CN106744855B - A kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel and preparation method thereof - Google Patents
A kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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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
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Abstract
The present invention provides a kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogels, including graphene three-dimensional framework and the black phosphorus quantum dot and phosphorous ionic liquid that are supported on the graphene three-dimensional framework, wherein the black phosphorus quantum dot is wrapped up by the phosphorous ionic liquid, and the graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel has three-dimensional porous reticular structure.The composite aerogel has high resiliency, high recovery and high conductivity, and there is very excellent stability, its product form for enriching black phosphorus, the application range for having expanded black phosphorus is expected to apply in the fields such as the energy (aluminium ion battery, solar battery, lithium ion battery etc.), catalysis, water process, photoelectricity and photo-thermal.The present invention also provides the preparation methods 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 quantum dot/contains
Phosphonium ion liquid composite aerogel and preparation method thereof.
Background technique
Black phosphorus is a kind of novel direct band gap two-dimensional material, and 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 with the light of infra-red range wavelength from visible light to communication, it is higher in addition
Carrier mobility (with a thickness of up to 1000cm when 10nm2˙v-1˙s-1) and higher make-to-break ratio (104), in semiconductor
The fields such as field, photoelectricity and photo-thermal show great potential advantages.
In practical applications, black phosphorus need to be stripped into single layer, few layer or multilayer black phosphorus (i.e. phosphorus alkene) competence exertion its
Excellent photoelectricity and light thermal property.Currently, 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 about black phosphorus aeroge is reported.And two-dimentional black phosphorus nanometer sheet and black phosphorus quantum dot are mostly with powder or molten
The form of liquid exists, this causes these black phosphorus materials to will be unable to recycling and reusing 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 is capable of forming three-dimensional
Structure, gel/aeroge, spongelike structure etc. can not only solve the stability problem of black phosphorus, and can sufficiently send out
Dig the potential application of black phosphorus, such as in dye-sensitized solar cells, lithium ion battery, aluminium ion battery, water process, partly lead
Application in the fields such as body, photoelectricity, photo-thermal, medicine.Therefore, developing a kind of aeroge based on black phosphorus seems extremely important.
Summary of the invention
In consideration of it, first aspect present invention provides a kind of graphene/black phosphorus quantum dot/compound airsetting of phosphorous ionic liquid
Glue, which has high resiliency, high recovery and high conductivity, and has very excellent stability, enriches
The product form of black phosphorus has expanded the application range of black phosphorus.
In a first aspect, the present invention provides a kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel, packet
The black phosphorus quantum dot and phosphorous ionic liquid for including graphene three-dimensional framework and being supported on the graphene three-dimensional framework,
Described in black phosphorus quantum dot wrapped up by the phosphorous ionic liquid, the graphene/black phosphorus quantum dot/phosphorous ionic liquid is compound
Aeroge has three-dimensional porous reticular structure.
It is weaker due to interacting between black phosphorus quantum dot, black phosphorus quantum dot 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 are easy to happen self assembly behavior and form graphene water
Gel, and can be used as carrier and load/adsorb other nano inorganic materials.
Graphene of the invention/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel, using graphene three-dimensional framework as
Carrier, wherein the cation (positively charged) and black phosphorus quantum dot of phosphorous ionic liquid have certain " cation-n electronics "
Interaction so that black phosphorus quantum dot is coated by phosphorous ionic liquid, this is not only prevented between black phosphorus quantum dot
Reunion and significantly improve the dispersibility of black phosphorus quantum dot, and substantially increase the stability of black phosphorus quantum dot, avoid oxygen
The degradation of gas and water to black phosphorus quantum dot.In addition, also there is " cation-π/π-with graphene surface in phosphorous ionic liquid
π " interaction, enables black phosphorus quantum dot to be adsorbed on the surface of graphene, so as to ultimately form uniform, stable stone
Black alkene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel.
In the present invention, the black phosphorus quantum dot is coated among the ontology of composite aerogel, is not exposed in air, can
From being oxidized.
