CN111362268A - MXene purple phosphorus alkene composite sponge and preparation method thereof - Google Patents

MXene purple phosphorus alkene composite sponge and preparation method thereof Download PDF

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CN111362268A
CN111362268A CN201911411815.8A CN201911411815A CN111362268A CN 111362268 A CN111362268 A CN 111362268A CN 201911411815 A CN201911411815 A CN 201911411815A CN 111362268 A CN111362268 A CN 111362268A
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mxene
phosphorus alkene
purple phosphorus
alkene composite
purple
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CN111362268B (en
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蒋旭
董大鹏
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Jiangsu Xfnano Materials Tech Co ltd
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Abstract

The invention discloses MXene purple phosphorus alkene composite sponge and a preparation method thereof, wherein the MXene purple phosphorus alkene composite sponge has a three-dimensional macrostructure, a continuous three-dimensional porous structure, micropores, mesopores and macropores, and the specific surface area of the MXene purple phosphorus alkene composite sponge is 3-500m2Between/g, the conductivity is between 0.01S/m and 1000S/cm. The preparation method comprises the following steps: under the protection of inert gas, adding the purple phosphorus alkene into MXene dispersion liquid for even dispersion, adding a cross-linking agent, standing for forming, performing solution replacement, and performing circulating freeze drying treatment to obtain the MXene purple phosphorus alkene composite sponge material. The MXene purple phosphorus provided by the inventionThe alkene composite sponge has high conductivity, high strength, high specific surface area and excellent photoelectric property, and has wide application prospect in the fields of electronic information, energy environment and the like.

Description

MXene purple phosphorus alkene composite sponge and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to MXene purple phosphorus alkene composite sponge and a preparation method thereof.
Background
The two-dimensional material has huge application prospect in the fields of catalysis, energy, electronic information and the like due to excellent physical and chemical properties. MXene, as a new member of a two-dimensional material family, has excellent conductivity, high specific surface area and good hydrophilicity, so that MXene has attracted attention in the fields of information, energy and environment. MXene is generally prepared by acid etching MAX phase ceramics to obtain two-dimensional flakes of nanometer or micrometer scale size, but in practical application, the MXene flakes of micro-scale are required to be assembled into macroscopic bodies to be practically applied. The MXene sheets have strong van der Waals force, so that the sheets are easy to agglomerate with each other to lose the characteristic of high specific surface area. In addition, MXene sheets are very temperature sensitive (Chemistry of materials,29(11), 4848-. Most of MXene materials prepared at present exist in the form of powder particles, and various binders are required to be added during use, so that the excellent properties of pure MXene materials are greatly lost. Therefore, how to assemble microscopic MXene sheets into macroscopic bodies while maintaining the excellent performance of the macroscopic bodies is a key engineering problem to be solved urgently in realizing MXene large-scale application.
Purple phosphorus is the most stable phosphorus allotrope, and purple phosphorus alkene more stable than black scale alkene can be obtained by stripping the purple phosphorus. Phosphorylene, like Hexagliene, is a semiconductor material with unique optoelectronic properties (Nature News,506(7486), 19.). If the purple phosphorus alkene and MXene can be compounded together, good photoelectric properties can be given to the MXene material, and a synergistic effect is realized. However, both two-dimensional materials belong to easily-oxidized materials, so that the problem that the nanocomposite is urgently needed to be solved is that the nanocomposite is assembled into a stable three-dimensional macroscopic body by a specific process means and the excellent characteristics of the macroscopic body are retained.
Disclosure of Invention
The invention mainly aims to provide MXene purple phosphorus alkene composite sponge and a preparation method thereof, overcomes the defects in the prior art, and mainly solves the problems that MXene and composite materials thereof are easy to oxidize and difficult to form a stable three-dimensional macroscopic body with high specific surface area in the assembly process.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
an MXene purple phosphorus alkene composite material is characterized in that MXene and purple phosphorus alkene are mutually overlapped to form a three-dimensional porous structure, and the three-dimensional porous structure comprises micropores below 2nm, mesopores of 2nm-50nm and macropores larger than 50 nm.
Furthermore, the MXene purple phosphorus alkene composite material has the pore size distribution of 0.1nm-1 μm.
Furthermore, the MXene purple phosphorus alkene composite material has the pore size distribution of 0.1nm-500 nm; the specific surface area is 3-500m2Per g, pore volume of 0.01cm3/g-5m3G, apparent density of 0.01g/cm3-100g/cm3The electrical conductivity is 0.01S/m to 1000S/cm, and the compressive strength is 0.1Pa to 1 GPa.
