CN106744856B

CN106744856B - A kind of graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel and preparation method thereof

Info

Publication number: CN106744856B
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: 2019-04-12
Anticipated expiration: 2036-12-29
Also published as: CN106744856A

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 the 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 reticular structure.The graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has high resiliency, high recovery, high conductivity, and has very excellent stability, enriches the product form of black phosphorus, has expanded the application range of black phosphorus.The present invention also provides the graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel preparation methods.

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 technique

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

In practical applications, black phosphorus block needs to be stripped into single layer, few layer or multilayer black phosphorus (i.e. phosphorus alkene) competence exertion Its excellent performance.Currently, 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 is reported about the research of black phosphorus aeroge.And two-dimentional black phosphorus quantum dot or black phosphorus quantum dot are mostly with powder or solution Form exists, this causes these black phosphorus materials to be not easy to recycling and reusing 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.However, if black phosphorus is capable of forming three-dimensional knot Structure, gel/aeroge, spongelike structure etc. can not only solve the stability problem of black phosphorus, and can sufficiently excavate The potential application of black phosphorus, such as dye-sensitized solar cells, lithium ion battery, aluminium ion battery, water process, semiconductor, Application in the fields such as photoelectricity, photo-thermal, medicine.Therefore, it is extremely important to develop a kind of aeroge based on black phosphorus.

Summary 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, it is described Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel 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/sulfur-containing anion liquid composite aerogel, institute Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is stated to include graphene three-dimensional framework and be supported on the stone 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 Package, the graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel have 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/sulfur-containing anion liquid composite aerogel, using graphene three-dimensional framework as Carrier, wherein the cation (positively charged) and 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 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 sulfur-containing anion 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/sulfur-containing anion liquid composite aerogel.

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

Preferably, the mass ratio of the graphene three-dimensional framework and black phosphorus quantum dot is 1:(0.375-8).Further preferably The mass ratio of ground, the graphene three-dimensional framework and black phosphorus quantum dot is 1:(2.5-8).

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

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

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

In the application, the sulfur-containing anion liquid, which refers in the cation for constituting the ionic liquid, contains 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、R₃The alkane for being separately 1-20 selected from carbon atom number Base.The sulfur-containing anion liquid has good electric conductivity, thermal stability and certain biocompatibility, is expected in gained two It ties up and plays specific synergistic effect in the subsequent applications of layered porous black phosphorus material.

Preferably, the R₁、R₂、R₃At least one of be alkyl that carbon atom number is 5-20.

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 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 of sulfonium cation or a variety of.

Preferably, the anion of the sulfur-containing anion liquid is selected from fluorine ion, chloride ion, 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, methane sulfonic acid root, chlorine aluminate, hexafluoro-phosphate radical, tetrafluoroborate, trifluoromethane sulfonic acid root, thiocyanate radical, acetic acid Root, bis- (2,4,4- tri-methyl-amyl) phosphinic acids roots, bis- (malonate conjunction) borates, borate, dicyandiamide base, chlorine aluminic acid Root, bis- (oxalate conjunction) borates, bis- (trifluoromethyl) imido grpups, bis- (fluoroform sulphonyl) imido grpups, bis- (phthalic acids Root closes) borate, bromine chlorate anions, decylbenzenesulfonic acid root, dichloro copper acid group, bis- (pentafluoroethyl group) phosphinic acids roots, bis- (salicylates Close) borate, bis- (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 of trifluoro phosphate radical and trifluoroacetic acid root or a variety of.

Graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel that first aspect present invention provides, with graphite Alkene three-dimensional framework be carrier, supported on carriers sulfur-containing anion liquid package black phosphorus quantum dot, the graphene/black phosphorus quantum dot/ Sulfur-containing anion liquid composite aerogel has high resiliency, high recovery and a high conductivity, and black phosphorus quantum dot be coated on it is described Among graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel ontology, it is not exposed in air, it can be from by oxygen Change, there is 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 expected to apply in the energy (aluminium ion battery, solar battery, lithium convenient for the recycling and reusing of black phosphorus material 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/sulfur-bearings as described in the first aspect of the invention The preparation method of ionic liquid composite aerogel, comprising 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 It is mixed evenly, obtains mixed solution；

