CN112999885A - MXene-GO composite membrane with humidity response and preparation method and application thereof - Google Patents

MXene-GO composite membrane with humidity response and preparation method and application thereof Download PDF

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CN112999885A
CN112999885A CN202110187351.8A CN202110187351A CN112999885A CN 112999885 A CN112999885 A CN 112999885A CN 202110187351 A CN202110187351 A CN 202110187351A CN 112999885 A CN112999885 A CN 112999885A
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mxene
composite membrane
solution
humidity
membrane
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CN112999885B (en
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张艳
贾广雯
章路
李玲
李辰星
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Shanghai University of Engineering Science
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
    • A61B5/0809—Detecting, measuring or recording devices for evaluating the respiratory organs by impedance pneumography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties

Abstract

The invention relates to an MXene-GO composite membrane with humidity response, a preparation method and application thereof3C2OX. The preparation method specifically comprises the following steps: (1) preparing MXene solution by adopting a liquid etching method and uniformly dispersing; (2) preparing graphene oxide into a GO solution, and uniformly dispersing; (3) adding the MXene solution prepared in the step (1) into the GO solution prepared in the step (2), and uniformly mixing by ultrasonic waves to obtain an MXene-GO solution; (4) MXene obtained in the step (3)And carrying out vacuum filtration on the GO solution to form a membrane, and drying to obtain the MXene-GO composite membrane. Compared with the prior art, the membrane material has good stability, better hydrophilicity, humidity sensitivity, conductivity and antibacterial property, and can be applied to a plurality of fields of water purification, intelligent driving, electricity, medical health and the like.

Description

MXene-GO composite membrane with humidity response and preparation method and application thereof
Technical Field
The invention belongs to the field of intelligent driving, and particularly relates to an MXene-GO composite membrane with humidity response, and a preparation method and application thereof.
Background
The intelligent material is a novel functional material capable of sensing environmental stimuli (such as light, heat, pH value and humidity) and generating corresponding responses, is one of important directions for the development and research of modern high-technology new materials, and is widely applied to emerging industries such as artificial muscles, bionic robots, self-activated switches and the like. Water is a rich and important resource in nature, and intelligent actuators responding to moisture or humidity stimuli are considered to be the most valuable actuators for research.
At present, the humidity driver is generally obtained by assembling a plurality of layers of different materials, and the preparation process is complex and tedious and is not beneficial to large-scale production. Also, asymmetric stresses exist in the interface between different materials, and the multilayer actuator is susceptible to delamination due to interlayer differences during motion. The homogeneous membrane structure is the best solution to solve the above problems, but the research on the actuator of the homogeneous structure is still in the initial stage.
MXene is a novel layered two-dimensional metal-based carbide material. The composite material is favored by researchers due to the fact that the composite material has rich surface functional groups, large specific surface area, high mechanical flexibility, good conductivity and easy film forming property, is widely applied to the fields of supercapacitors, water purification, catalysis, batteries, sensors and the like, and the researchers initially explore the application of the composite material in the aspect of humidity brakes and verify the feasibility of the composite material as a humidity gradient driver. However, the single MXene has a serious interlayer stacking phenomenon, is very easy to oxidize in a water/oxygen environment and cannot be stored stably for a long time, and the MXene is doped with other materials to obtain composite materials with more excellent performances, so that the MXene can be intercalated, modified, doped or compounded with other materials to prevent the MXene from stacking and inhibit the MXene from being oxidized, and the stability of the MXene is improved.
GO is one of the important derivatives of graphene-based materials, contains a large number of oxygen-containing functional groups on the surface, has hydrophilicity, and is easy to swell in a humid or aqueous environment. The mechanism of humidity braking is based on the expansion behavior of a material in response to changes in humidity. When humidity changes, a material with excellent swelling capacity can act as a driving layer that automatically provides the motive force to force the humidity actuator to bend. Therefore, GO is one of the best candidates for building a humidity brake. However, the pure GO film has a weak bending response degree to a humidity gradient, is too easy to swell in a humid or aqueous environment, has poor stability, is not favorable for repeated use under a high humidity condition, and has no conductivity.
Therefore, the present application is directed to provide an MXene-GO composite film and a method for preparing the same, which can significantly improve the humidity response sensitivity of the material, and because MXene has many excellent characteristics, the application field of the composite film is wider.
