CN107936266A - A kind of cellulose/black phosphorus nanometer sheet composite hydrogel and preparation method thereof - Google Patents
A kind of cellulose/black phosphorus nanometer sheet composite hydrogel and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of cellulose/black phosphorus nanometer sheet composite hydrogel, it is characterised in that the composite hydrogel includes cellulose three-dimensional net structure and the black phosphorus nanometer sheet being supported in the cellulose three-dimensional net structure.Black phosphorus nanometer sheet can be stably supported in the composite hydrogel system, it is not easy to reunite, the composite hydrogel has high photothermal conversion efficiency uniformly, stable, good with the compatibility of biological fluid, 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 black phosphorus based nano-material preparation field, and in particular to a kind of cellulose/black phosphorus nanometer sheet Compound Water
Gel and preparation method thereof.
Background technology
Black phosphorus (Black phosphorene) is a kind of new direct band gap two-dimensional material, its band gap can be from 0.3eV (this
Body state) it is adjusted to 1.5eV (individual layer) by its number of plies, it can absorb from visible ray to communication with infra-red range wavelength
Light, its higher carrier mobility, high make-to-break ratio, and good photothermal conversion effect and biocompatibility in addition, make
Obtain it and show great potential advantages in semiconductor applications, photoelectric field and biological field etc..
In biomedical sector, dispersiveness deficiency of the inorganic nano material-black phosphorus in biological fluid, it is heavy easily to occur
Drop, there are obvious geographic difference for its photo-thermal effect.And the structure of current black phosphorus sill is excessively single, and black phosphorus is at it
In stability it is poor, easy separate out, can not meet the targeting and persistence needed for tumor therapeutic procedure.Therefore, have
Necessity expands existence form of the black phosphorus 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/black phosphorus nanometer sheet composite hydrogel, black phosphorus nanometer sheet is in the Compound Water
High stability in gel, dispersiveness of the cellulose/black phosphorus nanometer sheet composite hydrogel in biological fluid is preferable, table
Reveal the excellent specific properties such as high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, biological safety, and have
There is preferable mechanical strength, be expected to apply in biomedical sector.
In a first aspect, the present invention provides a kind of cellulose/black phosphorus nanometer sheet composite hydrogel, the composite hydrogel bag
Include cellulose three-dimensional net structure and the black phosphorus nanometer sheet being supported on the cellulose three-dimensional net structure.
It is weaker due to interacting between black phosphorus nanometer sheet, black phosphorus nanometer sheet can not be built by self assembly behavior
Gel, the three-dimensional net structure mainly formed in of the invention by cellulosic molecule, the cellulose is wound into by black phosphorus nanometer sheet
In three-dimensional net structure, black phosphorus nanometer sheet is loaded in the system, form cellulose/black phosphorus nanometer sheet composite hydrogel.Its
In, the composite hydrogel significantly improves the dispersiveness of black phosphorus nanometer sheet, prevents the reunion between black phosphorus nanometer sheet.
Preferably, the thickness of the black phosphorus nanometer sheet is 1-25nm.More preferably 3-18nm.The two of nanometer grade thickness
Dimension stratified material can be loaded more firmly into the cellulose three-dimensional net structure.
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 100-800nm.The lateral dimension refers to two-dimensional layer
The length or width of material.
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 that cellulose and/or cellulose derivative are formed 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 30-300 μm.Preferably, the hole
The aperture of gap structure is 50-280 μm.More preferably 80-250 μm.
Wherein, the water content of the composite hydrogel is 85%-98%.The water content of the composite hydrogel is larger, is easy to
It is dispersed in aqueous solution or organism body fluid, there is excellent compatibility with body fluid, this can improve the black phosphorus nanometer sheet and life
The adhesiveness of object cell and tissue.
Wherein, the cellulose in the cellulose three-dimensional net structure and the mass ratio of black phosphorus nanometer sheet are 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.