In the present invention, optionally, the mass ratio of the graphene three-dimensional framework and the black phosphorus quantum dot is 1:(0.375-
It 8) is further, 1:(2.5-8).The mass ratio of the black phosphorus quantum dot and the phosphorous ionic liquid is 1:(6.25-
It 666.7) is further, 1:(100-666.7).Optionally, the mass ratio of the graphene and phosphorous ionic liquid is 1:
(25-2000) is further 1:(250-2000).
In the present invention, optionally, the graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel porosity
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 of 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) phosphines cation, two (cetyl) two (ethyl) phosphines cation, four (normal-butyl) phosphine sun from
Son, four (n-hexyl) phosphines cation, four (cetyl) phosphines cation, four (dodecyl) phosphines cation, three (ten alkyl) (second
Base) phosphine cation, three (ten alkyl) (normal-butyl) phosphines cation, three (cetyl) (methyl) phosphines cation or four (positive 20
Alkyl) phosphine cation.
In the present invention, optionally, the anion of the phosphorous ionic liquid is fluorine ion, chloride ion, 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, methane sulfonic acid root, chlorine aluminate, hexafluoro-phosphate radical, tetrafluoroborate, trifluoromethane sulfonic acid root, thiocyanic acid
Root, acetate, bis- (2,4,4- tri-methyl-amyl) phosphinic acids roots, bis- (malonate conjunction) borates, borate, dicyandiamide base,
Chlorine aluminate, bis- (oxalate conjunction) borates, bis- (trifluoromethyl) imido grpups, bis- (fluoroform sulphonyl) imido grpups, bis- (adjacent benzene
Diformazan acid group closes) borate, bromine chlorate anions, decylbenzenesulfonic acid root, dichloro copper acid group, bis- (pentafluoroethyl group) phosphinic acids roots, bis- (water
Poplar acid group closes) borate, bis- (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 quantum dot/phosphorous ionic liquid composite aerogel that first aspect present invention provides, with graphite
Alkene three-dimensional framework is carrier, and the black phosphorus quantum dot of the phosphorous ionic liquid package of supported on carriers, which has high-elastic
Property, high recovery and high conductivity, and there is very excellent stability, be expected to apply in the energy (aluminium ion battery, the sun
Can battery, lithium ion battery etc.), catalysis, water process, in the fields such as photoelectricity and photo-thermal.
Second aspect, the present invention provides a kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel systems
Preparation Method, comprising the following steps:
(1) by the solution containing black phosphorus quantum dot 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, is reacted 1-3 hours, reaction knot
Shu Hou obtains graphene/black phosphorus quantum dot/compound wet gel of phosphorous ionic liquid；
(3) successively use hydrophily organic molten the graphene/black phosphorus quantum dot/compound wet gel of phosphorous ionic liquid
Agent and deionized water remove extra reducing agent, are then freeze-dried, and graphene/black phosphorus quantum dot/containing phosphonium ion is obtained
Liquid composite aerogel.
Wherein, in step (1), in the solution containing black phosphorus quantum dot and phosphorous ionic liquid, black phosphorus quantum dot
Mass concentration is 0.8-1.5mg/mL, is further 1-1.5mg/mL.The matter of the black phosphorus quantum dot and 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 quantum dot and phosphorous ionic liquid
Solution solvent be hydrophilic organic solvent, specifically can be N-Methyl pyrrolidone (NMP), N- cyclohexyl -2- pyrrolidines
Ketone (CHP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), isopropanol (IPA) etc..
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 suitble to the graphene oxide of size and the number of plies to be more advantageous to graphene oxide
Three-dimensional porous Graphene gel is self-assembly of after being reduced into graphene under reducing agent effect.