Patent CN106290507A discloses a preparation method of a novel two-dimensional titanium carbide/graphene oxide (Ti3C2/GO) composite material capable of being ink-jet printed, which comprises the following steps; the two-dimensional Ti3C2 is prepared by etching Ti3AlC2 by mixing HCl and LiF; two-dimensional Ti3C2 and Graphene Oxide (GO) mixed, and ink-jet printing preparation of a two-dimensional titanium carbide/graphene oxide (Ti3C2/GO) sensor electrode. The method specifically comprises the following steps: 1) ball-milling Ti3AlC (2 is less than 40 mu m) for 8 hours according to the ball sample ratio of 10: 1; 2) mixing and stirring 30mL of 6M HCl and 1.98g of LiF; 3) adding 3g of Ti3AlC2 subjected to ball milling into the mixed solution, and magnetically stirring the mixed solution at 40 ℃ for reacting for 45 hours; 4) diluting the mixed solution by 40 times with deionized water, and centrifuging; the centrifugation speed is 7500rpm, and the centrifugation time is 15 min/time; 5) collecting precipitate, dissolving in deionized water, placing in ice water bath, and performing ultrasonic treatment; dissolving the precipitate with deionized water concentration of about 2g in 500mL of deionized water; the ultrasonic time is 2 hours, and nitrogen is introduced to remove oxygen during ultrasonic; 6) centrifuging after the ultrasonic treatment is finished; the centrifugation speed is 500rpm, and the centrifugation time is 10 min; 7) mixing a two-dimensional Ti3C2 solution and graphene oxide GO according to a certain proportion. This patent is for the field of hydrogen peroxide electrochemical sensors. This patent ground MAX (Ti) on the manufacturing process3AlC2) As the starting phase, using a hydrochloric acid concentration of6M, adding 1.98g of LiF, reacting for 45 hours, diluting by 40 times after the reaction is finished, and centrifuging at the speed of 7500rmp for 15 min. These methods are different from the method of the present invention. This patent measured MXene to GO in a ratio of 1: 1, magnetically stirring for 2 hours, carrying out water bath ultrasound for 10min, and printing the electrode on a conductive substrate by ink jet printing to detect hydrogen peroxide, wherein the concentration value of the electrode before compounding is not specified, and the compounding time is different from that of the invention.
The disadvantages of the CN106290507A patent are: GO is poor in conductivity, and MXene is compounded by taking GO as a carrier, so that the electrochemical detection activity can be reduced. 2. The step of introducing inert gas (nitrogen) is not mentioned in the magnetic stirring and ultrasonic process of compounding MXene and GO, and the MXene oxidation problem possibly exists in the process and influences the detection activity. 3. High sensitivity detection is realized only for a single substance of hydrogen peroxide.
Patent CN108584939B discloses a preparation method of graphene oxide composite film material. The method specifically comprises the following steps: firstly, preparing graphene oxide; secondly, preparing a mixed solution; thirdly, preparing TiC nanosheet solution; and fourthly, mixing, and performing vacuum filtration to obtain the high-dielectric titanium carbide/graphene oxide composite film material. The patent focuses on a preparation method of a graphene oxide and titanium carbide composite film, and relates to preparation of graphene oxide and preparation of titanium carbide. Wherein, the preparation of the titanium carbide uses concentrated sulfuric acid for etching, and the etching conditions and the etching time are different from those of the invention. In the patent, the cleaning solution is washed after etching until the PH value of the cleaning solution is neutral, but the invention is washed after etching until the PH value is 6. N, N-dimethylacetamide is also added into the ultrasonic generator, argon is introduced as inert gas, the concentration of the N, N-dimethylacetamide and the argon before compounding and the thickness of a lamella of the N, N-dimethylacetamide and the argon before compounding are not specified, and the ultrasonic power is different. This patent carries out the suction filtration with buchner funnel, adopts the mode that the room temperature dries naturally. The invention adopts a sand core funnel to carry out suction filtration and freeze drying to obtain the product. This patent only mentions the preparation of dielectric film materials and does not relate to the use.
The disadvantages of the CN108584939B patent are: 1. the preparation of titanium carbide uses concentrated sulfuric acid to carry out an etching reaction which is too violent and has high danger. 2. The whole preparation process is too complex when the graphene oxide is prepared. 3. Washing the etched solid material with distilled water may introduce some impurity ions, which affect the quality of the final product. 4. The step of introducing inert gas is not mentioned in the process of compounding, stirring and ultrasound of titanium carbide and GO, and the problem of titanium carbide oxidation possibly exists in the process, so that the product quality is influenced. 5. Titanium carbide is easy to oxidize, and the titanium carbide may react with water and oxygen in the air in the room-temperature airing process to influence the product quality.
Disclosure of Invention
The invention aims to provide an MXene-GO composite membrane with humidity response and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
the MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OX。
In the composite membrane, the mass fraction of MXene lamella is 50-80%, preferably 75%.
The thickness of the MXene lamella is 1-3nm, and the thickness of the graphene oxide lamella is 2-4 nm.
The composite membrane has a mass of 28-60 mg.
