CN107442044B - Graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel and preparation method thereof - Google Patents
Graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel, which comprises a graphene three-dimensional framework, and a black phosphorus nanosheet and a phosphorus-containing ionic liquid which are loaded on the graphene three-dimensional framework, wherein the black phosphorus nanosheet is wrapped by the phosphorus-containing ionic liquid, and the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel has a three-dimensional porous net-shaped structure. The composite aerogel has high elasticity, high resilience, high conductivity and excellent stability, enriches the product forms of black phosphorus, expands the application range of the black phosphorus, and is expected to be applied to the fields of energy sources (aluminum ion batteries, solar batteries, lithium ion batteries and the like), catalysis, water treatment, photoelectricity, photo-thermal and the like. The invention also provides a preparation method of the composite aerogel.
Description
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel and a preparation method thereof.
Background
Black phosphorus is a new type of direct band gap two-dimensional material whose band gap can be adjusted from 0.3eV (bulk state) to 1.5eV (single layer) by the number of layers, and thus is capable of absorbing light from visible to infrared wavelengths for communication, coupled with its high carrier mobility (up to 1000cm at a thickness of 10 nm)2˙v-1˙s-1) And a higher on-off ratio (10)4) The material has great potential advantages in the fields of semiconductors, photoelectricity, photothermal and the like.
In practical applications, black phosphorus needs to be stripped into a single layer, few layers, or multiple layers (i.e., phospholenes) to develop its excellent photoelectric and photothermal properties. At present, most research reports are based on two-dimensional black phosphorus nanosheets or black phosphorus quantum dots, and no research report about black phosphorus aerogel is seen for a while. The two-dimensional black phosphorus nanosheets and the black phosphorus quantum dots mostly exist in the form of powder or solution, so that the black phosphorus materials cannot be recycled after being used. In addition, the stability problem of two-dimensional black phosphorus nanosheets and black phosphorus quantum dots remains an extremely important research topic. However, if the black phosphorus can be formed into a three-dimensional structure such as a gel/aerogel, a sponge-like structure, etc., not only the stability problem of the black phosphorus can be solved, but also potential applications of the black phosphorus, such as applications in the fields of dye-sensitized solar cells, lithium ion batteries, aluminum ion batteries, water treatment, semiconductors, photoelectricity, photothermy, medicine, etc., can be sufficiently explored. Therefore, it is very important to develop a black phosphorus based aerogel.
Disclosure of Invention
In view of this, the first aspect of the present invention provides a graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel, which has high elasticity, high recoverability, high conductivity and very excellent stability, enriches the product forms of black phosphorus, and expands the application range of black phosphorus.
In a first aspect, the invention provides a graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel, which comprises a graphene three-dimensional skeleton, and a black phosphorus nanosheet and a phosphorus-containing ionic liquid loaded on the graphene three-dimensional skeleton, wherein the black phosphorus nanosheet is wrapped by the phosphorus-containing ionic liquid, and the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel has a three-dimensional porous network structure.
The interaction between the black phosphorus nanosheets is weak, and the gel of the pure black phosphorus nanosheets cannot be built through self-assembly behavior, so that the gel needs to be formed by taking a three-dimensional porous material as a carrier. Due to the strong hydrophobicity of graphene, the pi-pi accumulation effect between graphene sheet layers and the influence of a limited space, the graphene is easy to perform self-assembly to form graphene hydrogel and can be used as a carrier to load/adsorb other nano inorganic materials.
The graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel takes a graphene three-dimensional skeleton as a carrier, wherein cations (with positive charges) of the phosphorus-containing ionic liquid and the black phosphorus nanosheet have certain interaction of 'cation-n electrons', so that the black phosphorus nanosheet is coated by the phosphorus-containing ionic liquid, the agglomeration of the black phosphorus nanosheets is prevented, the dispersibility of the black phosphorus nanosheet is remarkably improved, the stability of the black phosphorus nanosheet is greatly improved, and the degradation of oxygen and water on the black phosphorus nanosheet is avoided. In addition, the phosphorus-containing ionic liquid and the surface of the graphene have a cation-pi/pi-pi interaction, so that the black phosphorus nanosheet can be adsorbed on the surface of the graphene, and uniform and stable graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel can be finally formed.
In the invention, the black phosphorus nanosheet is coated in the body of the composite aerogel, is not exposed in the air and can be prevented from being oxidized.
