CN106744856A

CN106744856A - A kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel and preparation method thereof

Info

Publication number: CN106744856A
Application number: CN201611244929.4A
Authority: CN
Inventors: 张晗; 邢晨阳; 张家宜
Original assignee: Shenzhen University
Current assignee: Shenzhen University
Priority date: 2016-12-29
Filing date: 2016-12-29
Publication date: 2017-05-31
Anticipated expiration: 2036-12-29
Also published as: CN106744856B

Abstract

The present invention discloses a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, including Graphene three-dimensional framework and the black phosphorus quantum dot and sulfur-containing anion liquid that are supported on the Graphene three-dimensional framework, wherein described black phosphorus quantum dot is wrapped up by the sulfur-containing anion liquid, and the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has three-dimensional porous network structure.The Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has high resiliency, recovery high, high conductivity, and with very excellent stability, its product form for enriching black phosphorus has expanded the range of application of black phosphorus.Present invention also offers the preparation method of the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel.

Description

A kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel and its preparation Method

Technical field

The invention belongs to electrodeless field of nano material preparation, and in particular to a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion Liquid composite aerogel and preparation method thereof.

Background technology

Black phosphorus (Black phosphorene) is a kind of new direct band gap two-dimensional material, and its band gap can be from 0.3eV (this Body state) it is adjusted by its number of plies to 1.5eV (individual layer), can absorb and infra-red range wavelength is used from visible ray to communication Light, (black phosphorus thickness may be up to 1000cm when being 10nm for its carrier mobility higher in addition²˙v^-1˙s^-1) and it is higher logical Break than (10⁴) so that it shows great potential advantages in semiconductor applications, photoelectric field and photo-thermal field etc..

In actual applications, black phosphorus block needs to be stripped into individual layer, few layer or multilayer black phosphorus (i.e. phosphorus alkene) competence exertion Its excellent performance.At present, most of research reports are all based on two-dimentional black phosphorus quantum dot or black phosphorus quantum dot, temporarily have no and appoint What research report on black phosphorus aeroge.And two-dimentional black phosphorus quantum dot or black phosphorus quantum dot are mostly with powder or solution Form is present, and this causes these black phosphorus materials to be not easy to recycling after use.In addition, two-dimentional black phosphorus quantum dot or black The stability problem of phosphorus quantum dot is still an extremely important research topic.If however, black phosphorus can form three-dimensional knot Structure, gel/aeroge, spongelike structure etc., can not only solve the stability problem of black phosphorus, and can fully excavate The potential application of black phosphorus, such as DSSC, lithium ion battery, aluminium ion battery, water process, semiconductor, Application in the fields such as photoelectricity, photo-thermal, medical science.Therefore, a kind of aeroge based on black phosphorus is developed extremely important.

The content of the invention

In view of this, the present invention provides a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, described Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has high resiliency, recovery high and high conductivity, and has Very excellent stability, its product form for enriching black phosphorus has expanded the range of application of black phosphorus.

In a first aspect, the invention provides a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, institute Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is stated including Graphene three-dimensional framework and the stone is supported on Black phosphorus quantum dot and sulfur-containing anion liquid on black alkene three-dimensional framework, wherein the black phosphorus quantum dot is by the sulfur-containing anion liquid Parcel, the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has three-dimensional porous network structure.

Because the interphase interaction of black phosphorus quantum dot is weaker, it is impossible to build black phosphorus quantum dot by self assembly behavior Gel, so needs form gel by a kind of three-dimensional porous material as carrier.And strong-hydrophobicity, the Graphene of Graphene Pi-pi accumulation effect and the influence of restricted clearance between lamella, Graphene are susceptible to self assembly behavior and form Graphene water Gel, and other nano inorganic materials can be loaded/adsorbed as carrier.

Graphene of the invention/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, using Graphene three-dimensional framework as Carrier, wherein, cation (positively charged) and the black phosphorus quantum dot of sulfur-containing anion liquid have certain " cation-n electronics " Interaction so that black phosphorus quantum dot is coated by sulfur-containing anion liquid, this is not only prevented between black phosphorus quantum dot Reunion and significantly improve the dispersiveness of black phosphorus quantum dot, and substantially increase the stability of black phosphorus quantum dot, it is to avoid oxygen The degradation of gas and water to black phosphorus quantum dot.In addition, sulfur-containing anion liquid also with graphenic surface exist " cation-π/π- π " is interacted so that black phosphorus quantum dot can be adsorbed on the surface of Graphene such that it is able to ultimately form the stone of homogeneous stabilization Black alkene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel.

Preferably, the porosity of the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is 70%- 94%.

Preferably, the Graphene three-dimensional framework and the mass ratio of black phosphorus quantum dot are 1：(0.375-8).Further preferably Ground, the Graphene three-dimensional framework is 1 with the mass ratio of black phosphorus quantum dot：(2.5-8).

Preferably, the Graphene three-dimensional framework and the mass ratio of sulfur-containing anion liquid are 1：(25-2000).It is further excellent Selection of land, the Graphene three-dimensional framework is 1 with the mass ratio of sulfur-containing anion liquid：(250-2000).

Preferably, the black phosphorus quantum dot and the mass ratio of sulfur-containing anion liquid are 1：(6.25-666.7).It is further excellent Selection of land, the black phosphorus quantum dot is 1 with the mass ratio of sulfur-containing anion liquid：(100-666.7).

Preferably, the size of the black phosphorus quantum dot is 1-5nm.

In the application, the sulfur-containing anion liquid refer to constitute the ionic liquid cation in contain element sulphur.

