CN109928713B - MXene hydrogel and liquid phase assembly method thereof - Google Patents
MXene hydrogel and liquid phase assembly method thereof Download PDFInfo
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Abstract
The MXene hydrogel is obtained by reacting the following raw materials in parts by mass, wherein the MXene comprises 1-20 parts of MXene, 0.5-1 part of graphene oxide and 0.1-0.5 part of initiator. According to the method, under the assistance of a common reducing agent, the MXene nanosheets are crosslinked by utilizing the partially reduced graphene oxide sheet layer, the liquid phase assembly of MXene is directionally guided, the MXene hydrogel with a stable three-dimensional structure and a contracted volume is obtained, the three-dimensional liquid phase assembly method of MXene is developed, the method with strong flexibility and high controllability is provided for constructing a three-dimensional MXene macroscopic body, the application space of MXene-based macroscopic materials is greatly widened, and the further development significance of the two-dimensional MXene is profound.
Description
Technical Field
The invention belongs to the technical field of two-dimensional material assembly, and particularly relates to MXene hydrogel and a liquid phase assembly method thereof.
Background
MXene is a two-dimensional transition metal carbide or nitride, obtained by removing inactive metal element by etching MAX phase with villiaumite and hydrochloric acid or hydrofluoric acid, and is separated by Mn+1XnAnd T represents. The graphene structure has a unique two-dimensional layered structure, provides a diffusion channel for the insertion/extraction of ions, and has a wide application prospect in lithium ion batteries and super capacitors. Meanwhile, the MXene material has huge specific surface area, higher conductivity, good electrolyte wettability, stronger tensile and compressive capacities and higher density (3.7 g/cm)3) The electrochemical material has excellent electrochemical performance as a super capacitor electrode material, and has outstanding advantages in volume performance. However, as with other two-dimensional materials, the layered structure of MXene also presents a series of problems, since the layer-by-layer stacking greatly reduces the utilization of its specific surface area. The design and development of some MXene-based composite materials effectively improve the problem, such as flexible 'sandwich' structure Ti prepared by adopting an alternative suction filtration method3C2Tx/CNT、Ti3C2Tx/rGO、Ti3C2Txthe/OLC composite membrane, but the limited mode of adjusting and controlling the interlayer spacing is still not beneficial to the further development of MXene.
In the field of energy storage, an MXene three-dimensional porous structure is designed, a reasonable electronic conduction network and an ion transmission channel are constructed in an assembly mode of regulating and controlling a lamella, the effective specific surface area of the MXene three-dimensional porous structure is improved, the tortuosity of ion shuttling in the material is reduced, the ion transmission efficiency is optimized, the MXene three-dimensional porous structure is an effective mode for improving the thickness of an electrode of an energy storage device, and the MXene three-dimensional porous structure is expected to solve the problem of low volume energy density on the device level. In addition, three-dimensional assembly is one of the commonly used strategies for improving the stacking problem of two-dimensional material sheets, and the three-dimensional porous network has the characteristics of mutual through ion channels, larger specific surface area, rich pore layers and the like, and has stronger advantages in the fields of energy storage, adsorption and the like, so that how to construct the three-dimensional porous network based on the two-dimensional layered material is particularly important for expanding the application space of MXene. However, the flexibility of the MXene material is not as good as that of graphene, and the MXene material is graphene hydrogel which is difficult to form a three-dimensional structure like graphene.
Disclosure of Invention
In view of the above, one of the main objects of the present invention is to provide an MXene hydrogel and a liquid phase assembly method thereof, which are intended to at least partially solve at least one of the above technical problems.
In order to achieve the above object, one aspect of the present invention provides an MXene hydrogel obtained by reacting raw materials including, by mass, 1 to 20 parts of MXene, 0.5 to 1 part of graphene oxide, and 0.1 to 0.5 part of an initiator.
The MXene hydrogel liquid-phase assembly method comprises the step of adding an initiator into a mixed solution of MXene and graphene oxide to react to obtain the MXene hydrogel.
As a further aspect of the present invention, there is also provided a three-dimensional MXene block obtained by drying the hydrogel or the hydrogel produced by the method.
