 Preparation of functional composite material:
mixing 5mL of deionized water and 2.5mL of ethanol uniformly in a beaker, then respectively weighing 0.875g of crystalline tin tetrachloride and 0.564g of thioacetamide, sequentially adding the materials into the beaker of the mixed solution of water and ethanol, and carrying out ultrasonic treatment at room temperature for 10min; taking 175 mu L of the existing uniformly dispersed MXene aqueous solution, adding the 175 mu L of the existing uniformly dispersed MXene aqueous solution into the mixed solution, and carrying out ultrasonic treatment for half an hour until the existing uniformly dispersed MXene aqueous solution is uniformly dispersed; transferring the mixed dispersion liquid into a 20mL polytetrafluoroethylene reaction kettle, heating and reacting in a constant temperature oven at 150 ℃, and preserving the heat for 2h; after cooling to room temperature, the resulting brown yellow powder was centrifuged, washed with deionized water and absolute ethanol multiple times, and dried at constant temperature to give (0.1 wt%) MXene/SnS 2 A functional composite material; after the materials are sufficiently ground, the materials are preserved for standby;
step 2, constructing a photoelectric signal sensing platform:
weighing (0.1 wt%) of MXene/SnS in step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain a uniform dispersion liquid with the concentration of 2 mg/mL; the indium tin oxide electrode is stuck and covered by an insulating tape which is subjected to pre-punching treatment (the aperture is 6 mm); then, 100 mu L of dispersion liquid is modified in small holes on the surface of an electrode for 3 times, and is dried under the illumination of an infrared lamp; after drying, MXene/SnS (0.1 wt.%) was obtained 2 And a photoelectric signal sensing platform modified by the functional composite material.
Example 2:
step 1, (0.2 wt%) MXene/SnS 2 Preparation of functional composite material:
taking 5mL of deionized water, 2Mixing 5mL of ethanol uniformly in a beaker, respectively weighing 0.875g of crystalline tin tetrachloride and 0.564g of thioacetamide, sequentially adding into the beaker of the mixed solution of water and ethanol, and carrying out ultrasonic treatment at room temperature for 10min; taking 350 mu L of the existing MXene aqueous solution with uniform dispersion, adding the solution into the mixed solution, and carrying out ultrasonic treatment for half an hour until the solution is uniformly dispersed; transferring the mixed dispersion liquid into a 20mL polytetrafluoroethylene reaction kettle, heating and reacting in a constant temperature oven at 150 ℃, and preserving the heat for 2h; after cooling to room temperature, the resulting brown yellow powder was centrifuged, washed with deionized water and absolute ethanol multiple times, and dried at constant temperature to give (0.2 wt%) MXene/SnS 2 A functional composite material; after the materials are sufficiently ground, the materials are preserved for standby;
step 2, constructing a photoelectric signal sensing platform:
weighing (0.2 wt%) of MXene/SnS in step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain a uniform dispersion liquid with the concentration of 2 mg/mL; the indium tin oxide electrode is stuck and covered by an insulating tape which is subjected to pre-punching treatment (the aperture is 6 mm); then, 100 mu L of dispersion liquid is modified in small holes on the surface of an electrode for 3 times, and is dried under the illumination of an infrared lamp; after drying, MXene/SnS (0.2 wt.%) was obtained 2 And a photoelectric signal sensing platform modified by the functional composite material.
Example 3:
step 1, (0.4 wt%) MXene/SnS 2 Preparation of functional composite material:
mixing 5mL of deionized water and 2.5mL of ethanol uniformly in a beaker, then respectively weighing 0.875g of crystalline tin tetrachloride and 0.564g of thioacetamide, sequentially adding the materials into the beaker of the mixed solution of water and ethanol, and carrying out ultrasonic treatment at room temperature for 10min; taking 700 mu L of the existing MXene aqueous solution with uniform dispersion, adding the 700 mu L of the MXene aqueous solution into the mixed solution, and carrying out ultrasonic treatment for half an hour until the MXene aqueous solution is uniformly dispersed; transferring the mixed dispersion liquid into a 20mL polytetrafluoroethylene reaction kettle, heating and reacting in a constant temperature oven at 150 ℃, and preserving the heat for 2h; after cooling to room temperature, the resulting brown yellow powder was centrifuged, washed with deionized water and absolute ethanol multiple times, and dried at constant temperature to give (0.4 wt%) MXene/SnS 2 Functional composite materialThe method comprises the steps of carrying out a first treatment on the surface of the After the materials are sufficiently ground, the materials are preserved for standby;
step 2, constructing a photoelectric signal sensing platform:
weighing (0.4 wt%) of MXene/SnS in step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain a uniform dispersion liquid with the concentration of 2 mg/mL; the indium tin oxide electrode is stuck and covered by an insulating tape which is subjected to pre-punching treatment (the aperture is 6 mm); then, 100 mu L of dispersion liquid is modified in small holes on the surface of an electrode for 3 times, and is dried under the illumination of an infrared lamp; drying to obtain (0.4 wt%) MXene/SnS 2 And a photoelectric signal sensing platform modified by the functional composite material.