In the present invention, optionally, the mass ratio of the graphene three-dimensional skeleton to the black phosphorus nanosheet is 1: (0.375-8), further 1: (2.5-8). The mass ratio of the black phosphorus nanosheet to the phosphorus-containing ionic liquid is 1: (6.25-666.7), further 1: (100-666.7). Optionally, the mass ratio of the graphene to the phosphorus-containing ionic liquid is 1: (25-2000), further 1: (250-2000).
In the invention, optionally, the porosity of the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel is 70% to 94%.
Wherein the cation of the phosphorus-containing ionic liquid is a quaternary phosphonium salt cation, and the structure of the cation is shown as the following formula:
wherein R is1、R2、R3、R4Independently selected from C1-20One of the alkyl groups.
Specifically, the quaternary phosphonium salt-based cation may be triethyl (methyl) phosphine cation, tri-n-butyl (methyl) phosphine cation, tripropyl (methyl) phosphine cation, tri-n-hexyl (methyl) phosphine cation, tri-n-octyl (methyl) phosphine cation, tri-n-dodecyl (methyl) phosphine cation, dihexyl (ethyl) (methyl) phosphine cation, di-n-butyl (ethyl) (methyl) phosphine cation, tridodecyl (methyl) phosphine cation, dihexadecyl (ethyl) phosphine cation, tetra (n-butyl) phosphine cation, tetra-n-hexyl) phosphine cation, tetrahexadecyl) phosphine cation, tetradodecyl) phosphine cation, tridecyl (ethyl) phosphine cation, tridecyl (n-butyl) phosphine cation, trihexadecyl (methyl) phosphine cation or tetra (n-eicosyl) phosphine cation.
In the present invention, optionally, the anion of the phosphorus-containing ionic liquid is fluoride, chloride, bromide, sulfate, hydrogensulfate, carbonate, phosphate, tosylate, dihydrogenphosphate, diethylphosphate, hydrogenphosphate, nitrate, methylsulfate, methylsulfonate, chloroaluminate, hexafluorophosphate, tetrafluoroborate, trifluoromethylsulfonate, thiocyanate, acetate, bis (2,4, 4-trimethylpentyl) phosphinate, bis (malonato) borate, dicyanamide, chloroaluminate, bis (oxalato) borate, bis (trifluoromethyl) imino, bis (trifluoromethanesulfonyl) imino, bis (phthalate) borate, bromochloride, decylphonate, dichlorocuprate, bis (pentafluoroethyl) phosphinate, bis (salicylato) borate, bis (trifluoromethanesulfonyl) methane, (dodecyl) benzene sulfonate, diethyl phosphonate, ethyl sulfate, ethyl sulfonate, tetracyanoborate, tetrakis (bisulfate) borate, tetrakis (methylsulfate) borate, tris (pentafluoroethyl) trifluorophosphate or trifluoroacetate.
The graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel provided by the first aspect of the invention takes a graphene three-dimensional framework as a carrier, and the black phosphorus nanosheet wrapped by the phosphorus-containing ionic liquid is loaded on the carrier.
In a second aspect, the invention provides a preparation method of a graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel, which comprises the following steps:
(1) mixing and stirring a solution containing black phosphorus nanosheets and a phosphorus-containing ionic liquid, a graphene oxide aqueous solution and a reducing agent uniformly to obtain a mixed solution;
(2) heating the mixed solution in a water bath at 75-100 ℃ under an oxygen-free condition, reacting for 1-3 hours, and obtaining graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel after the reaction is finished;
(3) and removing redundant reducing agents from the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel by sequentially adopting a hydrophilic organic solvent and deionized water, and then carrying out freeze drying to obtain the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel.
In the step (1), the mass concentration of the black phosphorus nanosheet in the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid is 0.8-1.5mg/mL, and further 1-1.5 mg/mL. The mass ratio of the black phosphorus nanosheet to the phosphorus-containing ionic liquid is 1: (6.25-666.7), further 1: (100-666.7). The solvent of the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid is a hydrophilic organic solvent, and specifically can be N-methylpyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone (CHP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Isopropanol (IPA) and the like. Preferably, the transverse dimension of the black phosphorus nanosheet is 100-800nm, and the number of layers is 5-20.
The concentration of the graphene oxide aqueous solution is 0.5-5 mg/mL; the transverse size of the graphene oxide is 3-20 mu m, and the number of layers of the graphene oxide is 1-10. Further preferably, the concentration of the graphene oxide aqueous solution is 1-4 mg/mL. The graphene oxide with the suitable size and the suitable number of layers is more beneficial to the self-assembly of the graphene oxide after the graphene oxide is reduced into graphene under the action of a reducing agent to form three-dimensional porous graphene gel.