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

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

In the present invention, the preparation method of the solution containing black phosphorus quantum dot and sulfur-containing anion liquid is unlimited, can be It is prepared in the following way:

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

More specifically may be used are as follows: nitrogen containing plasma 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 nitrogen containing plasma liquid be in mass ratio that 1:1-200 is added in agate mortar and carries out mechanical lapping, when grinding Between be 20-60 minutes；Black phosphorus/nitrogen containing plasma liquid compound is moved in round-bottomed flask after grinding, and hydrophily is added to have 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 for being bubbled deoxygenation is 20-60 minutes；Then in argon gas (Ar) atmosphere Enclose, under cooling water reflux and the experiment condition that is vigorously stirred in 100-160 DEG C reaction 3-10 hours, after reaction, be centrifuged Separation, takes supernatant, obtains the solution containing black phosphorus quantum dot and nitrogen containing plasma liquid.Wherein, the revolving 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 mass ratio of the bulk black phosphorus and sulfur-containing anion liquid is 1:(20-200).

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

In the application, the surface of the hydrophilic organic solvent can match with the surface of two-dimentional black phosphorus, therebetween There are certain interactions to balance energy required for removing the bulk black phosphorus.

Preferably, the hydrophilic organic solvent is selected from N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N- One of dimethylformamide (DMF), n-cyclohexyl-2-pyrrolidone (CHP) and isopropanol (IPA) are a variety of but unlimited In this.

In the present invention, selects the sulfur-containing anion liquid to carry out liquid phase removing as auxiliary agent and prepares black phosphorus quantum dot, wherein Sulfur-containing anion liquid is easily prepared, cost is relatively low, and has good electric conductivity, thermal stability and certain biocompatibility, Specific synergistic effect can be played with organic solvent in stripping process.Specifically, it is acted in organic solvent and probe type ultrasonic Under, blocky black phosphorus is lifted off of, but the secondary accumulation of gained black phosphorus quantum dot is a dynamic mistake after the removing and removing of black phosphorus Journey, gained black phosphorus quantum dot are easy to accumulate again, assemble, but when there are 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 to come Electrostatic interaction (i.e. " cation-n electronics " interact), this interaction so that black phosphorus quantum dot by sulfur-containing anion liquid It is coated, prevent the secondary agglomeration being stripped between the black phosphorus lamella to come or is accumulated again, improved black phosphorus quantum dot and exist Dispersibility in N-Methyl pyrrolidone, it is thus also avoided that oxygen and water obtain steady containing property the degradation of black phosphorus quantum dot The solution of fixed, compound with regular structure black phosphorus quantum dot.

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

Preferably, the mass ratio of the black phosphorus quantum dot and sulfur-containing anion liquid is 1:(6.25-666.7), further For 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 to be prepared by the following method: 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. The graphene oxide of suitable large scale and the number of plies is compound as the graphene/black phosphorus quantum dot/sulfur-containing anion liquid is prepared The raw material of aeroge is more advantageous to graphene oxide in this way and is reduced into large-sized graphene under reducing agent effect, is easier to Self assembly behavior occurs and forms three-dimensional porous Graphene gel skeleton, black phosphorus cladding gets up to form three dimensional gel knot convenient for the later period 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.Further preferably (80-200): 1mg/mL.More preferably (80-160): 1mg/mL.

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

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

Preferably, the reducing agent includes one in ascorbic acid, hydroiodic acid (HI), hydroquinone, buzane and ethylenediamine Kind is a variety of, but not limited to this.The reducing agent needs can be dissolved in water, sulfur-containing anion liquid, to obtain uniform solution.Institute (solid or liquid) can be added in its intrinsic form by stating reducing agent, soluble in water can also be added.

In the application step (3), the compound wet gel of gained is sequentially placed into hydrophilic organic solvent, is purified in water, first Purifying is to remove reducing agent small molecule in the hydrophilic organic solvent, while hydrophilic organic solvent can also avoid The oxidation of black phosphorus quantum dot, being then placed in deionized water again and carrying out purifying is to remove the reducing agent not eliminated and hydrophily 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 that the long period is carried out in hydrophilic organic solvent, can avoid the oxygen of black phosphorus quantum dot as far as possible 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 N-Methyl pyrrolidone (NMP).