Optionally, in the mixed solution, the quality of graphene oxide and the mass ratio of black phosphorus quantum dot are 1:(0.375-
8)。
Optionally, the graphene oxide water solution is pressed with the solution containing black phosphorus quantum dot and phosphorous ionic liquid
Quality: volume ratio is (10-200): 1mg/mL mixing, is further (80-200): 1mg/mL, 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 for for graphene oxide being reduced into graphene, and graphene is self-assembly of graphene three-dimensional framework again,
The reducing agent can be one of ascorbic acid, hydroiodic acid (HI), hydroquinone, buzane and ethylenediamine or a variety of.
In the present invention, the preparation method of the solution containing black phosphorus quantum dot and phosphorous ionic liquid is unlimited, can be
It is prepared in the following way:
It is ground after blocky black phosphorus, phosphorous ionic liquid are mixed, hydrophily, which is added, into grinding gained mixture has
Solvent, then under anaerobic, 100-160 DEG C back flow reaction 3-10 hours, after reaction, centrifuge separation, take supernatant
Liquid obtains the solution containing black phosphorus quantum dot and phosphorous ionic liquid.
More specifically may be used are as follows: phosphorous ionic liquid is first dried in vacuo 24-48h at 100-110 DEG C；It then will be blocky black
Phosphorus and it is dry after phosphorous ionic liquid be in mass ratio that 1:1-200 is added in agate mortar and carries out mechanical lapping, the time is
20-60 minutes；Black phosphorus/phosphorous ionic liquid compound is moved in round-bottomed flask after grinding, and it is organic molten that hydrophily is added
Agent obtains black phosphorus/phosphorous ionic liquid/hydrophilic organic solvent mixed liquor；Again by the black phosphorus/phosphorous ionic liquid/hydrophilic
Property organic solvent mixed liquor carry out bubbling argon deoxygenation, the time be 20-60 minutes；Then it is returned in argon gas (Ar) atmosphere, cooling water
Flow and the experiment condition that is vigorously stirred under 100-160 DEG C reaction 3-10 hours, after reaction, centrifuge separation takes supernatant,
Obtain the solution containing black phosphorus quantum dot and phosphorous ionic liquid.Wherein, the revolving speed of the centrifugation can for 1000 revs/min~
10000 revs/min.
The graphene oxide water solution can be prepared in the following way: graphene oxide powder is added to
In ionized water, is formed under ultrasonication and disperse uniform, stable graphene oxide water solution.
In step (3), optionally, the wet gel is placed in the hydrophilic organic solvent and is purified 4-10 days；It sets again
It is purified 1-5 days in deionized water.Hydrophilic organic solvent specifically can be N-Methyl pyrrolidone (NMP), N- cyclohexyl -2-
Pyrrolidones (CHP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), isopropanol (IPA) etc..Hydrophily is organic molten
Agent is in addition to can remove reduction agent molecule, moreover it is possible to avoid the oxidation of black phosphorus quantum dot as far as possible.Optionally, 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, graphene/black phosphorus quantum dot/phosphorous ionic liquid aeroge formation mechenism are as follows: 1) firstly, described
Solution containing black phosphorus quantum dot and phosphorous ionic liquid, wherein between black phosphorus quantum dot 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 quantum dot 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), in turn
Self assembly occurs, forms graphene/black phosphorus quantum dot/phosphorous ionic liquid plural gel.Due to phosphorous ionic liquid not only and
There is the interaction of " cation-n electronics " in black phosphorus quantum dot, and it has " cation-π/π-π " phase with graphene surface
Interaction, this enables black phosphorus quantum dot to be adsorbed on the surface of graphene, be finally capable of forming uniform, stable graphene/
Black phosphorus quantum dot/compound the wet gel of phosphorous ionic liquid.It 3), can be by graphene/black phosphorus in solution by Freeze Drying Technique
Quantum dot/compound wet gel of phosphorous ionic liquid is changed into graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel.
Graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel preparation side that second aspect of the present invention provides
Method, simple process, products obtained therefrom are had excellent performance, stable uniform.
Advantages of the present invention will be illustrated partially in the following description, and a part is apparent according to specification
, or can implementation through the embodiment of the present invention and know.
