CN107973920A - A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof - Google Patents
A kind of cellulose/two-dimensional layer Material cladding hydrogel and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of cellulose/two-dimensional layer Material cladding hydrogel, the composite hydrogel includes cellulose three-dimensional net structure and the two-dimensional material being supported in the cellulose three-dimensional net structure, and the two-dimensional layer material is two-dimentional transition metal carbide, nitride or carbonitride.Two-dimensional layer material can be stably supported in the composite hydrogel system, be not easy to reunite, and the compatibility of the composite hydrogel and biological fluid is good, and with complete biodegradability, high biological safety, available for biomedical sector.Present invention also offers the preparation method of the composite hydrogel.
Description
Technical field
The invention belongs to hydrogel preparation field, and in particular to a kind of cellulose/two-dimensional layer Material cladding hydrogel and
Its preparation method.
Background technology
Two-dimentional transition metal carbide or carbonitride (i.e. MXenes), a kind of New Two Dimensional material for being this year to find
Material, it has the characteristics that high-specific surface area, high conductivity, flexibly adjustable but also with component, the advantages such as minimum nanometer thickness is controllable,
Possess great potential in fields such as energy storage, electromagnetic shielding, water process, gas/bio-sensing and optical electro-chemistry catalysis.To emphasize
Its two-dimensional structure similar with graphene (graphene), this kind of compound Uniform Name is MXenes.
In biomedical sector, MXenes shows the photothermal conversion effect under excellent near infrared light (such as 808nm)
Rate, shows great advantage in photo-thermal therapy；However, dispersiveness deficiencies of the MXenes in biological fluid, it is heavy easily to occur
Drop, there are obvious geographic difference for its photo-thermal effect.And the structure of the material based on MXenes at present is excessively single,
And the stability of MXenes wherein is poor, easy separate out, can not meet the targeting needed for tumor therapeutic procedure and hold
Long property.Therefore, it is necessary to expand existence forms of the MXenes in biomedical sector.
Cellulose is renewable resource most abundant on the earth, has complete biocompatibility, completely biodegradable etc.
Advantage, but restricted by its high crystalline and intramolecular/intermolecular hydrogen bonding, cellulose indissoluble infusibility, results in difficult processing shaping,
This strongly limits development of the cellulose in bio-medical material.
The content of the invention
In consideration of it, the present invention provides a kind of cellulose/two-dimensional layer Material cladding hydrogel, two-dimensional layer material is multiple at this
High stability in Heshui gel, dispersiveness of the composite hydrogel in biological fluid preferably, show high photo-thermal and turn
Efficiency is changed, there is the excellent specific properties such as complete biocompatibility, biological safety, and there is preferable mechanical strength, is expected to apply
In biomedical sector.
In a first aspect, the present invention provides a kind of cellulose/two-dimensional layer Material cladding hydrogel, the composite hydrogel
It is described including cellulose three-dimensional net structure and the two-dimensional layer material being supported in the cellulose three-dimensional net structure
Two-dimensional layer material is two-dimentional transition metal carbide, nitride or carbonitride (MXenes).
Wherein, the chemical formula of the two-dimensional layer material (MXenes) is Mn+1XnTx, wherein, M is transition metal, X
For carbon and/or nitrogen, n is the integer of 1-3, TxRepresent surface group, T may be selected from O2-、OH-、F-And NH4 +In at least
It is a kind of.
Further, the two-dimensional layer material is Ti3C2Tx、Ti2CTx、(Ti0.5, Nb0.5)2CTx、(V0.5, Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8, Ti0.2)4C3Tx、(Nb0.8, Zr0.2)4C3Tx、Ti3CNTx、
Mo2TiC2Tx、Mo2Ti2C3TxAnd Cr2TiC2TxIn one or more.
In the present invention, the two-dimensional layer material can be stripping or not stripped MXenes materials.Preferably, it is described
Two-dimensional layer material is the two-dimensional layer material after liquid phase is peeled off, its thickness is nanoscale.
Preferably, the thickness of the two-dimensional layer material is 6-10nm.At this time, the two-dimensional layer material can be called
" two-dimensional material nanometer sheet ".The two-dimensional layer material of nanometer grade thickness can be loaded more firmly into the cellulose three-dimensional network
In structure.
Wherein, the number of plies of the two-dimensional layer material is 1-20 layers.More preferably 2-10 layers
Preferably, the lateral dimension of the two-dimensional layer material is 60-200nm.The lateral dimension refers to two-dimensional layer
The length or width of material.
Interaction between two-dimensional layer material MXenes is weaker, and pure MXenes can not be built by self assembly behavior
Gel, the present invention in mainly by cellulosic molecule formed three-dimensional net structure, by two-dimensional layer material MXenes wind
Into the cellulose three-dimensional net structure, two-dimensional layer material MXenes is loaded in the system, form cellulose/two-dimensional layer
Shape Material cladding hydrogel.Wherein, the composite hydrogel significantly improves the dispersiveness of two-dimensional layer material MXenes, prevents
Reunion between MXenes.