In graphene provided by the invention/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel preparation method, graphite Alkene/black phosphorus quantum dot/sulfur-containing anion liquid aeroge formation mechenism are as follows: containing black phosphorus quantum dot and sulfur-containing anion liquid In solution, there is the interaction of " cation-n electronics " between black phosphorus quantum dot and sulfur-containing anion liquid；Contain by described in later There is dispersion liquid of the mixed solution of black phosphorus quantum dot and sulfur-containing anion liquid as 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 not only there is the phase interaction of " cation-n electronics " between black phosphorus quantum dot in sulfur-containing anion liquid With and itself and graphene surface have " cation-π/π-π " and interact, what this to be coated by sulfur-containing anion liquid Black phosphorus quantum dot can be adsorbed on the surface of graphene, be finally capable of forming uniform, stable graphene/black phosphorus quantum dot/and contain The plural gel of sulphion liquid.The small molecule (such as reducing agent, organic solvent) in gel is removed by dialysis later, then The freeze-dried graphene by solution/black phosphorus quantum dot/compound wet gel of sulfur-containing anion liquid is changed into graphene/black phosphorus Quantum dot/sulfur-containing anion liquid graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel.

In graphene provided by the invention/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel preparation method, use Sulfur-containing anion liquid as auxiliary agent or additive, using Graphene gel as carrier or template, it is jointly compound with black phosphorus quantum dot The graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel is formed, the preparation method simple process is easy to operate, at This is low, and yield is higher, Yi Shixian industrialization production.The graphene obtained/black phosphorus quantum dot/compound the gas of sulfur-containing anion liquid Gel is a kind of novel product, with excellent performances such as high resiliency, high recovery, high conductivity, while also being had 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 battery, lithium ion battery etc.), catalysis, water process, photoelectricity and photo-thermal is established Basis is determined.

The advantages of embodiment of the present invention, will partially illustrate in the following description, a part according to specification be it is aobvious and Be clear to, 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/bis- (butyl) methyl sulfonium hexafluorophosphate/N- Methyl pyrrolidone gel (i.e. embodiment 1)；(C) graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/N-Methyl pyrrolidone Gel (comparative example 3)；(D) black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/N-Methyl pyrrolidone (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 is that gained graphene/black phosphorus quantum dot/sulfur-containing anion 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.

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

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

Step (1) prepares uniform, stable black phosphorus quantum dot solution by liquid phase stripping method, the specific steps of which are as follows:

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

1-b): by two (butyl) methyl sulfonium hexafluorophosphate 500mg (i.e. sulfur-containing anions after blocky black phosphorus 25mg and drying Liquid) it is added in agate mortar for 100:2000 in mass ratio and carries out mechanical lapping, the time is 40 minutes；Gained after grinding Mixture is transferred 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, carried out solvent thermal reaction 6 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 7000 revs/min), collects 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, for use.

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, it is water-soluble that ultrasound obtains the graphene oxide that concentration is 2mg/mL Liquid, for use.

Step (3) prepares graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, the specific steps of which are as follows:

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

3-b): by above-mentioned second mixed solution, lower progress heating water bath, reaction time are 2 small under 95 DEG C, oxygen free condition When.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, the side Bian Jiare It is bubbled, the bubbling time is 2h.After reaction, graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate is obtained Wet gel, for use.

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

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

For 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 being subjected to bubbling argon deoxygenation, the time is 40 minutes；Then in argon gas (Ar) atmosphere It encloses, carried out solvent thermal reaction 6 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 7000 revs/min), collects 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, for use.

Step (2) prepares black phosphorus quantum dot aeroge, the specific steps of which are as follows:

2-a): the ascorbic acid of the black phosphorus quantum dot solution of 5mL and 60mg is added in glass container, be stirred with It dissolves ascorbic acid sufficiently, obtains the second mixed solution of stable homogeneous.