Detailed description of the invention
Fig. 1 is the photomacrograph of W-response liquid after heating water bath in each comparative example and embodiment 1: (A) graphene/
N-Methyl pyrrolidone gel (comparative example 2)；(B) graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/
N-Methyl pyrrolidone gel (i.e. embodiment 1)；(C) graphene/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N- methylpyrrole
Alkanone gel (comparative example 3)；(D) black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone is (i.e.
Comparative example 1)；
Fig. 2 is the shape appearance figure for the black phosphorus quantum dot being prepared in the embodiment of the present invention 1；
Fig. 3 is that gained graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel is macro in the embodiment of the present invention 1
Take piece (Fig. 3 A) and microscopic appearance figure (Fig. 3 B) into consideration.
Specific 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, without departing from the principles of the embodiments of the present invention, several improvements and modifications can also be made, these improvement
Also it is considered as the protection scope of the embodiment of the present invention 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 specific embodiment below.Within the scope of the unchanged main rights, implementation can appropriate be changed.
Bulk black phosphorus as used in the following examples is commercial goods, is bought from Smart Elements Co., Ltd.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 graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 500mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:2000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is distributed in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) prepares graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
Specific step is as follows:
3-a): taking the above-mentioned black phosphorus quantum dot of the above-mentioned graphene oxide water solution of 500mg, 5mL/tri- normal-butyls (methyl) phosphine six
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 60mg are added in glass container, are stirred
The second mixed solution of stable homogeneous is obtained sufficiently to dissolve ascorbic acid.
3-b): above-mentioned second mixed solution being 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, bubbling time are 2h.After reaction, graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro phosphorus is obtained
Hydrochlorate wet gel, for use.
3-c): graphene obtained above/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate wet gel is first
It is placed in N-Methyl pyrrolidone and purifies 5 days, then be placed in deionized water and purify 2 days to remove small point of extra ascorbic acid
Son, then carries out being freeze-dried for 48 hours at -80 DEG C, finally obtains graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine
Hexafluorophosphate composite aerogel.
Comparative example 1
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
The mixed solution of phosphate (i.e. phosphorous ionic liquid)/N-Methyl pyrrolidone, the specific steps are the same as those in embodiment 1；
Step (2) takes the ascorbic acid of mixed solution obtained by 5mL step (1) and 60mg to be added in glass container, carries out
Stirring is sufficiently to dissolve the mixed solution that ascorbic acid has reached stable homogeneous；
2-b): by above-mentioned black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone/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, black phosphorus is obtained
Quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixed solution, but do not observe any solidifying
The formation of glue.
Comparative example 2
Step (1) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder is add to 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 graphene/N-Methyl pyrrolidone gel, the specific steps of which are as follows:
The ascorbic acid of the graphene oxide water solution of 500mg, the N-Methyl pyrrolidone of 5mL, 60mg are added to glass
In glass container, it is stirred so that ascorbic acid sufficiently 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, it sees
The reaction solution in glass container is examined, and is taken pictures, obtains graphene/N-Methyl pyrrolidone gel, for use.
Comparative example 3
Step (1) prepares phosphorous ionic liquid and the mixed solution of NMP:
Three normal-butyls (methyl) phosphine hexafluorophosphate 500mg after drying is added to the N-Methyl pyrrolidone of 180mL
(NMP) in, the mixed solution of three normal-butyls (methyl) phosphine hexafluorophosphate and NMP is obtained；
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder is add to deionized water, forms the oxidation stone that concentration is 2mg/mL under ultrasonication
Black aqueous solution, for use.
Step (3) prepares the aeroge of-three normal-butyl of graphene (methyl) phosphine hexafluorophosphate, the specific steps of which are as follows:
3-a) by the graphene oxide water solution of 500mg, three normal-butyls (methyl) the phosphine hexafluorophosphate of 5mL and NMP
The ascorbic acid of mixed solution and 60mg are added in glass container, are stirred so that ascorbic acid sufficiently 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, is bubbled the time
For 2h.After reaction, the reaction solution in glass container is observed, and is taken pictures, graphene/tri- normal-butyls (methyl) phosphine is obtained
Hexafluorophosphate/N-Methyl pyrrolidone gel, for use.