Preferably, the cation of the sulfur-containing anion liquid is sulfonium salt cationoid, shown in structural formula such as following formula (I)：

Wherein, R₁、R₂、R₃It is separately the alkane of 1-20 selected from carbon number Base.The sulfur-containing anion liquid has good electric conductivity, heat endurance and certain biocompatibility, is expected in gained two Tie up the specific synergy of performance in the subsequent applications of layered porous black phosphorus material.

Preferably, the R₁、R₂、R₃At least one of for carbon number for 5-20 alkyl.

It is further preferred that the sulfonium salt cationoid is selected from triethyl group sulfonium cation, tripropyl sulfonium cation, three positive fourths Base sulfonium cation, three amyl group sulfonium cations, three n-hexyl sulfonium cations, three positive decyl sulfonium cations, three (dodecyl) sulfoniums Cation, three (n-hexadecyl) sulfonium cations, two (ethyl) methyl sulfonium cations, two (butyl) methyl sulfonium cations, two (just Hexyl) methyl sulfonium cation, two (n-octyl) methyl sulfonium cations, two (dodecyl) methyl sulfonium cations and three (positive two Ten alkyl) one or more in sulfonium cation.

Preferably, the anion of the sulfur-containing anion liquid is selected from fluorine ion, chlorion, bromide ion, sulfate radical, hydrogen sulfate Root, carbonate, phosphate radical, tosylate, dihydrogen phosphate, p diethylaminobenzoic acid ester group, phosphoric acid hydrogen two, nitrate anion, methyl sulphur Acid group, pyrovinic acid root, chlorine aluminate, hexafluoro-phosphate radical, tetrafluoroborate, trifluoromethane sulfonic acid root, thiocyanate radical, acetic acid Root, double (2,4,4- tri-methyl-amyl) phosphinic acids roots, double (malonate conjunction) borates, borate, dicyandiamide base, chlorine aluminic acid Root, double (oxalate conjunction) borates, double (trifluoromethyl) imido grpups, double (fluoroform sulphonyl) imido grpups, double (phthalic acids Root is closed) borate, bromine chlorate anions, decylbenzenesulfonic acid root, dichloro copper acid group, double (pentafluoroethyl group) phosphinic acids roots, double (salicylates Close) borate, double (trifluoromethane sulfonyl group) methyls, (dodecyl) benzene sulfonic acid root, diethyl phosphine acid group, ethyl-sulfate Base, sulfonic acid base, four cyano borate, four (bisulfate ion conjunction) borates, four (methylsulfate conjunction) borates, three (five Fluoro ethyl) one or more in trifluoro phosphate radical and trifluoroacetic acid root.

Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel that first aspect present invention is provided, it is with graphite Alkene three-dimensional framework be carrier, supported on carriers sulfur-containing anion liquid parcel black phosphorus quantum dot, the Graphene/black phosphorus quantum dot/ Sulfur-containing anion liquid composite aerogel has high resiliency, recovery high and a high conductivity, and black phosphorus quantum dot be coated on it is described Among the body of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is not exposed in air, can be from by oxygen Change, with very excellent stability.The Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has been expanded black The product form of phosphorus, is easy to the recycling of black phosphorus material, is expected to apply in the energy (aluminium ion battery, solar cell, lithium Ion battery etc.), catalysis, water process, in the field such as photoelectricity and photo-thermal.

Second aspect, the invention provides a kind of Graphene/black phosphorus quantum dot/sulfur-bearing as described in the first aspect of the invention The preparation method of ionic liquid composite aerogel, comprises the following steps：

(1) by the solution containing black phosphorus quantum dot and sulfur-containing anion liquid and graphene oxide water solution and reducing agent Mixing and stirring, obtains mixed solution；

(2) mixed solution is carried out into heating water bath in 75-100 DEG C under anaerobic, is reacted 1-3 hours, reaction After end, the compound wet gel containing black phosphorus quantum dot is obtained；

(3) the compound wet gel containing black phosphorus quantum dot is sequentially placed into hydrophilic organic solvent and water is purified, It is freeze-dried again, obtain the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel containing black phosphorus quantum dot.

In the present invention, the preparation method of the solution containing black phosphorus quantum dot and sulfur-containing anion liquid is not limited, Ke Yishi Prepare in the following way：

In mass ratio it is 1 by block black phosphorus, sulfur-containing anion liquid：It is ground after (1-200) mixing, it is mixed to grinding gained Hydrophilic organic solvent is added in compound, then under anaerobic, in back flow reaction 3-10 hours at 100-160 DEG C, reaction After end, centrifugation takes supernatant, obtains the solution containing black phosphorus quantum dot and sulfur-containing anion liquid.

More specifically can be：Nitrogen containing plasma liquid is first vacuum dried 24-48h at 100-110 DEG C；Then it is bulk is black Phosphorus and dried nitrogen containing plasma liquid are 1 in mass ratio：1-200 is added to carries out mechanical lapping in agate mortar, during grinding Between be 20-60 minutes；The compound of black phosphorus/nitrogen containing plasma liquid is moved in round-bottomed flask after grinding, and adds the hydrophily to have Machine solvent, obtains black phosphorus/nitrogen containing plasma liquid/hydrophilic organic solvent mixed liquor；Again by the black phosphorus/nitrogen containing plasma liquid/ Hydrophilic organic solvent mixed liquor carries out bubbling deoxygenation, and the time of bubbling deoxygenation is 20-60 minutes；Then in argon gas (Ar) atmosphere Enclose, reacted 3-10 hour in 100-160 DEG C under cooling water backflow and the experiment condition that is stirred vigorously, after reaction terminates, be centrifuged Separate, take supernatant, obtain the solution containing black phosphorus quantum dot and nitrogen containing plasma liquid.Wherein, the rotating speed of the centrifugation It can be 1000 revs/min~10000 revs/min.The bubbling deoxygenation is carried out using inert gases such as nitrogen, argon gas.