A preparation method of the MXene-GO composite membrane specifically comprises the following steps:
(1) taking MAX (Ti)3AlC2) Preparing MXene solution by adopting a liquid etching method, and uniformly dispersing;
(2) preparing graphene oxide into a GO solution, and uniformly dispersing;
(3) adding the MXene solution prepared in the step (1) into the GO solution prepared in the step (2), and uniformly mixing by ultrasonic waves to obtain an MXene-GO solution;
(4) and (4) carrying out vacuum filtration on the MXene-GO solution obtained in the step (3) to form a film, and drying to obtain the MXene-GO composite film.
In the step (1), the concentration of MXene solution is 2 mg/ml.
In the step (1), ultrasonic treatment is adopted for 15-30min for dispersion.
In the step (2), the concentration of the GO solution is 2 mg/ml.
In the step (2), ultrasonic is adopted for dispersing, and inert gas is added in the ultrasonic process.
The inert gas is one of nitrogen or argon.
In the step (3), inert gas is introduced during ultrasonic mixing, the ultrasonic time is 15-30min, and the ultrasonic power is 200-250W.
The inert gas is one of nitrogen or argon.
In the step (3), the ratio of the mass of MXene in the added MXene solution to the mass of GO in the GO solution is (1-4):1, and preferably 3: 1.
And (4) in the step (4), freeze-drying the membrane obtained by suction filtration for 7-12 h.
The utility model provides an application as above-mentioned MXene-GO complex film, specifically regard MXene-GO complex film as humidity gradient stopper, can be used to a plurality of fields such as water purification, intelligent drive, electricity and medical health, when MXene-GO complex film is used for the respiratory monitoring in the medical health field, specifically is: different resistance signal responses are generated according to different humidity released by mouth and nose respiration of a human body to distinguish breathing modes, the higher the humidity released by respiration is, the larger the bending angle of the composite membrane is, and the larger the resistance change rate of the MXene-GO composite membrane is; and monitoring the respiratory frequency according to a membrane resistance change signal generated by the change of the humidity released by the continuous respiration of the human body.
Mxene is a layered two-dimensional metal-based carbide material. Has excellent hydrophilic performance, conductivity and antibacterial property. However, simple MXene films are highly susceptible to oxidative deterioration in a humid environment, eventually leading to TiO2And (4) forming nano crystals. This is a serious problem for most applications, including drives.
GO is one of important derivatives of graphene-based materials, although the highly conjugated structure of graphene is destroyed by the oxidation process, a large number of oxygen-containing functional groups are introduced, and water molecules can be combined with oxygen atoms in the groups through hydrogen bonds, so that the graphene-based materials have hydrophilicity. Therefore, GO is one of the best candidates to build humidity sensing smart drives. However, the presence of a large number of oxygen-containing functional groups on a pure GO membrane makes the resulting membrane highly hydrophilic and prone to swelling in humid or aqueous environments, resulting in poor membrane stability and unfavorable reuse under high humidity conditions.
According to the invention, GO is introduced into MXene, and the GO is coated on the surface of the MXene so as to prevent the MXene from directly contacting with an external environment and inhibit the MXene from being oxidized, thereby improving the stability of the actuator. Meanwhile, MXene nanosheets are inserted between GO layers, nanoscale gaps are formed among the layers, and the MXene reduces the pi-pi interaction between continuous GO nanosheets and increases the interlayer spacing between the nanosheets, so that a two-dimensional transportation nano channel is provided for moisture transmission, the interaction between water molecules in an oxidation area in the GO nanosheets and oxygen-containing functional groups is weakened, and the stability of the GO membrane is improved under a high humidity condition. The GO is introduced into the MXene membrane to provide more active sites for moisture adsorption, so that the moisture absorption swelling degree of the MXene membrane is improved, and the sensitivity, the response/recovery time, the repeatability and the long-term stability of the MXene-GO composite membrane are improved, so that the MXene-GO composite membrane can maintain high stability under aqueous conditions, which can be attributed to the fact that the GO and the MXene-GO are combined through hydrogen bonds. In addition, the conductivity of the single GO is very poor, and the MXene is added, so that the composite film has excellent conductivity, and tests show that the resistance of the composite film can change along with the change of humidity. With MGO3The discovery of the phenomenon that the resistance is 4.8 omega at a humidity of 20% and is increased to 10.08 omega at a humidity of 90% further expands the practical field of composite films, for example. As shown in fig. 4, before the composite film absorbs water, the volume of the film is small, after the composite film absorbs water, water enters between the MXene sheet layer and the graphene oxide sheet layer, and the composite film can realize water analysis through drying.