Example 4:
step 1, (0.7 wt%) MXene/SnS 2 Preparation of functional composite material:
mixing 5mL of deionized water and 2.5mL of ethanol uniformly in a beaker, then respectively weighing 0.875g of crystalline tin tetrachloride and 0.564g of thioacetamide, sequentially adding the materials into the beaker of the mixed solution of water and ethanol, and carrying out ultrasonic treatment at room temperature for 10min; adding 1225 mu L of the existing uniformly dispersed MXene aqueous solution into the mixed solution, and carrying out ultrasonic treatment for half an hour until the solution is uniformly dispersed; transferring the mixed dispersion liquid into a 20mL polytetrafluoroethylene reaction kettle, heating and reacting in a constant temperature oven at 150 ℃, and preserving the heat for 2h; after cooling to room temperature, the resulting brown yellow powder was centrifuged, washed with deionized water and absolute ethanol multiple times, and dried at constant temperature to give (0.7 wt%) MXene/SnS 2 A functional composite material; after the materials are sufficiently ground, the materials are preserved for standby;
step 2, constructing a photoelectric signal sensing platform:
weighing (0.7 wt%) of MXene/SnS in step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain a uniform dispersion liquid with the concentration of 2 mg/mL; the indium tin oxide electrode is stuck and covered by an insulating tape which is subjected to pre-punching treatment (the aperture is 6 mm); then, 100 mu L of dispersion liquid is modified in small holes on the surface of an electrode for 3 times, and is dried under the illumination of an infrared lamp; drying to obtain (0.7 wt%) MXene/SnS 2 And a photoelectric signal sensing platform modified by the functional composite material.
Example 5:
step 1, optimizing the use condition of a sensor:
the photoelectric sensing platforms with different modification amounts in the steps 1-4 and 2 are respectively placed in a three-electrode system for photoelectric performance test, phosphate buffer solution (pH=7.4) is used as electrolyte, and photocurrent signals of materials are compared to obtain the optimal doping mass ratio of MXene; the bias voltage of the sensor is optimized by adjusting the use parameters of the bias voltage.
Step 2, manufacturing a working electrode, and detecting Cr (VI):
diluting the potassium dichromate standard solution to obtain a series of Cr (VI) solution with concentration; respectively modifying 10 mu L of diluted potassium dichromate solution on the sensor in the step 2, illuminating for 30min under an infrared lamp to fully react, finally adding 10 mu L of naphthol solution (the mass percentage concentration of the naphthol solution is 1%) in the range of the small hole, and continuously drying under the illumination of the infrared lamp to obtain the working electrode to be tested;
and (3) displaying a photocurrent signal under the irradiation of a xenon lamp by using an electrochemical workstation, and detecting Cr (VI) aqueous solutions with different concentrations by comparing the change of the photocurrent signal so as to obtain a linear curve for detecting the Cr (VI).
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (7)
1. MXene/SnS-based 2 The method for detecting Cr (VI) in the water body by using the functional composite material is characterized by comprising the following steps:
step 1, preparation of MXene/SnS 2 Functional composite material for standby;
slowly adding the crystallized tin tetrachloride and thioacetamide into the mixed solution of water and ethanol in sequence according to the proportion, and performing ultrasonic dispersion at room temperature; then a certain amount of evenly dispersed MXene aqueous solution is added intoUltrasonic treatment is carried out in the mixed solution until the mixed solution is uniformly dispersed; transferring to a polytetrafluoroethylene reaction kettle, and heating in a constant-temperature oven for reaction; cooling to room temperature, centrifuging the brown yellow precipitate, washing with deionized water and anhydrous ethanol for several times, and drying at constant temperature to obtain MXene/SnS 2 Grinding the functional composite material for standby;
step 2, constructing a photoelectric signal sensing platform:
weighing MXene/SnS in the step 1 2 Dispersing the functional composite material into deionized water, and performing ultrasonic treatment until the functional composite material is uniform to obtain MXene/SnS 2 A functional composite dispersion;
the indium tin oxide glass electrode is stuck and covered by an insulating adhesive tape which is subjected to pre-punching treatment; then MXene/SnS is carried out 2 The functional composite material dispersion liquid is modified in small holes on the surface of the electrode for a plurality of times, and is dried under the illumination of an infrared lamp in sequence; drying to obtain MXene/SnS 2 A photoelectric signal sensing platform modified by a functional composite material;
step 3, preparing a working electrode, and detecting Cr (VI):
diluting the potassium dichromate standard solution to obtain a series of Cr (VI) solutions with different concentrations; respectively modifying potassium dichromate solutions with different concentrations into small holes on the photoelectric signal sensing platform in the step 2, enabling the potassium dichromate solutions to fully react under illumination of an infrared lamp, finally adding a naphthol solution into the small hole range, and continuously drying under illumination of the infrared lamp to obtain working electrodes modified by Cr (VI) ions with different concentrations;
the electrochemical working station is used for photoelectric performance test, under the irradiation of a xenon lamp, the working electrode shows the change of photocurrent signals with different degrees, and the change of the photocurrent signals is compared to detect Cr (VI) aqueous solutions with different concentrations, so that a linear curve for detecting Cr (VI) is obtained.