It is further preferred that the block black phosphorus is 1 with the mass ratio of sulfur-containing anion liquid：(20-200).

It is further preferred that the quality of the sulfur-containing anion liquid is 0.139- with the volume ratio of the hydrophilic organic solvent 27.77mg/mL。

In the application, the surface of the hydrophilic organic solvent be able to can match with the surface of two-dimentional black phosphorus, therebetween The energy required for peeling off the block black phosphorus is balanced in the presence of certain interaction.

Preferably, the hydrophilic organic solvent is selected from 1-METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO), N, N- One or more in dimethylformamide (DMF), CHP (CHP) and isopropanol (IPA), but do not limit In this.

In the present invention, select the sulfur-containing anion liquid to carry out liquid phase stripping as auxiliary agent and prepare black phosphorus quantum dot, wherein, Sulfur-containing anion liquid is easily prepared, cost is relatively low, and with good electric conductivity, heat endurance and certain biocompatibility, Specific synergy can be played in stripping process with organic solvent.Specifically, acted in organic solvent and probe type ultrasonic Under, block black phosphorus is lifted off of, but the secondary accumulation of gained black phosphorus quantum dot is a dynamic mistake after the stripping and stripping of black phosphorus Journey, gained black phosphorus quantum dot is easy to pile up again, assembles, but when there is a certain amount of sulfur-containing anion liquid in organic solvent When, the cation (positively charged) of sulfur-containing anion liquid exists preferable with the lone electron pair for being stripped the two-dimentional black phosphorus lamella for coming Electrostatic interaction (i.e. " cation-n electronics " interact), this interaction causes black phosphorus quantum dot by sulfur-containing anion liquid Coated, prevent the secondary agglomeration between the black phosphorus lamella for being stripped and coming or pile up again, improve black phosphorus quantum dot and exist Dispersiveness in 1-METHYLPYRROLIDONE, it is thus also avoided that oxygen and water obtain steady containing property to the degradation of black phosphorus quantum dot The fixed, solution of the black phosphorus quantum dot of compound with regular structure.

Preferably, in the solution containing black phosphorus quantum dot and sulfur-containing anion liquid, the mass concentration of black phosphorus quantum dot It is 0.8-1.5mg/mL.It is further 1-1.5mg/mL.

Preferably, the black phosphorus quantum dot and the mass ratio of sulfur-containing anion liquid are 1：(6.25-666.7), further It is 1：(100-666.7).

Preferably, the size of the black phosphorus quantum dot is 1-5nm.

Wherein, in the graphene oxide water solution, the concentration of graphene oxide is 0.5-5mg/mL.

The graphene oxide water solution is obtained using following methods：Graphene oxide powder is added to deionized water In, it is ultrasonically formed the graphene oxide water solution that concentration is 0.5-5mg/mL.

It is further preferred that the concentration of the graphene oxide water solution is 1-4mg/mL.

Preferably, the lateral dimension of the graphene oxide is 3-20 μm, and the number of plies of the graphene oxide is 1-10 layers. Suitable large scale and the graphene oxide of the number of plies are combined as the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid is prepared The raw material of aeroge, is so more beneficial for graphene oxide and is reduced into large-sized Graphene under reducing agent effect, is more easy to Generation self assembly behavior forms three-dimensional porous Graphene gel skeleton, is easy to the later stage that black phosphorus cladding gets up to form three dimensional gel knot Structure.

Preferably, in step (2), the quality of the graphene oxide water solution contains black phosphorus quantum dot and sulfur-bearing with described The volume ratio of the solution of ionic liquid is (10-200)：1mg/mL.More preferably (80-200)：1mg/mL.More preferably (80-160)：1mg/mL.

Preferably, the quality of the graphene oxide and the mass ratio of black phosphorus quantum dot are 1：(0.375-8).

Preferably, the reducing agent and the mass ratio of the graphene oxide are (25-150)：1.More preferably (30-150)：1.The reducing agent is mainly used in for graphene oxide being reduced into Graphene, and the Graphene for generating occurs certainly again Assembling forms Graphene three-dimensional framework, and then induces the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel Formed.

Preferably, the reducing agent includes in ascorbic acid, hydroiodic acid (HI), hydroquinones, buzane and ethylenediamine Plant or various, but not limited to this.The reducing agent needs that water, sulfur-containing anion liquid can be dissolved in, to obtain homogeneous solution.Institute Stating reducing agent can add (solid or liquid) in its intrinsic form, it is also possible to soluble in water to add.

In the application step (3), purified during the compound wet gel of gained is sequentially placed into hydrophilic organic solvent, water, first Purifying is in order to remove reducing agent small molecule, while hydrophilic organic solvent can also be avoided in the hydrophilic organic solvent The oxidation of black phosphorus quantum dot, is then placed in deionized water that purify be to remove the reducing agent and hydrophily that do not eliminate again Organic solvent.

Preferably, the time of the purifying in the hydrophilic organic solvent is 4-10 days；Purifying in the water Time is 1-5 days.The purifying of long period is carried out in hydrophilic organic solvent, the oxygen of black phosphorus quantum dot can be as far as possible avoided Change.

Preferably, the time of the freeze-drying is 24-72h；The temperature of the freeze-drying is -40~-80 DEG C.