According to the invention, GO and MXene are mixed, MXene can be well coated by GO nanosheets, and both the GO and the MXene have more oxygen-containing functional groups, spontaneous hydrogen bond combination is realized, and through the chemical combination, the MXene-GO composite membrane can be used as an intelligent driver, and good performance can be well ensured in stability test, repeatability test and sensitivity test of humidity gradient response, so that the MXene-GO composite membrane can be repeatedly used for a long time, and the structure cannot be collapsed even if the MXene-GO composite membrane is placed in water for a long time. Based on this property of the humidity gradient driver of the MXene-GO composite membrane, we designed the membrane for the respiratory monitoring field. Generally speaking, the humidity released by mouth breathing and nasal breathing of people is different, the membrane can change the resistance of the membrane according to the different humidity released by different breathing modes, the outlet breathing and the nasal breathing can be distinguished from different resistance change graphs, and meanwhile, the membrane is also researched and found to have antibacterial property and biocompatibility, which indicates that the composite membrane has potential for being used in the field of medical health.
In addition, the preparation method of the invention also specifically limits the adding proportion of each material component (MXene, GO, and the like) and the processing process conditions (such as drying time, processing temperature, and the like), namely if the adding proportion of the MXene is too high or too low and is not within the limited condition range of the invention, the sensitivity of humidity gradient response of the final product is reduced, and when the content of GO is too high, the conductivity of the composite membrane is deteriorated, and when the mass ratio of the MXene to GO is 4: 1, the film resistance is 3.4 omega in a dry environment, and the mass ratio of MXene to GO is 1: 1, the film resistance in a dry environment was 65. omega.
Compared with the prior art, the invention has the following advantages:
(1) MXene is a novel two-dimensional material that can collect hydrophilicity and electric conductivity in an organic whole, and after compounding with GO, the stability greatly increased of the MXene-GO complex film that makes, humidity braking response time is short. The humidity gradient is controlled by the water vapor evaporated, the higher the water temperature, the more the water evaporates, the greater the humidity gradient. When the humidity gradient is 40% (the water temperature is 90 ℃), the mass ratio of MXene to GO is 3: the composite film of 1 can achieve the maximum response within 5 seconds, and the bending angle reaches 160 degrees.
(2) Through a period of water adsorption/desorption tests, the humidity gradient intelligent brake prepared by the method is proved to have stable performance and can be repeatedly used.
(3) The film also has excellent electrical property, antibacterial property and biocompatibility, and is widely combined with the humidity gradient response performance to be applied to the field.
(4) The method has the advantages of simple and convenient operation process, good repeatability and high sensitivity, and is suitable for large-scale production and use.
Drawings
FIG. 1 is a scanning electron micrograph (7000 magnifications) of the composite films prepared in each example and each comparative example;
FIG. 2 is a graph comparing the test results of the bending angle of the composite films manufactured in each example and each comparative example with the humidity gradient change controlled by the water temperature;
FIG. 3 is a result of a reproducibility test of the composite film obtained in example 3;
FIG. 4 is a schematic diagram of the operation of MXene-GO composite membrane;
FIG. 5 is a diagram of MXene-GO composite membrane for breath detection;
fig. 6 is a biocompatibility map of an MXene-GO composite membrane.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, the mass of the MXene-GO composite film is 30mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. Collecting the precipitate, and removing by ultrasonic additionAnd (4) centrifuging the mixture in seed water for 5 minutes at 3500rmp to obtain the MXene lamella solution. Preparing the concentration of MXene solution to be 2mg/ml, and introducing inert gas (nitrogen) and then ultrasonically dispersing uniformly for 15min at the power of 25W;
(2) preparing GO into a 2mg/ml solution, introducing inert gas (nitrogen), and performing ultrasonic treatment at 200W for 10min to disperse uniformly;
(3) mixing MXene solution with GO solution (the adding volume ratio of MXene solution to GO solution is 1: 1, 15ml and 15ml respectively), introducing inert gas (nitrogen), and ultrasonically dispersing uniformly for 15min at the power of 250W;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) then the membrane is frozen and dried for 7h at the temperature of minus 78 ℃, and then the membrane is peeled off from the substrate to obtain the MXene-GO composite membrane which is named as MGO1The scanning electron micrograph of the film is shown in fig. 1, and it can be seen that the material is indeed a layer-by-layer structure with significant interlayer delamination. MGO1The membrane resistance in a dry environment was 65 Ω.
