CN112999885B - 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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CN112999885B
CN112999885B CN202110187351.8A CN202110187351A CN112999885B CN 112999885 B CN112999885 B CN 112999885B CN 202110187351 A CN202110187351 A CN 202110187351A CN 112999885 B CN112999885 B CN 112999885B
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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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Abstract

The invention relates to an MXene-GO composite membrane with humidity response, a preparation method and application thereof, wherein the composite membrane has a layer-by-layer stacked structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned at two sides of the MXene sheet layer, and the MXene sheet layer is Ti 3 C 2 O X . The preparation method specifically comprises the following steps: (1) Xx is prepared, and an MXene solution is prepared by a liquid etching method and uniformly dispersed; (2) Preparing graphene oxide into 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 to obtain an MXene-GO solution; (4) And (3) carrying out vacuum filtration on the MXene-GO solution obtained in the step (3) to form a film, and then drying to obtain the MXene-GO composite film. Compared with the prior art, the membrane material has good stability, good hydrophilicity, humidity sensitivity, conductivity and antibacterial property, and can be applied to multiple 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 stimulus (such as light, heat, PH value and humidity) and generating corresponding response, is one of important directions of development and research of new modern high-technology materials, and is widely applied to emerging industries such as artificial muscles, bionic robots, self-excited switches and the like. Water is a rich and important resource in nature, and intelligent actuators that respond to moisture or humidity stimuli are considered to be the most valuable actuators to study.
Currently, humidity drivers are usually obtained by assembling multiple layers of different materials, and the preparation process is complex and cumbersome, which is not beneficial to mass production. Also asymmetric stresses exist in the interface between the different materials and multilayer actuators are susceptible to delamination during movement due to interlayer differences. While the homogeneous membrane structure is the best solution to the above problems, current research into homogeneous structure actuators is still in the beginning.
MXene is a novel layered two-dimensional metal-based carbide material. The high-performance high-temperature-resistant ceramic material has rich surface functional groups, large specific surface area, high mechanical flexibility, good conductivity and easy film forming property, is favored by researchers, has wide application in the fields of super capacitors, water purification, catalysis, batteries, sensors and the like, and has been initially explored in the aspect of humidity brakes and validated to be used as a feasibility of a humidity gradient driver. However, pure MXene has serious interlayer stacking phenomenon, is extremely easy to oxidize in water/oxygen environment and cannot be stably stored for a long time, and it has been found that doping MXene with other materials can obtain a composite material with better performance, so that MXene can be intercalated, modified, doped or compounded with other materials to prevent MXene from stacking, inhibit oxidation and improve stability of MXene.
GO is one of the important derivatives of graphene-based materials, the surface of which contains a large number of oxygen-containing functional groups, is hydrophilic and is prone to swelling in humid or aqueous environments. The mechanism of humidity braking is based on the swelling behavior of the 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 power to force the humidity brake to bend. Therefore, GO is one of the best candidates for building a wet brake. However, the simple GO film has weak bending response to humidity gradient, is easy to swell in a humid or aqueous environment, has poor stability, is unfavorable for repeated use under high humidity conditions, and does not have conductive performance.
Therefore, the application aims to provide the MXene-GO composite film and the preparation method thereof, which can remarkably improve the humidity response sensitivity of materials, and the application field of the composite film is wider because the MXene has a plurality of excellent characteristics.