In an embodiment of the present invention, the hydrophilic organic solvent is 1-METHYLPYRROLIDONE (NMP).

In the preparation method of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel that the present invention is provided, graphite The formation mechenism of alkene/black phosphorus quantum dot/sulfur-containing anion liquid aeroge is：Containing black phosphorus quantum dot and sulfur-containing anion liquid In solution, in the presence of the interaction of " cation-n electronics " between black phosphorus quantum dot and sulfur-containing anion liquid；Contain described afterwards There is the mixed solution of black phosphorus quantum dot and sulfur-containing anion liquid as the dispersion liquid of graphene oxide, in the presence of a reducing agent, Graphene oxide is reduced to Graphene, and then self assembly behavior occurs, and forms Graphene/black phosphorus quantum dot/sulfur-containing anion liquid The plural gel of body.Because sulfur-containing anion liquid is not only and black phosphorus quantum dot between in the presence of the phase interaction of " cation-n electronics " With, and there is " cation-π/π-π " interaction with graphenic surface in it, and this causes what is coated by sulfur-containing anion liquid Black phosphorus quantum dot can be adsorbed on the surface of Graphene, can finally form the Graphene/black phosphorus quantum dot/contain of homogeneous stabilization The plural gel of sulphion liquid.The small molecule (such as reducing agent, organic solvent) in gel is removed by dialysis afterwards, then The compound wet gel of freeze-dried Graphene/black phosphorus quantum dot/sulfur-containing anion liquid by solution is changed into Graphene/black phosphorus The Graphene of quantum dot/sulfur-containing anion liquid/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel.

In the preparation method of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel that the present invention is provided, use Sulfur-containing anion liquid is combined jointly as auxiliary agent or additive, with Graphene gel as carrier or template with black phosphorus quantum dot The Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is formed, the preparation method process is simple is easy to operate, into This is low, and yield is higher, easily realizes industrialization production.The obtained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid is combined gas Gel is a kind of new product, and it has the excellent performances such as high resiliency, recovery high, high conductivity, while also having excellent Different stability and recuperability.The Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is black phosphorus material in energy Application in the fields such as source (aluminium ion battery, solar cell, lithium ion battery etc.), catalysis, water process, photoelectricity and photo-thermal is established Basis is determined.

The advantage of the embodiment of the present invention will be illustrated partly in the following description, a part according to specification be it is aobvious and It is clear to, 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) Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/N- Methyl pyrrolidone gel (i.e. embodiment 1)；(C) Graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE Gel (comparative example 3)；(D) black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE (i.e. comparative example 1)；

Fig. 2 is the electromicroscopic photograph of black phosphorus quantum dot obtained in the embodiment of the present invention 1；

Fig. 3 be the embodiment of the present invention 1 in gained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel it is grand 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, on the premise of embodiment of the present invention principle is not departed from, some improvements and modifications can also be made, these improvement With the protection domain that retouching is also considered as the embodiment of the present invention.

Multiple embodiments are divided to be further detailed the embodiment of the present invention below.Wherein, the embodiment of the present invention is not limited Due to following specific embodiment.In the range of constant principal right, can be appropriate carry out change implementation.

Unless otherwise noted, the raw material and other chemical reagent reagents that the embodiment of the present invention is used are all commercial goods.

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 by 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/sulfur-containing anion liquid composite aerogel, comprises the following steps：

Step (1) prepares the black phosphorus quantum dot solution of homogeneous stabilization by liquid phase stripping method, and it is comprised the following steps that：

1-a):Two (butyl) methyl sulfonium hexafluorophosphates (i.e. sulfur-containing anion liquid) are vacuum dried 48h at 110 DEG C；

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 500mg (i.e. sulfur-containing anion Liquid) in mass ratio it is 100:2000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；Gained after grinding Mixture is transferred in round-bottomed flask, and adds the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtains the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 6 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 140 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 7000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid)/N- first The mixed solution of base pyrrolidones, wherein, the concentration of black phosphorus quantum dot is about 1mg/mL, stand-by.

Step (2) prepares homogeneous, the stable graphene oxide water solution of dispersion, and it is comprised the following steps that：

Graphene oxide powder is added in deionized water, it is water-soluble that ultrasound obtains the graphene oxide that concentration is 2mg/mL Liquid, it is stand-by.

Step (3) prepares Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, and it is comprised the following steps that：

3-a)：Take the graphene oxide water solution of 500mg, the black phosphorus quantum dot solution of 5mL and the ascorbic acid of 60mg It is added in glass container, is stirred so that ascorbic acid fully dissolves, obtains the second mixed solution of stable homogeneous.

3-b)：By above-mentioned second mixed solution under 95 DEG C, the oxygen free condition under carry out heating water bath, the reaction time is 2 small When.Wherein, oxygen free condition is by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, in heating Bubbling, the bubbling time is 2h.After reaction terminates, Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate is obtained Wet gel, it is stand-by.

3-c)：(equivalent to " dialysis ") is purified during wet gel obtained above is sequentially placed into NMP and deionized water, To remove unnecessary ascorbic acid small molecule, NMP respectively, purifying total time is 7 days, wherein, purified 5 days in NMP, go from Purified 2 days in sub- water, period notes changing solvent.

3-d)：Freeze-drying 48 hours will be carried out at -80 DEG C by gained wet gel after purification, finally give Graphene/black The composite aerogel of phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate.

It is the effect of the prominent embodiment of the present invention, following comparative example is provided with for embodiment 1：

Comparative example 1

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 6 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 140 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 7000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid)/N- first The mixed solution of base pyrrolidones, it is stand-by.