As a further aspect of the invention, the application of the three-dimensional MXene block in the field of energy storage or adsorption is also provided.
Based on the technical scheme, compared with the prior art, the MXene hydrogel disclosed by the invention has at least one of the following advantages:
(1) under the assistance of a common reducing agent, the MXene nanosheets are crosslinked by utilizing the partially reduced graphene oxide lamella, the liquid phase assembly of MXene is directionally guided, the hydrogel with a stable three-dimensional structure and a contracted volume based on MXene is obtained, the MXene three-dimensional liquid phase assembly method is developed, and the method with strong flexibility and high controllability is provided for constructing a three-dimensional MXene macroscopic body;
(2) the invention provides the crosslinking and synergistic effect of the amphiphilic graphene oxide in MXene liquid phase assembly, effectively reduces the concentration threshold value of a dispersion liquid for constructing an MXene-based three-dimensional communication network, and further realizes the high-efficiency inhibition of the stacking problem of two-dimensional nanosheets;
(3) the hydrogel obtained by the assembling method of the novel two-dimensional crystal MXene hydrogel can further obtain two three-dimensional porous materials with completely different pore size distribution and density, namely MXene foam and hard rod, by regulating and controlling the moisture removal mode, wherein the specific surface areas of the MXene foam and the MXene hard rod are respectively 10-180 m2The sum of the amounts of the components is 80 to 250m2The density of the mixture is 20-30 mg/cm3And 1.5 to 2.5g/cm3The application space of the MXene-based macroscopic material is greatly widened, and the MXene-based macroscopic material has profound significance for further development of the two-dimensional material MXene.
Drawings
FIG. 1 is a schematic diagram of MXene hydrogel before (left) and after (right) gelling in accordance with the present invention;
FIG. 2 is a schematic diagram of the appearance and appearance of MXene three-dimensional foam (A picture) and MXene hard rod (B picture) in the invention;
FIG. 3 is a SEM structural representation of the MXene three-dimensional foam structure in the invention;
fig. 4 is a structural representation of SEM of the MXene hard rod structure of the present invention.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses MXene hydrogel which is prepared by reacting the following raw materials in parts by mass, wherein the MXene hydrogel comprises 1-20 parts of MXene, 0.5-1 part of graphene oxide and 0.1-0.5 part of initiator.
Preferably, the mass ratio of MXene to graphene oxide is (1-10) to 1.
Preferably, the initiator comprises at least one of ammonia, ethylenediamine, sodium hydroxide, ethanedithiol, phloroglucinol, cysteine, ascorbic acid, hydroiodic acid, sodium bisulfite, and sodium sulfide.
Preferably, the graphene oxide is prepared by a modified Hummer's method.
The invention also discloses a liquid phase assembly method of the MXene hydrogel, which comprises the following steps:
adding an initiator into the mixed solution of MXene and graphene oxide to react to obtain MXene hydrogel.
Preferably, the mixed solution of MXene and graphene oxide is a uniform mixed dispersion obtained by ultrasonically treating the MXene dispersion and the graphene oxide dispersion in an argon atmosphere, and preferably, introducing argon into an ice water bath for ultrasonic treatment.
Preferably, the concentration of the initiator is 10-100 mmol/L.
Preferably, the concentration of MXene in the mixed solution is 1-20 mg/mL.
Preferably, the concentration of the graphene oxide in the mixed solution is 0.5-2 mg/mL.
Preferably, the MXene dispersion is obtained by etching MAX raw materials into LiF solution dissolved in hydrochloric acid.
Preferably, the reaction condition is constant temperature at normal pressure, the constant temperature is 50-100 ℃, and the reaction duration is 6-24 hours.
The invention also discloses a three-dimensional MXene block which is obtained by drying the MXene hydrogel.
Preferably, the drying method is freeze drying or capillary evaporation drying.