Furthermore, the MXene purple phosphorus alkene composite material has the pore size distribution of 0.5nm-500 nm; the specific surface area is 100-500m2Per g, pore volume of 0.2cm3/g-5m3G, apparent density of 0.01g/cm3-100g/cm3The conductivity is 100S/m to 1000S/cm, and the compressive strength is 1KPa to 1 GPa.
The preparation method of the MXene purple phosphorus alkene composite material comprises the following steps:
step one, adding an ionene into an MXene dispersion liquid under an inert atmosphere, and mixing to obtain an MXene and ionene composite dispersion liquid;
step two, adding a cross-linking agent into the MXene purple phosphorus alkene composite dispersion liquid, and standing for a period of time to form the MXene purple phosphorus alkene composite dispersion liquid;
and step three, carrying out solvent replacement on the MXene purple phosphorus alkene composite wet sponge obtained by molding, and then carrying out circulating freeze drying treatment to obtain the MXene purple phosphorus alkene composite sponge.
Further, in the preparation method of the MXene purple phosphorus alkene composite material, in the first step, MXene in the MXene dispersion liquid comprises Ti2CTx、Nb2CTx、V2CTx、TiNbCTx、Ti3CNTx、Ti3C2Tx、Ta4C3TxOr Nb4C3TxAny one or any combination of two or more of them.
Further, in the preparation method of the MXene purple phosphorus alkene composite material, in the first step, the concentration of the MXene dispersion liquid is 0.05mg/mL-5mg/mlL, and the solvent used in the dispersion liquid is one or any combination of more than two of water, ethanol, DMSO, NMP or DMF.
Further, in the preparation method of the MXene purple phosphorus alkene composite material, the mass ratio of the purple phosphorus alkene to the MXene in the first step is 1:1-1: 10.
Further, the preparation method of the MXene purple phosphorus alkene composite material comprises the following mixing process in the first step:
(1) introducing one or any combination of argon and nitrogen into the dispersion liquid, wherein the aeration rate is 0.1mL/min-2L/min, and the aeration time is 1min-360 min;
(2) stirring the dispersion liquid in a cold trap at 0 ℃ for 0.5-4 hours, wherein the stirring comprises one or any combination of more than two of magnetic stirring, mechanical stirring and ultrasonic stirring;
(3) carrying out ultrasonic treatment on the dispersion liquid in an ice water bath for 0.1-2 hours, wherein the ultrasonic power is 40-1500W;
(4) and standing and freezing the dispersion liquid subjected to the ultrasonic treatment in a cold trap at the temperature of-10 ℃ for 0.5 to 10 hours, and then taking out and naturally returning to the room temperature to obtain the MXene purple phosphorus alkene composite dispersion liquid with uniform dispersion.
Furthermore, the MXene purple phosphorus alkene composite material preparation method, MXene flake diameter size that adopts in step one is 0.5nm-200 μm, and the thickness is 0.3nm-10 μm.
Further, in the preparation method of the MXene purple phosphorus alkene composite material, the size of the purple phosphorus alkene sheet diameter adopted in the step one is 1nm-10 μm, and the thickness is 1nm-1 μm.
Further, in the preparation method of the MXene purple phosphorus alkene composite material, the standing time in the second step is 0.5 to 72 hours; the temperature of the standing environment is between 5 ℃ and 35 ℃.
Further, the preparation method of the MXene purple phosphorus alkene composite material is added in the second stepThe cross-linking agent is ethylenediamine, triethylamine or Fe3+，Ca2+，La3+，K+Or Na+One or an arbitrary combination of two or more of them; the ratio of the cross-linking agent to MXene is 0.01:1-0.01: 10.
Further, the preparation method of the MXene purple phosphorus alkene composite material comprises the following steps of:
(1) soaking MXene purple phosphorus alkene composite sponge containing the solvent after the solvent replacement in deionized water for 1-12 hours;
(2) freezing the soaked MXene purple phosphorus alkene composite sponge in a cold trap at the temperature of 40-60 ℃ for 0.5-36 hours, and then recovering to the room temperature;
(3) putting the water-containing MXene purple phosphorus alkene composite sponge restored to the room temperature into a cold trap again for freezing at the temperature of between 20 ℃ below zero and 40 ℃ below zero for 0.5 to 36 hours, and then restoring to the room temperature;
(4) putting the MXene purple phosphorus alkene composite sponge which is recovered to the room temperature in the step (3) into a cold trap again for freezing at the temperature of-10 ℃ to-20 ℃ for 0.5-36 hours, and then recovering to the room temperature;
(5) putting the MXene purple phosphorus alkene composite sponge which is recovered to the room temperature in the step (4) into a cold trap again for freezing at the temperature of between-1 and-10 ℃ for 0.5 to 36 hours;
(6) placing the MXene purple phosphorus alkene composite sponge frozen in the step (5) into a vacuum kettle, wherein the pressure in the vacuum kettle is 10-12Pa-6000Pa, and drying in a vacuum kettle for 0.5-72 hours to obtain MXene composite sponge.