Wherein, the three dimensional network that the cellulose three-dimensional net structure includes cellulose or cellulose derivative itself connects into
Network structure, or the three-dimensional net structure formed for cellulose and/or cellulose derivative by crosslinking agent.
Wherein, the cellulose derivative includes at least one of oxidized graphene, chitosan, cyclodextrin and gelatin
The cellulose being modified, or the cellulose of carboxylated, silanization.
Preferably, the crosslinking agent includes at least one of epoxychloropropane and isocyanates, but not limited to this.
Wherein, the cellulose three-dimensional net structure has the pore structure that aperture is 40-130 μm.Preferably, the hole
The aperture of gap structure is 50-80 μm.
Wherein, the water content of the composite hydrogel is 85%-98%.The water content of the composite hydrogel is larger, is easy to
Be dispersed in aqueous solution or organism body fluid, there is excellent compatibility with body fluid, this can improve the two-dimensional layer material with
The adhesiveness of biological cell and tissue.
Wherein, the mass ratio of the cellulose in the cellulose three-dimensional net structure and the two-dimensional layer material is 100：
(0.0001~50), is preferably 100：(0.001~10), more preferably 100：(0.001~5), more preferably 100：
0.05。
In an embodiment of the present invention, the cellulose three-dimensional net structure for cellulosic molecule and cross-linking agents into
Three-dimensional net structure.
Wherein, the mass ratio of the cellulose in the cellulose three-dimensional net structure and crosslinking agent is 100：(1.372-
13.71).Preferably 100：(4.116-13.71), more preferably 100：(4.116-6.86).
Wherein, the cellulose is lignocellulosic, bamboo cellulose, lignose pulp, cotton cellulose, microcrystalline cellulose
One or more in element, hydroxyethyl cellulose, carboxymethyl cellulose.
The composite hydrogel for cellulose/two-dimensional layer material that first aspect present invention provides, it is with cellulose three dimensional network
Network structure is carrier, and two-dimensional layer material is stably loaded with the three-dimensional net structure, improves point of two-dimensional layer material
Property is dissipated, the reunion of two-dimensional layer material is prevented, has expanded the product form of the two-dimensional layer material.Cellulose/bis-
Tie up dispersiveness of the composite hydrogel of stratified material in biological fluid preferably, show high photothermal conversion efficiency, completely biology
The excellent specific properties such as compatibility, biological safety, and there is preferable mechanical strength, it is expected to apply in biomedical sector, especially
It is to be used for therapeutic field of tumor.
Second aspect, the present invention provides a kind of preparation method of cellulose/two-dimensional layer Material cladding hydrogel, including
Following steps：
(1) two-dimensional layer material is provided, the two-dimensional layer material is two-dimentional transition metal carbide, nitride or carbon nitrogen
Compound；
(2) mixed solvent containing highly basic, urea and water is prepared, and carries out precooling, after cellulose powder is added to precooling
The in the mixed solvent, be vigorously stirred, obtain cellulose solution；
(3) under the conditions of high-speed stirred, the two-dimensional layer material, crosslinking agent and the cellulose solution are mixed,
After supersound process, when progress cross-linking reaction 0.5-2 is small at 65-90 DEG C, cross-linking reaction thing is obtained；
(4) cellulose regenerated liquid immersion 30-60min is added into the cross-linking reaction thing, afterwards by the crosslinking after regeneration
Reactant, which is placed in water, dialyses, and obtains cellulose/two-dimensional layer Material cladding hydrogel.
Handed over using cellulose made from the above method/two-dimensional layer Material cladding hydrogel, including cellulose and crosslinking agent
The cellulose three-dimensional net structure being unified into, further includes the two-dimensional layer material being supported in the cellulose three-dimensional net structure.
Further, the surface of the two-dimensional layer material is covered by the cellulose three-dimensional net structure.
Wherein, in step (2), the mixed solvent is cooled to -15~-5 DEG C in advance.So be conducive to the cellulose powder
More good dissolving.Preferably, the mixed solvent is cooled to -12 DEG C in advance.
Alternatively, the particle diameter of the cellulose powder is 10-30 microns.
Wherein, in step (2), the rotating speed being vigorously stirred is 7000~10000rpm, the time being vigorously stirred
For 1~3 minute.
Wherein, in step (3), the rotating speed of the high-speed stirred is 7000~10000rpm, the time of the high-speed stirred
For 1~3 minute.Described be vigorously stirred may be the same or different with the speed of agitator of the high-speed stirred, mixing time.
In step (3), the crosslinking agent is preferably not exclusively hydrophobic material.Epoxy group (C- is carried in the crosslinking agent
O-C) and at least one of isocyanide ester base (NCO), these functional groups in so described crosslinking agent just can be with the fiber
- OH in plain strand crosslinks reaction.