Patent CN106290507A discloses a preparation method of a novel two-dimensional titanium carbide/graphene oxide (Ti 3C 2/GO) composite material capable of being subjected to ink-jet printingComprising; the two-dimensional Ti3C2 is prepared by mixing HCl and LiF and etching Ti3AlC 2; mixing two-dimensional Ti3C2 and Graphene Oxide (GO), and performing ink-jet printing on the two-dimensional titanium carbide/graphene oxide (Ti 3C 2/GO) sensor electrode. The method specifically comprises the following steps: 1) Ball milling Ti3AlC (2 < 40 μm) for 8h according to a ball sample ratio of 10:1; 2) 30mL of 6M HCl and 1.98g LiF were mixed and stirred; 3) Adding 3g of Ti3AlC2 after ball milling into the mixed solution, and magnetically stirring the mixed solution at 40 ℃ for reacting for 45h; 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 into ice water bath, and performing ultrasonic treatment; the precipitate was dissolved in 500mL deionized water for a deionized water concentration of about 2g of the precipitate; the ultrasonic time is 2h, and nitrogen is introduced to remove oxygen during ultrasonic treatment; 6) Centrifuging after the ultrasonic treatment is finished; the centrifugation speed is 500rpm, and the centrifugation time is 10min; 7) And mixing the two-dimensional Ti3C2 solution and the graphene oxide GO according to a certain proportion. This patent is for use in the field of hydrogen peroxide electrochemical sensors. In the preparation method, the patent grinds MAX (Ti 3 AlC 2 ) The crude phase was diluted 40-fold after the reaction was completed by adding LiF 1.98g with hydrochloric acid at a concentration of 6M for 45 hours, and centrifuged at 7500rmp for 15 minutes. These methods are different from the methods of the present invention. The patent combines MXene with GO at 1:1, magnetically stirring for 2 hours, carrying out water bath ultrasonic for 10 minutes, preparing an electrode on a conductive substrate by ink-jet printing to detect hydrogen peroxide, and not specifying concentration values before compounding the electrode and the conductive substrate, wherein the compounding time is different from that of the invention.
The deficiencies of the CN106290507a patent are: the conductivity of GO is poor, and the electrochemical detection activity may be reduced by using GO as a carrier to compound MXene. 2. The step of introducing inert gas (nitrogen) is not mentioned in the magnetic stirring and ultrasonic processes of the combination of MXene and GO, and the problem of MXene oxidation possibly exists in the process, so that the detection activity is affected. 3. And 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 comprises the following steps: 1. preparing graphene oxide; 2. preparing a mixed solution; 3. preparing TiC nanosheet solution; 4. mixing, vacuum filtering 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 concentrated sulfuric acid used for preparing titanium carbide is etched, and the etching conditions and time are different from those of the invention. In the patent, the pH of the cleaning liquid is neutral after etching, and the cleaning liquid is washed to be 6 after etching. The patent also adds N, N-dimethylacetamide, and the inert gas is argon, which does not prescribe the concentration before the two are compounded, the thickness of the two slices and the ultrasonic power are different. The patent uses a buchner funnel for suction filtration, and adopts a mode of naturally airing at room temperature. The invention adopts a sand core funnel to carry out suction filtration and freeze drying to obtain the product. The patent only mentions the preparation of dielectric film materials and does not relate to use.
The shortfalls of the CN108584939B patent are: 1. the preparation of titanium carbide uses concentrated sulfuric acid to carry out etching reaction too severely, and the danger is high. 2. Starting from graphene oxide, the whole preparation process is too complex. 3. Washing the etched solid material with distilled water may introduce some impurity ions, affecting the final product quality. 4. The step of introducing inert gas is not mentioned in the process of mixing titanium carbide and GO, and the problem of titanium carbide oxidation possibly exists in the process, so that the product quality is affected. 5. Titanium carbide is easy to oxidize, and in the process of airing at room temperature, the titanium carbide can react with water and oxygen in the air, so that the quality of a product is affected.
Disclosure of Invention
The invention aims to provide an MXene-GO composite membrane with humidity response, and a preparation method and application thereof.
The aim of the invention is achieved by the following technical scheme:
the MXene-GO composite film with the humidity response comprises a layer-by-layer stacked structure, wherein each layer is of a sandwich structure and comprises MXene sheets and graphene oxide sheets respectively positioned on two sides of the MXene sheets, and the MXene sheets are Ti 3 C 2 O X 。
In the composite film, the mass fraction of the MXene sheet layer is 50-80%, preferably 75%.
The thickness of the MXene lamellar layer is 1-3nm, and the thickness of the graphene oxide lamellar layer is 2-4nm.
The mass of the composite membrane is 28-60mg.
