WO2024066403A1 - 一种MXene制备残留物的回收利用方法及其在生物传感器中的应用 - Google Patents

一种MXene制备残留物的回收利用方法及其在生物传感器中的应用 Download PDF

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WO2024066403A1
WO2024066403A1 PCT/CN2023/095454 CN2023095454W WO2024066403A1 WO 2024066403 A1 WO2024066403 A1 WO 2024066403A1 CN 2023095454 W CN2023095454 W CN 2023095454W WO 2024066403 A1 WO2024066403 A1 WO 2024066403A1
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pva
alc
mxene
composite film
recycling method
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French (fr)
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石胜伟
徐金新
张琪
万剑波
刘天一
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武汉工程大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
    • G01L1/22—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention belongs to the technical field of functional materials, and in particular relates to a method for recycling MXene preparation residues and an application thereof in a biosensor.
  • MXene As a new type of two-dimensional material with stacked layers, MXene has the structural characteristics of traditional two-dimensional materials such as graphene and excellent photoelectric properties. In addition, its interlayer spacing is adjustable over a large range, and surface groups are easy to functionalize. Moreover, the variety of elements that make up MXene is very rich, making it possible to molecularly design and regulate the physical and chemical properties of MXene, and it has potential applications in many fields such as supercapacitors, electromagnetic shielding, sensors, and photocatalysis.
  • MXene have ultra-high sensitivity to stress-strain response, making its application in sensors attract much attention; currently, the strain sensitivity coefficient (gage factor, GF) of MXene used in piezoelectric sensors exceeds 180.
  • MXene is usually prepared by the minimum intensity layered separation (MILD) method.
  • MILD minimum intensity layered separation
  • the main components of the precipitate obtained by the MILD method are a blend of MXene (Ti 3 C 2 Tx) with different numbers of layers, a small amount of unetched MAX phase, and an incompletely etched MAX phase.
  • MXene Ti 3 C 2 Tx
  • the two-dimensional structure of MXene has excellent conductivity, and its outer layer contains abundant termination groups, which can form a good interaction with polymer materials such as PVA to form a composite material with stable structure
  • the unetched and incompletely etched three-dimensional structure of MAX phase has high mechanical strength, interlayer lubricity and corrosion resistance, and can provide good mechanical properties and environmental stability for the composite material. Therefore, the residues prepared by MXene are not actually completely waste.
  • the purpose of the present invention is to provide a method for recycling MXene preparation residues and its application in biosensors in response to the current situation of huge material waste in MXene preparation and the difficulty of recycling its residues; by compounding the residues of MXene prepared by MAX phase etching with polyvinyl alcohol (PVA), the obtained composite film has extremely high sensitivity and good stability, and can be well applied to the flexible connection and sensing of biosensors and robots; while realizing the effective resource utilization of MXene process residues, the present invention can effectively take into account the mechanical properties and conductive properties of the obtained composite film, and has extremely high sensitivity and good stability to stress and strain; it has both significant economic benefits and good environmental benefits, effectively reduces solid waste emissions, and provides a new product with high added value, which is suitable for promotion and application.
  • PVA polyvinyl alcohol
  • a method for recycling MXene preparation residues which includes recycling bottom layer residual precipitates obtained in the process of preparing MXene by MILD etching, mixing the bottom layer residual precipitates with a PVA melt, and drying the mixture to prepare a Ti 3 C 2 Tx -Ti 3 AlC 2 /PVA composite film, wherein the bottom layer precipitated byproduct is a Ti 3 C 2 Tx-Ti 3 AlC 2 -based mixture (mainly a mixture of Ti 3 C 2 Tx and Ti 3 AlC 2 ); the method specifically comprises the following steps:
  • PVA particles are added into water and heated until PVA is completely molten to obtain a PVA melt; then the MXene preparation residue is added into the PVA melt in proportion and stirred to mix evenly (heating temperature is 60-150°C, stirring rate is 100-500 rpm, time is 10-30 min), and then filtered and dried to obtain a Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film.
  • the etching step includes:
  • the particle size of the MXene preparation residue is 100-400 ⁇ m.
  • the etchant is HF, HCl/LiF, NaHF 2 , KHF 2 or NH 4 HF 2 , etc., and the mass ratio of the etchant to the MAX phase Ti 3 AlC 2 powder is 1:(0.5-3).
  • the stirring treatment in step 1) is carried out at a rotation speed of 400-1000 rpm and for a time of 48-72 hours.
  • the intercalant is one or more of ethanol, DMSO, TMAOH, TBAOH, etc., wherein the mass ratio of the intercalant to the MAX phase is 1:(5-20).
  • the stirring step in step 2) adopts a rotation speed of 100-1000rpm and a time of 1-8h;
  • the ultrasonic treatment adopts a power of 100-500W and a time of 0.5-5h;
  • the centrifugal treatment adopts a rotation speed of 2000-12000rpm, 1-6 times, and each time is 10-60min;
  • the vacuum degree adopted in vacuum drying is 0.05-0.1MPa, the temperature is 40-60°C, and the time is 12-48h.