2-b): above-mentioned second mixed solution is carried out heating water bath 2 hours down under 95 DEG C, oxygen free condition.Wherein, anaerobic Condition is to carry out deoxygenation by using inert gas bubbling argon, and the flow velocity of argon gas is 100mL/h, Bian Jiare snare drum bubble, when bubbling Between be 2h.After reaction, it is mixed to obtain black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/N-Methyl pyrrolidone Solution is closed, but is not observed in glass container by the formation of any gel.

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 Initial oxidation graphene aqueous solution is formed under effect, is then carried out low-speed centrifugal processing (revolving speed is 1000 revs/min), is dispersed Uniform, stable graphene oxide water solution, for use.

Step (2) prepares graphene/N-Methyl pyrrolidone hydrogel, 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 It in glass container, is stirred so that ascorbic acid sufficiently dissolves, obtains the mixed solution of stable homogeneous, and by above-mentioned mixed solution Lower under 95 DEG C, oxygen free condition to carry out heating water bath, the reaction time is 2 hours.Wherein, oxygen free condition is to pass through inert gas argon The bubbling deoxygenation of gas, the flow velocity of argon gas are mL/h, and the bubbling time is 2h.After reaction, the reaction solution in glass container is observed, And it takes pictures.Graphene/N-Methyl pyrrolidone hydrogel is obtained, for use.

Step (3) prepares the aeroge of graphene, the specific steps of which are as follows:

3-a) gel of above-mentioned gained Graphene gel/N-Methyl pyrrolidone is sequentially placed into NMP and deionized water It is purified and (is equivalent to " dialysis "), to remove extra ascorbic acid small molecule and NMP respectively, purifying total time is 7 days, In, it purifies in NMP 5 days, purifies 2 days in deionized water, during which pay attention to replacing solvent.

3-b) freeze-drying 48 hours will be carried out 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 contain only graphene in this gel, no black phosphorus quantum dot, without ionic liquid.

Comparative example 3

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

Two (butyl) methyl sulfonium hexafluorophosphate 500mg after drying are added to the N-Methyl pyrrolidone of 180mL (NMP) in, the mixed solution of two (butyl) methyl sulfonium hexafluorophosphates and NMP is obtained；

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 graphene-ionic liquid gel, the specific steps of which are as follows:

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 are added in glass container, are stirred so that ascorbic acid sufficiently dissolves, and are obtained uniform steady Fixed mixed solution；

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 100mL/h, and the bubbling time is 2h.After reaction, The reaction solution in glass container is observed, and is taken pictures, graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/N- methyl is obtained The gel of pyrrolidones, for use.

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

By Figure 1A (i.e. comparative example 2) it is found that graphene oxide can be sent out in organic solvent N-Methyl pyrrolidone Survive it is former be concurrently born from assembly behavior and form gel, but its gel content it is smaller (black is still presented in ie in solution, inside Graphene gel it is similar " jelly ").By the comparison of Fig. 1 D (i.e. comparative example 1) and Figure 1B (i.e. embodiment 1) it is found that in phase With under the conditions of, the black phosphorus quantum dot solution (black phosphorus quantum dot, sulfur-containing anion liquid, NMP) of comparative example 1 adds in progress water-bath Acquired solution is integrally presented light yellow after heat, does not observe gel, this shows black phosphorus quantum in simple black phosphorus quantum dot solution 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 implemented In example 1 (in Figure 1B), using the gel of graphene as template or carrier required for black phosphorus quantum dot gel-forming, in black phosphorus In quantum dot solution (black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate/N-Methyl pyrrolidone mixed solution), add After entering graphene oxide and reducing agent, reduction reaction occurs for graphene oxide, is concurrently born from assembly behavior and forms graphene/black phosphorus Quantum dot/sulfur-containing anion liquid plural gel.Moreover, the color (no black) of supernatant is it is found that gained after heating water bath Plural gel content is larger.

In addition, in order to preferably study sulfur-containing anion liquid-bis- (butyl) methyl sulfonium hexafluorophosphate in gel process Effect, the aqueous solution of graphene oxide and two (butyl) methyl sulfonium hexafluorophosphates/N-Methyl pyrrolidone are mixed, added After entering reducing agent, heating water bath is carried out, shown in acquired solution such as Fig. 1 C (comparative example 3).By Fig. 1 C it is found that in the same terms Under, in graphene/bis- (butyl) methyl sulfonium hexafluorophosphate/N-Methyl pyrrolidone solution without black phosphorus quantum dot, graphite Gelation equally has occurred in alkene, 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 N-Methyl pyrrolidone.

