CN107442044A - A kind of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel and preparation method thereof - Google Patents
A kind of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel and preparation method thereof Download PDFInfo
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- CN107442044A CN107442044A CN201611244232.7A CN201611244232A CN107442044A CN 107442044 A CN107442044 A CN 107442044A CN 201611244232 A CN201611244232 A CN 201611244232A CN 107442044 A CN107442044 A CN 107442044A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
Abstract
The invention provides a kind of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, including graphene three-dimensional framework and the black phosphorus nanometer sheet being supported on the graphene three-dimensional framework and phosphorous ionic liquid, wherein described black phosphorus nanometer sheet is wrapped up by the phosphorous ionic liquid, and the graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel has three-dimensional porous network structure.The composite aerogel has high resiliency, high recovery and high conductivity, and there is very excellent stability, it enriches the product form of black phosphorus, the application of black phosphorus has been expanded, has been expected to apply in the fields such as the energy (aluminium ion battery, solar cell, lithium ion battery etc.), catalysis, water process, photoelectricity and photo-thermal.Present invention also offers the preparation method of the composite aerogel.
Description
Technical field
The present invention relates to technical field of inorganic nano-material preparation, and more particularly to a kind of graphene ,/black phosphorus nanometer sheet/contains
Phosphonium ion liquid composite aerogel and preparation method thereof.
Background technology
Black phosphorus is a kind of new direct band gap two-dimensional material, and its band gap can be (single from 0.3eV (bulk state) to 1.5eV
Layer) it is adjusted by the number of plies, therefore can absorb from visible ray to communication with the light of infra-red range wavelength, it is higher in addition
Carrier mobility (thickness may be up to 1000cm when being 10nm2˙v-1˙s-1) and higher make-to-break ratio (104), it is in semiconductor
The fields such as field, photoelectricity and photo-thermal show great potential advantages.
In actual applications, black phosphorus need to be stripped into individual layer, few layer or multilayer black phosphorus (i.e. phosphorus alkene) competence exertion its
Excellent photoelectricity and light thermal property.At present, most of research reports are all based on two-dimentional black phosphorus nanometer sheet or black phosphorus quantum dot,
Temporarily have no that any research on black phosphorus aeroge is reported.And two-dimentional black phosphorus nanometer sheet and black phosphorus quantum dot are more with powder or molten
The form of liquid is present, and this causes these black phosphorus materials to will be unable to recycling after use.In addition, two-dimentional black phosphorus nanometer sheet and
The stability problem of black phosphorus quantum dot is still an extremely important research topic.However, if black phosphorus can form three-dimensional
Structure, gel/aeroge, spongelike structure etc., can not only solve the stability problem of black phosphorus, and can fully send out
The potential application of black phosphorus is dug, such as in DSSC, lithium ion battery, aluminium ion battery, water process, is partly led
Application in the fields such as body, photoelectricity, photo-thermal, medical science.Therefore, develop a kind of aeroge based on black phosphorus and seem extremely important.
The content of the invention
In consideration of it, first aspect present invention provides a kind of graphene/black phosphorus nanometer sheet/compound airsetting of phosphorous ionic liquid
Glue, the composite aerogel has high resiliency, high recovery and high conductivity, and has very excellent stability, and it is enriched
The product form of black phosphorus, the application of black phosphorus is expanded.
In a first aspect, the invention provides a kind of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, bag
Graphene three-dimensional framework and the black phosphorus nanometer sheet being supported on the graphene three-dimensional framework and phosphorous ionic liquid are included, its
Described in black phosphorus nanometer sheet wrapped up by the phosphorous ionic liquid, the graphene/black phosphorus nanometer sheet/phosphorous ionic liquid is compound
Aeroge has three-dimensional porous network structure.
Because the interphase interaction of black phosphorus nanometer sheet is weaker, black phosphorus nanometer sheet can not be built by self assembly behavior
Gel, so needing to form gel as carrier by a kind of three-dimensional porous material.And strong-hydrophobicity, the graphene of graphene
Pi-pi accumulation effect and the influence of restricted clearance, graphene between lamella easily occur self assembly behavior and form graphene water
Gel, and other nano inorganic materials can be loaded/adsorbed as carrier.
The present invention graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, using graphene three-dimensional framework as
Carrier, wherein, cation (positively charged) and the black phosphorus nanometer sheet of phosphorous ionic liquid have certain " cation-n electronics "
Interaction so that black phosphorus nanometer sheet is coated by phosphorous ionic liquid, this is not only prevented between black phosphorus nanometer sheet
Reunion and significantly improve the dispersiveness of black phosphorus nanometer sheet, and substantially increase the stability of black phosphorus nanometer sheet, avoid oxygen
The degradation of gas and water to black phosphorus nanometer sheet.In addition, phosphorous ionic liquid also with graphenic surface exist " cation-π/π-
π " interacts so that black phosphorus nanometer sheet can be adsorbed on the surface of graphene, so as to ultimately form homogeneous, stable stone
Black alkene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel.
In the present invention, the black phosphorus nanometer sheet is coated among the body of composite aerogel, is not exposed in air, can
From being oxidized.
In the present invention, alternatively, the mass ratio of the graphene three-dimensional framework and the black phosphorus nanometer sheet is 1：(0.375-
8) it is further, 1：(2.5-8).The mass ratio of the black phosphorus nanometer sheet and the phosphorous ionic liquid is 1：(6.25-
666.7) it is further, 1：(100-666.7).Alternatively, the mass ratio of the graphene and phosphorous ionic liquid is 1：
(25-2000), it is further 1：(250-2000).