Example 2
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, the mass of the MXene-GO composite film is 30mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. And (3) collecting the precipitate, adding the precipitate into deionized water by ultrasonic waves for 20 minutes, and centrifuging the solution at 3500rmp for 5 minutes to obtain the MXene lamella solution. MX is prepared fromThe concentration of the ene solution is configured to be 2mg/ml, and the uniform dispersion is carried out by ultrasonic for 15min with the power of 250W after the inert gas (nitrogen) is introduced;
(2) preparing GO into a solution of 2mg/ml, and introducing inert gas and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) mixing MXene solution with GO solution (the adding volume ratio of MXene solution to GO solution is 2: 1, and 20ml and 10ml respectively), introducing inert gas (nitrogen), and ultrasonically dispersing for 15min at 250W power;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) freeze drying the membrane at-78 deg.C for 7h, and peeling off the membrane from the substrate to obtain MXene-GO composite membrane named MGO2The scanning electron micrograph of the film is shown in fig. 1, and it can be seen that the material is indeed a layer-by-layer structure with significant interlayer delamination.
Example 3
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, the mass of the MXene-GO composite film is 30mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. And (3) collecting the precipitate, adding the precipitate into deionized water by ultrasonic waves for 20 minutes, and centrifuging the solution at 3500rmp for 5 minutes to obtain the MXene lamella solution. Preparing the concentration of MXene solution to be 2mg/ml, and introducing inert gas (nitrogen) and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(2) preparing GO into a solution of 2mg/ml, and introducing inert gas and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) mixing MXene solution and GO solution (the adding volume ratio of MXene solution to GO solution is 3: 1) 22.5ml and 7.5ml respectively, introducing inert gas (nitrogen), and ultrasonically dispersing for 15min at 250W power;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) freeze drying the membrane at-78 deg.C for 7h, and peeling off the membrane from the substrate to obtain MXene-GO composite membrane named MGO3The scanning electron micrograph of the film is shown in fig. 1, and it can be seen that the material is indeed a layer-by-layer structure with significant interlayer delamination. At a humidity of 20%, MGO3Has a resistance of 4.8 omega, and MGO when the humidity is 90%3The resistance of (2) rises to 10.08 omega.
Example 4
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, the mass of the MXene-GO composite film is 30mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. And (3) collecting the precipitate, adding the precipitate into deionized water by ultrasonic waves for 20 minutes, and centrifuging the solution at 3500rmp for 5 minutes to obtain the MXene lamella solution. Preparing the concentration of MXene solution to be 2mg/ml, and introducing inert gas (nitrogen) and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(2) preparing GO into a solution of 2mg/ml, and introducing inert gas and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) mixing MXene solution with GO solution (the adding volume ratio of MXene solution to GO solution is 4: 1, and is respectively 24ml and 6ml), introducing inert gas (nitrogen), and ultrasonically dispersing for 15min at the power of 250W;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) freeze drying the membrane at-78 deg.C for 7h, and peeling off the membrane from the substrate to obtain MXene-GO composite membrane named MGO4The scanning electron micrograph of the film is shown in fig. 1, and it can be seen that the material is indeed a layer-by-layer structure with significant interlayer delamination. MGO4The film resistance in a dry environment was 3.4 Ω.
Comparative example 1
MXene film with humidity response, wherein MXene is Ti3C2OXThe thickness is 1-3nm, and the preparation method comprises the following steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. Collecting the precipitate, adding the precipitate into deionized water by ultrasonic treatment for 20 minutes, and centrifuging the solution at 3500rmp for 5 minutes to obtain MXene lamella solution;
(2) preparing the concentration of MXene solution to be 2mg/ml, and introducing inert gas (nitrogen) and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) carrying out vacuum filtration on the uniformly dispersed MXene solution to form a film;
(4) and (3) freeze-drying the film at-78 ℃ for 7h, and peeling the film from the substrate to obtain the MXene film.
Comparative example 2
A GO membrane with humidity response is obtained by adopting the following preparation steps:
(1) preparing GO into a GO solution;
(2) the concentration of the GO solution is configured to be 2mg/ml, and the GO solution is uniformly dispersed by ultrasonic treatment for 15min at the power of 250W after inert gas is introduced;
(3) carrying out vacuum filtration on the uniformly dispersed GO solution to form a membrane;
(4) and (3) placing the membrane at-78 ℃ for freeze drying for 7h, and peeling the membrane from the substrate to obtain the GO membrane.
Performance testing
For the MGO prepared in example 11Bending test as humidity gradient driver, i.e. MGO1The membrane is cut into rectangular strips (3cm × 1cm), placed on a substrate with a rectangular hole in the center, the rectangular hole is used as a window for introducing heating water to generate a water vapor gradient, and ambient air (the same below) with an RH of 60% is placed above the substrate, so that the water temperature is changed to control the evaporation rate of water and further change the ambient humidity, and a certain humidity difference, namely a humidity gradient, exists between the upper part and the lower part of the membrane.
As shown in FIG. 2, MGO can be seen1The bending angle under the humidity gradient driving (the humidity is controlled by the water temperature, the water temperature is changed from 40 ℃ to 90 ℃, the humidity is gradually increased, the same is applied below) is 18-90 degrees, and the MXene-GO composite membrane can improve the sensitivity of a pure membrane material and has feasibility of practical application.