Further, the MXene purple phosphorus alkene composite material preparation method, MXene purple phosphorus alkene composite sponge that step three obtained can be the shape of any one in cube, cuboid, cylinder, centrum, spheroid.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for preparing the MXene purple phosphorus alkene composite sponge has the advantages of simple process, environmental protection, no need of high temperature and high pressure or toxic cross-linking agents, direct mild reaction at room temperature and liquid phase to form a three-dimensional macroscopic body, simple equipment, easy industrial amplification production and wide market prospect;
(2) the MXene purple phosphorus alkene composite sponge provided by the invention is prepared by adopting a unique cyclic freeze drying process method, so that the excellent performance of a two-dimensional material is effectively ensured, and the problem of performance loss in the MXene three-dimensional assembly process is solved;
(3) the MXene purple phosphorus alkene composite sponge provided by the invention not only has the characteristics of high conductivity and the like of the traditional MXene material, but also shows good photoelectric characteristics due to the introduction of the purple phosphorus alkene.
Drawings
FIG. 1a is a scanning electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 1 of the present invention;
FIG. 1b is a transmission electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 1 of the present invention;
FIG. 2a is a scanning electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 2 of the present invention;
FIG. 2b is a transmission electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 2 of the present invention;
FIG. 3a is a scanning electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 3 of the present invention;
FIG. 3b is a transmission electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 3 of the present invention;
FIG. 4a is a scanning electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 4 of the present invention;
FIG. 4b is a transmission electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 4 of the present invention;
FIG. 5a is a scanning electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 5 of the present invention;
FIG. 5b is a transmission electron microscope image of MXene purple phosphorus alkene composite sponge obtained in example 5 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution and implementation process and principles etc. will be further explained as follows.
The embodiment of the invention provides MXene purple phosphorus alkene composite sponge, which is mainly formed by mutually lapping MXene and purple phosphorus alkene to form a three-dimensional porous structure, wherein the porous structure comprises micropores below 2nm, mesopores of 2nm-50nm and macropores larger than 50 nm.
Preferably, the MXene purple phosphorus alkene composite sponge has a pore size distribution of 0.1nm-1 μm, and particularly preferably 1nm-500 nm; the specific surface area is 3-500m2Per g, pore volume of 0.01cm3/g-5m3G, apparent density of 0.01g/cm3-100g/cm3The electrical conductivity is 0.01S/m to 1000S/cm, and the compressive strength is 0.1Pa to 1 GPa.
More preferably, the pore size distribution of the MXene purple phosphorus alkene composite material is 0.5nm-500 nm; the specific surface area is 100-500m2Per g, pore volume of 0.2cm3/g-5m3G, apparent density of 0.01g/cm3-100g/cm3The conductivity is 100S/m to 1000S/cm, and the compressive strength is 1KPa to 1 GPa.
As one of the preferable schemes, the MXene comprises Ti2CTx、Nb2CTx、V2CTx、TiNbCTx、Ti3CNTx、Ti3C2Tx、Ta4C3TxOr Nb4C3TxAny one or any combination of two or more of them, but not limited thereto.
Furthermore, the MXene sheet diameter is 0.5nm to 200 μm, and the thickness is 0.3nm to 10 μm.
As one preferable embodiment, the solvent of the MXene dispersion is any one of water, ethanol, DMSO, NMP or DMF, or any combination of two or more of them, but is not limited thereto.
Further, the concentration of the MXene dispersion liquid is 0.05mg/ml-5 mg/ml.
Furthermore, the mass ratio of the purple phosphorus alkene to MXene is 1:1-1: 10.
As one of the preferable schemes, the sheet diameter of the purple phosphorus alkene is 10nm to 10 μm, and the thickness is 1nm to 1 μm.
MXene, as one member of a two-dimensional material family, has high conductivity, high specific surface area and good water solubility and has wide application prospect in the fields of environment, energy, catalysis and the like. For example, MXene is used as a negative electrode material of a lithium ion battery, so that the capacity and the cycle stability of the negative electrode material of the lithium ion battery can be greatly improved (see CN201610733989.6), and the negative electrode material also has excellent catalytic activity (see ACS Catalysis,7(1) and 494 500.). Similarly, the purple phosphorus alkene is used as a newly developed two-dimensional material, the excellent photoelectric property of the purple phosphorus alkene enables the purple phosphorus alkene to become a hotspot of current research, and the stability of the purple phosphorus alkene is superior to that of the current black tridymite, so that the purple phosphorus alkene is wider in application range, and has very wide application prospects in the fields of photoelectricity, information, energy and the like.