In the present invention, alternatively, the porosity of the graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel
For 70%-94%.
Wherein, the cation of the phosphorous ionic liquid is quaternary phosphonium salt cationoid, and structure is shown below：
Wherein, R1、R2、R3、R4Independently selected from C1-20One kind in alkyl.
Specifically, the quaternary phosphonium salt cationoid can be triethyl group (methyl) phosphine cation, three normal-butyls (methyl) phosphine
Cation, tripropyl (methyl) phosphine cation, three n-hexyls (methyl) phosphine cation, three n-octyls (methyl) phosphine cation, three
Dodecyl (methyl) phosphine cation, dihexyl (ethyl) (methyl) phosphine cation, di-n-butyl (ethyl) (methyl) phosphine sun
Ion, three (ten alkyl) (methyl) phosphine cations, two (cetyl) two (ethyl) phosphine cation, four (normal-butyl) phosphine sun from
Son, four (n-hexyl) phosphine cations, four (cetyl) phosphine cations, four (dodecyl) phosphine cations, three (ten alkyl) (second
Base) phosphine cation, three (ten alkyl) (normal-butyl) phosphine cations, three (cetyl) (methyl) phosphine cations or four (positive 20
Alkyl) phosphine cation.
In the present invention, alternatively, the anion of the phosphorous ionic liquid is fluorine ion, chlorion, bromide ion, sulfuric acid
Root, bisulfate ion, carbonate, phosphate radical, tosylate, dihydrogen phosphate, p diethylaminobenzoic acid ester group, phosphoric acid hydrogen two, nitric acid
Root, methylsulfate, pyrovinic acid root, chlorine aluminate, hexafluoro-phosphate radical, tetrafluoroborate, trifluoromethane sulfonic acid root, thiocyanic acid
Root, acetate, double (2,4,4- tri-methyl-amyl) phosphinic acids roots, double (malonate conjunction) borates, borate, dicyandiamide base,
Chlorine aluminate, double (oxalate conjunction) borates, double (trifluoromethyl) imido grpups, double (fluoroform sulphonyl) imido grpups, double (adjacent benzene
Diformazan acid group closes) borate, bromine chlorate anions, decylbenzenesulfonic acid root, dichloro copper acid group, double (pentafluoroethyl group) phosphinic acids roots, double (water
Poplar acid group closes) borate, double (trifluoromethane sulfonyl group) methyls, (dodecyl) benzene sulfonic acid root, diethyl phosphine acid group, sulfuric acid
Ethoxycarbonyl, sulfonic acid base, four cyano borate, four (bisulfate ion conjunction) borates, four (methylsulfate conjunction) borates, three
(pentafluoroethyl group) trifluoro phosphate radical or trifluoroacetic acid root.
Graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel that first aspect present invention provides, it is with graphite
Alkene three-dimensional framework is carrier, and the black phosphorus nanometer sheet of the phosphorous ionic liquid parcel of supported on carriers, the composite aerogel has high-elastic
Property, high recovery and high conductivity, and there is very excellent stability, it is expected to apply in the energy (aluminium ion battery, the sun
Can battery, lithium ion battery etc.), catalysis, water process, in the field such as photoelectricity and photo-thermal.
Second aspect, the invention provides a kind of system of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel
Preparation Method, comprise the following steps：
(1) by the solution containing black phosphorus nanometer sheet and phosphorous ionic liquid and graphene oxide water solution and reducing agent
It is mixed evenly, obtains mixed solution；
(2) mixed solution is subjected to 75-100 DEG C of heating water bath under anaerobic, reacted 1-3 hours, reaction knot
Shu Hou, obtain graphene/black phosphorus nanometer sheet/compound wet gel of phosphorous ionic liquid；
(3) it is the graphene/black phosphorus nanometer sheet/compound wet gel of phosphorous ionic liquid is organic molten using hydrophily successively
Agent and deionized water remove unnecessary reducing agent, are then freeze-dried, and obtain graphene/black phosphorus nanometer sheet/contain phosphonium ion
Liquid composite aerogel.
Wherein, in step (1), in the solution containing black phosphorus nanometer sheet and phosphorous ionic liquid, black phosphorus nanometer sheet
Mass concentration is 0.8-1.5mg/mL, is further 1-1.5mg/mL.The black phosphorus nanometer sheet and the matter of phosphorous ionic liquid
Amount is than being 1：(6.25-666.7), it is further 1：(100-666.7).It is described to contain black phosphorus nanometer sheet and phosphorous ionic liquid
The solvent of solution be hydrophilic organic solvent, can be specifically 1-METHYLPYRROLIDONE (NMP), N- cyclohexyl -2- pyrrolidines
Ketone (CHP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), isopropanol (IPA) etc..Preferably, the black phosphorus is received
The lateral dimension of rice piece is 100-800nm, and the number of plies is 5-20 layers.
The concentration of the graphene oxide water solution is 0.5-5mg/mL；The lateral dimension of the graphene oxide is 3-20
μm, the number of plies of the graphene oxide is 1-10 layers.It is further preferred that the concentration of the graphene oxide water solution is 1-
4mg/mL.It is adapted to the graphene oxide of size and the number of plies to be more beneficial for graphene oxide and is reduced into graphene under reducing agent effect
After be self-assembly of three-dimensional porous Graphene gel.
Alternatively, in the mixed solution, the quality of graphene oxide is 1 with the mass ratio of black phosphorus nanometer sheet：(0.375-
8)。
Alternatively, the graphene oxide water solution is pressed with the solution containing black phosphorus nanometer sheet and phosphorous ionic liquid
Quality：Volume ratio is (10-200)：1mg/mL is mixed, and is further (80-200)：1mg/mL, it is further (80-
160)：1mg/mL.