Preferably, one or more of the crosslinking agent in epoxychloropropane and isocyanates, but not limited to this.Into
Preferably, the crosslinking agent is epoxychloropropane to one step.At this time, the hydroxy functional group (- OH) meeting on cellulose molecular chain and ring
Necleophilic reaction occurs for the carbon atom in oxygen chloropropane on epoxy-functional (C-O-C), is cross-linked to form aquogel system.
Wherein, in step (3), the power of the supersound process is 300-500W, and the time is 10~30 minutes.
Preferably, in step (3), the temperature of the cross-linking reaction is 70-85 DEG C.Such as can be 72,75,78,80 or
82℃。
Wherein, in step (4), the cellulose regenerated liquid is the dilution heat of sulfuric acid that mass fraction is 5%~10%.
Preferably, the volume ratio of the cross-linking reaction thing and the dilution heat of sulfuric acid is 1：(2-3).Further, it is used
The volume of dilution heat of sulfuric acid is 10~15mL.Wherein, cross-linking reaction thing is cellulose/crosslinking agent/two-dimensional layer material/hydroxide
The hydrogel of sodium/urea.
Wherein, in step (4), the time of the dialysis is 3-7 days.The purpose of dialysis is primarily to remove highly basic, urine
Element and regenerated liquid.
Wherein, in step (2), the in the mixed solvent, the mass concentration of highly basic is 5-15%, and the mass concentration of urea is
10-15%.
Wherein, the highly basic is the one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
Wherein, in step (2), in the cellulose solution, the mass ratio of mixed solvent and cellulose is 100：(1~4).
Preferably, the volume of the cellulose solution and the volume ratio of the crosslinking agent are 100：(0.2-2.0).
Preferably, the mass ratio of the volume of the cellulose solution and the crosslinking agent is 100：(0.236-2.36)mL/
g。
Preferably, the mass ratio of the quality of the cellulose solution and the crosslinking agent is 100：(0.212-2.12).
Wherein, the cellulose and the mass ratio of two-dimentional transition metal carbide nanometer sheet are 100：(0.0001~50).
Such as can be 100：0.01,100：0.03,100：0.05,100：0.1,100：0.5,100：1,100：5,100：10.It is preferred that
For 100：(0.001~10), more preferably 100：(0.001~5), more preferably 100：0.05.
The two-dimensional layer material MXenes can produce heat under near infrared light (such as 808nm) irradiation, and temperature can be from room
Temperature rise up to 150 DEG C, by regulating and controlling its content in the composite hydrogel, can reach the required temperature for killing cancer cell
(such as 43-60 DEG C), compared with other common photothermal reagents (such as nanogold, nano Pd particle, CuS and porphyrin etc.), two-dimensional layer
Material MXenes has higher photothermal conversion efficiency and preferable biocompatibility and biological safety.
Alternatively, the mass ratio of the cellulose and the two-dimensional layer material is 100：(0.0001-0.01).At this time,
The composite hydrogel can be made in irradiation power to be 0.5/cm2808nm laser irradiation under, photo-thermal equilibrium temperature reaches 50.2-
60.2 DEG C, the composite hydrogel can be made in irradiation power to be 1.0/cm2808nm laser irradiation under, photo-thermal equilibrium temperature reaches
To 55.4-73.1 DEG C.As it can be seen that during two-dimensional layer material containing lower quality, the composite hydrogel just can be assigned well
The photo-thermal effect of killing tumor cell.
In the present invention, the two-dimensional layer material MXenes can be not stripped MXenes bulk materials, Ke Yizhi
Connect to stratiform presoma MAX (chemical formula Mn+1AXn) in element A (such as Al elements) carry out acid etch, high temperature etching or gas phase
Etching obtains.The two-dimensional layer material MXenes, which can also be, to carry out MXenes bulk materials to obtain after further peeling off.
Preferably, the thickness of the two-dimensional layer material is 6-10nm.At this time, the two-dimensional layer material can be called
" two-dimensional material nanometer sheet ".
Preferably, the number of plies of the two-dimensional layer material is 1-20 layers, more preferably 2-10 layers.
Preferably, the lateral dimension of the two-dimensional layer material is 60-200nm.The lateral dimension refers to two-dimensional layer
The length or width of material.
In the present invention, the preparation method of the two-dimensional material nanometer sheet is unlimited, can be prepared in the following way：
(a) by hydrofluoric acid and stratiform presoma MAX (chemical formula Mn+1AXn) be slowly mixed together, with layered forerunner
A bit elements in body MAX etch away, and obtain etching mixed liquor；
After being centrifuged to the etching mixed liquor, washing, collect solid precipitation, and carrying out vacuum to solid precipitation does
After dry, two-dimensional layer material body (being MXenes) is obtained；
(b) it is ground after mixing above-mentioned two-dimensional layer material body and organic solvent, into grinding gained mixture
The organic solvent is added, obtains dispersion liquid；The dispersion liquid is subjected to probe-type ultrasound in the case where power is 1000~1400W
When 30-60 is small, low-speed centrifugal is carried out to resulting solution after ultrasound, is collected supernatant, and by after the supernatant high speed centrifugation, received
Collect solid precipitation, the solid precipitation is vacuum dried, obtains the two-dimensional material nanometer sheet.