Optionally, in the mixed solution, the mass ratio of the graphene oxide to the black phosphorus nanosheets is 1: (0.375-8).
Optionally, the graphene oxide aqueous solution and the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid are mixed by mass: the volume ratio is (10-200): 1mg/mL, further (80-200): 1mg/mL, further (80-160): 1 mg/mL.
The mass ratio of the reducing agent to the graphene oxide is (25-150): 1, further (30-150): 1. the reducing agent is mainly used for reducing graphene oxide into graphene, the graphene is self-assembled to form a graphene three-dimensional framework, and the reducing agent can be one or more of ascorbic acid, hydroiodic acid (HI), hydroquinone, hydrazine and ethylenediamine.
In the invention, the preparation method of the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid is not limited, and the solution can be prepared in the following way:
mixing the blocky black phosphorus and the phosphorus-containing ionic liquid, then grinding, adding a hydrophilic organic solvent into the mixture obtained by grinding, then carrying out probe type ultrasonic treatment for 2-6h, after the reaction is finished, carrying out centrifugal separation, and taking supernatant to obtain the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid.
More specifically, it may be: firstly, vacuum drying the phosphorus-containing ionic liquid at the temperature of 100-110 ℃ for 24-48 h; then, mixing the blocky black phosphorus and the dried phosphorus-containing ionic liquid according to the mass ratio of 1: 1-200 of the powder is added into an agate mortar for mechanical grinding for 20-60 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding a hydrophilic organic solvent to obtain a black phosphorus/phosphorus-containing ionic liquid/hydrophilic organic solvent mixed solution; and then carrying out ultrasonic treatment on the mixed solution of the black phosphorus, the phosphorus-containing ionic liquid and the hydrophilic organic solvent for 2-6 hours by using a power probe of 100-900W, after the reaction is finished, carrying out centrifugal separation, and taking supernatant fluid to obtain the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid. Wherein the rotation speed of the centrifugation can be 1000-10000 rpm.
Optionally, the volume ratio of the mass of the phosphorus-containing ionic liquid to the hydrophilic organic solvent is 0.139 to 27.77 mg/mL.
Preferably, the mass ratio of the massive black phosphorus to the dried phosphorus-containing ionic liquid is 1: (20-200).
Under the action of an organic solvent and probe type ultrasonic waves, the ground block black phosphorus is stripped, but the stripping of the black phosphorus and the secondary accumulation of the black phosphorus of the obtained lamellar are dynamic processes, and the obtained two-dimensional black phosphorus lamellar is easy to accumulate and gather again. In the application, the phosphorus-containing ionic liquid is used as an assistant or an additive for preparing the black phosphorus nanosheet, and the organic solvent and the phosphorus-containing ionic liquid show cooperativity in stripping the blocky black phosphorus, the positive ions (with positive charges) of the phosphorus-containing ionic liquid and the stripped two-dimensional black phosphorus layer have the interaction of 'positive ions-n electrons (lone pair electrons)', the interaction enables the black phosphorus nanosheets to be coated by the phosphorus-containing ionic liquid, so that secondary agglomeration of stripped black phosphorus layers is prevented, the dispersion of the two-dimensional black phosphorus layers in N-methylpyrrolidone is improved, the degradation of the black phosphorus nanosheets by oxygen and water is avoided, and a solution (namely, a mixed solution containing the black phosphorus nanosheets, the phosphorus-containing ionic liquid and an organic solvent) containing the black phosphorus nanosheets with stable properties and regular structures is obtained.
The graphene oxide aqueous solution can be prepared by adopting the following method: adding the graphene oxide powder into deionized water, and forming a uniformly dispersed and stable graphene oxide aqueous solution under the ultrasonic action.
In the step (3), optionally, the wet gel is placed in the hydrophilic organic solvent for purification for 4 to 10 days; and then purified in deionized water for 1-5 days. The hydrophilic organic solvent may specifically be N-methylpyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone (CHP), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), isopropyl alcohol (IPA), or the like. The hydrophilic organic solvent can remove reducing agent molecules and avoid the oxidation of the black phosphorus nanosheet as much as possible. Alternatively, the freeze-drying time may be 24-72 hours, and the freeze-drying temperature may be-40 to-80 ℃.