Step (2) prepares black phosphorus quantum dot aeroge, and it is comprised the following steps that：

2-a)：The ascorbic acid of the black phosphorus quantum dot solution of 5mL and 60mg is added in glass container, be stirred with Ascorbic acid is fully dissolved, obtain the second mixed solution of stable homogeneous.

2-b)：By above-mentioned second mixed solution under 95 DEG C, the oxygen free condition under carry out heating water bath 2 hours.Wherein, anaerobic Condition is by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, side heating snare drum bubble, during bubbling Between be 2h.After reaction terminates, the mixed of black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE is obtained Solution is closed, but does not observe being formed by any gel in glass container.

Comparative example 2

Step (1) prepares homogeneous, the stable graphene oxide water solution of dispersion, 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 Initial oxidation graphene aqueous solution is formed under effect, low-speed centrifugal treatment (rotating speed is 1000 revs/min) is then carried out, is disperseed Homogeneous, stabilization graphene oxide water solution, it is stand-by.

Step (2) prepares the hydrogel of Graphene/1-METHYLPYRROLIDONE, and it is comprised the following steps that：

The ascorbic acid of the graphene oxide water solution of 500mg, the 1-METHYLPYRROLIDONE of 5mL, 60mg is added to glass In glass container, it is stirred so that ascorbic acid fully dissolves, obtains the mixed solution of stable homogeneous, and by above-mentioned mixed solution Heating water bath is carried out under under 95 DEG C, the oxygen free condition, the reaction time is 2 hours.Wherein, oxygen free condition is by inert gas argon The bubbling deoxygenation of gas, the flow velocity of argon gas is mL/h, and the bubbling time is 2h.After reaction terminates, the reaction solution in sight glass container, And taken pictures.The hydrogel of Graphene/1-METHYLPYRROLIDONE is obtained, it is stand-by.

Step (3) prepares the aeroge of Graphene, and it is comprised the following steps that：

3-a) gel of above-mentioned gained Graphene gel/1-METHYLPYRROLIDONE is sequentially placed into NMP and deionized water (equivalent to " dialysis ") is purified, to remove unnecessary ascorbic acid small molecule and NMP respectively, purifying total time is 7 days, its In, purified in NMP 5 days, purify 2 days in deionized water, period notes changing solvent.

Freeze-drying 3-b) will be carried out 48 hours by gained gel after purification, the temperature of freeze-drying is -40~-80 DEG C, most Graphene aerogel is obtained eventually.It should be noted that Graphene is comprised only in this gel, without black phosphorus quantum dot, without ionic liquid.

Comparative example 3

Step (1) prepares the mixed solution of sulfur-containing anion liquid and NMP:

Dried two (butyl) methyl sulfonium hexafluorophosphate 500mg are added to the 1-METHYLPYRROLIDONE of 180mL (NMP) in, the mixed solution of two (butyl) methyl sulfonium hexafluorophosphates and NMP is obtained；

Graphene oxide powder is added in deionized water, it is the oxidation stone of 2mg/mL that concentration is formed under ultrasonication Black aqueous solution, it is stand-by.

Step (3) prepares the gel of Graphene-ionic liquid, and it is comprised the following steps that：

By the graphene oxide water solution of 500mg, and by the ascorbic acid of 60mg, two (butyl) methyl sulfonium hexafluoros of 5mL The mixed solution of phosphate and NMP is added in glass container, is stirred so that ascorbic acid fully dissolves, and obtains homogeneous steady Fixed mixed solution；

Above-mentioned mixed solution is carried out into heating water bath under 95 DEG C, oxygen free condition, the reaction time is 2 hours.Wherein, anaerobic Condition is that the flow velocity of argon gas is 100mL/h, and the bubbling time is 2h by the bubbling deoxygenation of inert gas argon gas.After reaction terminates, Reaction solution in sight glass container, and taken pictures, obtain Graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/N- methyl The gel of pyrrolidones, it is stand-by.

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) Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/N- Methyl pyrrolidone gel (i.e. embodiment 1)；(C) Graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE Gel (comparative example 3)；(D) black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE solution is (i.e. right Ratio 1).

From Figure 1A (i.e. comparative example 2), graphene oxide can be sent out in organic solvent 1-METHYLPYRROLIDONE Original of surviving concurrently is conigenous assembly behavior and forms gel, but its gel content is smaller, and (ie in solution is still presented black, inside it Graphene gel it is similar " jelly ").From the contrast of Fig. 1 D (i.e. comparative example 1) and Figure 1B (i.e. embodiment 1), in phase Under the conditions of, the black phosphorus quantum dot solution (black phosphorus quantum dot, sulfur-containing anion liquid, NMP) of comparative example 1 adds carrying out water-bath Resulting solution is integrally presented light yellow after heat, does not observe gel, and this shows black phosphorus quantum in simple black phosphorus quantum dot solution Point cannot occur self assembly behavior and form gel, it is necessary to can form the carrier of three-dimensional material by other.And the present invention is implemented In example 1 (in Figure 1B), using template or carrier required for the gel of Graphene as black phosphorus quantum dot gel-forming, in black phosphorus In quantum dot solution (mixed solution of black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE), plus After entering graphene oxide and reducing agent, there is reduction reaction in graphene oxide, is concurrently conigenous assembly behavior and forms Graphene/black phosphorus The plural gel of quantum dot/sulfur-containing anion liquid.And, knowable to the color (without black) of supernatant after heating water bath, gained Plural gel content is larger.