Alternatively, the ratio between cumulative volume of the quality of the two-dimensional layer material body and the organic solvent is (0.25-1)
mg/mL。
Alternatively, the time of the grinding is 20-60min, and the grinding is to carry out under anaerobic.
The surface energy of the organic solvent and the surface energy of two-dimensional layer material body match, and exist therebetween certain
Interaction balance peel off the required energy of two-dimensional layer material body.Wherein, the organic solvent is selected from N- first
Base pyrrolidones (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), n-cyclohexyl-2-pyrrolidone (CHP)
With the one or more in isopropanol (IPA), but not limited to this.
Preferably, the rotating speed of the low-speed centrifugal is 5000-8000rpm, time 20-40min.It is further preferred that
The rotating speed of the low-speed centrifugal is 6000-8000rpm.
Preferably, the ultracentrifugal rotating speed is 15000-18000rpm, time 30-60min.Further preferably
Ground, the ultracentrifugal rotating speed are 16000-18000rpm.
Preferably, the vacuum drying drying temperature is 50-80 DEG C, drying time 12-24h.
The formation mechenism of cellulose provided by the invention/two-dimensional layer Material cladding hydrogel is：1) first, using hydrogen-oxygen
Change sodium, the low-temperature alkali mixed solvent of urea and water dissolves cellulose, can be by the hydrogen bond network between the strand of cellulose
It is gradually opened, forms the sodium ion and hydroxide ion of hydrate, new hydrogen bond network is formed with the strand of cellulose, and
Urea molecule hydrate prevents the self-association of cellulose molecular chain again, and final cellulose molecular chain is in the form of channel inclusion compound
Be dissolved in aqueous solution, which overcome high crystalline and intramolecular/intermolecular it is more difficult compared with the cellulose of strong hydrogen bonding be dissolved in including
The problem of usual vehicle including aqueous solvent.In addition, alkaline solution also contributes to improve two-dimentional transition metal carbide nanometer sheet
Stability, the two-dimentional transition metal carbide of protection aoxidized to prevent it.2) when by cellulose aqueous solution and two-dimensional layer material,
Crosslinking agent mixes, after ultrasound under high velocity agitation, and at a certain temperature, necleophilic reaction occurs for cellulose molecular chain and crosslinking agent,
Two-dimensional layer material is fitted together at the same time, two-dimensional layer material is in extremely stable state, forms tridimensional network
Cellulose/crosslinking agent/two-dimensional layer material/sodium hydroxide/urea hydrogel.3) cellulose/crosslinking agent/two-dimensional layer
After the immersion by dilution heat of sulfuric acid, orthogenesis occurs the hydrogel of shape material/sodium hydroxide/urea for cellulose, i.e., fine
Precipitation phenomenon occurs for the plain strand of dimension, is taken out easy to the hydrogel after regenerating, after the immersion of water, sodium hydroxide and urea can
It is removed, finally obtains the composite hydrogel of cellulose/two-dimensional layer material.
In the composite hydrogel of the cellulose/two-dimensional layer material, two-dimensional layer material is by steady load in cellulose
With cross-linking agents into three-dimensional net structure in, due to the obstruction of cellulose macromolecule chain, two-dimensional layer material is in extremely
Stable state, is not susceptible to sedimentation of reuniting so that the composite hydrogel has photo-thermal effect that is more uniform, stablizing, its light
Thermal effect there's almost no region gender gap.Secondly, the moisture of abundance is contained in the composite hydrogel, is readily dispersed in water-soluble
In liquid or organism body fluid, there is excellent compatibility with body fluid, this can improve the two-dimensional layer material and biological cell
With the adhesiveness of tissue.Furthermore due to the gelation of the composite hydrogel, when as anticancer therapy system, it can pass through
The mode of " intratumor injection ", is injected directly into tumor locus.It is in addition, solidifying based on cellulose in the composite hydrogel
Glue frame frame can also fix other hydrophily cancer therapy drugs, assign its realize to the targeted therapy of tumour cell, photo-thermal therapy with
And the multi-mode complex treatment of chemotherapy.Finally, due to the cellulose, two-dimensional layer material are good biocompatibilities
Material, makes the composite hydrogel also have the excellent specific properties such as complete biocompatibility, biological safety.
The preparation method for cellulose/two-dimensional layer Material cladding hydrogel that second aspect of the present invention provides, technique is simple,
It is environmentally protective, products obtained therefrom excellent performance, stable uniform.
The advantages of embodiment of the present invention, will partly illustrate 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 Ti used in the embodiment of the present invention3C2TxTransmission electron microscope (TEM) photo of nanometer sheet：(a) it is low
Differentiate photo (scale 100nm)；(b) high-resolution pattern photo (scale 20nm)；(c) selective electron diffraction photo.