  • the solid-to-liquid ratio of PVA to water in the PVA melt is 1g:0.02-1ml.
  • the amount of the Ti 3 C 2 Tx-Ti 3 AlC 2 mixture is 10-25% of the mass of the PVA particles, the heating temperature is 60-150° C., the stirring rate is 100-500 rpm, and the time is 10-30 min.
  • the amount of the Ti 3 C 2 Tx-Ti 3 AlC 2 mixture is 8-18% of the mass of the PVA particles.
  • the amount of the Ti 3 C 2 Tx-Ti 3 AlC 2 mixture is 10-15% of the mass of the PVA particles.
  • the Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film prepared according to the above scheme is applied to prepare biosensors, showing excellent sensitivity (response time ⁇ 100ms) and flexibility, and can recover to its original state in a short time after bending, and has good stability.
  • the principle of the present invention is:
  • the present invention utilizes a large amount of residues (Ti 3 C 2 Tx-Ti 3 AlC 2 mixture) generated in the MXene etching process and further composites it with PVA, wherein the two-dimensional structured MXene has excellent electrical conductivity, and its outer layer contains abundant termination groups, which can form a good interaction with polymer materials such as PVA, thereby forming a structurally stable composite material; in addition, the introduced unetched and incompletely etched three-dimensional structured MAX phase has high mechanical strength, interlayer lubricity and corrosion resistance, and can provide the composite material with better mechanical properties and environmental stability; the obtained composite film has good mechanical properties and electrical conductivity.
  • the present invention has the following beneficial effects:
  • the obtained Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film can be used as a flexible biosensor to monitor the activities of human joints such as fingers and wrists by tracking the change in resistance after bending. It has extremely high sensitivity and good flexibility. In addition, the sensor can recover to its original state in a short time after bending and has good stability. It has potential applications in wearable electronics.
  • Ti 3 C 2 T x -Ti 3 AlC 2 itself has good mechanical strength
  • the obtained Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film has high tensile strength and can be used for biological sensing.
  • the Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film has high tensile strength and elongation, it is expected to be potentially used in flexible connection and sensing of robots.
  • FIG. 1 is a schematic diagram of a method for recycling MXene preparation residues and a preparation process of a Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film in Example 1.
  • FIG. 1 is a schematic diagram of a method for recycling MXene preparation residues and a preparation process of a Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film in Example 1.
  • FIG. 2 shows (a) X-ray diffraction (XRD) and (b) Fourier transform infrared absorption spectrum (FTIR) of Ti 3 C 2 Tx-Ti 3 AlC 2 used in Example 1.
  • XRD X-ray diffraction
  • FTIR Fourier transform infrared absorption spectrum
  • FIG3 is a scanning electron microscope (SEM) image of the composite films with different Ti 3 C 2 Tx-Ti 3 AlC 2 contents in Example 1; (a) 10%, (b) 20%, (c) 25%, (d) 30%.
  • SEM scanning electron microscope
  • FIG. 4 is a tensile stress-strain curve diagram of the 25% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film obtained in Example 2 and a pure PVA film.
  • Figure 5 shows the resistance variation of the 25% Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film obtained in Example 2, (a) resistance variation at different bending radii, (b) output current variation of the film at different bending radii at a given voltage of 1 V, and (c) variation of film resistance with tensile strain.
  • FIG6 shows the application effect of the composite film obtained in Example 2 in preparing the biosensor, (a) index finger, (b) middle finger, (c) ring finger, (d) little finger, (e) wrist joint bending, (f) wrist joint twisting.
  • FIG. 7 is a graph showing tensile stress-strain curves of Ti 3 C 2 Tx -Ti 3 AlC 2 /PVA composite films with different contents and pure PVA films in Examples 3-5.
  • FIG8 is a graph showing tensile stress-strain curves of 5% and 30% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite films obtained in Comparative Examples 1 and 2 and a pure PVA film.
  • the Ti 3 C 2 Tx -Ti 3 AlC 2 mixture is the bottom residual precipitate collected during the preparation of the Ti 3 C 2 Tx filter membrane by etching MXene using the MILD method.
  • the specific preparation method includes:
  • DMSO was added to the beaker containing the primary MXene product, stirred for 4 hours, and then ultrasonically treated (150 W, 2 hours). Subsequently, deionized water was added thereto for centrifugal treatment (speed 8000 rpm, time 5 minutes) to wash away the intercalation agent and collect the main product; deionized water was continued to be added for centrifugal treatment (speed 3500 rpm, time 30 minutes), and finally the residual precipitate at the bottom layer was dried under vacuum to obtain Ti 3 C 2 Tx-Ti 3 AlC 2 , whose main component was a mixture of incompletely etched Ti 3 C 2 Tx and Ti 3 AlC 2 .
  • a method for recycling MXene preparation residues specifically comprises the following steps:
  • FIG1 is a method for recycling the MXene preparation residue described in Example 1 and the preparation process of the Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film.