Preferably, it is obtained by freeze-dryingThe obtained three-dimensional MXene block is of an MXene three-dimensional foam structure, and the specific surface area of the MXene block is 10-180 m2The density of the mixture is 20-30 mg/cm3(ii) a The three-dimensional MXene block obtained by capillary evaporation drying is an MXene hard rod structure, and the specific surface area of the MXene hard rod structure is 80-250 m2A density of 1.5 to 2.5g/cm3。
Preferably, the MXene hydrogel is washed by deionized water to remove impurities and then dried.
The invention also discloses an application of the three-dimensional MXene block in the fields of energy storage and adsorption.
In a preferred embodiment, the invention adopts the following technical scheme:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min to obtain a uniform mixed dispersion liquid I;
step four, adding an initiator into the mixed dispersion liquid obtained in the step three, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container to perform constant-temperature reaction under normal pressure to obtain MXene-based hydrogel;
and step six, cleaning the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rods (obtaining macroporous foam by freeze drying and obtaining microporous hard rods by capillary evaporation drying).
As an improvement of the assembly method, in the first mixed dispersion liquid in the third step, the mass ratio of MXene to graphene oxide is (1-10) to 1.
As an improvement of the assembly method, in the first mixed dispersion liquid in the third step, the concentration of the graphene oxide is 0.5-2 mg/mL.
As an improvement of the assembly method, in the first mixed dispersion liquid in the third step, the concentration of MXene is 1-20 mg/mL.
As an improvement of the above assembling method, the initiator in step four includes at least one of ammonia, ethylenediamine, sodium hydroxide, ethanedithiol, phloroglucinol, cysteine, ascorbic acid, hydroiodic acid, sodium bisulfite, and sodium sulfide.
As an improvement of the assembly method, the concentration of the initiator in the step four is 10-100 mmol/L.
As an improvement of the assembly method, the temperature of the constant-pressure constant-temperature reaction in the step five is 50-100 ℃, and the reaction duration is 6-24 hours.
As an improvement of the assembling method, in the sixth step, the specific surface areas of the MXene foam and the MXene hard rod obtained by the different drying modes are respectively 10-180 m2The sum of the amounts of the components is 80 to 250m2The density of the mixture is 20-30 mg/cm3And 1.5 to 2.5g/cm3。
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Example 1
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 2mg/mL, and the concentration of graphene oxide is 2 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the proportion of 10mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 1/2 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 167m2G, density 21mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 245m2G, density 1.62g/cm3；
The MXene three-dimensional foam and the MXene hard rod are analyzed by an electron microscope, the structural schematic diagram of the MXene three-dimensional foam under SEM is shown in figure 3, and the structural schematic diagram of the MXene hard rod under SEM is shown in figure 4. In the liquid phase assembly process, the two-dimensional MXene nanosheets and the reduced graphene oxide sheets are mutually crosslinked, the graphene oxide sheets are assembled on a solid-liquid interface under the combined action of a pi-pi acting force and a van der Waals force between sheet layers in the process of gradually weakening the hydrophilicity, and the MXene nanosheets are jointly assembled under the crosslinking traction of the flexible graphene sheets to form a stable continuous three-dimensional network. The traction force borne by the three-dimensional network of the obtained assembly is changed by regulating and controlling the moisture removal process, and then MXene three-dimensional blocks with different densities are obtained.
Example 2
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 5mg/mL, and the concentration of graphene oxide is 0.5 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the proportion of 10mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 8 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 8/9 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 56m2G, density of 30mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 92m2G, density of 2.5g/cm3。
Example 3
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 4mg/mL, and the concentration of graphene oxide is 1 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the proportion of 10mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel, wherein the MXene-based hydrogel is shown in the right diagram of figure 1;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam (shown as a diagram A in figure 2) or hard rods (shown as a diagram B in figure 2).