Fig. 2 is the Ti provided in the present invention3C2TxThe aqueous solution of nanometer sheet place at room temperature 24 it is small when before (a), rear (b)
Photomacrograph, and cellulose/Ti in the cellulose aquagel of comparative example 4 and embodiment 2,4,6 and 73C2TxNanometer sheet is answered
The macroscopic view photo (c) in kind of Heshui gel.
Fig. 3 is scanning electron microscope (SEM) photo of the freeze-dried rear gained aeroge of hydrogel：(a) it is fiber
The corresponding aeroge of hydrogel (comparative example 4)；(b) cellulose/Ti3C2TxThe composite hydrogel (embodiment 4) of nanometer sheet is corresponding
Aeroge.
Embodiment
As described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.Wherein, the embodiment of the present invention is unlimited
Due to following specific embodiment.In the range of constant principal right, make a change that can be appropriate is implemented.
Unless otherwise noted, the raw material and other chemical reagent that the embodiment of the present invention uses are all commercial goods.
Embodiment 1
A kind of cellulose/few layer Ti3C2TxThe preparation method of the composite hydrogel of nanometer sheet, including：
Step (1) prepares few layer Ti by liquid phase stripping method3C2TxNanometer sheet, it is comprised the following steps that：
1-a):Multilayer Ti is prepared by hydrofluoric acid etch3C2TxMaterial, material concrete operations are as follows：By powdery ternary layers
Shape nitride Ti3AlC2Add with hydrofluoric acid aqueous solution (mass fraction of HF is 10%~40%) by solid content ratio for 10g/100mL
Enter into vinyon beaker and reacted.Wherein, ternary layered nitride Ti3C2TxNeed to be slowly added into hydrofluoric acid water
In solution, time for being slowly added to is 10 minutes~30 minutes, after addition, reacted under reaction temperature 12 it is small when~it is 24 small
When.After reaction, gained etching mixed liquor is centrifuged 35 minutes under the rotating speed of 17000rpm, collects solid precipitation, and it is right
It is washed with absolute ethyl alcohol and deionized water repeatedly, until solution is in neutrality.The precipitation obtained after washing is that binary is more
Layer Ti3C2Tx；Finally by gained be deposited in vacuum drying 48~64 it is small when, it is stand-by；
1-b):By above-mentioned two-dimentional multilayer Ti3C2TxMXene materials and 1-methyl-2-pyrrolidinone (NMP) are by solid content ratio
500mg/10mL, which is added in agate mortar, carries out mechanical lapping, and the time is 30 minutes；The compound for grinding gained is moved to
In 100mL reaction bulbs, and the NMP of 90mL is added, obtain dispersion liquid, two-dimentional multilayer Ti3C2TxMXene materials are in total NMP
Solid content be 5mg/mL.
1-c):Above-mentioned dispersion liquid is subjected to probe sonication, ultrasonic power 600W, when the time is 50 small, is obtained containing two dimension
Few layer Ti3C2TxThe solution of nanometer sheet, i.e., layer Ti less3C2TxThe mixed solution of nanometer sheet and NMP, it is stand-by.
1-d):By above-mentioned few layer Ti3C2TxNanometer sheet solution is centrifuged, rotating speed 7000rpm, and the time is 25 minutes, is delayed
The supernatant of slow taking-up 3/4.
1-e):Then high speed centrifugation, rotating speed 17000rpm are carried out to above-mentioned supernatant, the time is 35 minutes, is slowly fallen
Go out supernatant, collect few layer Ti3C2TxNanometer sheet solid.
1-f):By above-mentioned few layer Ti3C2TxNanometer sheet solid in vacuum drying chamber it is dry 20 it is small when, temperature is 75 DEG C, most
Few layer of Ti of drying is obtained eventually3C2TxNanometer sheet solid, it is stand-by.
Step (2) prepares the alkaline aqueous solution of transparent homogeneous cellulose, it is comprised the following steps that：
2-a):Sodium hydroxide, urea and deionized water are added to according to the ratio that mass ratio is 7%/12%/81%
In the beaker of 200mL, mixed solvent is obtained, the wherein quality of deionized water is 81.0g, i.e. the cumulative volume of mixed solvent is
100mL；Mixed solvent is subjected to precooling 30 minutes, its temperature is reached -12 DEG C, it is stand-by.
2-b):Cellulose powder is added to the in the mixed solvent after above-mentioned precooling, wherein mixed solvent and cellulose
Mass ratio is 100：4；Then obtained cellulose suspension is vigorously stirred, mixing speed 7500rpm, the time 2
Minute, finally obtain homogeneous, transparent cellulose solution, i.e. the mixing of cellulose/sodium hydroxide/urea/deionized water is molten
Liquid, it is stand-by.
Step (3) prepares cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, it is comprised the following steps that：
3-a):The cellulose solution 5mL in step (2) is taken, takes few layer of Ti in step (1)3C2TxNanometer sheet solid, its
Middle cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：0.0001, take epoxychloropropane 0.5mL, i.e. cellulose solution
It is 100 with the ratio between the volume of epoxychloropropane：10；By three's high agitation, mixing speed 7500rpm, the time is 2 minutes；
Then water bath sonicator, ultrasonic power 300W, time are 15 minutes, obtain the mixed liquor after ultrasound, i.e. cellulose/epoxy chloropropionate
Alkane/few layer Ti3C2TxThe mixed solution of nanometer sheet/sodium hydroxide/urea/deionized water.