3-c) by above-mentioned gained graphene/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone gel
It is first placed in N-Methyl pyrrolidone and purifies 5 days, then be placed in deionized water and purify 2 days to remove small point of extra ascorbic acid
Son, then carries out being freeze-dried for 48 hours at -80 DEG C, finally obtains graphene/tri- normal-butyls (methyl) phosphine hexafluorophosphate
Aeroge.It should be noted that containing only graphene and three normal-butyls (methyl) phosphine hexafluorophosphate, no black phosphorus in this gel
Quantum dot.
Fig. 1 is the photomacrograph of W-response liquid after heating water bath in each comparative example and embodiment 1: (A) graphene/
N-Methyl pyrrolidone gel (comparative example 2)；(B) graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/
N-Methyl pyrrolidone gel (i.e. embodiment 1)；(C) graphene/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N- methylpyrrole
Alkanone gel (comparative example 3)；(D) black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Liquid (i.e. comparative example 1).
By Figure 1A (i.e. comparative example 2) it is found that graphene oxide can occur also in organic solvent N-Methyl pyrrolidone
Original is concurrently born from assembly behavior and forms gel, but its gel content is smaller that (ie in solution is still presented black, 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. embodiment
1) comparison is it is found that under the same conditions, black phosphorus quantum dot solution (the black phosphorus quantum dot, phosphorous ionic liquid of comparative example 1
Body, NMP) acquired solution integrally presents light yellow after carrying out heating water bath, do not observe gel, this shows simple black phosphorus amount
Son point can not occur self assembly behavior and form gel, need 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 quantum dot formed gel need template or carrier, black
Phosphorus quantum dot solution (black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixed solution)
In, after graphene oxide and reducing agent is added, reduction reaction occurs for graphene oxide, is concurrently born from assembly behavior and forms graphite
Alkene/black phosphorus quantum dot/phosphorous ionic liquid plural gel.Moreover, the color (no black) of supernatant can after heating water bath
Know, gained plural gel content is larger.
In addition, the present invention has studied effect of three normal-butyls (methyl) phosphine hexafluorophosphate during gel-forming.Such as
Fig. 1 C, which is shown, mutually mixes the aqueous solution of graphene oxide and three normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone
It closes, after reducing agent is added, carries out hydro-thermal reaction, acquired solution photo.By Fig. 1 C it is found that under the same conditions, being free of black phosphorus amount
In the solution of son point, gelation is equally had occurred in graphene, this shows compared with Figure 1A, three normal-butyls (methyl) phosphine hexafluorophosphoric acid
Salt can remarkably promote gelation of the graphene in organic solvent N-Methyl pyrrolidone.
Fig. 2 is the shape appearance figure for the black phosphorus quantum dot being prepared in the embodiment of the present invention 1, it can be seen from the figure that quantum
The size of point is about 2-5nm.
Fig. 3 is gained graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate in the embodiment of the present invention 1
The photomacrograph (Fig. 3 A) and microscopic appearance figure (Fig. 3 B) of composite aerogel.It is by Fig. 3 A it is found that compound obtained by the embodiment of the present invention
Aeroge has very excellent macroscopic properties, convenient for realizing that the recycling to black phosphorus (can directly will be big in application process
The composite aerogel of block takes out from applied system).By Fig. 3 B it is found that composite aerogel obtained by the embodiment of the present invention is main
It is built by large stretch of graphene film and black phosphorus quantum dot by accumulation, integrally shows cellular structure, it is with higher
Porosity (about 75%), shows higher specific surface area.
Embodiment 2
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): being in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 25mg after blocky black phosphorus 25mg and drying
100:100, which is added in agate mortar, carries out mechanical lapping, and the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 2mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 1mg/mL, for use.