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 4/5 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 126m2G, density 27mg/cm3(ii) a The obtained MXene hard rod has a specific surface area of 187m2G, density of 2.2g/cm3。
Example 4
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 4mg/mL, and the concentration of graphene oxide is 1 mg/mL;
step four, adding sodium bisulfite serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the concentration of 50mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 80 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: MXene hydrogelThe shape of the reaction vessel was matched, the hydrogel contracted to 1/3 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 138m2G, density of 30mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 198m2A density of 2.43g/cm3。
Example 5
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 4mg/mL, and the concentration of graphene oxide is 1 mg/mL;
step four, adding ethanedithiol serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the ratio of 100mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 24 hours at the temperature of 90 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 9/10 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 92m2G, density 20mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 162m2G, density 1.95g/cm3。
Example 6
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 20mg/mL, and the concentration of graphene oxide is 2 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the concentration of 30mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 8 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 19/20 of the original solution volume, and the remaining solution was colorless and transparent. The MXene three-dimensional foam obtained by the method has the specific surface area of 34m2G, density of 30mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 108m2G, density of 2.48g/cm3。
Example 7
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 10mg/mL, and the concentration of graphene oxide is 2 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to the ratio of 20mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 5/6 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 89m2G, density of 26mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 174m2G, density of 2.2g/cm3。
Example 8
A liquid phase assembly method of MXene hydrogel comprises the following steps:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining uniform mixed dispersion liquid I, wherein the concentration of MXene is 14mg/mL, and the concentration of graphene oxide is 2 mg/mL;
step four, adding ethylenediamine serving as a cross-linking agent into the mixed dispersion liquid obtained in the step three according to a ratio of 25mmol/L, and uniformly stirring to obtain a mixed dispersion liquid II;
step five, adding the mixed dispersion liquid obtained in the step four into a closed container, and carrying out constant-temperature reaction for 8 hours at the temperature of 95 ℃ under normal pressure to obtain MXene-based hydrogel;
and step six, washing the hydrogel obtained in the step five by using deionized water to remove impurities, and then carrying out freeze drying or capillary evaporation drying to remove water to obtain MXene-based three-dimensional foam or hard rod.
Practice shows that: the MXene hydrogel shape conformed to the reaction vessel, the hydrogel shrunk to 4/5 of the original solution volume, and the remaining solution was colorless and transparent. The specific surface area of MXene three-dimensional foam obtained by the method is 76m2G, density 27mg/cm3(ii) a The obtained MXene hard rod has the specific surface area of 151m2G, density of 2.6g/cm3。
Comparative example 1
A comparative case without initiator addition comprising the steps of:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step three, mixing the MXene dispersion liquid obtained in the step one with the graphene oxide dispersion liquid obtained in the step two, and introducing argon into an ice water bath for ultrasonic treatment for 30min under the protection of argon; obtaining a uniform mixed dispersion liquid I, wherein the concentration of MXene is 4mg/mL, and the concentration of graphene oxide is 1 mg/mL;
step four, adding the mixed dispersion liquid obtained in the step three into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure, so that MXene hydrogel cannot be obtained.
Practice shows that: when no initiator is involved, the graphene oxide nanosheet and the MXene nanosheet cannot be crosslinked with each other, and then gelation is achieved.
Comparative example 2
This comparative example provides a comparative case without the addition of graphene oxide, comprising the steps of:
step one, taking MAX raw materials, and etching the MAX raw materials in LiF solution dissolved in hydrochloric acid to obtain MXene dispersion liquid;
step two, preparing the MXene dispersion liquid obtained in the step one into 4mg/mL MXene dispersion liquid, adding ethylenediamine serving as a cross-linking agent according to 50mmol/L, and uniformly stirring to obtain a mixed dispersion liquid;
and step three, adding the mixed dispersion liquid obtained in the step two into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure, so that MXene hydrogel cannot be obtained.
Practice shows that: when no graphene oxide participates, MXene nanosheets cannot be crosslinked with each other to form gel.
Comparative example 3
This comparative example provides a comparative case without MXene addition comprising the following steps:
step one, preparing graphene oxide dispersion liquid by adopting an improved Hummer's method;
step two, conducting ultrasonic treatment on the MXene dispersion liquid obtained in the step one for 30min in an ice water bath under the protection of argon, wherein the concentration of the graphene oxide is 0.5 mg/mL;
step three, adding ethylenediamine serving as a cross-linking agent into the graphene oxide dispersion liquid obtained in the step two according to the proportion of 10mmol/L, and uniformly stirring to obtain a mixed dispersion liquid;
step four, adding the mixed dispersion liquid obtained in the step three into a closed container, and carrying out constant-temperature reaction for 8 hours at the temperature of 95 ℃ under normal pressure, so that MXene hydrogel cannot be obtained.