The method comprises the steps of enabling MXene lamella and purple phosphorus alkene lamella to mutually form a three-dimensional network structure in a chemical crosslinking mode, and then obtaining a three-dimensional macroscopic body with a regular shape through an initiated circulating freeze drying process. The MXene macroscopic assembly is realized through the series of process means, the excellent performance of the MXene is maintained, and the excellent photoelectric characteristics of the MXene material are simultaneously endowed through introducing the purple phosphorus alkene. The key point of the preparation of the MXene purple phosphorus alkene composite material is gradient assembly at low temperature, and firstly, two-dimensional lamellar is crosslinked and lapped by a crosslinking agent to form a primary three-dimensional network framework. And then, obtaining the final composite sponge through a circulating freeze drying process. Wherein, the first cycle freezing process of the cycle freezing and drying is freezing at extremely low ambient temperature, and water in the three-dimensional channel can rapidly form fine ice crystals to form a secondary three-dimensional channel. And by analogy, the freezing temperature is reduced in sequence, so that ice crystals formed in the pore channel are enlarged more and more, and finally a multi-level pore channel structure is formed. Meanwhile, the whole preparation process of the MXene purple phosphorus alkene composite sponge is carried out at room temperature or below, so that the condition that the two-dimensional material cannot be oxidized to lose the excellent performance of the two-dimensional material is well ensured.
Another aspect of the embodiments of the present invention provides a preparation method of the MXene purple phosphorus alkene composite sponge, including:
adding an appropriate amount of purple phosphorus alkene into the MXene dispersion liquid under an inert atmosphere, and mixing to obtain MXene purple phosphorus alkene composite dispersion liquid;
adding a cross-linking agent into the MXene purple phosphorus alkene composite dispersion liquid, and standing for a period of time to form the MXene purple phosphorus alkene composite dispersion liquid;
and (3) treating the MXene purple phosphorus alkene composite wet sponge with a certain shape by a circulating cold drying process to obtain the MXene purple phosphorus alkene composite sponge.
As one preferable scheme, the concentration of the MXene dispersion liquid is 0.05mg/ml-5 mg/ml.
Preferably, the MXene dispersion liquid comprises Ti2CTx、Nb2CTx、V2CTx、TiNbCTx、Ti3CNTx、Ti3C2Tx、Ta4C3TxOr Nb4C3TxAny one or any combination of two or more of them, but not limited thereto;
preferably, the inert gas used in the inert atmosphere includes any combination of two or more of nitrogen, helium, argon, neon and xenon, but is not limited to these.
More preferably, the inert gas is one or any combination of two of nitrogen and argon.
Further, the combination ratio of the nitrogen to the argon is nitrogen: and argon gas accounts for 0.01: 100-100: 0.01. As one of the preferred solutions, the aeration rate is between 0.1ml/min and 2L/min.
Further, the ventilation time is between 1min and 360 min.
As one of the preferable schemes, the mixed environment temperature is 0-35 ℃.
Further, the mixing manner includes any one or any combination of two or more of magnetic stirring, mechanical stirring and ultrasonic stirring, but is not limited thereto.
Further, the mixing time is 0.5 to 4 hours.
Preferably, the mixing process comprises subjecting the dispersion to ultrasound in an ice-water bath.
Further, the ultrasonic time is 0.1-2 hours.
Furthermore, the ultrasonic power is 40-1500W.
Preferably, the mixing process comprises freezing the sonicated dispersion in a-10 ℃ cold trap.
Further, the freezing time is 0.5 to 10 hours.
As one preferable scheme, the cross-linking agent comprises ethylenediamine, triethylamine and Fe3+，Ca2+，La3+，K+Or Na+One or any combination of two or more of them, but not limited thereto.
Further, the ratio of the cross-linking agent to MXene is between 0.01:1 and 0.01 and 10.
As one of the preferable schemes, the standing time is 0.5 to 72 hours;
further, the temperature of the standing environment is 5-35 ℃;
as one of the preferable schemes, the circulation freezing and drying process comprises solvent replacement, circulation freezing and drying.
Further, the solvent replacement comprises soaking MXene purple phosphorus alkene composite sponge containing solvent in deionized water.
Furthermore, the soaking time is 1-12 hours, and the repeated times are 1-100 times.
Further, the first step of the cyclic freezing is to freeze the aqueous MXene purple phosphorus alkene composite sponge in a cold trap.
Preferably, the freezing temperature is between-40 and-60 ℃, the freezing time is 0.5 to 36 hours, and then the temperature is returned to the room temperature.