Step (3) takes the above-mentioned black phosphorus quantum dot of the above-mentioned graphene oxide water solution of 500mg, 5mL/tri- normal-butyls (methyl)
Phosphine hexafluorophosphate/mixed solution of N-Methyl pyrrolidone and the ascorbic acid of 60mg are added in glass container, according to
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of embodiment 1.
Embodiment 3
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 5000mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:20000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
The compound of body moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro of the graphene oxide water solution of 500mg, 5mL
The ascorbic acid of phosphate/N-Methyl pyrrolidone mixed solution and 60mg are added in glass container, according to embodiment 1
Mode graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared.
Embodiment 4
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 500mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:2000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 0.5mg is added in 1mL deionized water, ultrasound obtains dispersing uniform, stable concentration
For the graphene oxide water solution of 0.5mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 500mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 60mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
Embodiment 5
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 500mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:2000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 5mg is added in 1.25mL deionized water, ultrasound obtains dispersing uniform, stable concentration
For the graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 500mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 60mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
Embodiment 6
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 1000mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:4000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro of the graphene oxide water solution of 50mg, 5mL
The ascorbic acid of phosphate/N-Methyl pyrrolidone mixed solution and 30mg are added in glass container, according to embodiment 1
Mode graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared.
Embodiment 7
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 500mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:2000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 5mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 800mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 100mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
Embodiment 8
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 5000mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:20000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
The compound of body moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 1000mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 100mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
Embodiment 9
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 500mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:2000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 0.5mg is added in 1mL deionized water, ultrasound obtains dispersing uniform, stable concentration
For the graphene oxide water solution of 0.5mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 400mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 30mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
Embodiment 10
A kind of preparation method of graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel,
The following steps are included:
Step (1) prepares uniform, stable black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluoro by solvent-thermal method
Phosphate/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:
1-a): three normal-butyls (methyl) phosphine hexafluorophosphate is dried in vacuo 48h at 110 DEG C respectively；
1-b): in mass ratio by three normal-butyls (methyl) the phosphine hexafluorophosphate 250mg after blocky black phosphorus 25mg and drying
It is added in agate mortar for 100:1000 and carries out mechanical lapping, the time is 40 minutes；By black phosphorus/phosphorous ionic liquid after grinding
Compound move in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixing
Solution, for use.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) takes black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine six of the graphene oxide water solution of 500mg, 5mL
The ascorbic acid of fluorophosphate/N-Methyl pyrrolidone mixed solution and 60mg are added in glass container, according to implementation
Graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel is prepared in the mode of example 1.
By high resiliency prepared by comparative example 1, Examples 1 to 10, highly conductive graphene/black phosphorus quantum dot/tri- normal-butyls
The test of (methyl) phosphine hexafluorophosphate aeroge progress 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 mode.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 graphene in a 1-10/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate composite aerogel electric conductivity and power
Learn recoverability.
Table 1
As shown in Table 1, the black phosphorus quantum dot (i.e. comparative example 1) of independent component can not due to can not form gel and aeroge
Test its electric conductivity and mechanical recovery performance.However, Examples 1 to 10 can test out its electric conductivity in the present invention and mechanics is extensive
Renaturation energy.As shown in Table 1, Examples 1 to 10 all has higher electric conductivity in the present invention；For embodiment 7, preceding body
The concentration of body graphene oxide is 5mg/mL, the quality of three normal-butyl of phosphorous ionic liquid (methyl) phosphine hexafluorophosphate is
It 500mg and is added in black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate/N-Methyl pyrrolidone mixed solution
Graphene oxide quality be 1000mg when, gained graphene/black phosphorus quantum dot/tri- normal-butyls (methyl) phosphine hexafluorophosphate
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 all have higher recovery, and the response rate that reciprocal rear aeroge is stretched at four times is above 95%, show excellent
Mechanical recovery.