In the invention, the formation mechanism of the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid aerogel is as follows: 1) firstly, the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid, wherein the black phosphorus nanosheet and the phosphorus-containing ionic liquid have a cation-n electron interaction; 2) taking the mixed solution of the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid as a dispersion liquid of graphene oxide, reducing the graphene oxide into graphene in the presence of a reducing agent (such as ascorbic acid), and further performing self-assembly to form the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite gel. Due to the fact that the phosphorus-containing ionic liquid has the interaction of 'cation-n electrons' with the black phosphorus nanosheet and has the interaction of 'cation-pi/pi-pi' with the surface of the graphene, the black phosphorus nanosheet can be adsorbed on the surface of the graphene, and finally the uniform and stable graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel can be formed. 3) Through a freeze drying technology, the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel in the solution can be converted into graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel.
The preparation method of the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel provided by the second aspect of the invention is simple in process, and the obtained product is excellent in performance, stable and uniform.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
FIG. 1 is a macroscopic photograph of the entire reaction solution after heating in the water bath in each comparative example and example 1: (A) graphene/N-methylpyrrolidone gel (comparative example 2); (B) graphene/black phosphorus nanoplatelet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone gel (i.e., example 1); (C) graphene/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone gel (comparative example 3); (D) black phosphorus nanoplate/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone (i.e., comparative example 1);
fig. 2 is a macro photo (fig. 2A) and a micro topography (fig. 2B) of the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel obtained in example 1 of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
The block black phosphorus used in the following examples is a commercially available product, purchased from Smart Elements, Inc. The lateral dimension of the graphene oxide used in each embodiment is 3-20 μm, and the number of layers of the graphene oxide is 1-10.
Example 1
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 500mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:2000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for standby, and the concentration of the black phosphorus nanosheet is about 1 mg/mL.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
dispersing 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
Step (3), preparing the graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel, which comprises the following specific steps:
3-a): and adding 500mg of the graphene oxide aqueous solution, 5mL of the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 60mg of ascorbic acid into a glass container, and stirring to fully dissolve the ascorbic acid to obtain a uniform and stable second mixed solution.
3-b): and heating the second mixed solution in a water bath under an anaerobic condition, wherein the temperature is 95 ℃, the reaction time is 2 hours, and the anaerobic condition is to remove oxygen by bubbling inert gas argon at the flow rate of 100mL/h while heating, and the bubbling time is 2 hours. And after the reaction is finished, obtaining the graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate wet gel for later use.
3-c): and (3) putting the obtained graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate wet gel into N-methylpyrrolidone for purification for 5 days, then putting the gel into deionized water for purification for 2 days to remove redundant ascorbic acid micromolecules, and then carrying out freeze drying at-80 ℃ for 48 hours to finally obtain the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel.
Comparative example 1
Step (1), a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate (namely phosphorus-containing ionic liquid)/N-methylpyrrolidone is prepared by a solvothermal method, and the specific steps are the same as those in example 1;
step (2), adding 5mL of the mixed solution obtained in the step (1) and 60mg of ascorbic acid into a glass container, and stirring to fully dissolve the ascorbic acid to obtain a uniform and stable mixed solution;
2-b): and (3) heating the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone/ascorbic acid in water bath at the temperature of 95 ℃ under an oxygen-free condition for 2 hours. Wherein, the oxygen-free condition is to remove oxygen by bubbling inert gas argon, the flow rate of the argon is 100mL/h, and the bubbling time is 2 h. After the reaction was completed, a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone was obtained, but no formation of any gel was observed.
Comparative example 2
Step (1), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding graphene oxide powder into deionized water, wherein the concentration of the graphene oxide is 2mg/mL, and forming a graphene oxide aqueous solution under the ultrasonic action for later use.
Step (2), preparing graphene/N-methyl pyrrolidone gel, which comprises the following specific steps:
adding 500mg of graphene oxide aqueous solution, 5mL of N-methylpyrrolidone and 60mg of ascorbic acid into a glass container, stirring to fully dissolve the ascorbic acid to obtain uniform and stable mixed solution,
and heating the mixed solution in water bath at 95 ℃ under an oxygen-free condition, wherein the reaction time is 2 hours. Wherein, the oxygen-free condition is to remove oxygen by bubbling inert gas argon, the flow rate of the argon is mL/h, and the bubbling time is 2 h. And after the reaction is finished, observing the reaction liquid in the glass container, and taking a picture to obtain the gel of the graphene/N-methylpyrrolidone for later use.
Comparative example 3
Preparing a mixed solution of phosphorus-containing ionic liquid and NMP:
adding 500mg of dried tri-N-butyl (methyl) phosphine hexafluorophosphate into 180mL of N-methylpyrrolidone (NMP) to obtain a mixed solution of tri-N-butyl (methyl) phosphine hexafluorophosphate and NMP;
step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding the graphene oxide powder into deionized water, and forming a graphene oxide aqueous solution with the concentration of 2mg/mL under the ultrasonic action for later use.