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 is that gained graphene/black phosphorus quantum dot/sulfur-containing anion 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.By Fig. 3 A it is found that the embodiment of the present invention obtained by graphene/black phosphorus quantum dot/ 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 be directly by the graphene of bulk/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel from applied body It is taken out in system).By Fig. 3 B it is found that graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel obtained by the embodiment of the present invention It is mainly built by the black phosphorus quantum dot of large stretch of graphene film and nano-scale by accumulation, integrally shows porosity knot Structure, porosity (about 75%) with higher, shows higher specific surface area.

Embodiment 2

1-b): by two (butyl) methyl sulfonium hexafluorophosphate 25mg (i.e. sulfur-containing anions after blocky black phosphorus 25mg and drying Liquid) it is added in agate mortar for 100:100 in mass ratio and carries out mechanical lapping, the time is 40 minutes；Gained after grinding Mixture is transferred 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, carried out solvent thermal reaction 6 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 7000 revs/min), collects 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, for use.

Graphene oxide powder is add to deionized water, it is water-soluble that ultrasound obtains the graphene oxide that concentration is 1mg/mL Liquid, for use.

3-b): above-mentioned second mixed solution being subjected to heating water bath under 95 DEG C, oxygen free condition, 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, is bubbled the time and is 2h.After reaction, graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) is obtained Wet gel, for use.

3-c): the obtained wet gel of above-mentioned 3-b) is sequentially placed into N-Methyl pyrrolidone and deionized water carry out it is pure Change, to remove extra ascorbic acid small molecule, purification time is 7 days, during which pays attention to replacing solvent.

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

Embodiment 3

1-b): by blocky black phosphorus 25mg and it is dry after two (butyl) methyl sulfonium hexafluorophosphate 5000mg (i.e. sulfur-bearing from Sub- liquid) it is added in agate mortar for 100:20000 in mass ratio and carries out mechanical lapping, the time is 40 minutes；After grinding Gained mixture is transferred 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, carried out solvent thermal reaction 6 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 7000 revs/min), collects 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, for use.

Graphene oxide powder is add to 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, for use.

3-d): freeze-drying 48 hours will be carried out at -80 DEG C by gained wet gel after purification, and finally obtain 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 add to deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 0.5mg/mL, for use.

3-d): gained wet gel will be freeze-dried 48 hours at -80 DEG C after purification, and finally obtain graphene/black phosphorus amount The composite aerogel of sub- point/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid).

Embodiment 5

1-b): by two (butyl) methyl sulfonium hexafluorophosphate 500mg (i.e. sulfur-containing anions after blocky black phosphorus 25mg and drying Liquid) it is added in agate mortar for 100:2000 in mass ratio and carries out mechanical lapping, the time is 40 minutes；It will be black after grinding Phosphorus/sulfur-containing anion liquid compound moves in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains One mixed solution；

Graphene oxide powder is add to deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 4mg/mL, for use.

Step (3) prepares high resiliency, highly conductive graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) aeroge, the specific steps of which are as follows:

Embodiment 6

1-b): by blocky black phosphorus 25mg and it is dry after two (butyl) methyl sulfonium hexafluorophosphate 1000mg (i.e. sulfur-bearing from Sub- liquid) it is added in agate mortar for 100:2000 in mass ratio and carries out mechanical lapping, the time is 40 minutes；Institute after grinding It obtains mixture to be transferred in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, obtain 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, carried out solvent thermal reaction 6 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 140 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 7000 revs/min), collects 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, for use.

Graphene oxide powder is add to deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 2mg/mL, for use.

Embodiment 7

Graphene oxide powder is add to deionized water, the concentration that graphene oxide is formed under ultrasonication is The graphene oxide water solution of 5mg/mL, for use.