The mass ratio of the reducing agent and the graphene oxide is (25-150)：1, it is further (30-150)：1.
Reducing agent is mainly used in graphene oxide being reduced into graphene, and graphene is self-assembly of graphene three-dimensional framework again,
The reducing agent can be the one or more in ascorbic acid, hydroiodic acid (HI), hydroquinones, buzane and ethylenediamine.
In the present invention, the preparation method of the solution containing black phosphorus nanometer sheet and phosphorous ionic liquid is unlimited, Ke Yishi
It is prepared in the following way：
It is ground after block black phosphorus, phosphorous ionic liquid are mixed, adding hydrophily into grinding gained mixture has
Solvent, probe type ultrasonic 2-6h is then carried out, after reaction terminates, centrifuge, take supernatant, obtain described receiving containing black phosphorus
The solution of rice piece and phosphorous ionic liquid.
More specifically can be：Phosphorous ionic liquid is first dried in vacuo 24-48h at 100-110 DEG C；Then will be block black
Phosphorus and dried phosphorous ionic liquid are 1 in mass ratio：1-200, which is added in agate mortar, carries out mechanical lapping, and the time is
20-60 minutes；The compound of black phosphorus/phosphorous ionic liquid is moved in round-bottomed flask after grinding, and it is organic molten to add hydrophily
Agent, obtain black phosphorus/phosphorous ionic liquid/hydrophilic organic solvent mixed liquor；Again by the black phosphorus/phosphorous ionic liquid/hydrophilic
Property organic solvent mixed liquor with 100-900W power probe ultrasound 2-6 hours, after reaction terminates, centrifuge, take supernatant,
Obtain the solution containing black phosphorus nanometer sheet and phosphorous ionic liquid.Wherein, the rotating speed of the centrifugation can be 1000 revs/min~
10000 revs/min.
Alternatively, the quality of phosphorous ionic liquid and the volume ratio of the hydrophilic organic solvent are 0.139-27.77mg/
mL。
Preferably, the mass ratio of the block black phosphorus and dried phosphorous ionic liquid is 1：(20-200).
Organic solvent and probe type ultrasonic effect under, the block black phosphorus after grinding is lifted off of, but the stripping of black phosphorus and
The secondary accumulation of gained lamella black phosphorus is a dynamic process after stripping, and gained two dimension black phosphorus lamella is easy to accumulate again, gathered
Collection.Phosphorous ionic liquid is as the auxiliary agent or additive for preparing black phosphorus nanometer sheet in the application, the organic solvent and phosphorous
Ionic liquid shows concertedness in the block black phosphorus of stripping, on the one hand, the cation (positively charged) of the phosphorous ionic liquid
The interaction of " cation-n electronics (lone pair electrons) ", this interaction with being stripped the two-dimentional black phosphorus lamella to come be present
So that black phosphorus nanometer sheet is coated by phosphorous ionic liquid, the secondary group between the black phosphorus lamella for being stripped and coming not only is prevented
It is poly-, it is scattered in 1-METHYLPYRROLIDONE to improve two-dimentional black phosphorus lamella, it is thus also avoided that oxygen and water are to black phosphorus nanometer sheet
Degradation, the solution of stable, compound with regular structure the black phosphorus nanometer sheet containing property is obtained (that is, containing black phosphorus nanometer sheet, containing phosphonium ion
The mixed solution of liquid, organic solvent).
The graphene oxide water solution can be prepared in the following way：Graphene oxide powder is added to
In ionized water, scattered homogeneous, stable graphene oxide water solution is formed under ultrasonication.
In step (3), alternatively, the wet gel is placed in the hydrophilic organic solvent and purified 4-10 days；Put again
Purified 1-5 days in deionized water.Hydrophilic organic solvent can be specifically 1-METHYLPYRROLIDONE (NMP), N- cyclohexyl -2-
Pyrrolidones (CHP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), isopropanol (IPA) etc..Hydrophily is organic molten
Agent is except that can remove reduction agent molecule, moreover it is possible to avoid the oxidation of black phosphorus nanometer sheet as far as possible.Alternatively, the time of freeze-drying can
To be 24-72 hours, the temperature of freeze-drying is -40~-80 DEG C.
In the present invention, the formation mechenism of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid aeroge is：1) it is first, described
Between solution containing black phosphorus nanometer sheet and phosphorous ionic liquid, wherein black phosphorus nanometer sheet and phosphorous ionic liquid exist " sun from
The interaction of son-n electronics "；2) using the mixed solution of the above-mentioned solution for containing black phosphorus nanometer sheet and phosphorous ionic liquid as
The dispersion liquid of graphene oxide, graphene oxide is reduced to graphene in the presence of reducing agent (such as ascorbic acid), and then
Generation self assembly, form graphene/black phosphorus nanometer sheet/phosphorous ionic liquid plural gel.Due to phosphorous ionic liquid not only and
There is the interaction of " cation-n electronics " in black phosphorus nanometer sheet, and it has " cation-π/π-π " phase with graphenic surface
Interaction, this enable black phosphorus nanometer sheet adsorb on the surface of graphene, can finally be formed homogeneous, stable graphene/
Black phosphorus nanometer sheet/compound the wet gel of phosphorous ionic liquid.3), can be by graphene/black phosphorus in solution by Freeze Drying Technique
Nanometer sheet/compound wet gel of phosphorous ionic liquid is changed into graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel.