Additionally, in order to preferably study sulfur-containing anion liquid-bis- (butyl) methyl sulfonium hexafluorophosphate in gel process Effect, the aqueous solution of graphene oxide is mixed with two (butyl) methyl sulfonium hexafluorophosphates/1-METHYLPYRROLIDONE, plus After entering reducing agent, heating water bath is carried out, shown in resulting solution such as Fig. 1 C (comparative example 3).From Fig. 1 C, in the same terms Under, in Graphene/bis- (butyl) the methyl sulfonium hexafluorophosphate/1-METHYLPYRROLIDONE solution without black phosphorus quantum dot, graphite Alkene equally there occurs gelation, and compared with Figure 1A (comparative example 2), this shows that two (butyl) methyl sulfonium hexafluorophosphates can be with Remarkably promote gelation of the Graphene in organic solvent 1-METHYLPYRROLIDONE.

Fig. 2 is the electromicroscopic photograph of black phosphorus quantum dot obtained in the embodiment of the present invention 1, as can be seen from the figure black phosphorus amount The size of son point is 3-4.5nm.

Fig. 3 be the embodiment of the present invention 1 in gained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel it is grand Take piece (Fig. 3 A) and microscopic appearance figure (Fig. 3 B) into consideration.From Fig. 3 A, Graphene/black phosphorus quantum dot obtained by the embodiment of the present invention/ Sulfur-containing anion liquid composite aerogel has very excellent macroscopic properties, is highly convenient for it in application process to black phosphorus material Recycling (can directly by the Graphene of bulk/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel from the body applied Taken out in system).From Fig. 3 B, embodiment of the present invention gained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel The main black phosphorus quantum dot by large stretch of graphene film and nano-scale is built by accumulation, integrally shows porous knot Structure, with porosity (about 75%) higher, shows specific surface area higher.

Embodiment 2

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 25mg (i.e. sulfur-containing anion Liquid) in mass ratio it is 100:100 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；Gained after grinding Mixture is transferred in round-bottomed flask, and adds the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtains the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 6 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 140 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 7000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid)/N- first The mixed solution of base pyrrolidones, wherein, the concentration of black phosphorus quantum dot is about 0.8mg/mL, stand-by.

Graphene oxide powder is added in deionized water, it is water-soluble that ultrasound obtains the graphene oxide that concentration is 1mg/mL Liquid, it is stand-by.

3-b)：Above-mentioned second mixed solution is carried out into heating water bath under 95 DEG C, oxygen free condition, the reaction time is 2 hours. Wherein, oxygen free condition is that, by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, the bubbling time is 2h.After reaction terminates, Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) is obtained Wet gel, it is stand-by.

3-c)：By above-mentioned 3-b) wet gel that obtains carried out in being sequentially placed into 1-METHYLPYRROLIDONE and deionized water it is pure Change, to remove unnecessary ascorbic acid small molecule, purification time is 7 days, and period notes changing solvent.

3-d)：Freeze-drying 48 hours will be carried out at -80 DEG C by gained wet gel after purification, finally give Graphene/black Phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) composite aerogel.

Embodiment 3

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 5000mg (i.e. sulfur-bearing from Sub- liquid) in mass ratio it is 100:20000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；After grinding Gained mixture is transferred in round-bottomed flask, and adds the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtains the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 6 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 140 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 7000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid)/N- first The mixed solution of base pyrrolidones, wherein, the concentration of black phosphorus quantum dot is about 1.5mg/mL, stand-by.

Graphene oxide powder is added in deionized water, wherein, the concentration of graphene oxide is 2mg/mL, in ultrasound The concentration that graphene oxide is formed under effect is the graphene oxide water solution of 2mg/mL, stand-by.

3-d)：Freeze-drying 48 hours will be carried out at -80 DEG C by gained wet gel after purification, finally give Graphene/black The composite aerogel of phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid).

Embodiment 4

Graphene oxide powder is added in deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 0.5mg/mL, it is stand-by.

3-d)：Gained wet gel freeze-drying 48 hours at -80 DEG C after purification are incited somebody to action, Graphene/black phosphorus amount is finally given The composite aerogel of sub- point/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid).

Embodiment 5

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 500mg (i.e. sulfur-containing anion Liquid) in mass ratio it is 100:2000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；Will be black after grinding The compound of phosphorus/sulfur-containing anion liquid is moved in round-bottomed flask, and adds the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtains One mixed solution；

Graphene oxide powder is added in deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 4mg/mL, it is stand-by.

Step (3) prepares Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate of high resiliency, high connductivity (i.e. sulfur-containing anion liquid) aeroge, it is comprised the following steps that：

Embodiment 6

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 1000mg (i.e. sulfur-bearing from Sub- liquid) in mass ratio it is 100:2000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；Institute after grinding Obtain mixture to be transferred in round-bottomed flask, and add the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtain the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 6 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 140 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 7000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid)/N- first The mixed solution of base pyrrolidones, wherein, the concentration of black phosphorus quantum dot is about 1.2mg/mL, stand-by.

Graphene oxide powder is added in deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 2mg/mL, it is stand-by.

Embodiment 7

Graphene oxide powder is added in deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 5mg/mL, it is stand-by.

3-a)：Take the graphene oxide water solution of 800mg, the black phosphorus quantum dot solution of 5mL and the ascorbic acid of 100mg It is added in glass container, is stirred so that ascorbic acid fully dissolves, obtains the second mixed solution of stable homogeneous.

Embodiment 8

3-a)：Take the graphene oxide water solution of 1000mg, the black phosphorus quantum dot solution of 5mL and the Vitamin C of 100mg Acid is added in glass container, is stirred so that ascorbic acid fully dissolves, and obtains the second mixed solution of stable homogeneous.