Step (3), preparing the aerogel of graphene-tri-n-butyl (methyl) phosphine hexafluorophosphate, which comprises the following specific steps:
3-a) adding 500mg of graphene oxide aqueous solution, 5mL of mixed solution of tri-n-butyl (methyl) phosphine hexafluorophosphate and NMP and 60mg of ascorbic acid into a glass container, and stirring to fully dissolve the ascorbic acid to obtain uniform and stable mixed solution;
3-b) heating the mixed solution obtained in the step (3-a) in water bath at 95 ℃ under oxygen-free conditions, wherein the reaction time is 2 hours. Wherein, the oxygen-free condition is to remove oxygen by bubbling inert gas argon, the flow rate of the argon is 100mL/h, and the bubbling time is 2 h. And after the reaction is finished, observing the reaction liquid in the glass container, and taking a picture to obtain the gel of the graphene/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
3-c) purifying the obtained graphene/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone gel in N-methylpyrrolidone for 5 days, then purifying in deionized water for 2 days to remove redundant ascorbic acid micromolecules, and then carrying out freeze drying at-80 ℃ for 48 hours to finally obtain the graphene/tri-N-butyl (methyl) phosphine hexafluorophosphate aerogel. Note that this gel contained only graphene and tri-n-butyl (methyl) phosphine hexafluorophosphate, and no black phosphorus nanoplate.
FIG. 1 is a macroscopic photograph of the entire reaction solution after heating in the water bath in each comparative example and example 1: (A) graphene/N-methylpyrrolidone gel (comparative example 2); (B) graphene/black phosphorus nanoplatelet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone gel (i.e., example 1); (C) graphene/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone gel (comparative example 3); (D) black phosphorus nanoplate/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone mixed liquor (i.e., comparative example 1).
As shown in fig. 1A (i.e., comparative example 2), graphene oxide can be reduced in an organic solvent N-methylpyrrolidone and self-assembled to form a gel, but the gel content is small (i.e., the solution still appears black, and the graphene gel inside the solution resembles a "jelly"), which is shown in the case that the supernatant is black. As can be seen from the comparison between fig. 1D (i.e., comparative example 1) and fig. 1B (i.e., example 1), under the same conditions, the whole solution obtained after the black phosphorus nanosheet solution (black phosphorus nanosheet, phosphorus-containing ionic liquid, NMP) of comparative example 1 is heated in a water bath is light yellow, and no gel is observed, which indicates that the pure black phosphorus nanosheet cannot perform self-assembly to form a gel, and needs to be supported by other carriers capable of forming three-dimensional materials. In embodiment 1 (in fig. 1B) of the present invention, a graphene gel is used as a template or a carrier required for forming a black phosphorus nanosheet gel, and after adding graphene oxide and a reducing agent into a black phosphorus nanosheet solution (a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone), the graphene oxide undergoes a reduction reaction and undergoes a self-assembly behavior to form a graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite gel. Further, as is clear from the color (no black color) of the supernatant after heating in a water bath, the content of the obtained composite gel was large.
In addition, the present inventors investigated the role of tri-n-butyl (methyl) phosphine hexafluorophosphate in the gel formation process. As shown in fig. 1C, an aqueous solution of graphene oxide was mixed with tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone, and after a reducing agent was added, a hydrothermal reaction was performed, and a photograph of the resulting solution was obtained. As can be seen from fig. 1C, under the same conditions, the graphene is also gelated in the solution without black phosphorus nanoplatelets, which indicates that tri-N-butyl (methyl) phosphine hexafluorophosphate can significantly promote the gelation of graphene in the organic solvent N-methylpyrrolidone compared to fig. 1A.
Fig. 2 is a macro-photograph (fig. 2A) and a micro-topography (fig. 2B) of the graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel obtained in example 1 of the present invention. As can be seen from fig. 2A, the composite aerogel obtained in the embodiment of the present invention has very excellent macroscopic characteristics, which facilitates the recycling of black phosphorus during the application process (the large composite aerogel can be directly taken out of the system in which it is applied). As can be seen from fig. 2B, the composite aerogel obtained in the embodiment of the present invention is mainly built by stacking large graphene sheets and black phosphorus nanosheets, and has a porous structure as a whole, a high porosity (about 75%), and a high specific surface area.
Example 2
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 25mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:100 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 2mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 1mg/mL for later use.
And (3) taking 5mL of the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 3
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 5000mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:20000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
And (3) taking 5mL of the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 4
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 500mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:2000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 0.5mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 0.5mg/mL for later use.