The preparation side for graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel that second aspect of the present invention provides
Method, technique is simple, products obtained therefrom excellent performance, stable uniform.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is the photomacrograph of W-response liquid after heating water bath in each comparative example and embodiment 1：(A) graphene/
1-METHYLPYRROLIDONE gel (comparative example 2)；(B) normal-butyl (methyl) the phosphine hexafluorophosphate of graphene/black phosphorus nanometer sheet/tri-/
1-METHYLPYRROLIDONE gel (i.e. embodiment 1)；(C) normal-butyl (methyl) the phosphine hexafluorophosphate of graphene/tri-/N- methylpyrroles
Alkanone gel (comparative example 3)；(D) normal-butyl (methyl) the phosphine hexafluorophosphate of black phosphorus nanometer sheet/tri-/1-METHYLPYRROLIDONE is (i.e.
Comparative example 1)；
Fig. 2 is the grand of gained graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel in the embodiment of the present invention 1
Take piece (Fig. 2A) and microscopic appearance figure (Fig. 2 B) into consideration.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to following specific embodiment.In the range of constant principal right, can be suitably carry out change implementation.
Block black phosphorus used is commercial goods in following embodiments, is bought from Smart Elements Co., Ltds.Respectively
The lateral dimension of graphene oxide used in embodiment is 3-20 μm, and the number of plies of the graphene oxide is 1-10 layers.
Embodiment 1
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg in mass ratio
For 100:2000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, stand-by, the concentration of wherein black phosphorus nanometer sheet is about 1mg/mL.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is distributed in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) prepares normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-, its
Comprise the following steps that：
3-a)：Take normal-butyl (methyl) phosphine six of the above-mentioned black phosphorus nanometer sheet of the above-mentioned graphene oxide water solutions of 500mg, 5mL/tri-
The mixed solution of fluorophosphate/1-METHYLPYRROLIDONE and 60mg ascorbic acid are added in glass container, are stirred
The second mixed solution of stable homogeneous is obtained fully to dissolve ascorbic acid.
3-b)：Above-mentioned second mixed solution is subjected to heating water bath under anaerobic, temperature is 95 DEG C, and the reaction time is
2 hours, wherein, oxygen free condition is to carry out deoxygenation by using inert gas bubbling argon, and the flow velocity of argon gas is 100mL/h, Bian Jia
Hot snare drum bubble, the bubbling time is 2h.After reaction terminates, normal-butyl (methyl) the phosphine hexafluoro phosphorus of graphene/black phosphorus nanometer sheet/tri- is obtained
Hydrochlorate wet gel, it is stand-by.
3-c)：Graphene obtained above/black phosphorus nanometer sheet/tri- normal-butyl (methyl) phosphine hexafluorophosphate wet gels are first
It is placed in 1-METHYLPYRROLIDONE and purifies 5 days, then is placed in deionized water and purifies 2 days to remove small point of unnecessary ascorbic acid
Son, then carries out being freeze-dried for 48 hours at -80 DEG C, finally gives normal-butyl (methyl) phosphine of graphene/black phosphorus nanometer sheet/tri-
Hexafluorophosphate composite aerogel.
Comparative example 1
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate (i.e. phosphorous ionic liquid)/1-METHYLPYRROLIDONE, its specific steps is the same as embodiment 1；
Step (2) takes mixed solution and 60mg ascorbic acid obtained by 5mL steps (1) to be added in glass container, carries out
Stir fully to dissolve the mixed solution that ascorbic acid has reached stable homogeneous；
2-b)：By normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned black phosphorus nanometer sheet/tri-/1-METHYLPYRROLIDONE/anti-bad
The mixed solution of hematic acid carries out heating water bath under 95 DEG C, oxygen free condition, and the reaction time is 2 hours.Wherein, oxygen free condition is logical
The bubbling deoxygenation of inert gas argon gas is crossed, the flow velocity of argon gas is 100mL/h, and the bubbling time is 2h.After reaction terminates, black phosphorus is obtained
The mixed solution of normal-butyl (methyl) the phosphine hexafluorophosphate of nanometer sheet/tri-/1-METHYLPYRROLIDONE, but observe any solidifying
The formation of glue.
Comparative example 2
Step (1) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder is added in deionized water, wherein, the concentration of graphene oxide is 2mg/mL, in ultrasound
It is stand-by that graphene oxide water solution is formed under effect.
Step (2) prepares the gel of graphene/1-METHYLPYRROLIDONE, and it is comprised the following steps that：
500mg graphene oxide water solution, 5mL 1-METHYLPYRROLIDONE, 60mg ascorbic acid are added to glass
In glass container, it is stirred so that ascorbic acid fully dissolves, obtains the mixed solution of stable homogeneous,
Above-mentioned mixed solution is subjected to heating water bath under 95 DEG C, oxygen free condition, the reaction time is 2 hours.Wherein, anaerobic
Condition is the bubbling deoxygenation by inert gas argon gas, and the flow velocity of argon gas is mL/h, and the bubbling time is 2h.After reaction terminates, see
The reaction solution in glass container is examined, and is taken pictures, obtains the gel of graphene/1-METHYLPYRROLIDONE, it is stand-by.
Comparative example 3
Step (1) prepares the mixed solution of phosphorous ionic liquid and NMP:
Dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg is added to 180mL 1-METHYLPYRROLIDONE
(NMP) in, three normal-butyls (methyl) phosphine hexafluorophosphate and NMP mixed solution are obtained；
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder is added in deionized water, the oxidation stone that concentration is 2mg/mL is formed under ultrasonication
Black aqueous solution, it is stand-by.