Embodiment 11
A kind of preparation method of graphene/black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite composite aerogel, including it is following
Step:
Step (1) prepares uniform, stable black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite/N- by solvent-thermal method
The mixed solution of methyl pyrrolidone, the specific steps of which are as follows:
1-a): triethyl group (methyl) phosphine villiaumite is dried in vacuo 48h at 110 DEG C respectively；
1-b): be in mass ratio 100 by triethyl group (methyl) the phosphine villiaumite 250mg after blocky black phosphorus 25mg and drying:
1000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；It is after grinding that black phosphorus/phosphorous ionic liquid is compound
Object moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite/N-Methyl pyrrolidone mixed solution, to
With.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) prepares high resiliency, highly conductive graphene/black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite airsetting
Glue, the specific steps of which are as follows:
3-a): taking the graphene oxide water solution of 500mg, black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite/N- of 5mL
The mixed solution of methyl pyrrolidone and the ascorbic acid of 60mg are added in glass container, are stirred anti-with abundant dissolution
Bad hematic acid obtains the second mixed solution of stable homogeneous.
3-b): above-mentioned second mixed solution being 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, bubbling time are 3h.After reaction, it is wet solidifying to obtain graphene/black phosphorus quantum dot/triethyl group (methyl) phosphine villiaumite
Glue, for use.
3-c): graphene obtained above/black phosphorus quantum dot/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 extra ascorbic acid small molecule, then-
It carries out being freeze-dried for 48 hours at 80 DEG C, finally obtains graphene/black phosphorus quantum dot/compound airsetting of triethyl group (methyl) phosphine villiaumite
Glue.
Embodiment 12
A kind of preparation method of graphene/black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite composite aerogel, including it is following
Step:
Step (1) prepares uniform, stable black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite/N- by solvent-thermal method
The mixed solution of methyl pyrrolidone, the specific steps of which are as follows:
1-a): tripropyl (methyl) phosphine villaumite is dried in vacuo 48h at 110 DEG C respectively；
1-b): be in mass ratio 100 by tripropyl (methyl) the phosphine villaumite 250mg after blocky black phosphorus 25mg and drying:
1000 are added in agate mortar and carry out mechanical lapping, and the time is 40 minutes；It is after grinding that black phosphorus/phosphorous ionic liquid is compound
Object moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；
1-c): above-mentioned first mixed solution being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere
It encloses, carry out back flow reaction under high temperature under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C, and the time is 6 small
When.After reaction, it is cooled at room temperature to solution, acquired solution carries out high speed centrifugation processing (revolving speed is 7000 revs/min), obtains
To black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite/N-Methyl pyrrolidone mixed solution, to
With.
Step (2) preparation disperses uniform, stable graphene oxide water solution, the specific steps of which are as follows:
Graphene oxide powder 2mg is added in 1mL deionized water, ultrasound obtain dispersing uniform, stable concentration be
The graphene oxide water solution of 2mg/mL, for use.
Step (3) prepares high resiliency, highly conductive graphene/black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite airsetting
Glue, the specific steps of which are as follows:
3-a): taking the graphene oxide water solution of 500mg, black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite/N- of 5mL
The mixed solution of methyl pyrrolidone and the ascorbic acid of 60mg are added in glass container, are stirred anti-with abundant dissolution
Bad hematic acid obtains the second mixed solution of stable homogeneous.
3-b): above-mentioned second mixed solution being subjected to heating water bath under anaerobic, temperature is 100 DEG C, the reaction time
It is 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, it is wet to obtain graphene/black phosphorus quantum dot/tripropyl (methyl) phosphine villaumite
Gel, for use.
3-c): graphene obtained above/black phosphorus quantum dot/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 extra ascorbic acid small molecule, then-
It carries out being freeze-dried for 48 hours at 80 DEG C, finally obtains graphene/black phosphorus quantum dot/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 quantum dot/phosphorous ionic liquid is prepared
Composite aerogel.