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

Embodiment 8

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

Embodiment 9

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

Embodiment 10

1-b): by two (butyl) methyl sulfonium hexafluorophosphate 250mg (i.e. sulfur-containing anions after blocky black phosphorus 25mg and drying Liquid) it is added in agate mortar for 100:1000 in mass ratio and carries out mechanical lapping, the time is 40 minutes；Gained after grinding Mixture is transferred in round-bottomed flask, and the N-Methyl pyrrolidone (NMP) of 180mL is added, and obtains the first mixed solution；

3-a): by 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 sufficiently dissolves, obtains the second mixed solution of stable homogeneous.

3-b): above-mentioned second mixed solution being subjected to heating water bath under 95 DEG C, oxygen free condition, 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, is bubbled the time and is 2h.After reaction, graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate (i.e. sulfur-containing anion liquid) is obtained Gel, for use.

3-c): the obtained gel of above-mentioned 3-b) is sequentially placed into N-Methyl pyrrolidone and deionized water and is purified, To remove extra ascorbic acid small molecule, purification time is 7 days, during which pays attention to replacing solvent.

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

The aerogel products that 1 products obtained therefrom of comparative example, Examples 1 to 10 are prepared carry out 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 Mode.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 compound in the product and embodiment 1-10 of 1 comparative example 1 of table The electric conductivity and mechanical recovery performance of aeroge

In order to preferably prove the (graphene/black phosphorus quantum dot/compound airsetting of sulfur-containing anion liquid of products therefrom in the present invention Glue) superior physical properties, table 1 gives the electric conductivity and 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 can not form gel and aeroge, therefore is unable to test Its electric conductivity and mechanical recovery performance.And product obtained by the preparation method that 1-10 of the embodiment of the present invention is provided can test out Its electric conductivity and mechanics restorability.As shown in Table 1, higher electric conductivity is all had obtained by Examples 1 to 10 in the present invention.Its In, 7 gained graphene of embodiment/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has best electric conductivity (i.e. resistance It is minimum, be 1.2 ohm).In addition, as shown in Table 1, in the present invention Examples 1 to 10 product also reply all with higher Property, the response rate that reciprocal rear aeroge is stretched at four times 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, comprising:

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

1-b): being in mass ratio that 100:1000 is added by the triethyl group sulfonium villiaumite 250mg after blocky black phosphorus 25mg and drying 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 The N-Methyl pyrrolidone (NMP) for entering 180mL, 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, carried out solvent thermal reaction 10 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 100 DEG C；Reaction knot Shu Hou is cooled to room temperature to system, and gained reaction solution is carried out low-speed centrifugal processing (revolving speed is 5000 revs/min), collects supernatant Liquid obtains black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/triethyl group sulfonium villiaumite/N-Methyl pyrrolidone mixed solution, to With.

3-b): above-mentioned second mixed solution being subjected to heating water bath under 75 DEG C, oxygen free condition, 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, is bubbled the time and is 2h.After reaction, graphene/black phosphorus quantum dot/bis- (butyl) methyl sulfonium hexafluorophosphate wet gel is obtained, for use.

3-c): the obtained wet gel of above-mentioned 3-b) being sequentially placed into N-Methyl pyrrolidone and deionized water and is purified To remove extra ascorbic acid small molecule, purification time is 7 days, during which pays attention to replacing solvent.

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

Embodiment 12

Step (1) prepares uniform, stable black phosphorus quantum dot/tripropyl sulfonium villaumite (i.e. sulfur-bearing by liquid phase stripping method Ionic liquid)/N-Methyl pyrrolidone mixed solution, the specific steps of which are as follows:

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

1-b): the tripropyl sulfonium villaumite 250mg (i.e. sulfur-containing anion liquid) after blocky black phosphorus 25mg and drying is pressed into quality Mechanical lapping is carried out than being added in agate mortar for 100:1000, the time is 40 minutes, and gained mixture after grinding is shifted To 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, carried out solvent thermal reaction 3 hours under the experiment condition that cooling water is flowed back and is vigorously stirred, temperature is 160 DEG C；Reaction terminates Afterwards, it is cooled to room temperature to system, gained reaction solution is subjected to low-speed centrifugal processing (revolving speed is 6000 revs/min), collects supernatant, Obtain black phosphorus quantum dot solution, i.e. black phosphorus quantum dot/tripropyl sulfonium villaumite (i.e. sulfur-containing anion liquid)/N-Methyl pyrrolidone Mixed solution, for use.