Step (3) prepares the aeroge of the normal-butyl of graphene-three (methyl) phosphine hexafluorophosphate, and it is comprised the following steps that：
3-a) by 500mg graphene oxide water solution, 5mL three normal-butyls (methyl) phosphine hexafluorophosphate and NMP
Mixed solution and 60mg ascorbic acid are added in glass container, are stirred so that ascorbic acid fully dissolves, are obtained
The mixed solution of stable homogeneous；
The mixed solution of above-mentioned steps (3-a) 3-b) is subjected to heating water bath under 95 DEG C, oxygen free condition, the reaction time is
2 hours.Wherein, oxygen free condition is the bubbling deoxygenation by inert gas argon gas, and the flow velocity of argon gas is 100mL/h, the bubbling time
For 2h.After reaction terminates, the reaction solution in sight glass container, and being taken pictures, normal-butyl (methyl) phosphine of graphene/tri- is obtained
The gel of hexafluorophosphate/1-METHYLPYRROLIDONE, it is stand-by.
3-c) by the gel of normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned gained graphene/tri-/1-METHYLPYRROLIDONE
First it is placed in 1-METHYLPYRROLIDONE and purifies 5 days, then is placed in deionized water and purifies 2 days to remove small point of unnecessary ascorbic acid
Son, then carries out being freeze-dried for 48 hours at -80 DEG C, finally gives normal-butyl (methyl) the phosphine hexafluorophosphate of graphene/tri-
Aeroge.It should be noted that graphene and three normal-butyls (methyl) phosphine hexafluorophosphate, no black phosphorus are comprised only in this gel
Nanometer sheet.
Fig. 1 is the photomacrograph of W-response liquid after heating water bath in each comparative example and embodiment 1：(A) graphene/
1-METHYLPYRROLIDONE gel (comparative example 2)；(B) normal-butyl (methyl) the phosphine hexafluorophosphate of graphene/black phosphorus nanometer sheet/tri-/
1-METHYLPYRROLIDONE gel (i.e. embodiment 1)；(C) normal-butyl (methyl) the phosphine hexafluorophosphate of graphene/tri-/N- methylpyrroles
Alkanone gel (comparative example 3)；(D) normal-butyl (methyl) the phosphine hexafluorophosphate of black phosphorus nanometer sheet/tri-/1-METHYLPYRROLIDONE mixing
Liquid (i.e. comparative example 1).
From Figure 1A (i.e. comparative example 2), graphene oxide can occur also in organic solvent 1-METHYLPYRROLIDONE
Original is concurrently born from assembly behavior and forms gel, but its gel content is smaller that (black is still presented in ie in solution, its internal stone
Black alkene gel is similar " jelly "), this can be seen that from supernatant for black.By Fig. 1 D (i.e. comparative example 1) and Figure 1B (i.e. embodiments
1) knowable to contrast, under the same conditions, black phosphorus nanometer sheet solution (black phosphorus nanometer sheet, the phosphorous ionic liquid of comparative example 1
Body, NMP) resulting solution integrally presents light yellow after heating water bath is carried out, do not observe gel, this shows that simple black phosphorus is received
Rice piece can not occur self assembly behavior and form gel, it is necessary to by other carriers that can form three-dimensional material.And the present invention is real
Apply in example 1 (in Figure 1B), using the gel of graphene as black phosphorus nanometer sheet formed gel need template or carrier, black
Phosphorus nanometer sheet solution (mixed solution of normal-butyl (methyl) the phosphine hexafluorophosphate of black phosphorus nanometer sheet/tri-/1-METHYLPYRROLIDONE)
In, after adding graphene oxide and reducing agent, reduction reaction occurs for graphene oxide, is concurrently born from assembly behavior and forms graphite
The plural gel of alkene/black phosphorus nanometer sheet/phosphorous ionic liquid.Moreover, the color (no black) of supernatant can after heating water bath
Know, gained plural gel content is larger.
In addition, the present invention have studied effect of three normal-butyls (methyl) the phosphine hexafluorophosphate during gel-forming.Such as
Fig. 1 C, which are shown, mutually mixes the aqueous solution of graphene oxide and three normal-butyls (methyl) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE
Close, after adding reducing agent, carry out hydro-thermal reaction, resulting solution photo.From Fig. 1 C, under the same conditions, received without black phosphorus
In the solution of rice piece, equally there occurs gelation, this shows compared with Figure 1A graphene, three normal-butyls (methyl) phosphine hexafluorophosphoric acid
Salt can remarkably promote gelation of the graphene in organic solvent 1-METHYLPYRROLIDONE.
Fig. 2 is gained normal-butyl (methyl) phosphine hexafluorophosphate of graphene/black phosphorus nanometer sheet/tri- in the embodiment of the present invention 1
The photomacrograph (Fig. 2A) and microscopic appearance figure (Fig. 2 B) of composite aerogel.It is compound obtained by the embodiment of the present invention from Fig. 2A
Aeroge has very excellent macroscopic properties, be easy in application process realize to black phosphorus recycling (can directly will greatly
The composite aerogel of block takes out from the system applied).From Fig. 2 B, composite aerogel obtained by the embodiment of the present invention is main
Built by the graphene film and black phosphorus nanometer sheet of sheet by accumulation, integrally show cellular structure, have higher
Porosity (about 75%), shows higher specific surface area.
Embodiment 2
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):It is in mass ratio by block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 25mg
100:100 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound is moved in round-bottomed flask, and adds 180mL 1-METHYLPYRROLIDONE (NMP), obtains the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 2mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
1mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned black phosphorus nanometer sheets of 5mL/tri-/1-METHYLPYRROLIDONE
Mixed solution, normal-butyl (methyl) the phosphine hexafluoro phosphorus of graphene/black phosphorus nanometer sheet/tri- is prepared in the way of embodiment 1
Hydrochlorate composite aerogel.