The preparation method of the MXene-GO composite membrane specifically comprises the following steps:
(1) Taking MAX (Ti) 3 AlC 2 ) Preparing an MXene solution by adopting a liquid etching method, and uniformly dispersing;
(2) Preparing graphene oxide into 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 to obtain an MXene-GO solution;
(4) And (3) carrying out vacuum filtration on the MXene-GO solution obtained in the step (3) to form a film, and then drying to obtain the MXene-GO composite film.
In step (1), the concentration of the MXene solution is 2mg/ml.
In the step (1), the dispersion is carried out by adopting ultrasonic waves for 15-30 min.
In step (2), the concentration of the GO solution is 2mg/ml.
In the step (2), ultrasonic is adopted for dispersion, and inert gas is added in the ultrasonic process.
The inert gas is one of nitrogen and 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 and argon.
In 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, preferably 3:1.
In the step (4), the membrane obtained by suction filtration is freeze-dried for 7-12h.
The application of the MXene-GO composite membrane is that the MXene-GO composite membrane is used as a humidity gradient brake, and can be used in a plurality of fields such as water purification, intelligent driving, electricity and medical health, and when the MXene-GO composite membrane is used for respiratory monitoring in the medical health field, the application is as follows: different resistance signal responses are generated according to different humidity released by breathing of the mouth and nose of a human body to distinguish breathing modes, the higher the humidity released by breathing is, the larger the bending angle of the composite film is, and the larger the resistance change rate of the MXene-GO composite film is; and monitoring the respiratory rate according to a membrane resistance change signal generated by humidity change released by 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 very susceptible to oxidative deterioration in humid environments, ultimately leading to TiO 2 Formation of nanocrystals. This is a serious problem for most applications, including drives.
GO is one of the important derivatives of graphene-based materials, and although the oxidation process breaks the highly conjugated structure of graphene, 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 to make the graphene-based materials hydrophilic. Therefore, GO is one of the best candidates for building humidity sensing smart drivers. However, the presence of a large number of oxygen-containing functional groups on a simple GO membrane renders the resulting membrane highly hydrophilic and susceptible to swelling in a humid or aqueous environment, resulting in poor stability of the membrane, which is not conducive to repeated use under high humidity conditions.
According to the invention, GO is introduced into the MXene, and the GO is coated on the surface of the MXene to prevent the MXene from directly contacting with the external environment and inhibit oxidation of the MXene, so that the stability of the actuator is improved. Meanwhile, MXene nano-sheets are inserted between GO sheets, nanoscale gaps are formed between the layers, pi-pi interaction between continuous GO nano-sheets is reduced due to the existence of MXene, and the interlayer spacing between the nano-sheets is increased, so that a two-dimensional transportation nano-channel is provided for water transmission, interaction between water molecules and oxygen-containing functional groups in an oxidation area in the GO nano-sheets is weakened, and the stability of the GO film is increased under a high humidity condition. The introduction of GO into the MXene film can provide more active sites for moisture adsorption, thereby improving the hygroscopic expansion of the MXene film, as well as sensitivity, response/recovery time, repeatability and long-term stabilityQualitative, such that the MXene-GO composite membrane also remains highly stable under aqueous conditions, which can be attributed to the hydrogen bonding of the two. In addition, the pure GO has very poor conductivity, and the addition of MXene leads the composite film to have excellent conductivity, and the test shows that the resistance of the composite film can change along with the change of humidity. By MGO 3 For example, when the humidity is 20%, the resistance is 4.8 omega, and when the humidity is 90%, the resistance is increased to 10.08 omega, and the discovery of the phenomenon further expands the practical field of the composite film. As shown in fig. 4, before the composite membrane absorbs water, the volume of the membrane is smaller, after the composite membrane absorbs water, water enters between the MXene sheet layer and the graphene oxide sheet layer, and the composite membrane can realize water analysis by drying.