And (3) taking 5mL of the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 5
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 500mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:2000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 5mg of graphene oxide powder into 1.25mL of deionized water, and performing ultrasonic treatment to obtain a graphene oxide aqueous solution with uniform dispersion and stable concentration of 2mg/mL for later use.
And (3) taking 5mL of the mixed solution of the black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 6
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 1000mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:4000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
And (3) adding 50mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 30mg of ascorbic acid into a glass container, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 7
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 500mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:2000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 5mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
And (3) adding 800mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 100mg of ascorbic acid into a glass container, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 8
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 5000mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:20000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
And (3) adding 1000mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 100mg of ascorbic acid into a glass container, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 9
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 500mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:2000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 0.5mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 0.5mg/mL for later use.
And (3) adding 400mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 30mg of ascorbic acid into a glass container, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
Example 10
A preparation method of graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying tri-n-butyl (methyl) phosphine hexafluorophosphate for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 250mg of dried tri-n-butyl (methyl) phosphine hexafluorophosphate into an agate mortar according to the mass ratio of 100:1000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 3 hours, wherein the ultrasonic power is 600W; and (3) carrying out centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant, wherein the supernatant is a black phosphorus nanosheet solution, namely a mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
And (3) adding 500mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone and 60mg of ascorbic acid into a glass container, and preparing the graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate composite aerogel according to the method in the embodiment 1.
And (3) testing the mechanical property and the conductivity of the high-elasticity and high-conductivity graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate aerogel prepared in the comparative example 1 and the examples 1 to 10. The test conditions for mechanical properties were as follows: the instrument equipment comprises: instron 9566, pressure transducer: 500N; testing a clamp: a compression type jig; and (3) testing conditions are as follows: room temperature; compression speed: 1 mm/min; detection mode: the recovery mode is compressed. The test conditions for electrical properties were as follows: the instrument equipment comprises: mitsubishi chemical low resistance meter (four-probe method).
In order to better demonstrate the excellent physical properties of the composite aerogel obtained by the present invention, table 1 shows the conductivity and mechanical recovery properties of the graphene/black phosphorus nanosheet/tri-n-butyl (methyl) phosphine hexafluorophosphate composite aerogel in comparative example 1 and examples 1-10.
TABLE 1
As can be seen from table 1, the black phosphorus nanoplate of the individual components (i.e., comparative example 1) could not be tested for conductivity and mechanical recovery properties due to the failure to form gel and aerogel. However, the conductivity and mechanical recovery performance of the conductive material can be tested in the embodiments 1-10 of the present invention. As can be seen from Table 1, examples 1 to 10 of the present invention all had high conductivity; in example 7, when the concentration of the precursor graphene oxide was 5mg/mL, the mass of the phosphorus-containing ionic liquid tri-N-butyl (methyl) phosphine hexafluorophosphate was 500mg, and the mass of the graphene oxide added to the mixed solution of black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate/N-methylpyrrolidone was 1000mg, the obtained graphene/black phosphorus nanosheet/tri-N-butyl (methyl) phosphine hexafluorophosphate aerogel had the best conductivity (i.e., the lowest resistance of 1.2 ohms). In addition, as can be seen from table 1, examples 1 to 10 of the present invention all have high recovery, and the recovery of the aerogel after four stretching passes is higher than 95%, showing excellent mechanical recovery.
Example 11
A preparation method of graphene/black phosphorus nanosheet/triethyl (methyl) phosphine fluoride salt composite aerogel comprises the following steps:
step (1), preparing a uniform and stable mixed solution of black phosphorus nanosheet/triethyl (methyl) phosphine villiaumite/N-methylpyrrolidone by a solvothermal method, and specifically comprising the following steps:
1-a) respectively drying triethyl (methyl) phosphine fluoride salt at 110 ℃ for 48h in vacuum;
1-b) adding 25mg of blocky black phosphorus and 250mg of dried triethyl (methyl) phosphine fluoride salt into an agate mortar according to the mass ratio of 100:1000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c), performing probe ultrasound on the first mixed solution for 4 hours at the power of 700W, performing centrifugal treatment at 5000rpm after ultrasound, and collecting supernatant to obtain a black phosphorus nanosheet solution, namely the mixed solution of black phosphorus nanosheets/triethyl (methyl) phosphine villiaumite/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
Step (3), preparing high-elasticity and high-conductivity graphene/black phosphorus nanosheet/triethyl (methyl) phosphine villiaumite aerogel, which comprises the following specific steps:
3-a): and adding 500mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/triethyl (methyl) phosphine villiaumite/N-methylpyrrolidone and 60mg of ascorbic acid into a glass container, and stirring to fully dissolve the ascorbic acid to obtain a uniform and stable second mixed solution.