Further, the second step of the cyclic freezing is to put the aqueous MXene purple phosphorus alkene composite sponge which is recovered to the room temperature into a cold trap again for freezing;
preferably, the freezing temperature is between-20 ℃ and-40 ℃, the freezing time is between 0.5 hours and 36 hours, and then the temperature is returned to the room temperature.
Further, the third step of the cyclic freezing is to put the water-containing MXene purple phosphorus alkene composite sponge which is restored to the room temperature into the cold trap again for freezing;
preferably, the freezing temperature is between-10 ℃ and-20 ℃, the freezing time is between 0.5 and 36 hours, and then the temperature is returned to the room temperature.
Further, the fourth step of cyclic freezing is to put the MXene purple phosphorus alkene composite sponge which is restored to room temperature and contains water into the cold trap again for freezing;
preferably, the freezing temperature is-1 ℃ to-10 ℃ and the freezing time is 0.5 to 36 hours.
Further, the step of freeze drying is to put the frozen MXene purple phosphorus alkene composite sponge into a vacuum kettle for freeze drying;
preferably, the pressure in the vacuum kettle for vacuum freeze drying is 10-12Pa to 6000 Pa.
More preferably, the drying time in the vacuum kettle is 0.5 to 72 hours.
The technical solution of the present invention is further described in detail by referring to several embodiments and the accompanying drawings. The examples, then, were chosen only to illustrate the invention and not to limit the scope of the invention.
Example 1
(1) Preparing an MXene purple phosphorus alkene mixed solution: 5mg of purple phosphorus alkene is added into 10ml of MXene aqueous dispersion with the concentration of 5mg/ml, and then argon gas is introduced into the dispersion at the rate of 10ml/min for 30 min. The dispersion after the inert gas introduction was magnetically stirred in a cold trap at 0 ℃ for 1 hour and then placed in an ice water bath and sonicated at 100W for 3 hours. And finally, standing and freezing the ultrasonic dispersion liquid in a cold trap at the temperature of-10 ℃ for 1 hour, and then taking out and naturally recovering to room temperature to obtain the uniformly dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 36 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 4 hours, repeated 20 times. Freezing the cleaned composite sponge in a-60 ℃ cold trap for 30min, and taking out to recover to the room temperature. Then placed in a-40 ℃ cold trap for 1 hour, and taken out to return to room temperature. Then, the mixture was put into a cold trap at-20 ℃ again to be frozen for 2 hours, and then taken out to return to room temperature. And finally, placing the sponge into a-8 ℃ cold trap for freezing for 5 hours, then placing the sponge into a vacuum drying kettle, keeping the pressure in the kettle to be less than 100Pa, and drying for 72 hours to obtain the MXene composite sponge.
The structure and performance of the MXene purple phosphorus alkene composite sponge obtained in this example are characterized: the MXene sheet diameter was 10nm and the thickness was 0.7nm, the purple phospholene sheet diameter was 10nm and the thickness was 3nm as determined by SEM and TEM tests. The BET test shows that the specific surface area of the composite sponge is 350m2The specific surface area is/g, the aperture is 4nm, the conductivity is 80000S/m, the scanning electron microscope picture is shown in figure 1a, the transmission electron microscope picture is shown in figure 1b, and the rest parameters are shown in table 1.
Example 2
(1) Preparing an MXene purple phosphorus alkene mixed solution: 1mg of purple phosphorus alkene is added into 50ml of 1mg/ml MXene aqueous dispersion, and then argon gas is introduced into the dispersion at a rate of 200ml/min for 120 min. The dispersion liquid which is completely filled with inert gas is at 0℃The cold trap of (1) was magnetically stirred for 2 hours and then placed in an ice-water bath to sonicate at 600W for 0.5 hour. Finally, the ultrasonic dispersion is carried out at-10℃And standing and freezing the mixed solution for 1.5 hours in the cold trap, and then taking out the mixed solution and naturally returning the mixed solution to room temperature to obtain the uniformly dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 24 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 6 hours, repeated 10 times. Freezing the cleaned composite sponge in a-60 ℃ cold trap for 30min, and taking out to recover to the room temperature. Then placed in a-40 ℃ cold trap for 1 hour, and taken out to return to room temperature. Then, the mixture was put into a cold trap at-20 ℃ again to be frozen for 2 hours, and then taken out to return to room temperature. And finally, placing the sponge into a-8 ℃ cold trap for freezing for 5 hours, then placing the sponge into a vacuum drying kettle, keeping the pressure in the kettle to be less than 30Pa, and drying for 40 hours to obtain the MXene composite sponge.