According to the invention, the GO and the MXene are mixed, the GO nano-sheet can well coat the MXene, and the two nano-sheets have more oxygen-containing functional groups, spontaneous hydrogen bonding is combined, through the chemical combination, the MXene-GO composite film can be used as an intelligent driver, and good performance can be well ensured no matter in a stability test, a repeatability test or a sensitivity test of humidity gradient response, so that the composite film can be repeatedly used for a long time, and even if the composite film is placed in a water structure for a long time, the composite film cannot be broken down. Based on this characteristic of the humidity gradient driver of MXene-GO composite membranes, we designed the membranes for use in the respiratory monitoring field. In general, the humidity released by the oral respiration and the nasal respiration of a person is different, the membrane can change the resistance of the membrane according to the humidity released by different respiration modes, and the outlet respiration and the nasal respiration can be distinguished from different resistance change diagrams, and meanwhile, the membrane is also found to have antibacterial property and biocompatibility, which shows that the composite membrane has potential for being used in the medical health field.
In addition, the preparation method of the invention also specifically limits the addition proportion of each material component (MXene, GO, etc.) and the treatment process conditions (such as drying time, treatment temperature, etc.), namely if the addition proportion of MXene is not within the above-defined condition range of the invention, if the addition proportion of MXene is too high or too low, the sensitivity of humidity gradient response of the final product is reduced, and when the GO content is too high, the conductivity of the composite film is deteriorated, and when the mass ratio of MXene to GO is 4:1, the membrane resistance is 3.4 omega under the dry environment, and the mass ratio of MXene to GO is 1:1, the film resistance was 65Ω in a dry environment.
Compared with the prior art, the invention has the following advantages:
(1) The MXene is a novel two-dimensional material which integrates hydrophilicity and conductivity, and after the MXene is compounded with GO, the stability of the prepared MXene-GO composite film is greatly increased, and the humidity braking response time is short. The humidity gradient is controlled by the water vapor of the water evaporation, and the higher the water temperature is, the larger the water evaporation is, and the higher the humidity gradient is. At a humidity gradient of 40% (water temperature 90 ℃), the mass ratio of MXene and GO is 3:1 can reach maximum response in 5 seconds, and the bending angle reaches 160 degrees.
(2) The humidity gradient intelligent brake prepared by the method has stable performance and can be repeatedly used through a period of moisture adsorption/desorption test.
(3) The film also has excellent electrical property, antibacterial property and biocompatibility, and is widely applicable to the field of combination with humidity gradient response performance.
(4) The invention has simple operation process, good repeatability and high sensitivity, and is suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron micrograph (magnification 7000) of a composite film obtained in each example and each comparative example;
FIG. 2 is a graph showing comparison of the results of the test of the change of the bending angle of the composite film according to the humidity gradient of the water temperature control, obtained in each example and each comparative example;
FIG. 3 is a graph showing the results of a repeatability test of the composite film prepared in example 3;
FIG. 4 is a schematic diagram of the operation of an MXene-GO composite membrane;
FIG. 5 is a graph of a MXene-GO composite membrane for breath detection;
FIG. 6 is a graph of biocompatibility of a MXene-GO composite membrane.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
The MXene-GO composite membrane with the humidity response has a layer-by-layer stacked structure, wherein each layer is of a sandwich structure and comprises MXene sheets and graphene oxide sheets respectively positioned on two sides of the MXene sheets, and the MXene sheets are Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, and the mass of the MXene-GO composite film is 30mg, and the preparation method comprises the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting the precipitate, adding the precipitate into deionized water for 20 minutes by ultrasonic treatment, and centrifuging at 3500rmp for 5 minutes to obtain the MXene lamellar solution. The concentration of the MXene solution is configured to be 2mg/ml, and the MXene solution is uniformly dispersed by ultrasonic treatment with power of 25W for 15min after inert gas (nitrogen) is introduced;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas (nitrogen), and performing ultrasonic treatment with 200W power for 10min to uniformly disperse;
(3) Mixing the MXene solution and the GO solution (the adding volume ratio of the MXene solution to the GO solution is 1:1, 15ml and 15ml respectively), introducing inert gas (nitrogen), and uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Then the membrane is freeze-dried for 7 hours at the temperature of minus 78 ℃, and then the membrane is peeled off from the substrate, thus obtaining the MXene-GO composite membrane named as MGO 1 The sem image of the film is shown in fig. 1, and it can be seen that the material is truly a layer-by-layer stacked structure with significant delamination between layers. MGO (media-purpose oxygen) 1 The film resistance in dry environment was 65Ω.