3-b): and heating the second mixed solution in a water bath under an anaerobic condition, wherein the temperature is 75 ℃, the reaction time is 3 hours, and the anaerobic condition is to remove oxygen by bubbling inert gas argon at the flow rate of 100mL/h while heating, and the bubbling time is 3 hours. And after the reaction is finished, obtaining the graphene/black phosphorus nanosheet/triethyl (methyl) phosphine fluoride salt wet gel for later use.
3-c): and (3) purifying the obtained graphene/black phosphorus nanosheet/triethyl (methyl) phosphine villiaumite wet gel in N-methylpyrrolidone for 5 days, then purifying the gel in deionized water for 2 days to remove redundant ascorbic acid micromolecules, and then carrying out freeze drying at-80 ℃ for 48 hours to finally obtain the graphene/black phosphorus nanosheet/triethyl (methyl) phosphine villiaumite composite aerogel.
Example 12
A preparation method of graphene/black phosphorus nanosheet/tripropyl (methyl) phosphonium chloride composite aerogel comprises the following steps:
the method comprises the following steps of (1) preparing a uniform and stable mixed solution of black phosphorus nanosheet/tripropyl (methyl) phosphine chloride salt/N-methylpyrrolidone by a solvothermal method, wherein the method comprises the following specific steps:
1-a) respectively drying the tripropyl (methyl) phosphine chloride salt for 48h under vacuum at 110 ℃;
1-b) adding 25mg of blocky black phosphorus and 250mg of dried tripropyl (methyl) phosphine chloride salt into an agate mortar according to the mass ratio of 100:1000 for mechanical grinding for 40 minutes; after grinding, transferring the black phosphorus/phosphorus-containing ionic liquid compound into a round-bottom flask, and adding 180mL of N-methylpyrrolidone (NMP) to obtain a first mixed solution;
1-c) performing probe ultrasonic treatment on the first mixed solution for 4 hours at the power of 700W, performing centrifugal treatment at 5000rpm after ultrasonic treatment, and collecting supernatant to obtain a black phosphorus nanosheet solution, namely the mixed solution of black phosphorus nanosheets/tripropyl (methyl) phosphine chloride salt/N-methylpyrrolidone for later use.
Step (2), preparing a uniformly dispersed and stable graphene oxide aqueous solution, which comprises the following specific steps:
adding 2mg of graphene oxide powder into 1mL of deionized water, and performing ultrasonic treatment to obtain a uniformly dispersed and stable graphene oxide aqueous solution with the concentration of 2mg/mL for later use.
Step (3), preparing high-elasticity and high-conductivity graphene/black phosphorus nanosheet/tripropyl (methyl) phosphine chloride aerogel, which comprises the following specific steps:
3-a): and adding 500mg of graphene oxide aqueous solution, 5mL of mixed solution of black phosphorus nanosheet/tripropyl (methyl) phosphine chloride salt/N-methylpyrrolidone and 60mg of ascorbic acid into a glass container, and stirring to fully dissolve the ascorbic acid to obtain a uniform and stable second mixed solution.
3-b): and heating the second mixed solution in a water bath under an anaerobic condition, wherein the temperature is 100 ℃, the reaction time is 1 hour, and the anaerobic condition is to remove oxygen by bubbling inert gas argon at the flow rate of 100mL/h while heating, and the bubbling time is 1 hour. And after the reaction is finished, obtaining the graphene/black phosphorus nanosheet/tripropyl (methyl) phosphine chloride wet gel for later use.
3-c): and (3) firstly placing the obtained graphene/black phosphorus nanosheet/tripropyl (methyl) phosphonium chloride wet gel in N-methylpyrrolidone for purification for 5 days, then placing the gel in deionized water for purification for 2 days to remove redundant ascorbic acid micromolecules, and then carrying out freeze drying at-80 ℃ for 48 hours to finally obtain the graphene/black phosphorus nanosheet/tripropyl (methyl) phosphonium chloride composite aerogel.
Examples 13 to 53
The phosphorus-containing ionic liquid of tri-n-butyl (methyl) phosphine hexafluorophosphate in example 1 is changed to the phosphorus-containing ionic liquid shown in table 2, and other experimental conditions are the same as in example 1, so that the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid aerogel is prepared.