The structure and performance of the MXene purple phosphorus alkene composite sponge obtained in this example are characterized: the MXene sheet diameter was found to be 25nm and the thickness to be 8nm by SEM and TEM tests, and the thickness to be 5nm by the alkadiene sheet diameter. The BET test shows that the specific surface area of the composite sponge is 400m2The specific surface area is/g, the aperture is 22nm, the conductivity is 60000S/m, the scanning electron microscope picture is shown in figure 2a, the transmission electron microscope picture is shown in figure 2b, and the rest parameters are shown in table 1.
Example 3
(1) Preparing an MXene purple phosphorus alkene mixed solution: 1mg of purple phosphorus alkene is added into 100ml of MXene aqueous dispersion with the concentration of 1mg/ml, and then argon gas is introduced into the dispersion at the rate of 2ml/min for 60 min. The dispersion after the inert gas introduction was magnetically stirred in a cold trap at 0 ℃ for 1 hour and then placed in an ice water bath and sonicated at 100W for 4 hours. And finally, standing and freezing the ultrasonic dispersion liquid in a cold trap at the temperature of-10 ℃ for 1 hour, and then taking out and naturally recovering to room temperature to obtain the uniformly dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 36 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 2 hours, repeated 60 times. Freezing the cleaned composite sponge in a-60 ℃ cold trap for 30min, and taking out to recover to the room temperature. Then placed in a-40 ℃ cold trap for 1 hour, and taken out to return to room temperature. Then, the mixture was put into a cold trap at-20 ℃ again to be frozen for 2 hours, and then taken out to return to room temperature. And finally, placing the sponge into a cold trap at the temperature of-8 ℃, freezing for 5 hours, then placing the sponge into a vacuum drying kettle, keeping the pressure in the kettle to be less than 0.1Pa, and drying for 5 hours to obtain the MXene composite sponge.
The structure and performance of the MXene purple phosphorus alkene composite sponge obtained in this example are characterized: MXene was found by SEM and TEM tests to have a disc diameter of 30nm and a thickness of 20nm, and the purple phospholene was found to have a disc diameter of 15nm and a thickness of 10 nm. The BET test shows that the specific surface area of the composite sponge is 210m2(g), the pore diameter is 100nm, the conductivity is 10000S/m, the scanning electron microscope picture is shown in figure 3a, the transmission electron microscope picture is shown in figure 3b, and the rest parameters are shown in table 1.
Example 4
(1) Preparing an MXene purple phosphorus alkene mixed solution: 2mg of purple phosphorus alkene is added into 50ml of MXene water dispersion liquid with the concentration of 3mg/ml, and then argon gas is introduced into the dispersion liquid for 120min at the speed of 200 ml/min. The dispersion after the inert gas introduction was magnetically stirred in a cold trap at 0 ℃ for 2 hours and then placed in an ice water bath and sonicated at 600W for 1 hour. And finally, standing and freezing the ultrasonic dispersion liquid in a cold trap at the temperature of-10 ℃ for 1.5 hours, and then taking out and naturally recovering to room temperature to obtain the uniformly dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 24 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 10 hours, repeated 5 times. Freezing the cleaned composite sponge in a-60 ℃ cold trap for 30min, and taking out to recover to the room temperature. Then placed in a-40 ℃ cold trap for 1 hour, and taken out to return to room temperature. Then, the mixture was put into a cold trap at-20 ℃ again to be frozen for 2 hours, and then taken out to return to room temperature. And finally, placing the sponge into a-8 ℃ cold trap for freezing for 5 hours, then placing the sponge into a vacuum drying kettle, keeping the pressure in the kettle to be less than 20Pa, and drying for 20 hours to obtain the MXene composite sponge.
The structure and performance of the MXene purple phosphorus alkene composite sponge obtained in this example are characterized: MXene was found to have a disc diameter of 500nm and a thickness of 50nm by SEM and TEM tests, and an alkadiene disc diameter of 50nm and a thickness of 25 nm. The BET test shows that the specific surface area of the composite sponge is 160m2The specific surface area is/g, the pore diameter is 126nm, the conductivity is 3000S/m, the scanning electron microscope picture is shown in figure 4a, the transmission electron microscope picture is shown in figure 4b, and the rest parameters are shown in table 1.