3-b):Mixed liquor after above-mentioned ultrasound is placed in 70 DEG C of oil bath and carries out chemical crosslink reaction, the reaction time is
1.5 it is small when, obtain cross-linking reaction thing, i.e. cellulose/epoxychloropropane/few layer Ti3C2TxNanometer sheet/sodium hydroxide/urea/is gone
The hydrogel of ionized water.
3-c):15mL is added into above-mentioned cross-linking reaction thing, the dilution heat of sulfuric acid that mass fraction is 8%, acid soak 40 is divided
Clock, so that cellulose regenerated behavior, i.e. cellulose molecular chain separates out.Then, the cross-linking reaction thing after regeneration is placed in
In ionized water, dialyse 5 days, come so that sodium hydroxide, urea, sulfuric acid gradually give, finally obtain cellulose/few layer Ti3C2Tx
The composite hydrogel of nanometer sheet.
Cellulose made from the embodiment of the present invention/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, including cellulosic molecule
With cross-linking agents into three-dimensional net structure, and few layer of Ti being supported in the three-dimensional net structure3C2TxNanometer sheet.
Embodiment 2
Prepare cellulose/few layer Ti3C2TxNanometer sheet/composite hydrogel, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：0.01.
Embodiment 3
Prepare cellulose/few layer Ti3C2TxNanometer sheet/composite hydrogel, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：0.03.
Embodiment 4
Prepare cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：0.05.
Embodiment 5
Prepare cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：5.
Embodiment 6
Prepare cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：10.
Embodiment 7
Prepare cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet, difference lies in step 3-a with embodiment 1)
In, cellulose and few layer Ti3C2TxThe mass ratio of nanometer sheet is 100：50.
To protrude beneficial effects of the present invention, while provide following comparative example：
Comparative example 1
Cellulose aquagel is prepared, including:
Step (1) prepares the alkaline aqueous solution of transparent homogeneous cellulose, it is comprised the following steps that：
1-a):Sodium hydroxide, urea and deionized water are added to according to the ratio that mass ratio is 7%/12%/81%
In the beaker of 200mL, mixed solvent is obtained, the wherein quality of deionized water is 81.0g, i.e. the cumulative volume of mixed solvent is
100mL；Mixed solvent is subjected to precooling 30 minutes, its temperature is reached -12 DEG C, it is stand-by.
1-b):Cellulose powder is added to the in the mixed solvent after above-mentioned precooling, wherein mixed solvent and cellulose
Mass ratio is 100：1；Then obtained cellulose suspension is vigorously stirred, mixing speed 7500rpm, the time 2
Minute, finally obtain homogeneous, transparent cellulose solution, i.e. the mixing of cellulose/sodium hydroxide/urea/deionized water is molten
Liquid.
Step (2) prepares cellulose aquagel, it is comprised the following steps that：
2-a):The cellulose solution 5mL in step (1) is taken, takes epoxychloropropane 0.1mL, i.e. cellulose solution and epoxy
The ratio between volume of chloropropane is 100：2；By three's high agitation, mixing speed 7500rpm, the time is 2 minutes；Then water-bath
Ultrasound, ultrasonic power 300W, time are 15 minutes, obtain the mixed liquor after ultrasound, i.e. cellulose/epoxychloropropane/hydroxide
The mixed solution of sodium/urea/deionized water, it is stand-by.
2-b):Mixed solution after above-mentioned ultrasound is placed in 70 DEG C of oil bath chemical crosslink reaction occurs, the reaction time
For 1.5 it is small when, obtain cross-linking reaction thing, i.e. the hydrogel of cellulose/epoxychloropropane/sodium hydroxide/urea/deionized water,
It is stand-by.
2-c):15mL is added into above-mentioned cross-linking reaction thing, the dilution heat of sulfuric acid that mass fraction is 8% carries out 40 points of immersion
Clock, so that cellulose regenerated behavior.Then, the cross-linking reaction thing after regeneration is placed in deionized water, dialysed 5 days, so that hydrogen
Sodium oxide molybdena and urea, which gradually give, to be come, and finally obtains the hydrogel of cellulose/epoxychloropropane, (referred to as cellulose water-setting
Glue).
Comparative example 2：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：2,
The ratio between volume of cellulose solution and epoxychloropropane is 100：4.
Comparative example 3：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：3,
The ratio between volume of cellulose solution and epoxychloropropane is 100：6.
Comparative example 4：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：10.
Comparative example 5：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：14.
Comparative example 6：Difference lies in the mass ratio of mixed solvent and cellulose is 100 with comparative example 1：4,
The ratio between volume of cellulose solution and epoxychloropropane is 100：20.