Example 2
The MXene-GO composite membrane with the humidity response has a layer-by-layer stacked structure, wherein each layer is of a sandwich structure and comprises MXene sheets and graphene oxide sheets respectively positioned on two sides of the MXene sheets, and the MXene sheets are Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, and the mass of the MXene-GO composite film is 30mg, and the preparation method comprises the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting the precipitate, adding the precipitate into deionized water for 20 minutes by ultrasonic treatment, and centrifuging at 3500rmp for 5 minutes to obtain the MXene lamellar solution. The concentration of the MXene solution is configured to be 2mg/ml, and the MXene solution is uniformly dispersed by ultrasonic treatment with the power of 250W for 15min after inert gas (nitrogen) is introduced;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas, and performing ultrasonic treatment with power of 250W for 15min to uniformly disperse;
(3) Mixing the MXene solution and the GO solution (the adding volume ratio of the MXene solution to the GO solution is 2:1 and respectively 20ml and 10 ml), introducing inert gas (nitrogen), and uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Freeze drying the membrane at-78deg.C for 7 hr, and peeling the membrane from the substrate to obtain MXene-GO composite membrane named MGO 2 The sem image of the film is shown in fig. 1, and it can be seen that the material is truly a layer-by-layer stacked structure with significant delamination between layers.
Example 3
An MXene-GO composite film with humidity response has a layer-by-layer stacked structure, each layer is of a sandwich structure and comprises an MXene sheet layer and a plurality of layersGraphene oxide sheets on both sides of the MXene sheet, the MXene sheet being Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, and the mass of the MXene-GO composite film is 30mg, and the preparation method comprises the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting the precipitate, adding the precipitate into deionized water for 20 minutes by ultrasonic treatment, and centrifuging at 3500rmp for 5 minutes to obtain the MXene lamellar solution. The concentration of the MXene solution is configured to be 2mg/ml, and the MXene solution is uniformly dispersed by ultrasonic treatment with the power of 250W for 15min after inert gas (nitrogen) is introduced;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas, and performing ultrasonic treatment with power of 250W for 15min to uniformly disperse;
(3) Mixing an MXene solution and a GO solution (the adding volume ratio of the MXene solution to the GO solution is 3:1), respectively 22.5ml and 7.5ml, introducing inert gas (nitrogen), and uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Freeze drying the membrane at-78deg.C for 7 hr, and peeling the membrane from the substrate to obtain MXene-GO composite membrane named MGO 3 The sem image of the film is shown in fig. 1, and it can be seen that the material is truly a layer-by-layer stacked structure with significant delamination between layers. At 20% humidity, MGO 3 Has a resistance of 4.8Ω and when the humidity is 90%, MGO 3 The resistance of (2) rises to 10.08 omega.
Example 4
The MXene-GO composite film with humidity response has a layer-by-layer stacked structure, and each layer is of a sandwich structure and comprises an MXene sheet layer and two sides of the MXene sheet layerThe graphene oxide sheet layer of (2) is Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, and the mass of the MXene-GO composite film is 30mg, and the preparation method comprises the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting the precipitate, adding the precipitate into deionized water for 20 minutes by ultrasonic treatment, and centrifuging at 3500rmp for 5 minutes to obtain the MXene lamellar solution. The concentration of the MXene solution is configured to be 2mg/ml, and the MXene solution is uniformly dispersed by ultrasonic treatment with the power of 250W for 15min after inert gas (nitrogen) is introduced;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas, and performing ultrasonic treatment with power of 250W for 15min to uniformly disperse;
(3) Mixing the MXene solution and the GO solution (the adding volume ratio of the MXene solution to the GO solution is 4:1, and 24ml and 6ml respectively), introducing inert gas (nitrogen), and uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Freeze drying the membrane at-78deg.C for 7 hr, and peeling the membrane from the substrate to obtain MXene-GO composite membrane named MGO 4 The sem image of the film is shown in fig. 1, and it can be seen that the material is truly a layer-by-layer stacked structure with significant delamination between layers. MGO (media-purpose oxygen) 4 The film resistance in dry environment was 3.4Ω.