Embodiment 9

3-a)：Take the graphene oxide water solution of 400mg, the black phosphorus quantum dot solution of 5mL and the ascorbic acid of 30mg It is added in glass container, is stirred so that ascorbic acid fully dissolves, obtains the second mixed solution of stable homogeneous.

Embodiment 10

1-b):By block black phosphorus 25mg and dried two (butyl) methyl sulfonium hexafluorophosphates 250mg (i.e. sulfur-containing anion Liquid) in mass ratio it is 100:1000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes；Gained after grinding Mixture is transferred in round-bottomed flask, and adds the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtains the first mixed solution；

3-a)：By the graphene oxide water solution of 500mg, the black phosphorus quantum dot solution and the ascorbic acid of 60mg of 5mL It is added in glass container, is stirred so that ascorbic acid fully dissolves, obtains the second mixed solution of stable homogeneous.

3-b)：Above-mentioned second mixed solution is carried out into heating water bath under 95 DEG C, oxygen free condition, the reaction time is 2 hours. Wherein, oxygen free condition is that, by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, the bubbling time is 2h.After reaction terminates, Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) is obtained Gel, it is stand-by.

3-c)：By above-mentioned 3-b) gel that obtains purified in being sequentially placed into 1-METHYLPYRROLIDONE and deionized water, To remove unnecessary ascorbic acid small molecule, purification time is 7 days, and period notes changing solvent.

3-d)：Freeze-drying 48 hours will be carried out at -80 DEG C by gained gel after purification, finally give Graphene/black phosphorus Quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) composite aerogel.

The aerogel products that the products obtained therefrom of comparative example 1, embodiment 1~10 are prepared are carried out into mechanical property and electric conductivity Test.The test condition of mechanical property is as follows：Instrument and equipment：Instron puller system (Instron9566), pressure sensing Device：500N；Test fixture：Compression-type fixture；Test condition：Room temperature；Compression speed：1mm/min；Detection pattern：Compression reaction Pattern.The test of electric conductivity is tested using Mitsubishi Chemical's low-resistance instrument (four probe method).

Gained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid is combined in the product and embodiment 1-10 of the comparative example 1 of table 1 The electric conductivity and mechanical recovery performance of aeroge

In order to preferably prove the present invention in products therefrom (Graphene/black phosphorus quantum dot/sulfur-containing anion liquid is combined airsetting Glue) superior physical properties, table 1 gives electric conductivity and the mechanical recovery of products therefrom in comparative example 1 and embodiment 1-10 Energy.As shown in Table 1, the black phosphorus quantum dot (comparative example 1) of independent component is because that cannot form gel and aeroge, therefore cannot test Its electric conductivity and mechanical recovery performance.And the product obtained by the preparation method that embodiment of the present invention 1-10 is provided can be tested out Its electric conductivity and mechanics restorability.As shown in Table 1, the gained of embodiment 1~10 is respectively provided with electric conductivity higher in the present invention.Its In, the gained Graphene of embodiment 7/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has best electric conductivity (i.e. resistance It is minimum, be 1.2 ohm).Additionally, as shown in Table 1, the product of the institute of embodiment 1~10 is also all with reply higher in the present invention Property, the response rate of its aeroge after four stretchings are reciprocal is above 95%, shows its excellent mechanical recovery.

Embodiment 11

A kind of preparation method of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, including：

1-a):Triethyl group sulfonium villiaumite (i.e. sulfur-containing anion liquid) is vacuum dried 48h at 110 DEG C；

1-b):In mass ratio it is 100 by block black phosphorus 25mg and dried triethyl group sulfonium villiaumite 250mg:1000 add Mechanical lapping is carried out in agate mortar, the time is 40 minutes；Gained mixture after grinding is transferred in round-bottomed flask, and is added Enter the 1-METHYLPYRROLIDONE (NMP) of 180mL, obtain the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 10 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 100 DEG C；Reaction knot Shu Hou, the system for the treatment of is cooled to room temperature, and gained reaction solution is carried out into low-speed centrifugal treatment (rotating speed is 5000 revs/min), collects supernatant Liquid, obtains the mixed solution of black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/triethyl group sulfonium villiaumite/1-METHYLPYRROLIDONE, treats With.

3-b)：Above-mentioned second mixed solution is carried out into heating water bath under 75 DEG C, oxygen free condition, the reaction time is 2 hours. Wherein, oxygen free condition is that, by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, the bubbling time is 2h.After reaction terminates, the wet gel of Graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate is obtained, it is stand-by.

3-c)：By above-mentioned 3-b) wet gel that obtains purified in being sequentially placed into 1-METHYLPYRROLIDONE and deionized water To remove unnecessary ascorbic acid small molecule, purification time is 7 days, and period notes changing solvent.

3-d)：Freeze-drying 48 hours will be carried out at -60 DEG C by gained wet gel after purification, finally give Graphene/black Phosphorus quantum dot/triethyl group sulfonium villiaumite (i.e. sulfur-containing anion liquid) composite aerogel.