3-b): above-mentioned second mixed solution being subjected to heating water bath under 100 DEG C, oxygen free condition, the reaction time is 1 small When.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, is bubbled the time For 1h.After reaction, graphene/black phosphorus quantum dot/compound wet gel of tripropyl sulfonium villaumite is obtained, for use.

3-c): the obtained wet gel of above-mentioned 3-b) is sequentially placed into N-Methyl pyrrolidone and deionized water carry out it is pure Change, to remove extra 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, and finally obtain 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 be season sulfonium salt class sulfur-containing anion liquid, other experiment conditions such as embodiment 1 is identical, and to product obtained carry out The test of electric conductivity and mechanical recovery performance, 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 2 embodiment 13-51 of table The electric conductivity and mechanical recovery performance of bluk recombination aeroge

The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly It encloses, those skilled in the art can understand all or part of the processes for realizing the above embodiment, and wants according to right of the present invention Made equivalent variations is sought, is still belonged to the scope covered by the invention.

Claims

1. a kind of graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, which is characterized in that including graphene three-dimensional Skeleton and the black phosphorus quantum dot and sulfur-containing anion liquid being supported on the graphene three-dimensional framework, wherein the black phosphorus amount Son point is wrapped up by the sulfur-containing anion liquid, and the graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has three Tie up porous network structure；The mass ratio of the graphene three-dimensional framework and black phosphorus quantum dot is 1:(0.375-8)；The black phosphorus amount Son point and the mass ratio of sulfur-containing anion liquid are 1:(6.25-666.7)；The cation of the sulfur-containing anion liquid is sulfonium salt class sun Ion, shown in structural formula such as following formula (I):

Wherein, R₁、R₂、R₃The alkyl for being separately 1-20 selected from carbon atom number.

2. graphene as described in claim 1/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel, which is characterized in that institute Stating graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel porosity is 70%-94%.

3. a kind of graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel preparation method, which is characterized 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 It stirs evenly, obtains mixed solution；Wherein, the cation of the sulfur-containing anion liquid is sulfonium salt cationoid, and structural formula is as follows Shown in formula (I):

Wherein, R₁、R₂、R₃The alkyl for being separately 1-20 selected from carbon atom number；

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

(3) the compound wet gel of the quantum dot containing black phosphorus is sequentially placed into hydrophilic organic solvent and water purifies, then passed through Freeze-drying, obtains graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel of the quantum dot containing black phosphorus, the graphite Alkene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel includes graphene three-dimensional framework and is supported on the graphene three The black phosphorus quantum dot and sulfur-containing anion liquid on skeleton are tieed up, wherein the black phosphorus quantum dot is wrapped up by the sulfur-containing anion liquid, The graphene/black phosphorus quantum dot/sulfur-containing anion liquid composite aerogel has three-dimensional porous reticular structure；The graphene three The mass ratio for tieing up skeleton and black phosphorus quantum dot is 1:(0.375-8)；The mass ratio of the black phosphorus quantum dot and sulfur-containing anion liquid For 1:(6.25-666.7).

4. preparation method as claimed in claim 3, 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 of the graphene oxide is 1- 10 layers.

5. preparation method as claimed in claim 3, which is characterized 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.

6. preparation method as claimed in claim 3, which is characterized in that the mass ratio of the reducing agent and the graphene oxide For (25-150): 1.

7. preparation method as claimed in claim 5, which is characterized in that described containing black phosphorus quantum dot and sulfur-containing anion liquid Solution is prepared in the following way:

In mass ratio be 1:(1-200 by blocky black phosphorus, sulfur-containing anion liquid) mixing after grind, to grinding gained mixture Middle addition hydrophilic organic solvent, then under anaerobic, 100-160 DEG C back flow reaction 3-10 hours, after reaction, from Heart separation, takes supernatant, obtains the solution containing black phosphorus quantum dot and sulfur-containing anion liquid.