Embodiment 3
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 5000mg in mass ratio
For 100:20000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
The compound of body is moved in round-bottomed flask, and adds 180mL 1-METHYLPYRROLIDONE (NMP), obtains the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned black phosphorus nanometer sheets of 5mL/tri-/1-METHYLPYRROLIDONE
Mixed solution, normal-butyl (methyl) the phosphine hexafluoro phosphorus of graphene/black phosphorus nanometer sheet/tri- is prepared in the way of embodiment 1
Hydrochlorate composite aerogel.
Embodiment 4
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg in mass ratio
For 100:2000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 0.5mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration
It is stand-by for 0.5mg/mL graphene oxide water solution.
Step (3) takes normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned black phosphorus nanometer sheets of 5mL/tri-/1-METHYLPYRROLIDONE
Mixed solution, normal-butyl (methyl) the phosphine hexafluoro phosphorus of graphene/black phosphorus nanometer sheet/tri- is prepared in the way of embodiment 1
Hydrochlorate composite aerogel.
Embodiment 5
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg in mass ratio
For 100:2000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 5mg is added in 1.25mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration
It is stand-by for 2mg/mL graphene oxide water solution.
Step (3) takes normal-butyl (methyl) the phosphine hexafluorophosphate of above-mentioned black phosphorus nanometer sheets of 5mL/tri-/1-METHYLPYRROLIDONE
Mixed solution, normal-butyl (methyl) the phosphine hexafluoro phosphorus of graphene/black phosphorus nanometer sheet/tri- is prepared in the way of embodiment 1
Hydrochlorate composite aerogel.
Embodiment 6
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 1000mg in mass ratio
For 100:4000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) the phosphine hexafluoro of 50mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tri-
The mixed solution of phosphate/1-METHYLPYRROLIDONE and 30mg ascorbic acid are added in glass container, according to embodiment 1
Mode normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri- is prepared.
Embodiment 7
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg in mass ratio
For 100:2000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 5mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) phosphine six of 800mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tri-
The mixed solution of fluorophosphate/1-METHYLPYRROLIDONE and 100mg ascorbic acid are added in glass container, according to implementation
Normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri- is prepared in the mode of example 1.
Embodiment 8
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 5000mg in mass ratio
For 100:20000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
The compound of body is moved in round-bottomed flask, and adds 180mL 1-METHYLPYRROLIDONE (NMP), obtains the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) phosphine six of 1000mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tri-
The mixed solution of fluorophosphate/1-METHYLPYRROLIDONE and 100mg ascorbic acid are added in glass container, according to implementation
Normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri- is prepared in the mode of example 1.
Embodiment 9
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 500mg in mass ratio
For 100:2000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 0.5mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration
It is stand-by for 0.5mg/mL graphene oxide water solution.
Step (3) takes normal-butyl (methyl) phosphine six of 400mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tri-
The mixed solution of fluorophosphate/1-METHYLPYRROLIDONE and 30mg ascorbic acid are added in glass container, according to implementation
Normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri- is prepared in the mode of example 1.
Embodiment 10
A kind of preparation method of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri-,
Comprise the following steps：
Step (1) prepares normal-butyl (methyl) the phosphine hexafluoro of homogeneous, stable black phosphorus nanometer sheet/tri- by solvent-thermal method
The mixed solution of phosphate/1-METHYLPYRROLIDONE, it is comprised the following steps that：
1-a):Three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b):By block black phosphorus 25mg and dried three normal-butyl (methyl) phosphine hexafluorophosphate 250mg in mass ratio
For 100:1000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and add 180mL 1-METHYLPYRROLIDONE (NMP), obtain the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 3h, ultrasonic power 600W；In 5000rpm after ultrasound
Lower carry out centrifugal treating, supernatant is collected, supernatant is black phosphorus nanometer sheet solution, i.e. normal-butyl (the first of black phosphorus nanometer sheet/tri-
Base) phosphine hexafluorophosphate/1-METHYLPYRROLIDONE mixed solution, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) takes normal-butyl (methyl) phosphine six of 500mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tri-
The mixed solution of fluorophosphate/1-METHYLPYRROLIDONE and 60mg ascorbic acid are added in glass container, according to implementation
Normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene/black phosphorus nanometer sheet/tri- is prepared in the mode of example 1.
By the normal-butyl of high resiliency, highly conductive graphene/black phosphorus nanometer sheet prepared by comparative example 1, embodiment 1~10/tri-
(methyl) phosphine hexafluorophosphate aeroge carries out the test of mechanical property and electric conductivity.The test condition of mechanical property is as follows：Instrument
Device equipment：Instron puller system (Instron 9566), pressure sensor：500N；Test fixture：Compression-type fixture；Test
Condition：Room temperature；Compression speed：1mm/min；Detection pattern：Compression reaction pattern.The test condition of electric property is as follows：Instrument
Equipment：Mitsubishi Chemical's low-resistance instrument (four probe method).
In order to preferably prove the excellent physical property of composite aerogel obtained by the present invention, table 1 gives comparative example 1 and reality
Apply the electric conductivity and power of normal-butyl (methyl) the phosphine hexafluorophosphate composite aerogel of graphene in a 1-10/black phosphorus nanometer sheet/tri-
Learn recoverability.