Embodiment 12

Step (1) prepares homogeneous, stabilization black phosphorus quantum dot/tripropyl sulfonium villaumite (i.e. sulfur-bearing by liquid phase stripping method Ionic liquid)/1-METHYLPYRROLIDONE mixed solution, it is comprised the following steps that：

1-a):Tripropyl sulfonium villaumite (i.e. sulfur-containing anion liquid) is vacuum dried 48h at 110 DEG C；

1-b):Block black phosphorus 25mg and dried tripropyl sulfonium villaumite 250mg (i.e. sulfur-containing anion liquid) is pressed into quality Than being 100:1000 are added to mechanical lapping are carried out in agate mortar, and the time is 40 minutes, by gained mixture transfer after grinding To round-bottomed flask, and the 1-METHYLPYRROLIDONE (NMP) of 180mL is added, obtain the first mixed solution；

1-c):Above-mentioned first mixed solution is carried out into bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere Enclose, carry out solvent thermal reaction 3 hours under cooling water backflow and the experiment condition that is stirred vigorously, temperature is 160 DEG C；Reaction terminates Afterwards, treat that system is cooled to room temperature, gained reaction solution carried out into low-speed centrifugal treatment (rotating speed is 6000 revs/min), collect supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tripropyl sulfonium villaumite (i.e. sulfur-containing anion liquid)/1-METHYLPYRROLIDONE Mixed solution, it is stand-by.

3-b)：Above-mentioned second mixed solution is carried out into heating water bath under 100 DEG C, oxygen free condition, the reaction time is 1 small When.Wherein, oxygen free condition is by the way that using inert gas bubbling argon, come deoxygenation, the flow velocity of argon gas is 100mL/h, bubbling time It is 1h.After reaction terminates, the compound wet gel of Graphene/black phosphorus quantum dot/tripropyl sulfonium villaumite is obtained, it is stand-by.

3-c)：By above-mentioned 3-b) wet gel that obtains carried out in being sequentially placed into 1-METHYLPYRROLIDONE and deionized water it is pure Change, to remove unnecessary ascorbic acid small molecule, purification time is 7 days.

3-d)：Freeze-drying 48 hours will be carried out at -40 DEG C by gained gel after purification, finally give Graphene/black phosphorus Quantum dot/tripropyl sulfonium villaumite (i.e. sulfur-containing anion liquid) composite aerogel.

Embodiment 13-51

Two (butyl) methyl sulphur hexafluorophosphate sulfur-containing anion liquid in embodiment 1 are changed to as shown in table 2 respectively Cation for season sulfonium salt class sulfur-containing anion liquid, other experiment conditions such as embodiment 1 is identical, and obtained product is carried out The test of electric conductivity and mechanical recovery performance, it is as a result also as shown in table 2.

The selection of sulfur-containing anion liquid and gained Graphene/black phosphorus quantum dot/sulfur-containing anion liquid in the embodiment 13-51 of table 2 The electric conductivity and mechanical recovery performance of bluk recombination aeroge

Above disclosed is only present pre-ferred embodiments, can not limit the right model of the present invention with this certainly Enclose, one of ordinary skill in the art will appreciate that all or part of flow of above-described embodiment is realized, and will according to right of the present invention Made equivalent variations are sought, the covered scope of invention is still fallen within.

Claims

1. a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is characterised in that three-dimensional including Graphene Skeleton and the black phosphorus quantum dot and sulfur-containing anion liquid that are supported on the Graphene three-dimensional framework, wherein the black phosphorus amount By sulfur-containing anion liquid parcel, the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has three to son point Dimension porous network structure.

2. Graphene as claimed in claim 1/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is characterised in that institute It is 1 that Graphene three-dimensional framework is stated with the mass ratio of black phosphorus quantum dot：(0.375-8)；The black phosphorus quantum dot and sulfur-containing anion liquid The mass ratio of body is 1：(6.25-666.7).

3. Graphene as claimed in claim 1/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is characterised in that institute The porosity for stating Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is 70%-94%.

4. Graphene as claimed in claim 1/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is characterised in that institute The cation of sulfur-containing anion liquid is stated for sulfonium salt cationoid, shown in structural formula such as following formula (I)：

Wherein, R₁、R₂、R₃It is separately the alkyl of 1-20 selected from carbon number.

5. the preparation method of a kind of Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, it is characterised in that including Following steps：

(1) solution containing black phosphorus quantum dot and sulfur-containing anion liquid is mixed with graphene oxide water solution and reducing agent Stir, obtain mixed solution；

(2) mixed solution is carried out into heating water bath in 75-100 DEG C under anaerobic, is reacted 1-3 hours, reaction terminates Afterwards, the compound wet gel containing black phosphorus quantum dot is obtained；

(3) the compound wet gel containing black phosphorus quantum dot is sequentially placed into hydrophilic organic solvent and water is purified, then passed through Freeze-drying, obtains the Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel containing black phosphorus quantum dot.

6. preparation method as claimed in claim 5, 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 of the graphene oxide is 1- 10 layers.

7. preparation method as claimed in claim 5, it is characterised in that described containing black phosphorus quantum dot and sulfur-containing anion liquid In solution, the mass concentration of black phosphorus quantum dot is 0.8-1.5mg/mL；The quality of the black phosphorus quantum dot and sulfur-containing anion liquid Than being 1：(6.25-666.7).

8. preparation method as claimed in claim 5, it is characterised in that the quality of the graphene oxide and black phosphorus quantum dot Mass ratio is 1：(0.375-8).

9. preparation method as claimed in claim 5, it is characterised in that the mass ratio of the reducing agent and the graphene oxide It is (25-150)：1.

10. preparation method as claimed in claim 7, it is characterised in that described containing black phosphorus quantum dot and sulfur-containing anion liquid Solution prepare in the following way：

In mass ratio it is 1 by block black phosphorus, sulfur-containing anion liquid：It is ground after (1-200) mixing, to grinding gained mixture Middle addition hydrophilic organic solvent, then under anaerobic, 100-160 DEG C back flow reaction 3-10 hours, reaction terminate after, from The heart is separated, and takes supernatant, obtains the solution containing black phosphorus quantum dot and sulfur-containing anion liquid.