Example 5
(1) Preparing an MXene purple phosphorus alkene mixed solution: 1mg of purple phosphorus alkene is added into 50ml of 1.5mg/ml MXene aqueous dispersion, and then argon gas is introduced into the dispersion at a rate of 200ml/min for 120 min. The dispersion after the inert gas introduction was magnetically stirred in a cold trap at 0 ℃ for 2 hours and then placed in an ice water bath and sonicated at 600W for 1 hour. And finally, standing and freezing the ultrasonically-treated dispersion liquid in a cold trap at the temperature of-10 ℃ for 1.5 hours, and then taking out the dispersion liquid and naturally returning the dispersion liquid to the room temperature to obtain the uniformly-dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 24 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 6 hours, repeated 10 times. Freezing the cleaned composite sponge in a-60 ℃ cold trap for 30min, and taking out to recover to the room temperature. Then placed in a-40 ℃ cold trap for 1 hour, and taken out to return to room temperature. Then, the mixture was put into a cold trap at-20 ℃ again to be frozen for 2 hours, and then taken out to return to room temperature. And finally, placing the sponge into a-8 ℃ cold trap for freezing for 5 hours, then placing the sponge into a vacuum drying kettle, keeping the pressure in the kettle to be less than 30Pa, and drying for 40 hours to obtain the MXene composite sponge.
The structure and performance of the MXene purple phosphorus alkene composite sponge obtained in this example are characterized: the MXene sheet diameter was 1500nm and the thickness was 50nm, the purple phospholene sheet diameter was 100nm and the thickness was 32nm as determined by SEM and TEM tests. The BET test shows that the specific surface area of the composite sponge is 113m2The specific surface area is/g, the aperture is 207nm, the conductivity is 700S/m, the scanning electron microscope picture is shown in figure 5a, the transmission electron microscope picture is shown in figure 5b, and the rest parameters are shown in table 1.
Comparative example
(1) Preparing an MXene purple phosphorus alkene mixed solution: 1mg of purple phosphorus alkene is added into 50ml of 1.5mg/ml MXene aqueous dispersion, and then argon gas is introduced into the dispersion at a rate of 200ml/min for 120 min. The dispersion after the inert gas introduction was magnetically stirred in a cold trap at 0 ℃ for 2 hours and then placed in an ice water bath and sonicated at 600W for 1 hour. And finally, standing and freezing the ultrasonically-treated dispersion liquid in a cold trap at the temperature of-10 ℃ for 1.5 hours, and then taking out the dispersion liquid and naturally returning the dispersion liquid to the room temperature to obtain the uniformly-dispersed MXene purple phosphorus alkene composite dispersion liquid.
(2) Preparing MXene purple phosphorus alkene composite sponge: adding diethylamine with one weight percent of MXene into the mixed dispersion liquid, and standing for 24 hours at 25 ℃ to obtain the block composite sponge. The composite sponge was then soaked in deionized water for 6 hours, repeated 10 times. Freezing the cleaned composite sponge in a cold trap at the temperature of-60 ℃ for 30min, taking out, recovering to room temperature, placing in a vacuum drying kettle, keeping the pressure in the kettle to be less than 30Pa, and drying for 40 hours to obtain the MXene composite sponge.
The BET test of the comparative example shows that the specific surface area of the composite sponge is about 5m2The Young modulus of the mechanical property is about 0.01KPa, the product is loose and can be dispersed by slight touch, and the product is unqualified, so that other parameter detection is not carried out.
Table 1 examples 1-5MXene purple phosphene composite sponge performance parameters.
Figure BDA0002350174820000101
Through the embodiments 1-5, the MXene purple phosphorus alkene composite sponge obtained by the technical scheme of the invention has excellent performance, the preparation process is green and environment-friendly, continuous industrial production can be realized, and the application prospect is wide.
In the above embodiments, in the preparation process of the MXene purple phosphorus alkene composite sponge, if only the first step of the freeze drying process is performed and the freeze drying of other steps is not performed (comparative example), the performance index of the MXene purple phosphorus alkene composite sponge obtained finally will be greatly reduced compared with the performance index of the whole four steps of freeze drying process, and through detection, only one step of freeze drying process is adopted, and the specific surface area of the obtained product is basically 5m2The mechanical strength is very weak, the Young modulus is about 0.01KPa, the sponge can be broken off by slight touch and is not easy to form, and the further analysis reason is that the specific surface area and the mechanical strength of the final MXene purple phosphorus alkene composite sponge are obviously reduced because a graded porous structure is difficult to obtain by only one-step freeze drying.
It should be understood that the above describes only some embodiments of the present invention, and that various other changes and modifications can be made by one skilled in the art without departing from the inventive concept herein.

Claims (10)

1. The MXene purple phosphorus alkene composite material is characterized in that MXene and purple phosphorus alkene are mutually overlapped to form a three-dimensional porous structure, and the three-dimensional porous structure comprises micropores below 2nm, mesopores of 2nm-50nm and macropores larger than 50 nm.
2. The MXene purple phosphorus alkene composite of claim 1, wherein the MXene purple phosphorus alkene composite has a pore size distribution of 0.1nm to 1 μm.