Table 1
As shown in Table 1, the black phosphorus nanometer sheet (i.e. comparative example 1) of independent component can not because it can not form gel and aeroge
Test its electric conductivity and mechanical recovery performance.However, embodiment 1~10 can test out its electric conductivity in the present invention and mechanics is extensive
Renaturation energy.As shown in Table 1, embodiment 1~10 is respectively provided with higher electric conductivity in the present invention；For embodiment 7, its preceding body
The concentration of body graphene oxide is 5mg/mL, the quality of the normal-butyl of phosphorous ionic liquid three (methyl) phosphine hexafluorophosphate is
500mg and it is added in the mixed solution of normal-butyl (methyl) the phosphine hexafluorophosphate of black phosphorus nanometer sheet/tri-/1-METHYLPYRROLIDONE
The quality of graphene oxide when being 1000mg, normal-butyl (methyl) the phosphine hexafluorophosphate of gained graphene/black phosphorus nanometer sheet/tri-
Aeroge has best electric conductivity (1.2 ohm of i.e. minimum resistance).In addition, as shown in Table 1, embodiment 1 in the present invention~
10 are respectively provided with higher recovery, and the response rate of its aeroge after four stretchings are reciprocal is above 95%, shows excellent
Mechanical recovery.
Embodiment 11
A kind of preparation method of graphene/black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite composite aerogel, including it is following
Step：
Step (1) prepares homogeneous, stable black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite/N- by solvent-thermal method
The mixed solution of methyl pyrrolidone, it is comprised the following steps that：
1-a):Triethyl group (methyl) phosphine villiaumite is dried in vacuo 48h at 110 DEG C respectively；
1-b):It is 100 in mass ratio by block black phosphorus 25mg and dried triethyl group (methyl) phosphine villiaumite 250mg:
1000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By the compound of black phosphorus/phosphorous ionic liquid after grinding
Thing is moved in round-bottomed flask, and adds 180mL 1-METHYLPYRROLIDONE (NMP), obtains the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 4h, power 700W, entered after ultrasound under 5000rpm
Row centrifugal treating, supernatant is collected, obtains black phosphorus nanometer sheet solution, i.e. black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite/N- first
The mixed solution of base pyrrolidones, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) prepares high resiliency, highly conductive graphene/black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite airsetting
Glue, it is comprised the following steps that：
3-a)：Take 500mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite/N-
The mixed solution of methyl pyrrolidone and 60mg ascorbic acid are added in glass container, are stirred anti-with abundant dissolving
Bad hematic acid obtains the second mixed solution of stable homogeneous.
3-b)：Above-mentioned second mixed solution is subjected to heating water bath under anaerobic, temperature is 75 DEG C, and the reaction time is
3 hours, wherein, oxygen free condition is to carry out deoxygenation by using inert gas bubbling argon, and the flow velocity of argon gas is 100mL/h, Bian Jia
Hot snare drum bubble, the bubbling time is 3h.After reaction terminates, it is wet solidifying to obtain graphene/black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite
Glue, it is stand-by.
3-c)：Graphene obtained above/black phosphorus nanometer sheet/triethyl group (methyl) phosphine villiaumite wet gel is first placed in N- first
Purified 5 days in base pyrrolidones, then be placed in deionized water and purify 2 days to remove unnecessary ascorbic acid small molecule, then-
Carry out being freeze-dried for 48 hours at 80 DEG C, finally give graphene/black phosphorus nanometer sheet/compound airsetting of triethyl group (methyl) phosphine villiaumite
Glue.
Embodiment 12
A kind of preparation method of graphene/black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite composite aerogel, including it is following
Step：
Step (1) prepares homogeneous, stable black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite/N- by solvent-thermal method
The mixed solution of methyl pyrrolidone, it is comprised the following steps that：
1-a):Tripropyl (methyl) phosphine villaumite is dried in vacuo 48h at 110 DEG C respectively；
1-b):It is 100 in mass ratio by block black phosphorus 25mg and dried tripropyl (methyl) phosphine villaumite 250mg:
1000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；By the compound of black phosphorus/phosphorous ionic liquid after grinding
Thing is moved in round-bottomed flask, and adds 180mL 1-METHYLPYRROLIDONE (NMP), obtains the first mixed solution；
1-c):Above-mentioned first mixed solution is subjected to probe sonication 4h, power 700W, entered after ultrasound under 5000rpm
Row centrifugal treating, supernatant is collected, obtains black phosphorus nanometer sheet solution, i.e. black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite/N- first
The mixed solution of base pyrrolidones, it is stand-by.
Step (2) prepares scattered homogeneous, stable graphene oxide water solution, and it is comprised the following steps that：
Graphene oxide powder 2mg is added in 1mL deionized waters, ultrasound obtains scattered homogeneous, stable concentration and is
2mg/mL graphene oxide water solution, it is stand-by.
Step (3) prepares high resiliency, highly conductive graphene/black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite airsetting
Glue, it is comprised the following steps that：
3-a)：Take 500mg graphene oxide water solution, 5mL black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite/N-
The mixed solution of methyl pyrrolidone and 60mg ascorbic acid are added in glass container, are stirred anti-with abundant dissolving
Bad hematic acid obtains the second mixed solution of stable homogeneous.
3-b)：Above-mentioned second mixed solution is subjected to heating water bath under anaerobic, temperature is 100 DEG C, the reaction time
For 1 hour, wherein, oxygen free condition is to carry out deoxygenation by using inert gas bubbling argon, and the flow velocity of argon gas is 100mL/h, side
Snare drum bubble is heated, the bubbling time is 1h.After reaction terminates, it is wet to obtain graphene/black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite
Gel, it is stand-by.