  • layered MXene is obtained through repeated centrifugation (taking the supernatant), which can be used for other experiments, and the clay-like mixture precipitated at the bottom of the centrifuge tube is extracted by filtration and drying to obtain the MXene preparation residue (Ti 3 C 2 Tx-Ti 3 AlC 2 ) used in the present invention; then Ti 3 C 2 Tx-Ti 3 AlC 2 in different proportions is ground into powder and blended with PVA, and finally naturally dried to obtain the composite film, such a process can ensure that the obtained film has good flexibility and mechanical strength.
  • Figure 2a is the XRD pattern of 25% Ti 3 C 2 Tx-Ti 3 AlC 2 obtained in this example. It can be seen that: in addition to the (002) peak at 9.5°, which is the same as the MAX phase, and the (104) peak at 39.5°, which is the characteristic peak of Al, the obtained bottom precipitate has a stronger peak at a low angle of 9.5°, which is located at 6.2°, which is the same angle as the (002) peak of DMSO-MXene. It can be seen that the obtained bottom precipitate is mainly a mixture of MAX and MXene.
  • Figure 2b is the Fourier transform infrared absorption spectrum (FTIR) of the Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA (20%) composite film obtained in this example.
  • FTIR Fourier transform infrared absorption spectrum
  • FIG3 is a scanning electron microscope (SEM) image of the composite film obtained under different Ti 3 C 2 Tx-Ti 3 AlC 2 contents in Example 1.
  • the image shows that in the sample containing 10% Ti 3 C 2 Tx-Ti 3 AlC 2 mixture, blocky particles are scattered in the PVA (FIG3a).
  • the layered structure can be seen to be stacked obviously, but a continuous conductive network has not been formed.
  • the layers overlap and cross each other, and are stacked together, but there are still gaps. Further increasing the proportion of the mixture to 25% (FIG3c), a relatively flat surface and uniform distribution of Ti 3 C 2 Tx-Ti 3 AlC 2 can be seen.
  • a method for recycling MXene preparation residues and its application in biosensors comprising the following steps:
  • FIG4 is a tensile stress-strain curve of 25% Ti 3 C 2 Tx -Ti 3 AlC 2 /PVA composite film and pure PVA film in Example 2.
  • the addition of a small amount of Ti 3 C 2 Tx-Ti 3 AlC 2 will produce hydrogen bonding in PVA, which is beneficial to improve the tensile strength of the material.
  • the improvement of the tensile strength of the material is limited. More Ti 3 C 2 Tx-Ti 3 AlC 2 will destroy the hydrogen bonding between PVA, making the strength of the material weakened.
  • Ti 3 C 2 Tx -Ti 3 AlC 2 significantly reduces the tensile strength of PVA.
  • the content of Ti 3 C 2 Tx-Ti 3 AlC 2 is 25%, its elongation at break is 78.9%, its tensile strength is 17.6MPa, and its Young's modulus is 1.1GPa.
  • its resistance is 1.25 ⁇ 10 6 ⁇ .
  • FIG5 shows the resistance change of the 25% Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film in Example 2, wherein FIG5a shows the resistance change at different bending radii.
  • FIG5a shows the resistance change at different bending radii.
  • the resistance change of the film is more obvious.
  • the resistance increases by 17%.
  • the resistance increases by about 60%.
  • the resistance changes by 80%.
  • the resistance of the film can be restored to the initial value after the bending process, which proves that the composite film has good flexibility and stability.
  • FIG5b shows the output current change of the film at different bending radii when the given voltage is 1 V.
  • Figure 6 shows the change in bending resistance of the composite film obtained in Example 2 when applied to different active parts, where (a) is the index finger, (b) is the middle finger, (c) is the ring finger, (d) is the little finger, (e) is the wrist joint bending, and (f) is the wrist joint.
  • Figures 6a-d show that after the finger is bent, it can be clearly observed that the resistance increases, and the response time is extremely short ( ⁇ 100ms), showing extremely high sensitivity (due to the difference in the flexibility of the finger joints of the testers, the resistance change obtained from the test will be slightly different). It takes a certain amount of time for the resistance to return to the initial value after bending.
  • the resistance will increase slightly. This is because the internal MXene undergoes a dislocation and reconnection process during the film recovery process, but the torsional resistance recovery process takes a shorter time than the bending resistance recovery process. This result shows that the Ti 3 C 2 Tx-Ti 3 AlC 2 /PVA composite film can be fully used for biosensors.
  • a method for recycling MXene preparation residues comprises the following steps:
  • Example 7 shows the tensile stress-strain curves of the 10% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film and the pure PVA film in Example 3; the elongation at break of the composite film reaches 147.0%, the tensile strength is 29.0 MPa, the Young's modulus is 2.1 GPa; and the electrical resistance is 8.5 ⁇ 10 6 ⁇ .
  • the obtained composite film has high sensitivity in detecting small-scale activity changes (response time ⁇ 100ms), and has good mechanical properties, and can be fully used in various types of sensors.
  • a method for recycling MXene preparation residues comprises the following steps:
  • Example 7 shows the tensile stress-strain curves of the 15% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film and the pure PVA film in Example 4; the elongation at break of the composite film reaches 145.2%, the tensile strength is 29.2 MPa, the Young's modulus is 3.5 GPa, and the electrical resistance is 6.5 ⁇ 10 6 ⁇ .