3. The MXene purple phosphorus alkene composite of claim 2, wherein the MXene purple phosphorus alkene composite has a pore size distribution of 0.1nm to 500 nm; the specific surface area is 3-500m2Per g, pore volume of 0.01cm3/g -5m3G, apparent density of 0.01g/cm3-100g/cm3The electrical conductivity is 0.01S/m to 1000S/cm, and the compressive strength is 0.1Pa-1 GPa.
4. The preparation method of the MXene purple phosphorus alkene composite material of claim 1, which is characterized by comprising the following steps:
step one, adding an ionene into an MXene dispersion liquid under an inert atmosphere, and mixing to obtain an MXene and ionene composite dispersion liquid;
step two, adding a cross-linking agent into the MXene purple phosphorus alkene composite dispersion liquid, and standing for a period of time to form the MXene purple phosphorus alkene composite dispersion liquid;
and step three, carrying out solvent replacement on the MXene purple phosphorus alkene composite wet sponge obtained by molding, and then carrying out circulating freeze drying treatment to obtain the MXene purple phosphorus alkene composite sponge.
5. The method of claim 4, wherein MXene dispersion liquid of MXene comprises Ti2CTx、Nb2CTx、V2CTx、TiNbCTx、Ti3CNTx、Ti3C2Tx、Ta4C3TxOr Nb4C3TxAny one or any combination of two or more of them.
6. The method for preparing the MXene purple phosphorus alkene composite material of claim 4, wherein the concentration of the MXene dispersion liquid in the first step is 0.05mg/mL-5mg/mlL, and the solvent used in the dispersion liquid is one or any combination of more than two of water, ethanol, DMSO, NMP or DMF.
7. The method for preparing the MXene purple phosphorus ene composite material according to claim 4, wherein the mass ratio of the purple phosphorus ene to the MXene in the first step is 1:1-1: 10.
8. The method for preparing MXene purple phosphorus alkene composite material of claim 4, wherein the process of mixing in step one comprises the following steps:
(1) introducing one or any combination of argon and nitrogen into the dispersion liquid, wherein the aeration rate is 0.1mL/min-2L/min, and the aeration time is 1min-360 min;
(2) stirring the dispersion liquid in a cold trap at 0 ℃ for 0.5-4 hours, wherein the stirring comprises one or any combination of more than two of magnetic stirring, mechanical stirring and ultrasonic stirring;
(3) carrying out ultrasonic treatment on the dispersion liquid in an ice water bath for 0.1-2 hours, wherein the ultrasonic power is 40-1500W;
(4) and standing and freezing the dispersion liquid subjected to the ultrasonic treatment in a cold trap at the temperature of-10 ℃ for 0.5 to 10 hours, and then taking out and naturally returning to the room temperature to obtain the MXene purple phosphorus alkene composite dispersion liquid with uniform dispersion.
9. The method for preparing MXene purple phosphorus alkene composite material of claim 4, wherein the cross-linking agent added in step two is ethylenediamine, triethylamine, Fe3+，Ca2+，La3+，K+Or Na+One or an arbitrary combination of two or more of them; the ratio of the cross-linking agent to MXene is 0.01:1-0.01: 10.
10. The method for preparing MXene purple phosphorus alkene composite material of claim 4, characterized in that, the three-step circulation freeze drying treatment comprises the following steps:
(1) soaking MXene purple phosphorus alkene composite sponge containing the solvent after the solvent replacement in deionized water for 1-12 hours;
(2) freezing the soaked MXene purple phosphorus alkene composite sponge in a cold trap at the temperature of 40-60 ℃ for 0.5-36 hours, and then recovering to the room temperature;
(3) putting the water-containing MXene purple phosphorus alkene composite sponge restored to the room temperature into a cold trap again for freezing at the temperature of between 20 ℃ below zero and 40 ℃ below zero for 0.5 to 36 hours, and then restoring to the room temperature;
(4) putting the MXene purple phosphorus alkene composite sponge which is recovered to the room temperature in the step (3) into a cold trap again for freezing at the temperature of-10 ℃ to-20 ℃ for 0.5-36 hours, and then recovering to the room temperature;
(5) putting the MXene purple phosphorus alkene composite sponge which is recovered to the room temperature in the step (4) into a cold trap again for freezing at the temperature of between-1 and-10 ℃ for 0.5 to 36 hours;
(6) placing the MXene purple phosphorus alkene composite sponge frozen in the step (5) into a vacuum kettle, wherein the pressure in the vacuum kettle is 10-12Pa-6000Pa, and drying in a vacuum kettle for 0.5-72 hours to obtain MXene composite sponge.
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