Fig. 1 is few layer of Ti used in the embodiment of the present invention3C2TxThe transmission electron microscope microscopic appearance of nanometer sheet
Figure, (a) is low resolution photo；(b) it is high-resolution photo.Few layer Ti3C2TxThe microscopic appearance test condition of nanometer sheet is as follows：Instrument
Device equipment：High resolution transmission electron microscopy；Model：FEI Tecnai G2F30；Testing high voltage：300kV.
In Fig. 1 (a), few layer Ti3C2TxAbout 60 nanometers × 200 nanometers of the size of nanometer sheet；(b) can in Fig. 1
Know, few layer Ti3C2TxNanometer sheet shows obvious multiple layer structures, shows few layer Ti in the present invention3C2TxNanometer sheet has
There is preferable two-dimensional layered structure.In addition, gained lacks layer Ti3C2TxThe number of plies of nanometer sheet is 6~10 layers.In Fig. 1 (c),
Gained lacks layer Ti3C2TxNanometer sheet has fainter selective electron diffraction structure, shows few layer Ti3C2TxNanometer sheet has certain
Crystal structure.
Fig. 2 provides the few layer Ti of gained3C2TxThe aqueous solution (100ppm) of nanometer sheet place at room temperature 24 it is small when it is front and rear
Photomacrograph, and the cellulose aquagel of comparative example 4 and cellulose/few layer Ti3C2TxNanometer sheet (embodiment 2,4,6 and 7) multiple
Heshui gel macroscopic view photo in kind.As shown in Figure 2, few layer Ti3C2TxBefore nanometer sheet aqueous solution is when 24 is small, be uniformly dispersed (Fig. 2
In (a))；But stand 24 it is small when after, few layer Ti3C2TxSignificant settling behavior occurs for nanometer sheet aqueous solution, and solution colour shoals
(in Fig. 2 (c)), shows few layer Ti3C2TxNanometer sheet it is water-soluble poor.In Fig. 2 (c), pure cellulose hydrogel is (right
Ratio 4) it is in integrally semi-transparent clear shape " jelly type " macro morphology；And in few layer of Ti3C2TxAfter nanometer sheet is successfully introduced into, gained
Cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet is overall with few layer of Ti3C2TxThe increase of nanometer sheet content and darkly
Color, the two is contrasted with strikingly color.
Fig. 3 provides cellulose aquagel ((a), comparative example 4) and cellulose/few layer Ti3C2TxThe compound water congealing of nanometer sheet
The electron scanning micrograph of the corresponding aeroge of glue ((b), embodiment 4) gained after freeze-drying.Test condition is as follows：For
Retain the macromolecular loose structure in cellulose aquagel, the hydrogel (cellulose aquagel and embodiment of comparative example 4 of test
4 cellulose/few layer Ti3C2TxThe composite hydrogel of nanometer sheet) first passing around freeze-drying process, to obtain corresponding airsetting cementing
Structure, wherein the experiment condition being freeze-dried：Temperature：-80℃；Time：72 it is small when.Then the test of microscopic appearance is carried out, is used
Instrument and equipment：Cold field emission scanning electron microscope；Model：SEM-Hitachi SU8010；Test voltage：3kV；Sample table
The silver-colored time is crossed in face：20 seconds.
From the figure 3, it may be seen that this two aerogel-like shows obvious porosity, this is the three dimensional gell network by cellulose
Structure is determined.But it is significantly cellulose produced by the present invention/few layer Ti3C2TxCorresponding to the composite hydrogel of nanometer sheet
The cavernous structure distribution uniform of aeroge, aperture are 50-80 μm, and the porosity is about 75%.
By cellulose made from comparative example 1~6/epoxychloropropane hydrogel and cellulose prepared by embodiment 1~7/
Few layer Ti3C2TxThe composite hydrogel of nanometer sheet carries out Mechanics Performance Testing and light thermal property test respectively, and the results are shown in Table 1.
The basis and performance parameter of hydrogel in table 1 comparative example 1-6 and embodiment 1-7
Table 1 gives the typical case's composition and physical property of comparative example 1-6 and embodiment 1-7 in patent of the present invention.Can by table 1
Know, in comparative example 1-6, with the raising of the volume fraction of crosslinking agent epoxychloropropane, its final gained cellulose aquagel
Mechanical strength be also to significantly increase substantially.For example, when the volume ratio 100 of cellulose solution and epoxychloropropane：When 0.2
(i.e. comparative example 1), its compression modulus are 19.4kPa；When the volume ratio of cellulose solution and epoxychloropropane increases to 100：1.0
(i.e. comparative example 4) and 100：When 2.0 when (comparative example 6), its corresponding compression modulus increase to respectively 60.8kPa and
79.1kPa, this is because caused by more content of crosslinking agent make it that the chemical crosslinking degree of cellulose aquagel greatly improves.So
And pure cellulose hydrogel lacks any feature, it does not show any photo-thermal effect, its photo-thermal equilibrium temperature is 25
DEG C, it is essentially identical with room temperature.