  • the obtained composite film has high sensitivity in detecting small-scale activity changes (response time ⁇ 100ms), and has good mechanical properties, and can be fully used in various types of sensors.
  • a method for recycling MXene preparation residues comprises the following steps:
  • Example 7 is a tensile stress-strain curve of the 20% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film and the pure PVA film in Example 5; the elongation at break of the composite film is 109.7%, the tensile strength is 19.9 MPa, the Young's modulus is 1.1 GPa; and the electrical resistance is 3.4 ⁇ 10 6 ⁇ .
  • a method for recycling MXene preparation residues comprises the following steps:
  • a method for recycling MXene preparation residues comprises the following steps:
  • Figure 8 is a tensile stress-strain curve of the 30% Ti 3 C 2 T x -Ti 3 AlC 2 /PVA composite film and the pure PVA film in Comparative Example 2; although the obtained film has good conductivity and a resistance of 1 ⁇ 10 6 ⁇ , the addition of too much Ti 3 C 2 T x -Ti 3 AlC 2 significantly reduces the elongation and tensile strength of PVA; its elongation at break is only 24%, the tensile strength is 10.9 MPa, and the Young's modulus is 2.0 GPa, which is not suitable for stress-strain sensors.

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Abstract

本发明公开了一种MXene制备残留物的回收利用方法，包括如下步骤：回收MILD法刻蚀制备MXene过程中得到的底层残留沉淀物，将其与PVA熔融液进行混合、干燥，制备Ti3C2Tx-Ti3AlC2/PVA复合薄膜。本发明在实现MXene工艺残留物资源化利用的同时，可有效兼顾所得复合薄膜的力学性能和导电性能，同时对应力应变具有极高的灵敏度和良好的稳定性，适用于生物传感器、机器人等柔性连接和传感领域；同时具有显著的经济效益和环境效益，适合推广应用。

Description

一种MXene制备残留物的回收利用方法及其在生物传感器中的应用 技术领域
本发明属于功能材料技术领域，具体涉及一种MXene制备残留物的回收利用方法及其在生物传感器中的应用。
背景技术
MXene作为一种新型的片层堆叠的二维材料，具有传统二维材料如石墨烯的结构特点，光电性能优异；此外，其层间距在较大范围内可调，表面基团易于实现功能化；而且组成MXene的元素种类很丰富，使得对MXene的物理和化学性能进行分子设计和调控成为了可能，在超级电容器、电磁屏蔽、传感器以及光催化等众多领域都有着潜在的应用。特别是，MXene的电学性能对于应力应变响应具有超高的灵敏性，使其在传感器中的应用备受关注；目前，MXene用于压电传感器的应变灵敏系数(gage factor,GF)超过了180。
通常采用最小强度层状分离法(MILD)制备MXene，然而使用MILD法刻蚀制备得到MXene后，底层的大量沉淀物往往由于得不到合适的回收和利用，而作为废弃物被丢弃，造成了巨大的材料浪费，也增加了MXene生产和后续处置成本。
MILD法所得沉淀物的主要成分为不同层数的MXene(Ti3C2Tx)、未刻蚀的少量MAX相以及刻蚀不完全的MAX相的共混物。其中二维结构的MXene具有优异的导电性能，而且其外层含有丰富的终止基团，这些终止基团可以与PVA等聚合物材料之间形成良好的相互作用，从而形成结构稳定的复合材料；未刻蚀和刻蚀不完全的三维结构的MAX相具有较高的力学强度、层间润滑性和耐腐蚀性，能够为复合材料提供较好的力学性能和环境稳定性。因此，MXene制备的残留物实际上并非完全是废料，若能加以合理利用，既能降低MXene的生产成本，也能够额外提供高附加值的新产品，无疑具有潜在的应用前景和环保价值。但是目前MXene制备的残留物为很粘稠的一种褐色物质，用常规的方法很难实现分离回收和有效利用。