For the MGO prepared in example 22Bending test as humidity gradient driver, as shown in FIG. 2, MGO can be seen2The bending angle under the humidity gradient driving is 35-112 degrees, and the MXene-GO composite membrane can improve the sensitivity of a pure membrane material.
For MGO prepared in example 33Bending test and repeatability capability test as humidity gradient driver, as shown in FIG. 2, MGO can be seen3The bending angle is 49-160 degrees under the drive of the humidity gradient, which shows that the MXene-GO composite membrane can improve the sensitivity of a pure membrane material, and as shown in figure 3, MGO3There was not much change in bend angle over 50 bend/recovery cycles (on means test and off means no test), indicating thatThe MXene-GO composite membrane has excellent repeatability, and indirectly shows that the stability of the MXene composite membrane is obviously improved after the MXene-GO composite membrane is compounded. Furthermore, MGO at a humidity gradient of 40%3The composite film can reach the maximum response within 5 seconds, and the bending angle reaches 160 degrees.
For MGO prepared in example 44The composite membrane performs bending as a humidity gradient driver, as shown in FIG. 2, where MGO can be seen4The bending angle is 43-138 degrees under the driving of the humidity gradient, and the MXene-GO composite membrane can improve the sensitivity of a pure membrane material.
The combination of example 1 and example 2 shows that the sensitivity of a single membrane material can be further improved by increasing the content of MXene in the MXene-GO composite membrane, and the combination of example 1, example 2, example 3 and example 4 shows that the sensitivity of the membrane material cannot be improved by increasing the content of MXene in the MXene-GO composite membrane.
The MXene film prepared in the comparative example 1 is used as a humidity gradient driver to be subjected to a tortuosity test, as shown in FIG. 2, the bending angle of the MXene film driven by the humidity gradient is 11-68 degrees, which indicates that the simple MXene film has a normal braking performance.
The GO membrane prepared in the comparative example 2 is used as a humidity gradient driver to carry out a bending test, as shown in fig. 2, the bending angle of the GO membrane driven by the humidity gradient is 3-14 degrees, which indicates that the braking performance of the pure GO membrane is poor.
Combining example 1, example 2, comparative example 1 and comparative example 2, it can be seen that the MXene-GO composite membrane has a high sensitivity to humidity.
Example 5
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, and the mass of the MXene-GO composite film is 28mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. Collecting the precipitate, adding the precipitate into deionized water by ultrasonic waves for 20 minutes, centrifuging the solution at 3500rmp for 5 minutes to obtain MXene lamella solution, configuring the concentration of the MXene lamella solution to be 2mg/ml, and introducing inert gas (nitrogen) and then dispersing the solution uniformly by ultrasonic waves at the power of 250W for 15 minutes;
(2) preparing GO into a solution of 2mg/ml, and introducing inert gas and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) mixing the MXene solution with the GO solution (the adding volume ratio of the MXene solution to the GO solution is 3:1, and the adding volume ratio is 10.5ml and 3.5ml respectively), introducing inert gas (nitrogen), and performing ultrasonic treatment at 250W power for 15min to uniformly disperse the MXene solution and the GO solution;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) freeze drying the membrane at-78 deg.C for 7h, and peeling off the membrane from the substrate to obtain MXene-GO composite membrane named MGO3-1。
Example 6
The MXene-GO composite membrane with humidity response has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OXThe thickness of the MXene sheet layer is 1-3nm, the thickness of the graphene oxide sheet layer is 2-4nm, and the mass of the MXene-GO composite film is 60mg, and the MXene-GO composite film is obtained by adopting the following specific steps:
(1) taking MAX (Ti)3AlC2) MXene solution is prepared by adopting a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCl and stirred for 30min, then 2g Ti was slowly added3AlC2Continuously stirring for 24 hours at 35 ℃ to obtain Ti3C2Tx. The obtained multilayer Ti3C2TxAdding deionized water, and repeatedly carrying out ultrasonic washing until the pH value is 6. Multilayer Ti3C2TxSonicate in ethanol for 1h and centrifuge. Collecting the precipitate, adding the precipitate into deionized water by ultrasonic waves for 20 minutes, centrifuging the solution at 3500rmp for 5 minutes to obtain MXene lamella solution, configuring the concentration of the MXene lamella solution to be 2mg/ml, and introducing inert gas (nitrogen) and then dispersing the solution uniformly by ultrasonic waves at the power of 250W for 15 minutes;
(2) preparing GO into a solution of 2mg/ml, and introducing inert gas and then ultrasonically dispersing uniformly for 15min at the power of 250W;
(3) mixing MXene solution with GO solution (the adding volume ratio of MXene solution to GO solution is 3:1, and 22.5ml and 7.5ml respectively), introducing inert gas (nitrogen), and ultrasonically dispersing uniformly for 15min at 250W power;
(4) carrying out vacuum filtration on the uniformly mixed MXene-GO solution to form a film;
(5) freeze drying the membrane at-78 deg.C for 12h, and peeling off the membrane from the substrate to obtain MXene-GO composite membrane named MGO3-2。
MGO prepared in example 53-1 bending degree test of the composite membrane as a humidity gradient driver (the specific test process is the same as above), and obtaining MGO3-1 bending angle under humidity gradient drive of 33-140 °, indicating MGO3The sensitivity of the membrane material with low quality of the composite membrane is reduced.