The selection of phosphorous ionic liquid and the electric conductivity and mechanical recovery of gained composite aerogel in 2 embodiment 13-53 of table
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
It can change and modify the above embodiment.Therefore, the invention is not limited to specific realities disclosed and described above
Mode is applied, some equivalent modifications of the invention and change should also be as within scope of protection of the claims of the invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (8)
1. a kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel, which is characterized in that including graphene three-dimensional
Skeleton and the black phosphorus quantum dot and phosphorous ionic liquid being supported on the graphene three-dimensional framework, wherein the black phosphorus amount
Son point is wrapped up by the phosphorous ionic liquid, and the graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel has three
The mass ratio of dimension porous network structure, the graphene three-dimensional framework and the black phosphorus quantum dot is 1:(0.375-8)；It is described black
The mass ratio of phosphorus quantum dot and the phosphorous ionic liquid is 1:(6.25-666.7), the cation of the phosphorous ionic liquid is
Quaternary phosphonium salt cationoid, structure are shown below:
Wherein, R1、R2、R3、R4Independently selected from C1-20One of alkyl.
2. graphene as described in claim 1/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel, which is characterized in that institute
Stating graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel porosity is 70%-94%.
3. graphene as described in claim 1/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel, which is characterized in that institute
Stating quaternary phosphonium salt cationoid is 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 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) phosphines cation, four (normal-butyl) phosphines cation, four (n-hexyl) phosphines cation, four
(cetyl) phosphine cation, four (dodecyl) phosphines cation, three (ten alkyl) (ethyl) phosphines cation, three (ten alkyl)
(normal-butyl) phosphine cation, three (cetyl) (methyl) phosphines cation or four (n-eicosane base) phosphines cation.
4. a kind of graphene/black phosphorus quantum dot/phosphorous ionic liquid composite aerogel preparation method, which is characterized in that including
Following steps:
(1) solution containing black phosphorus quantum dot and phosphorous ionic liquid is mixed with graphene oxide water solution and reducing agent
It stirs evenly, obtains mixed solution；In the mixed solution, the mass ratio of the black phosphorus quantum dot and phosphorous ionic liquid is 1:
The mass ratio of (6.25-666.7), the graphene oxide and black phosphorus quantum dot is 1:(0.375-8), the phosphorous ionic liquid
Cation be quaternary phosphonium salt cationoid, structure is shown below:
Wherein, R1、R2、R3、R4Independently selected from C1-20One of alkyl；
(2) mixed solution is subjected to 75-100 DEG C of heating water bath under anaerobic, reacts 1-3 hours, after reaction,
Obtain graphene/black phosphorus quantum dot/compound wet gel of phosphorous ionic liquid；
(3) by the graphene/black phosphorus quantum dot/compound wet gel of phosphorous ionic liquid successively use hydrophilic organic solvent and
Deionized water removes extra reducing agent, is then freeze-dried, and graphene/black phosphorus quantum dot/phosphorous ionic liquid is obtained
Composite aerogel.
5. preparation method as claimed in claim 4, which is characterized in that described containing black phosphorus quantum dot and phosphorous ionic liquid
In solution, the mass concentration of black phosphorus quantum dot is 0.8-1.5mg/mL.
6. preparation method as claimed in claim 4, which is characterized 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.
7. preparation method as claimed in claim 4, which is characterized in that in the mixed solution, the reducing agent and the oxygen
The mass ratio of graphite alkene is (25-150): 1.
8. preparation method as claimed in claim 4, which is characterized in that described containing black phosphorus quantum dot and phosphorous ionic liquid
Solution is prepared in the following way:
It is ground after blocky black phosphorus, phosphorous ionic liquid are mixed, it is organic molten that hydrophily is added into grinding gained mixture
Agent, then under anaerobic, 100-160 DEG C back flow reaction 3-10 hours, after reaction, centrifuge separation, take supernatant, obtain
To the solution containing black phosphorus quantum dot and phosphorous ionic liquid.
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| CN105217611A (en) * | 2015-09-21 | 2016-01-06 | 东南大学 | The preparation method of black phosphorus alkene quantum dot-graphene nanometer sheet three-dimensional composite material |
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