However, as striking contrast, the cellulose provided in embodiment 1-7/few layer Ti3C2TxThe Compound Water of nanometer sheet
In gel, due to few layer of Ti3C2TxThe introducing of nanometer sheet, its final photo-thermal equilibrium temperature significantly raise.For example, work as fiber
Element and few layer Ti3C2TxThe mass ratio 100 of nanometer sheet：When 0.0001 (i.e. embodiment 1), the final light thermal balance of composite hydrogel
Temperature is in 0.5 and 1.0W/cm2When be able to reach 50.2 and 55.4 DEG C, compared with pure cellulose hydrogel, there is about 25.2 Hes
30.4 DEG C of raising.As continuation increased fiber element/few layer Ti3C2TxFew layer Ti in the composite hydrogel of nanometer sheet3C2TxNanometer sheet
Mass fraction when, this photo-thermal equilibrium temperature significantly increases the detection range for being even more than thermal imaging system.For example, when fibre
Dimension element and few layer Ti3C2TxThe mass ratio 100 of nanometer sheet：When 5 (i.e. embodiment 5), the final light thermal equilibrium temperature of composite hydrogel
In 0.5 and 1.0W/cm2When respectively 122 and 135.7 DEG C；When cellulose and few layer Ti3C2TxThe mass ratio 100 of nanometer sheet：10
(i.e. embodiment 6) and 100：When 50 (i.e. embodiment 7), the final light thermal equilibrium temperature of composite hydrogel is higher than 150 DEG C, exceedes
The detection range of thermal imaging system.
Result above shows that two-dimensional layer material (specially lacks layer Ti3C2TxNanometer sheet) introducing not only significantly improve
The mechanical strength of cellulose aquagel, and can actually assign cellulose aquagel excellent Photothermal characterisation, and also this is special
Property can pass through few layer of Ti3C2TxThe content of nanometer sheet is adjusted.And as the few layer of Ti using lower quality3C2TxDuring nanometer sheet,
With regard to the photo-thermal equilibrium temperature that the composite hydrogel can be made to reach higher.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of cellulose/two-dimensional layer Material cladding hydrogel, it is characterised in that the composite hydrogel includes cellulose iii
Dimension network structure and the two-dimensional material being supported in the cellulose three-dimensional net structure, the two-dimensional layer material are two
Tie up transition metal carbide, nitride or carbonitride.
2. composite hydrogel as claimed in claim 1, it is characterised in that the thickness of the two-dimensional layer material is 6-10nm.
3. composite hydrogel as claimed in claim 1, it is characterised in that the cellulose three-dimensional net structure includes cellulose
Or the three-dimensional net structure that cellulose derivative itself connects into, or cellulose and/or cellulose derivative pass through crosslinking agent
The three-dimensional net structure of formation.
4. the composite hydrogel as described in claim 1 or 3, it is characterised in that the cellulose three-dimensional net structure has hole
Footpath is 50-80 μm of pore structure.
5. composite hydrogel as claimed in claim 1 or 2, it is characterised in that the fibre in the cellulose three-dimensional net structure
It is 100 to tie up the plain and mass ratio of the two-dimensional material nanometer sheet：(0.0001~50).
6. composite hydrogel as claimed in claim 2, it is characterised in that the cellulose in the cellulose three-dimensional net structure
Mass ratio with crosslinking agent is 100：(1.372~13.71).
7. the preparation method of a kind of cellulose/two-dimensional material nanometer sheet composite hydrogel, it is characterised in that comprise the following steps：
(1) two-dimensional layer material is provided, the two-dimensional layer material is two-dimentional transition metal carbide, nitride or carbon nitridation
Thing；
(2) mixed solvent containing highly basic, urea and water is prepared, and carries out precooling, institute cellulose powder being added to after precooling
In the mixed solvent is stated, is vigorously stirred, obtains cellulose solution；
(3) under the conditions of high-speed stirred, the two-dimensional layer material, crosslinking agent and the cellulose solution are mixed, ultrasound
After processing, when progress cross-linking reaction 0.5-2 is small at 65-90 DEG C, cross-linking reaction thing is obtained；
(4) cellulose regenerated liquid immersion 30-60min is added into the cross-linking reaction thing, afterwards by the cross-linking reaction after regeneration
Thing, which is placed in water, dialyses, and obtains cellulose/two-dimensional layer Material cladding hydrogel.
8. preparation method as claimed in claim 7, it is characterised in that the in the mixed solvent, the mass concentration of highly basic is 5-
15%, the mass concentration of urea is 10-15%.
9. preparation method as claimed in claim 7, it is characterised in that in the cellulose solution, mixed solvent and cellulose
Mass ratio be 100：(1~4)；The mass ratio of the volume of the cellulose solution and the crosslinking agent is 100：(0.212~
2.12)。
10. preparation method as claimed in claim 7, it is characterised in that in step (3), the cellulose regenerated liquid is quality
Fraction is 5%~10% dilution heat of sulfuric acid；The volume ratio of the cross-linking reaction thing and the dilution heat of sulfuric acid is 1：(2-3).
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