MGO prepared in example 63-2 bending degree test of the composite membrane as a humidity gradient driver (the specific test process is the same as above), and obtaining MGO3-2 bending angle at 37-126 ° driven by humidity gradient, indicating MGO3The sensitivity of the membrane material is reduced when the quality of the composite membrane is too high.
In combination with examples 1 to 6, the MXene-GO composite membrane is shown to have a fixed MXene-GO mass ratio of 3:1, the sensitivity of the composite membrane is higher when the mass is between 28 and 60 mg.
The application comprises the following steps:
based on this property of moisture gradient driver of MXene-GO composite membrane, we designed MGO prepared in example 33Use of a membrane for respiratory monitoringThe field of the technology. Generally, the humidity released by human mouth and nose breathing is different and the membrane is fabricated into rectangular strips (3cm x 1cm) into a resistance tester by passing MGO through3The rectangular human mouth nose department of being close to, the micro-humidity signal of human breathing release can be collected by this membrane, and the humidity difference according to different breathing mode releases changes the resistance of self, obtain numerical value by the monitoring of resistance tester, the test result is shown in figure 5, we can distinguish export breathing and nose breathing in the resistance change picture of follow difference, and can distinguish normal nose breathing and slow nose breathing, resistance change rate is big and change fast and breathe for normal mouth, resistance change rate is little and change fast and breathe for normal nose, resistance change rate is little and change slow and breathe for slow nose.
The biocompatibility of the composite membrane was also investigated, and the experiment was performed using human skin cells, and the composite membrane was MGO from example 33MXene adopts the comparative example 1, graphene oxide adopts the comparative example 2, the blank group is a normal human body cell culture medium, optical density detection is carried out after a period of cultivation time, and the higher the optical density value is, the stronger the reactive cell activity is. As shown in FIG. 6, MGO increased with the number of days3The optical density value of (A) increases with the increase in the speed of the other groups, indicating that MGO is faster3The composite membrane has no toxic action on human cells and good biocompatibility, which shows that the composite membrane has the potential of being used in the field of medical health.
The MXene-GO composite membrane can also be used in the fields of water purification, intelligent driving, electricity and the like.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. The MXene-GO composite membrane with humidity response is characterized in that the composite membrane has a layer-by-layer stacking structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned on two sides of the MXene sheet layer, and the MXene sheet layer is Ti3C2OX。
2. The MXene-GO composite membrane with humidity response of claim 1, wherein the mass fraction of MXene sheets in the composite membrane is 50-80%.
3. The MXene-GO composite membrane with humidity response according to claim 1, wherein the thickness of the MXene sheet layer is 1-3nm, and the thickness of the graphene oxide sheet layer is 2-4 nm.
4. A method for preparing an MXene-GO composite membrane according to any one of claims 1 to 3, comprising the steps of:
(1) taking MAX (Ti)3AlC2) Preparing MXene solution by adopting a liquid etching method, and uniformly dispersing;
(2) preparing graphene oxide into a GO solution, and uniformly dispersing;
(3) adding the MXene solution prepared in the step (1) into the GO solution prepared in the step (2), and uniformly mixing by ultrasonic waves to obtain an MXene-GO solution;
(4) and (4) carrying out vacuum filtration on the MXene-GO solution obtained in the step (3) to form a film, and drying to obtain the MXene-GO composite film.
5. The method for preparing the MXene-GO composite membrane according to claim 4, wherein the concentration of the MXene solution in the step (1) is 2 mg/ml.
6. The method for preparing the MXene-GO composite membrane according to claim 4, wherein in the step (1), the dispersion is performed by ultrasonic for 10-20 min.
7. The method for preparing MXene-GO composite membrane according to claim 4, wherein in step (2), the concentration of GO solution is 2 mg/ml; in the step (2), ultrasonic is adopted for dispersing, and inert gas is added in the ultrasonic process.