TABLE 2 selection of phosphorus-containing ionic liquids and conductivity and mechanical recovery properties of the resulting composite aerogels in examples 13-53
It should be noted that, according to the disclosure and the explanation of the above description, the person skilled in the art can make variations and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and variations of the present invention should be covered by the protection 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 (8)
1. A graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel, comprising a graphene three-dimensional skeleton, and a black phosphorus nanosheet and a phosphorus-containing ionic liquid loaded on the graphene three-dimensional skeleton, wherein the black phosphorus nanosheet is wrapped by the phosphorus-containing ionic liquid, the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel has a three-dimensional porous net-shaped structure, and the mass ratio of the graphene three-dimensional skeleton to the black phosphorus nanosheet is 1: (0.375-8); the mass ratio of the black phosphorus nanosheet to the phosphorus-containing ionic liquid is 1: (6.25-666.7), wherein the cation of the phosphorus-containing ionic liquid is a quaternary phosphonium salt cation, and the structure of the cation is shown as the following formula:
wherein R is1、R2、R3、R4Independently selected from C1-20One of the alkyl groups.
2. The graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel of claim 1, wherein the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel has a porosity of 70% to 94%.
3. The graphene/black phosphorus nanoplate/phosphorus-containing ionic liquid composite aerogel according to claim 1, wherein the quaternary phosphonium salt-based cation is triethyl (methyl) phosphine cation, tri-n-butyl (methyl) phosphine cation, tripropyl (methyl) phosphine cation, tri-n-hexyl (methyl) phosphine cation, tri-n-octyl (methyl) phosphine cation, tri-n-dodecyl (methyl) phosphine cation, dihexyl (ethyl) (methyl) phosphine cation, di-n-butyl (ethyl) (methyl) phosphine cation, tridodecyl) (methyl) phosphine cation, dihexadecyl (di) phosphine cation, tetra (n-butyl) phosphine cation, tetra (n-hexyl) phosphine cation, tetra (hexadecyl) phosphine cation, tetra (dodecyl) phosphine cation, tri (decyl) (ethyl) phosphine cation, a tri (dodecyl) (n-butyl) phosphine cation, a tri (hexadecyl) (methyl) phosphine cation, or a tetra (n-eicosyl) phosphine cation.
4. A preparation method of graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel is characterized by comprising the following steps:
(1) mixing and stirring a solution containing black phosphorus nanosheets and a phosphorus-containing ionic liquid, a graphene oxide aqueous solution and a reducing agent uniformly to obtain a mixed solution; in the mixed solution, the mass ratio of the black phosphorus nanosheet to the phosphorus-containing ionic liquid is 1: (6.25-666.7), wherein the mass ratio of the graphene oxide to the black phosphorus nanosheets is 1: (0.375-8), wherein the cation of the phosphorus-containing ionic liquid is a quaternary phosphonium salt cation, and the structure is shown as the following formula:
wherein R is1、R2、R3、R4Independently selected from C1-20One of alkyl groups;
(2) heating the mixed solution in a water bath at 75-100 ℃ under an oxygen-free condition, reacting for 1-3 hours, and obtaining graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel after the reaction is finished;
(3) and removing redundant reducing agents from the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite wet gel by sequentially adopting a hydrophilic organic solvent and deionized water, and then carrying out freeze drying to obtain the graphene/black phosphorus nanosheet/phosphorus-containing ionic liquid composite aerogel.
5. The preparation method of claim 4, wherein the mass concentration of the black phosphorus nanosheets in the solution comprising black phosphorus nanosheets and the phosphorus-containing ionic liquid is from 0.8 to 1.5 mg/mL.
6. The preparation method according to claim 4, wherein the concentration of graphene oxide in the graphene oxide aqueous solution is 0.5-5mg/mL, the lateral dimension of the graphene oxide is 3-20 μm, and the number of layers is 1-10.
7. The preparation method according to claim 4, wherein the mass ratio of the reducing agent to the graphene oxide in the mixed solution is (25-150): 1.
8. the preparation method according to claim 4, wherein the solution containing the black phosphorus nanoplates and the phosphorus-containing ionic liquid is prepared by:
mixing the blocky black phosphorus and the phosphorus-containing ionic liquid, then grinding, adding a hydrophilic organic solvent into the mixture obtained by grinding, then carrying out probe type ultrasonic treatment for 2-6h, after the reaction is finished, carrying out centrifugal separation, and taking supernatant to obtain the solution containing the black phosphorus nanosheet and the phosphorus-containing ionic liquid.
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| EP2236824A2 (en) * | 2009-03-13 | 2010-10-06 | Karlsruher Institut für Technologie | Nanoporous carbon actuator |
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