发明内容
本发明的目的在于针对MXene制备中存在的巨大材料浪费的现状和其残留物回收利用的难题，提供了一种MXene制备残留物的回收利用方法及其在生物传感器中的应用；通过将MAX相刻蚀制备MXene的残留物与聚乙烯醇(PVA)进行复合，所得复合薄膜具有极高的灵敏度和良好的稳定性，可很好应用于生物传感器和机器人的柔性连接和传感；本发明在实现MXene工艺残留物资源化有效利用的同时，可有效兼顾所得复合薄膜的力学性能和导电性能，对应力应变具有极高的灵敏度和良好的稳定性；兼具显著的经济效益和良好的环境效益，既有效降低了固体废弃物排放，又提供了一种高附加值的新产品，适合推广应用。
为实现上述目的，本发明采用的技术方案为：
一种MXene制备残留物的回收利用方法，回收MILD法刻蚀制备MXene过程中得到的底层残留沉淀物，将其与PVA熔融液进行混合、干燥制备Ti3C2Tx-Ti3AlC2/PVA复合薄膜，其中底层沉淀副产物为Ti3C2Tx-Ti3AlC2基混合物(主要为Ti3C2Tx和Ti3AlC2形成的混合物)；具体包括如下步骤：
1)采用MILD法对Ti3AlC2粉末进行刻蚀，加水进行多次离心分离，将离心后底层残留的沉淀物进行回收、干燥，得到MXene制备残留物(Ti3C2Tx-Ti3AlC2混合物)；
2)将PVA颗粒加入水中，加热至PVA呈完全熔融状态，得PVA熔液；然后将MXene制备残留物按比例添加至PVA熔液中，并搅拌混合均匀(加热温度为60-150℃，搅拌速率为100-500rpm，时间为10-30min)，再经过滤干燥得到Ti3C2Tx-Ti3AlC2/PVA复合薄膜。
上述方案中，所述刻蚀步骤包括：
1)向刻蚀剂水溶液中加入MAX相Ti3AlC2粉末进行搅拌处理，对MAX相进行化学刻蚀，然后加水进行离心处理，同时调节溶液的pH值为6-7，并洗掉残留的刻蚀剂，得初步刻蚀的MXene初产物；
2)向MXene初产物溶液中加入插层剂，进行搅拌、超声和离心处理；
3)将离心后的底层沉淀物进行回收，进行真空干燥，得MXene制备残留物(Ti3C2Tx-Ti3AlC2混合物)。
上述方案中，所述MXene制备残留物的粒径为100-400μm。
上述方案中，所述刻蚀剂为HF、HCl/LiF、NaHF2、KHF2或NH4HF2等，其与MAX相Ti3AlC2粉末的质量比为1:(0.5-3)。
上述方案中，步骤1)中所述搅拌处理采用的转速为400-1000rpm，时间为48-72h。
上述方案中，所述插层剂为乙醇、DMSO、TMAOH、TBAOH等中的一种或几种，其中插层剂与MAX相的质量比为1:(5-20)。
上述方案中，步骤2)中所述搅拌步骤采用的转速为100-1000rpm，时间为1-8h；超声处理采用的功率为100-500W，时间为0.5-5h；离心处理采用的转速为2000-12000rpm，次数为1-6次，每次时间为10-60min；真空干燥采用的真空度为0.05-0.1MPa，温度为40-60℃，时间为12-48h。
上述方案中，所述PVA熔融液中PVA与水的固液比为1g:0.02-1ml。
上述方案中，所述Ti3C2Tx-Ti3AlC2混合物的用量占PVA颗粒质量的10-25％，加热温度为60～150℃，搅拌速率为100-500rpm，时间为10-30min。
优选的，所述Ti3C2Tx-Ti3AlC2混合物的用量占PVA颗粒质量的8-18％。
更优选的，所述Ti3C2Tx-Ti3AlC2混合物的用量占PVA颗粒质量的10-15％。
根据上述方案制备得到的Ti3C2Tx-Ti3AlC2/PVA复合薄膜，将其应用于制备生物传感器，表现出优异的灵敏度(响应时间＜100ms)和柔韧性，且弯曲后短时间内即可恢复原有的状态，具有良好的稳定性。
本发明的原理为：
本发明利用MXene刻蚀工艺中产生的大量残留物(Ti3C2Tx-Ti3AlC2混合物)，将其进一步与PVA复合，其中二维结构的MXene具有优异的导电性能，且其外层含有丰富的终止基团，可与PVA等聚合物材料之间形成良好的相互作用，从而形成结构稳定的复合材料；此外，引入的未刻蚀和刻蚀不完全的三维结构的MAX相具有较高的力学强度、层间润滑性和耐腐蚀性，能够为复合材料提供较好的力学性能和环境稳定性；所得复合薄膜具有良好的力学性能和导电性能。
与现有技术相比，本发明的有益效果为：
1)首次提出回收利用MXene刻蚀工艺中的大量残留物，并将其进一步与PVA进行复合，制备复合薄膜，可实现难以分离的很粘稠的Ti3C2Tx-Ti3AlC2混合物的资源化利用，同时可兼顾所得薄膜良好的力学性能和导电性能；具有显著的经济和环境效益；
2)所得Ti3C2Tx-Ti3AlC2/PVA复合薄膜，通过对弯曲后电阻的变化情况的跟踪，作为柔性生物传感器，可以实现对人体的手指和手腕等关节的活动进行监测，具有极高的灵敏度和良好的柔韧性，并且该传感器在弯曲后短时间内即可恢复原有的状态，具有很好的稳定性，在可穿戴电子中具有潜在的应用；
3)由于Ti3C2Tx-Ti3AlC2本身具有较好的力学强度，所得的Ti3C2Tx-Ti3AlC2/PVA复合薄膜具有较高的拉伸强度，可用于生物体的传感。此外由于基于Ti3C2Tx-Ti3AlC2/PVA复合薄膜具有较高的拉伸强度和伸长率，有望在机器人的柔性连接和传感中得到潜在应用。
附图说明
图1为实施例1中MXene制备残留物的回收利用方法以及Ti3C2Tx-Ti3AlC2/PVA复合薄膜的制备流程示意图。