Comparative example 1
MXene film with humidity response, with MXene being Ti 3 C 2 O X The thickness is 1-3nm, and the preparation method comprises the following steps:
(1) Taking MAX (Ti) 3 AlC 2 ) Preparation of M by liquid etchingXene solution. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting the precipitate, adding the precipitate into deionized water for 20 minutes by ultrasonic treatment, and centrifuging 3500rmp for 5 minutes to obtain an MXene lamellar solution;
(2) The concentration of the MXene solution is configured to be 2mg/ml, and the MXene solution is uniformly dispersed by ultrasonic treatment with the power of 250W for 15min after inert gas (nitrogen) is introduced;
(3) Vacuum filtering the uniformly dispersed MXene solution to form a film;
(4) And (3) freeze-drying the membrane at the temperature of minus 78 ℃ for 7 hours, and peeling the membrane from the substrate to obtain the MXene membrane.
Comparative example 2
The GO film with the humidity response is obtained by adopting the following preparation steps:
(1) Preparing GO into GO solution;
(2) Preparing the concentration of the GO solution to be 2mg/ml, introducing inert gas, and uniformly dispersing the GO solution by ultrasonic waves with the power of 250W for 15 min;
(3) Vacuum filtering the uniformly dispersed GO solution to form a film;
(4) And (3) freeze-drying the film at the temperature of minus 78 ℃ for 7 hours, and peeling the film from the substrate to obtain the GO film.
Performance testing
For the MGO prepared in this example 1 1 Bending test as humidity gradient driver, namely MGO 1 The film was cut into rectangular strips (3 cm x 1 cm) and placed on a substrate with a rectangular hole in the center, which was used as a window for introducing heated water to create a water vapor gradient, above which was ambient air with rh=60% (the same applies below), and the evaporation rate of water was controlled by changing the water temperature to change the ambient humidity, so that there was a certain humidity difference between the upper and lower portions of the film, i.e., the humidity gradient.
As shown in FIG. 2, it can be seen that MGO 1 In wet stateThe bending angle under gradient driving (humidity is controlled by water temperature, the water temperature is changed from 40 ℃ to 90 ℃, the humidity is gradually increased, and the following is the same) is 18-90 degrees, which shows that the MXene-GO composite membrane can improve the sensitivity of a pure membrane material and has practical application feasibility.
For the MGO prepared in this example 2 2 Bending test as humidity gradient driver as shown in fig. 2, it can be seen that the MGO 2 The bending angle under the drive of humidity gradient is 35-112 degrees, which shows that the MXene-GO composite membrane can improve the sensitivity of the pure membrane material.
For the MGO prepared in this example 3 3 As a humidity gradient driver for bending test and repeatability test, as shown in FIG. 2, it can be seen that MGO 3 The bending angle under the drive of humidity gradient is 49-160 degrees, which shows that the MXene-GO composite film can improve the sensitivity of the pure film material, as shown in figure 3, MGO 3 In 50 bending/recovery cycles (on for test and off for no test), the bending angle did not change much, indicating excellent repeatability of the MXene-GO composite membrane, indirectly indicating a significant improvement in stability of the MXene composite membrane after compositing. Furthermore, at a humidity gradient of 40%, the MGO 3 The maximum response of the composite film can be achieved in 5 seconds, and the bending angle reaches 160 degrees.
For the MGO prepared in this example 4 4 The composite membrane was subjected to bending as a humidity gradient driver, as shown in FIG. 2, and it can be seen that MGO 4 The bending angle under the drive of humidity gradient is 43-138 degrees, which shows that the MXene-GO composite membrane can improve the sensitivity of the pure membrane material.
From the results of examples 1 and 2, it was shown that increasing the content of MXene in the MXene-GO composite membrane further improved the sensitivity of the pure membrane material, and from the results of examples 1, 2, 3 and 4, it was shown that too high content of MXene in the MXene-GO composite membrane was not beneficial to improve the sensitivity of the membrane material.