3-c)：Graphene obtained above/black phosphorus nanometer sheet/tripropyl (methyl) phosphine villaumite wet gel is first placed in N- first
Purified 5 days in base pyrrolidones, then be placed in deionized water and purify 2 days to remove unnecessary ascorbic acid small molecule, then-
Carry out being freeze-dried for 48 hours at 80 DEG C, finally give graphene/black phosphorus nanometer sheet/compound airsetting of tripropyl (methyl) phosphine villaumite
Glue.
Embodiment 13-53
The phosphorous ionic liquid of three normal-butyls (methyl) phosphine hexafluorophosphate in embodiment 1 is changed to as shown in table 2
Phosphorous ionic liquid, other experiment conditions such as embodiment 1 is identical, and graphene/black phosphorus nanometer sheet/phosphorous ionic liquid is prepared
Aeroge.
The selection of phosphorous ionic liquid and electric conductivity and the mechanical recovery of gained composite aerogel in the embodiment 13-53 of table 2
Performance
It should be noted that according to the above description the announcement of book and with illustrate, those skilled in the art in the invention also
Above-mentioned embodiment can be changed and changed.Therefore, the invention is not limited in disclosed and described above specific real
Mode is applied, some equivalent modifications and change to the present invention should also be as within the scope of the claims of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Form any restrictions.
Claims (10)
1. a kind of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that three-dimensional including graphene
Skeleton and the black phosphorus nanometer sheet being supported on the graphene three-dimensional framework and phosphorous ionic liquid, wherein the black phosphorus is received
Rice piece is wrapped up by the phosphorous ionic liquid, and the graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel has three
Tie up porous network structure.
2. graphene as claimed in claim 1/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that institute
The mass ratio for stating graphene three-dimensional framework and the black phosphorus nanometer sheet is 1：(0.375-8)；The black phosphorus nanometer sheet contains with described
The mass ratio of phosphonium ion liquid is 1：(6.25-666.7).
3. graphene as claimed in claim 1/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that institute
The porosity for stating graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel is 70%-94%.
4. graphene as claimed in claim 1/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that institute
The cation for stating phosphorous ionic liquid is quaternary phosphonium salt cationoid, and structure is shown below：
Wherein, R1、R2、R3、R4Independently selected from C1-20One kind in alkyl.
5. graphene as claimed in claim 4/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that institute
It is triethyl group (methyl) phosphine cation to state quaternary phosphonium salt cationoid, three normal-butyls (methyl) phosphine cation, tripropyl (methyl) phosphine
Cation, three n-hexyls (methyl) phosphine cation, three n-octyls (methyl) phosphine cation, three dodecyls (methyl) phosphine sun from
Son, dihexyl (ethyl) (methyl) phosphine cation, di-n-butyl (ethyl) (methyl) phosphine cation, three (ten alkyl) (methyl) phosphines
Cation, two (cetyl) two (ethyl) phosphine cation, four (normal-butyl) phosphine cations, four (n-hexyl) phosphine cations, four
(cetyl) phosphine cation, four (dodecyl) phosphine cations, three (ten alkyl) (ethyl) phosphine cations, three (ten alkyl)
(normal-butyl) phosphine cation, three (cetyl) (methyl) phosphine cations or four (n-eicosane base) phosphine cations.
A kind of 6. preparation method of graphene/black phosphorus nanometer sheet/phosphorous ionic liquid composite aerogel, it is characterised in that including
Following steps：
(1) solution containing black phosphorus nanometer sheet and phosphorous ionic liquid is mixed with graphene oxide water solution and reducing agent
Stir, obtain mixed solution；
(2) mixed solution is subjected to 75-100 DEG C of heating water bath under anaerobic, reacted 1-3 hours, after reaction terminates,
Obtain graphene/black phosphorus nanometer sheet/compound wet gel of phosphorous ionic liquid；
(3) by the graphene/black phosphorus nanometer sheet/compound wet gel of phosphorous ionic liquid successively using hydrophilic organic solvent and
Deionized water removes unnecessary reducing agent, is then freeze-dried, obtains graphene/black phosphorus nanometer sheet/phosphorous ionic liquid
Composite aerogel.
7. preparation method as claimed in claim 6, it is characterised in that described containing black phosphorus nanometer sheet and phosphorous ionic liquid
In solution, the mass concentration of black phosphorus nanometer sheet is 0.8-1.5mg/mL, the black phosphorus nanometer sheet and the quality of phosphorous ionic liquid
Than for 1：(6.25-666.7).
8. preparation method as claimed in claim 6, it is characterised in that in the graphene oxide water solution, graphene oxide
Concentration be 0.5-5mg/mL, the lateral dimension of the graphene oxide is 3-20 μm, and the number of plies is 1-10 layers.
9. preparation method as claimed in claim 6, it is characterised in that in the mixed solution, the quality of graphene oxide with
The mass ratio of black phosphorus nanometer sheet is 1：(0.375-8), the mass ratio of the reducing agent and the graphene oxide is (25-150)：
1。
10. preparation method as claimed in claim 6, it is characterised in that described to contain black phosphorus nanometer sheet and phosphorous ionic liquid
Solution be prepared in the following way：
It is ground after block black phosphorus, phosphorous ionic liquid are mixed, it is organic molten to add hydrophily into grinding gained mixture
Agent, probe type ultrasonic 2-6h is then carried out, after reaction terminates, centrifuge, take supernatant, obtain described containing black phosphorus nanometer sheet
With the solution of phosphorous ionic liquid.
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