图2为实施例1采用的Ti3C2Tx-Ti3AlC2的(a)X射线衍射(XRD)和(b)傅立叶变换红外吸收光谱图(FTIR)。
图3为实施例1中不同Ti3C2Tx-Ti3AlC2含量复合薄膜的扫描电子显微镜图(SEM)；(a)10％，(b)20％，(c)25％，(d)30％。
图4为实施例2所得25％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图。
图5为实施例2所得25％Ti3C2Tx-Ti3AlC2/PVA复合薄膜的电阻变化情况，(a)在不同弯曲半径下的电阻变化，(b)在给定1V电压下薄膜在不同弯曲半径的输出电流变化，(c)薄膜电阻随拉伸应变的变化。
图6为实施例2所得复合薄膜制备生物传感器的应用效果，(a)食指，(b)中指，(c)无名指，(d)小拇指，(e)腕关节弯曲，(f)腕关节扭曲。
图7为实施例3-5中不同含量Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图。
图8为对比例1和2中所得5％和30％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图。
具体实施方式
为了更好的理解本发明，下面结合具体实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
以下实施例中，Ti3C2Tx-Ti3AlC2混合物为采用MILD法刻蚀MXene制备Ti3C2Tx滤膜过程中收集得到的底层残留沉淀物，具体制备方法包括：
1)将2g LiF与40ml 9M盐酸在聚四氟乙烯的烧杯中搅拌30min；然后将烧杯置于冰水中，向烧杯中缓慢加入2g Ti3AlC2，待Ti3AlC2添加完毕后，把反应温度调至40℃，持续搅拌45h；待反应完成后将所得混合液进行离心，同时调节溶液的pH值为6-7，再经超声、真空抽滤、干燥，得到黑色的MXene(Ti3C2Tx)初产物；
2)在装有MXene初产物的烧杯中加入DMSO，搅拌4h，然后进行超声处理(150W，2h)，接着向其中加入去离子水进行离心处理(转速8000rpm，时间5min)，以洗掉其中的插层剂，并收集主要产物；继续加入去离子水进行离心处理(转速3500rpm，时间30min)，最后将底层残留沉淀物在真空下进行干燥，得到Ti3C2Tx-Ti3AlC2，其主要成分为刻蚀不完全的Ti3C2Tx和Ti3AlC2的混合物。
实施例1
一种MXene制备残留物的回收利用方法，其制备流程如图1所示；具体包括如下步骤：
1)将Ti3C2Tx-Ti3AlC2混合物研磨成细小颗粒(100-400μm)备用；取1g聚乙烯醇(PVA)加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，选取不同含量的PVA(Ti3C2Tx-Ti3AlC2分别占PVA质量的10％、20％、25％和30％)，继续搅拌混合均匀(温度为100℃，搅拌速率为120rpm，时间为15min)， 在PVA开始固化之前；将所得共混液经纱布过滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，即得具有良好韧性的PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图1为实施例1中所述MXene制备残留物的回收利用方法以及Ti3C2Tx-Ti3AlC2/PVA复合薄膜的制备过程。在刻蚀及使用DMSO插层后，经过反复的离心过程(取上清液)获得了层状的MXene，可以用于其他实验，而沉淀在底离心管底部的黏土状混合物通过抽滤和干燥等操作提取出来，得到本发明采用的MXene制备残留物(Ti3C2Tx-Ti3AlC2)；然后将不同比例的Ti3C2Tx-Ti3AlC2研磨成粉末并与PVA进行共混，最后进行自然干燥得所述复合薄膜，这样的过程可保证所得薄膜具有良好的柔韧性及机械强度。
图2a为本实施例所得25％Ti3C2Tx-Ti3AlC2的XRD图，可以看出：所得底层沉淀物中除了具有与MAX相相同的9.5°的(002)峰和Al的特征峰39.5°的(104)峰以外，在9.5°的低角度存在一个较强的峰，该峰位于6.2°，这与DMSO-MXene的(002)峰所处的角度相同；可以看出所得底层沉淀物主要为MAX与MXene的混合物。
图2b为本实施例所得Ti3C2Tx-Ti3AlC2/PVA(20％)复合薄膜的傅立叶变换红外吸收光谱图(FTIR)，图中显示：在MXene-MAX中3430cm-1处为O-H的伸缩振动峰，而在Ti3C2Tx-Ti3AlC2/PVA薄膜样品则产生了明显的红移(3250cm-1)，证明在加入Ti3C2Tx-Ti3AlC2后，可与PVA分子链产生氢键作用，同样在1550cm-1处的O-H振动峰也观察到了同样的红移现象。
图3为实施例1中不同Ti3C2Tx-Ti3AlC2含量条件下所得复合薄膜的扫描电子显微镜图(SEM)，图中显示：含有10％Ti3C2Tx-Ti3AlC2混合物的样品当中，块状的颗粒散乱地分布在PVA中(图3a)，在更高倍率下可以看到层状结构明显的堆叠，但并未形成连续的导电网络。在将混合物的含量提升到20％后(图3b)，片层相互重叠交叉，相互堆叠在一起，但仍有空隙。进一步提升混合物的比例到25％(图3c)，可看到相对平整的表面以及Ti3C2Tx-Ti3AlC2的均匀分布。在放大5000倍后可以看到具有二维层状结构的MXene堆叠在其中，这也证明了对于导电性的提升主要是其中的Ti3C2Tx在发挥作用(Ti3AlC2不导电)。