As shown in FIG. 2, the MXene film prepared in comparative example 1 was subjected to bending test as a humidity gradient actuator, and the bending angle of the MXene film under the humidity gradient actuation was 11-68 degrees, which indicates that the braking property of a pure MXene film is general.
The bending test of the GO film prepared in the comparative example 2 as a humidity gradient driver shows that the bending angle of the GO film under the humidity gradient driving is 3-14 degrees as shown in fig. 2, which shows that the braking performance of the pure GO film is very poor.
In combination with example 1, example 2, comparative example 1 and comparative example 2, it can be seen that the MXene-GO composite membrane has a very high sensitivity to humidity.
Example 5
The MXene-GO composite membrane with the humidity response has a layer-by-layer stacked structure, wherein each layer is of a sandwich structure and comprises MXene sheets and graphene oxide sheets respectively positioned on two sides of the MXene sheets, and the MXene sheets are Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, and the mass of the MXene-GO composite film is 28mg, and the preparation method comprises the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting precipitate, adding into deionized water by ultrasonic treatment for 20min, centrifuging at 3500rmp for 5min to obtain MXene lamellar solution, preparing the concentration of MXene solution into 2mg/ml, introducing inert gas (nitrogen), and dispersing uniformly by ultrasonic treatment at 250W for 15 min;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas, and performing ultrasonic treatment with power of 250W for 15min to uniformly disperse;
(3) Mixing the MXene solution with the GO solution (the adding volume ratio of the MXene solution to the GO solution is 3:1, 10.5ml and 3.5ml respectively), introducing inert gas (nitrogen), and uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Freeze drying the membrane at-78deg.C for 7 hr, and peeling the membrane from the substrate to obtain MXene-GO composite membrane named MGO 3 -1。
Example 6
The MXene-GO composite membrane with the humidity response has a layer-by-layer stacked structure, wherein each layer is of a sandwich structure and comprises MXene sheets and graphene oxide sheets respectively positioned on two sides of the MXene sheets, and the MXene sheets are Ti 3 C 2 O X The thickness of the MXene lamellar layer is 1-3nm, the thickness of the graphene oxide lamellar layer is 2-4nm, the mass of the MXene-GO composite film is 60mg, and the method is characterized by comprising the following specific steps:
(1) Taking MAX (Ti) 3 AlC 2 ) The MXene solution is prepared by a liquid etching method. Specifically, 2g LiF was mixed with 40mL 9M HCL and stirred for 30min, then 2g Ti was slowly added 3 AlC 2 Continuously stirring at 35 ℃ for 24 hours to obtain Ti 3 C 2 T x . The obtained multi-layer Ti 3 C 2 T x Repeated ultrasonic washing was performed with deionized water until ph=6. Multilayer Ti 3 C 2 T x After 1h of sonication in ethanol, centrifugation. Collecting precipitate, adding into deionized water by ultrasonic treatment for 20min, centrifuging at 3500rmp for 5min to obtain MXene lamellar solution, preparing the concentration of MXene solution into 2mg/ml, introducing inert gas (nitrogen), and dispersing uniformly by ultrasonic treatment at 250W for 15 min;
(2) Preparing GO into a solution of 2mg/ml, introducing inert gas, and performing ultrasonic treatment with power of 250W for 15min to uniformly disperse;
(3) Mixing the MXene solution and the GO solution (the adding volume ratio of the MXene solution to the GO solution is 3:1 and is respectively 22.5ml and 7.5 ml), introducing inert gas (nitrogen), and then uniformly dispersing by ultrasonic waves with the power of 250W for 15 min;
(4) Vacuum filtering the uniformly mixed MXene-GO solution to form a film;
(5) Freeze drying the membrane at-78deg.C for 12 hr, and peeling the membrane from the substrate to obtain MXene-GO composite membrane named MGO 3 -2。
The embodiment will be described5 MGO prepared in 3 -1 bending test of the composite membrane as humidity gradient driver (specific test procedure is the same as above), the obtained MGO 3 -1 bending angle under humidity gradient drive is 33-140 °, indicating MGO 3 The sensitivity of the composite membrane material is reduced due to the too low quality of the composite membrane.