2. An MXene/SnS-based alloy according to claim 1 2 A method for detecting Cr (VI) in a water body by using a functional composite material is characterized in that in the step 1,
the molar mass ratio of the crystalline tin tetrachloride to the thioacetamide is 1:3, in the mixed solution of water and ethanol, the volume ratio of water to ethanol is 2:1;
the mass concentration of the MXene aqueous solution is 5mg/mL;
the temperature of the heating reaction is 150 ℃, and the heat preservation time is 2 hours;
centrifugal washing for 10 times, wherein the centrifugal rotating speed is 5000rpm, and the time is 3min;
the constant temperature drying temperature is 60 ℃ and the holding time is 5h.
3. An MXene/SnS-based alloy according to claim 1 2 A method for detecting Cr (VI) in water by using a functional composite material is characterized in that in the step 2, MXene/SnS 2 The concentration of the functional composite material dispersion liquid is 2mg/mL, and the dosage is 100 mu L; the modification mode is as follows: 100. Mu.L MXene/SnS 2 The functional composite dispersion is modified for 3 times.
4. An MXene/SnS-based alloy according to claim 1 2 A method for detecting Cr (VI) in water by using a functional composite material is characterized in that in the step 2, the size of an indium tin oxide electrode is 1 multiplied by 2cm 2 The size of the pretreated insulating tape is 1X 1cm 2 The aperture of the upper hole of the insulating tape is 6mm.
5. An MXene/SnS-based alloy according to claim 1 2 A method for detecting Cr (VI) in water by using a functional composite material is characterized in that in the step 3, the modification amount of a potassium dichromate solution is 10 mu L, and the concentration is 10 -4 ～10 5 nmol/L, the time of the illumination reaction under an infrared lamp is 30min.
6. An MXene/SnS-based alloy according to claim 1 2 The method for detecting Cr (VI) in the water body by using the functional composite material is characterized in that in the step 3, the adding amount of a naphthol solution is 10 mu L, and the mass percentage concentration of the naphthol solution is 1%.
7. An MXene/SnS-based alloy according to claim 1 2 Functional composite material for detecting C in water bodyThe method of r (VI) is characterized in that in step 3, a three-electrode system is used in the photoelectrochemical detection process, a calomel electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a Phosphate Buffer Solution (PBS) with ph=7.4 is used as an electrolyte.
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| CN106430195A (en) * | 2016-10-14 | 2017-02-22 | 北京大学 | MXene material and preparation method and application thereof |
| CN109085226A (en) * | 2018-10-23 | 2018-12-25 | 青岛大学 | Competitive type electrochemistry aptamer sensor based on MXene is used for the detection of Mucin1 |
| CN112018354A (en) * | 2020-08-14 | 2020-12-01 | 五邑大学 | Array-shaped SnS2Preparation method of/MXene composite material |
| CN112316157A (en) * | 2020-11-12 | 2021-02-05 | 苏州北科纳米科技有限公司 | Preparation method and application of antioxidant MXenes material |
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| CN106430195A (en) * | 2016-10-14 | 2017-02-22 | 北京大学 | MXene material and preparation method and application thereof |
| CN109085226A (en) * | 2018-10-23 | 2018-12-25 | 青岛大学 | Competitive type electrochemistry aptamer sensor based on MXene is used for the detection of Mucin1 |
| CN112018354A (en) * | 2020-08-14 | 2020-12-01 | 五邑大学 | Array-shaped SnS2Preparation method of/MXene composite material |
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