实施例2
一种MXene制备残留物的回收利用方法及其在生物传感器中的应用，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2的质量含量为PVA质量的25％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)，在PVA开始固化之前，将所得溶液经纱布过 滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图4为实施例2中25％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图。少量Ti3C2Tx-Ti3AlC2的加入会在PVA中产生氢键结合，有利于提升材料的拉伸强度，但是随着Ti3C2Tx-Ti3AlC2量的不断增加，对材料的拉伸强度的提升有限，更多的Ti3C2Tx-Ti3AlC2反而会破坏了PVA间的氢键结合，使得材料的强度减弱，如图4所示，25％Ti3C2Tx-Ti3AlC2的加入明显降低了PVA的拉伸强度。当Ti3C2Tx-Ti3AlC2的含量为25％，其断裂伸长率为78.9％，拉伸强度为17.6MPa，杨氏模量为1.1GPa。此外，其电阻为1.25×106Ω。
图5为实施例2中25％Ti3C2Tx-Ti3AlC2/PVA复合薄膜的电阻变化情况，其中图5a为在不同弯曲半径下的电阻的变化，随着弯曲半径的逐渐减小薄膜电阻的变化也更明显，当弯曲半径仅有1cm时，电阻变大了17％，弯曲半径达到0.8cm时，电阻增大了约60％，而当弯曲半径达到0.5cm时，电阻变化了80％。而且薄膜在经历弯曲过程之后电阻能够恢复到初始值，这证明了复合薄膜具有良好的柔韧性和稳定性。图5b为在给定电压为1V时，薄膜在不同弯曲半径下的输出电流变化，当弯曲半径大于1时，输出电流的变化不大，而随着弯曲程度增大电阻变大，输出电流相应变小。而当弯曲半径小于0.4cm时，电流的变化相对稳定，这是由于在材料内部建立起了有效的连接，即使完全对折薄膜依旧具有导电性。图5c为薄膜电阻拉伸随应变的变化，当拉伸应变小于10％时，GF为533，表现出非常高的灵敏度，而当应变超过10％时，GF仍然达到290，当拉伸应变超过52％之后，由于薄膜内部连接发生断裂，此时的薄膜基本没有导电性。通过对材料GF测定可以看出，Ti3C2Tx-Ti3AlC2/PVA在检测小范围的活动变化具有较高的灵敏度，完全可以用于各种类型的传感器。
图6为实施例2所得复合薄膜应用于不同活动部位的弯曲电阻变化情况，其中(a)为食指处，(b)为中指处，(c)为无名指处，(d)为小拇指处，(e)为腕关节弯曲处，(f)为腕关节处。图6a-d显示：手指弯曲后可以明显的观察到电阻增大，而且响应时间极短(＜100ms)，展现了极高的灵敏度(由于受到测试人员的指关节灵活度的差别，测试得到的电阻变化会略有差别)。弯曲后电阻恢复到初始值需要一定的时间，这是由于在弯曲后薄膜内部的连接产生了一定的断裂，因此在恢复过程中需要一定的时间重建内部连接。图6e-f显示：腕关节同样具有优异的效应速度和灵敏度，弯曲后电阻明显的增大，但相较于指关节活动需要恢复的时间也更久，较大范围的活动对于材料内部的影响也更大，所以恢复需要更多的时间。手腕扭曲与弯曲的电阻变化明显的不同，扭曲后电阻不是增大而是明显的减小，这可能是因为扭曲会使薄膜内部未连接的Ti3C2Tx MXene而交叉堆叠在一起，使薄膜的电阻能够明显降低。手腕扭曲的响应时间同样很短，扭曲后电阻明显减少了50％。在扭曲回复后电阻会略微升高然 后再下降，这是由于内部的MXene在薄膜回复过程中经历了错位和再连接的过程，但扭曲电阻恢复过程比弯曲电阻恢复过程所需要的时间更短。本结果表明Ti3C2Tx-Ti3AlC2/PVA复合薄膜完全可用于生物传感器。
实施例3
一种MXene制备残留物的回收利用方法，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2占PVA用量的10％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)，在PVA开始固化之前；再将所得溶液经纱布过滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图7给出了实施例3中10％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图；所得复合薄膜的断裂伸长率达到147.0％，拉伸强度为29.0MPa，杨氏模量为2.1GPa；电阻为8.5×106Ω。
经测试，所得复合薄膜在检测小范围的活动变化具有较高的灵敏度(响应时间＜100ms)，同时具有良好的力学性能，完全可以用于各种类型的传感器。
实施例4
一种MXene制备残留物的回收利用方法，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2占PVA质量的15％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)，在PVA开始固化之前，再将所得溶液经纱布过滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图7给出了实施例4中15％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图；所得复合薄膜的断裂伸长率达到145.2％，拉伸强度为29.2MPa，杨氏模量为3.5GPa，且电阻为6.5×106Ω。