MGO prepared in this example 6 3 -2 bending test of the composite membrane as humidity gradient driver (specific test procedure is the same as above), the obtained MGO 3 -2 has a bending angle of 37-126 ° under humidity gradient drive, indicating an MGO 3 The sensitivity of the composite membrane material is reduced due to the excessive quality of the composite membrane.
From a review of examples 1-6, it is shown that in the MXene-GO composite membrane, the mass ratio of fixed MXene to GO is 3:1, the mass of the composite membrane is higher in sensitivity of 28mg-60 mg.
Application:
based on this characteristic of the humidity gradient driver of the MXene-GO composite film, we designed the MGO prepared in example 3 3 The membrane is used in the field of respiratory monitoring. In general, the humidity released by the mouth and nose respiration of a person is different, the film is made into a rectangular strip (3 cm. Times.1 cm) and connected to a resistance tester by MGO 3 The rectangular human mouth and nose department that is close to, the trace humidity signal that human breathing released can be collected by this membrane to according to the humidity difference that different breathing modes released, monitor by resistance tester and obtain the numerical value, test result is as shown in fig. 5, and we can distinguish export breathing and nose breathing from different resistance change diagrams, can distinguish normal nose breathing and slow nose breathing moreover, and the resistivity is big and change quick and be normal mouth breathing, and resistivity is little and change quick and be normal nose breathing, and resistivity is little and change slow is slow nose breathing.
Meanwhile, the biocompatibility of the composite membrane is also explored, the experiment is carried out by adopting human skin cells, and the composite membrane adopts MGO of the embodiment 3 3 MXene adopts comparative example 1, graphene oxide adopts comparative example 2, blank group is normal human body cell culture medium, optical density detection and optical density detection are carried out after a period of incubation timeThe greater the degree value, the more reactive the cell activity. As shown in FIG. 6, with increasing days, MGO 3 With increasing optical density values and increasing faster than other groups, indicating MGO 3 The composite membrane has no toxic or harmful effect on human cells and good biocompatibility, which shows that the composite membrane has potential for the medical health field.
The MXene-GO composite membrane can also be used in the fields of water purification, intelligent driving, electricity and the like.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (1)

1. The application of the MXene-GO composite film with the humidity response is characterized in that the MXene-GO composite film is used in the fields of intelligent driving, electricity and medical health;
when the MXene-GO composite membrane is used for respiratory monitoring in the medical health field, the method specifically comprises the following steps: different resistance signal responses are generated according to different humidity released by breathing of the mouth and nose of a human body to distinguish breathing modes, and the higher the humidity released by breathing is, the larger the resistance change rate of the MXene-GO composite film is; and monitoring respiratory rate according to a membrane resistance change signal generated by humidity change released by continuous respiration of the human body;
the MXene-GO composite membrane has a layer-by-layer stacked structure, each layer is of a sandwich structure and comprises an MXene sheet layer and graphene oxide sheet layers respectively positioned at two sides of the MXene sheet layer, wherein the MXene sheet layer is Ti 3 C 2 O X ；
In the composite film, the mass fraction of the MXene sheet layer is 50-80%;
the thickness of the MXene lamellar layer is 1-3nm, and the thickness of the graphene oxide lamellar layer is 2-4nm;
the MXene-GO composite membrane is prepared through the following steps:
(1) Taking MAX (Ti) 3 AlC 2 ) Preparing an MXene solution by adopting a liquid etching method, and uniformly dispersing;
(2) Preparing graphene oxide into 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 to obtain an MXene-GO solution;
(4) Vacuum filtering 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 the MXene solution is 2mg/ml;
in the step (1), ultrasonic treatment is adopted for 10-20min for dispersion;
in the step (2), the concentration of the GO solution is 2mg/ml; in the step (2), ultrasonic is adopted for dispersion, and inert gas is added in the ultrasonic process;
in the step (3), inert gas is introduced during ultrasonic mixing, the ultrasonic time is 15-30min, and the ultrasonic power is 200-250W;
in the step (4), the membrane obtained by suction filtration is freeze-dried for 8-12h.
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