8. The method for preparing the MXene-GO composite membrane according to claim 4, wherein in the step (3), inert gas is introduced during ultrasonic mixing, the ultrasonic time is 15-30min, and the ultrasonic power is 200-250W.
9. The method for preparing the MXene-GO composite membrane according to claim 4, wherein in the step (4), the membrane obtained by suction filtration is subjected to freeze drying for 8-12 h.
10. Use of an MXene-GO composite membrane according to any one of claims 1-3 for water purification, smart drive, electricity and medical health applications;
when the MXene-GO composite membrane is used for respiratory monitoring in the field of medical health, the MXene-GO composite membrane specifically comprises the following components: different resistance signal responses are generated according to different humidity released by mouth and nose respiration of a human body to distinguish breathing modes, and the higher the humidity released by the respiration is, the higher the resistance change rate of the MXene-GO composite membrane is; and monitoring the respiratory frequency according to a membrane resistance change signal generated by the change of the humidity released by the continuous respiration of the human body.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113648850A (en) * 2021-09-01 2021-11-16 北京理工大学 Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate
CN113692211A (en) * 2021-08-09 2021-11-23 中国人民解放军陆军工程大学 Preparation method of composite film electromagnetic protection material based on MXene-rGO
CN113804732A (en) * 2021-08-24 2021-12-17 湘潭大学 Wearable humidity sensing device for detecting human body sweating rate and manufacturing method thereof
CN114454573A (en) * 2021-12-28 2022-05-10 成都大学 Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof
CN114738216A (en) * 2022-03-18 2022-07-12 哈尔滨工业大学 Skipjack meal humidity driving film and preparation method and application thereof
CN117488482A (en) * 2023-12-29 2024-02-02 东华大学 Asymmetric deformed fiber membrane and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106725490A (en) * 2017-01-23 2017-05-31 中国科学院合肥物质科学研究院 A kind of humidity sensor and the breathing detection system using the humidity sensor
CN108489644A (en) * 2018-02-12 2018-09-04 华中科技大学 High sensitive sensor based on MXene/rGO complex three-dimensional structures
CN110124529A (en) * 2019-05-28 2019-08-16 北京理工大学 A kind of preparation method and application of graphene oxide/MXene composite membrane
CN110975655A (en) * 2019-11-22 2020-04-10 成都理工大学 Novel RGO/MXene composite membrane and preparation method thereof
CN111252768A (en) * 2020-01-20 2020-06-09 北京航空航天大学 Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film
KR20200122670A (en) * 2019-04-18 2020-10-28 한양대학교 산학협력단 Nano channel structure and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106725490A (en) * 2017-01-23 2017-05-31 中国科学院合肥物质科学研究院 A kind of humidity sensor and the breathing detection system using the humidity sensor
CN108489644A (en) * 2018-02-12 2018-09-04 华中科技大学 High sensitive sensor based on MXene/rGO complex three-dimensional structures
KR20200122670A (en) * 2019-04-18 2020-10-28 한양대학교 산학협력단 Nano channel structure and manufacturing method thereof
CN110124529A (en) * 2019-05-28 2019-08-16 北京理工大学 A kind of preparation method and application of graphene oxide/MXene composite membrane
CN110975655A (en) * 2019-11-22 2020-04-10 成都理工大学 Novel RGO/MXene composite membrane and preparation method thereof
CN111252768A (en) * 2020-01-20 2020-06-09 北京航空航天大学 Preparation method and application of titanium carbide MXene functionalized graphene nanocomposite film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LULU LI等: "具有多响应驱动能力和高电磁干扰屏蔽性能的智能Mxene基二维薄膜", 《CARBON》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113692211A (en) * 2021-08-09 2021-11-23 中国人民解放军陆军工程大学 Preparation method of composite film electromagnetic protection material based on MXene-rGO
CN113692211B (en) * 2021-08-09 2024-02-20 中国人民解放军陆军工程大学 Preparation method of composite film electromagnetic protection material based on MXene-rGO
CN113804732A (en) * 2021-08-24 2021-12-17 湘潭大学 Wearable humidity sensing device for detecting human body sweating rate and manufacturing method thereof
CN113648850A (en) * 2021-09-01 2021-11-16 北京理工大学 Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate
CN114454573A (en) * 2021-12-28 2022-05-10 成都大学 Ti3C2TxMXene/GO heterogeneous membrane and preparation method and application thereof
CN114738216A (en) * 2022-03-18 2022-07-12 哈尔滨工业大学 Skipjack meal humidity driving film and preparation method and application thereof
CN114738216B (en) * 2022-03-18 2022-11-22 哈尔滨工业大学 Skipjack meal humidity driving film and preparation method and application thereof
CN117488482A (en) * 2023-12-29 2024-02-02 东华大学 Asymmetric deformed fiber membrane and preparation method and application thereof

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