经测试，所得复合薄膜在检测小范围的活动变化具有较高的灵敏度(响应时间＜100ms)，同时具有良好的力学性能，完全可以用于各种类型的传感器。
实施例5
一种MXene制备残留物的回收利用方法，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2占PVA质量的20％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)，在PVA开始固化之前，再将所得溶液经纱布过滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图7为实施例5中20％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图；所得复合薄膜的断裂伸长率为109.7％，拉伸强度为19.9MPa，杨氏模量为1.1GPa；其电阻为3.4×106Ω。
对比例1
一种MXene制备残留物的回收利用方法，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2占PVA质量的为5％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)，在PVA开始固化之前，将所得溶液经纱布过滤后倒入7.5×10×1cm3的标准聚四氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合薄膜。
图8为对比例1中5％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图；其断裂伸长率达到134.8％，拉伸强度为53.9MPa，杨氏模量为2.1GPa，但是该薄膜基本不导电，不适合于应力应变传感器。
对比例2
一种MXene制备残留物的回收利用方法，包括如下步骤：
1)取1g的PVA，加入50ml去离子水中，在100℃下加热至完全变为熔融态，得PVA熔融液；
2)向Ti3C2Tx-Ti3AlC2混合物中加入20ml去离子水超声分散均匀，在搅拌条件下缓慢倒入所得PVA熔融液中，其中Ti3C2Tx-Ti3AlC2的质量含量为30％，继续搅拌均匀(温度为120℃，搅拌速率为80rpm，时间为20min)；再将所得溶液经纱布过滤后倒入7.5×10×1cm3的标准聚四 氟乙烯模具中，自然干燥48h，得到具有PVA/Ti3C2Tx-Ti3AlC2复合材料薄膜。
图8为对比例2中30％Ti3C2Tx-Ti3AlC2/PVA复合薄膜与纯PVA薄膜的拉伸应力应变曲线图；所得薄膜虽然其具有较好的导电性能，电阻为1×106Ω，但是过多Ti3C2Tx-Ti3AlC2的加入显著降低了PVA的伸长率和拉伸强度；其断裂伸长率仅为24％，拉伸强度为10.9MPa，杨氏模量为2.0GPa，并不适合于应力应变传感器。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (9)

  1. 一种MXene制备残留物的回收利用方法，其特征在于，包括如下步骤：回收MILD法刻蚀制备MXene过程中得到的底层残留沉淀物，将其与PVA熔融液进行混合、干燥，制备Ti3C2Tx-Ti3AlC2/PVA复合薄膜；其中底层残留沉淀物为Ti3C2Tx-Ti3AlC2基混合物。
  2. 根据权利要求1所述的回收利用方法，其特征在于，所述刻蚀步骤包括：
    1)向刻蚀剂水溶液中加入MAX相粉末，并进行搅拌加热，然后加水进行离心处理，同时调节溶液的pH值为6-7，再经超声、抽滤、干燥，得初步刻蚀的MXene初产物；
    2)向MXene初产物溶液中加入插层剂，进行搅拌、超声和离心处理；
    3)将离心后的底层沉淀物进行回收，真空干燥至恒重，得MXene制备残留物。
  3. 根据权利要求2所述的回收利用方法，其特征在于，所述刻蚀剂为HF、HCl/LiF、NaHF2、KHF2或NH4HF2；引入的刻蚀剂与MAX相粉末的质量比为1:(0.5-3)。
  4. 根据权利要求2所述的回收利用方法，其特征在于，步骤1)中所述加热搅拌反应采用的温度为40-80℃，时间为12-96h。
  5. 根据权利要求2所述的回收利用方法，其特征在于，所述插层剂为乙醇、DMSO、TMAOH、TBAOH中的一种或几种，其中插层剂与MAX相粉末的质量比为1:(5-20)。
  6. 根据权利要求2所述的回收利用方法，其特征在于，所述PVA熔融液中PVA与水的固液比为1g:0.02-1ml；加热熔融温度为60～150℃。
  7. 根据权利要求2所述的回收利用方法，其特征在于，所述Ti3C2Tx-Ti3AlC2混合物的用量占PVA颗粒质量的10-25％。
  8. 权利要求1～7任一项所述回收方法制备的为Ti3C2Tx-Ti3AlC2/PVA复合薄膜。
  9. 权利要求8所述Ti3C2Tx-Ti3AlC2/PVA复合薄膜在生物传感器领域中的应用，其特征在于，当应变为10％以下时，GF高达533，应变大于10％时，GF达299。
PCT/CN2023/095454 2022-09-30 2023-05-22 一种MXene制备残留物的回收利用方法及其在生物传感器中的应用 WO2024066403A1 (zh)

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