Comparative example 4
(on the basis of comparative example 3, the type and concentration of the initiator are changed into one number) step one, preparing graphene oxide dispersion liquid by adopting a modified Hummer's method;
step two, conducting ultrasonic treatment on the MXene dispersion liquid obtained in the step one for 30min in an ice water bath under the protection of argon, wherein the concentration of graphene oxide is 1 mg/mL;
step three, adding ethylenediamine serving as a cross-linking agent into the graphene oxide dispersion liquid obtained in the step two according to a ratio of 20mmol/L, and uniformly stirring to obtain a mixed dispersion liquid;
step four, adding the mixed dispersion liquid obtained in the step three into a closed container, and carrying out constant-temperature reaction for 6 hours at the temperature of 95 ℃ under normal pressure, so that MXene hydrogel cannot be obtained.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (16)
1. The MXene hydrogel is obtained by reacting the following raw materials in parts by mass, wherein the MXene hydrogel comprises 1-20 parts of MXene, 0.5-1 part of graphene oxide and 0.1-0.5 part of initiator; the initiator comprises at least one of ammonia water, ethylenediamine, sodium hydroxide, ethanedithiol, phloroglucinol, cysteine, ascorbic acid, hydroiodic acid and sodium sulfide;
wherein the mass ratio of MXene to graphene oxide is (5-10) to 1.
2. The MXene hydrogel according to claim 1, characterized in that,
the graphene oxide is prepared by adopting an improved Hummer's method.
3. The liquid phase assembly method of MXene hydrogel according to claim 1 or 2, comprising adding an initiator into the mixed solution of MXene and graphene oxide to react to obtain MXene hydrogel.
4. The method of assembling of claim 3,
the concentration of the initiator is 10-100 mmol/L.
5. The method of assembling of claim 3,
the concentration of MXene in the mixed solution is 1-20 mg/m L.
6. The method of assembling of claim 3,
the concentration of the graphene oxide in the mixed solution is 0.5-2 mg/mL.
7. The method of assembling of claim 3,
the mixed solution of MXene and graphene oxide is a uniform mixed dispersion liquid obtained by ultrasonically treating MXene dispersion liquid and graphene oxide dispersion liquid in an argon atmosphere.
8. The method of assembling of claim 7,
introducing argon gas into the MXene dispersion liquid and the graphene oxide dispersion liquid in an ice water bath in advance for ultrasonic treatment.
9. The method of assembling of claim 7,
the MXene dispersion liquid is obtained by putting MAX raw materials into LiF solution dissolved in hydrochloric acid and etching.
10. The method of assembling of claim 3,
the reaction condition is constant temperature at normal pressure, the constant temperature is 50-100 ℃, and the reaction duration is 6-24 hours.
11. A three-dimensional MXene block obtained by drying the hydrogel according to claim 1 or 2 or the hydrogel formed by the assembly method according to any one of claims 3 to 10.
12. The three-dimensional MXene block of claim 11,
the drying method is freeze drying or capillary evaporation drying.
13. The three-dimensional MXene block of claim 12,
the three-dimensional MXene block obtained by the freeze drying method is of a three-dimensional MXene foam structure, and the specific surface area of the three-dimensional MXene block is 10-180 m2The density of the mixture is 20-30 mg/cm3。
14. The three-dimensional MXene block of claim 12,
the three-dimensional MXene block obtained by capillary evaporation drying is an MXene hard rod structure, and the specific surface area of the MXene hard rod structure is 80-250 m2A density of 1.5 to 2.5g/cm3。
15. The three-dimensional MXene block of claim 11,
the MXene hydrogel is washed by deionized water to remove impurities and then dried.
16. The application of the three-dimensional MXene block as defined in any one of claims 11-15 in the field of energy storage or adsorption.
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| CN112537773B (en) * | 2019-09-20 | 2022-07-22 | 浙江工业大学 | Method for vertically growing MXene on conductive substrate |
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