Cellulose/black phosphorus nanometer sheet composite hydrogel that first aspect present invention provides, it is with cellulose three-dimensional network knot
Structure is carrier, and black phosphorus nanometer sheet is stably loaded with the three-dimensional net structure, improves the dispersiveness of black phosphorus nanometer sheet, is prevented
Reunion between black phosphorus nanometer sheet, has expanded the product form of black phosphorus.The cellulose/black phosphorus nanometer sheet composite hydrogel exists
In biological fluid dispersiveness preferably, show high photothermal conversion efficiency, complete biodegradability, complete biocompatibility,
The excellent specific properties such as biological safety, and there is preferable mechanical strength, it is expected to apply in biomedical sector, in particular for
Therapeutic field of tumor.
Second aspect, the present invention provides a kind of preparation method of cellulose/black phosphorus nanometer sheet composite hydrogel, including with
Lower step：
(1) 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；
(2) under the conditions of high-speed stirred, black phosphorus nanometer sheet, crosslinking agent and the cellulose solution are mixed, at ultrasound
After reason, when progress cross-linking reaction 0.5-2 is small at 65-90 DEG C, cross-linking reaction thing is obtained；
(3) add cellulose regenerated liquid into the cross-linking reaction thing and carry out immersion 30-60min, afterwards by after regeneration
Cross-linking reaction thing, which is placed in water, dialyses, and obtains cellulose/black phosphorus nanometer sheet composite hydrogel.
Using cellulose made from the above method/black phosphorus nanometer sheet composite hydrogel, including cellulose and cross-linking agents
Into cellulose three-dimensional net structure, further include the black phosphorus nanometer sheet being supported in the cellulose three-dimensional net structure.Into one
Step ground, the black phosphorus nanometer sheet surface is covered by the cellulose three-dimensional net structure.
Wherein, in step (1), 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 (1), the rotating speed being vigorously stirred is 7000~10000rpm, the time being vigorously stirred
For 1-3 minutes.
In step (2), 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 (2), the rotating speed of the high-speed stirred is 7000~10000rpm, the time of the high-speed stirred
For 1-3 minutes.Described be vigorously stirred may be the same or different with the speed of agitator of the high-speed stirred, mixing time.
Wherein, in step (2), the power of the supersound process is 300-500W, and the time is 10-30 minutes.
Preferably, in step (2), 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 (3), 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 for cellulose/crosslinking agent/black phosphorus nanometer sheet/sodium hydroxide/
The hydrogel of urea.
Wherein, in step (3), 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 (1), 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 (1), 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 black phosphorus 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.Preferably 100：(0.001-
10) it is more preferably, 100：(0.001-5), more preferably 100：0.05.
The black phosphorus nanometer sheet can produce heat under near infrared light (such as 808nm) irradiation, and temperature can rise to height from room temperature
Up to 150 DEG C, by regulating and controlling its content in the composite hydrogel, required temperature (such as 43-60 for killing cancer cell can reach
DEG C), compared with other common photothermal reagents (such as nanogold, nano Pd particle, CuS and porphyrin etc.), black phosphorus nanometer sheet can be in life
Biodegradable behavior occurs in object, its catabolite is the phosphate of security, show preferable biocompatibility and
Biological safety.
Alternatively, the cellulose and the mass ratio of black phosphorus nanometer sheet are 100：(0.0001-0.01).At this time, institute can be made
It is 0.5/cm that composite hydrogel, which is stated, in irradiation power2808nm laser irradiation under, photo-thermal equilibrium temperature reaches 43.5-60 DEG C, can
The composite hydrogel is set in irradiation power to be 1.0/cm2808nm laser irradiation under, photo-thermal equilibrium temperature reaches 48-75 DEG C.
As it can be seen that during black phosphorus nanometer sheet containing lower quality, the light of the good killing tumor cell of the composite hydrogel can be just assigned
Thermal effect.
Preferably, the thickness of the black phosphorus nanometer sheet is 1-25nm.More preferably 3-18nm.
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 100-800nm.The lateral dimension refers to two-dimensional layer
The length or width of material.
In the present invention, the preparation method of the black phosphorus nanometer sheet is unlimited, can be prepared in the following way：
It is ground, is added into grinding gained mixture described organic molten after block black phosphorus and organic solvent are mixed
Agent, obtains dispersion liquid；By the dispersion liquid when progress probe-type ultrasound 30-60 is small under power is 1000~1400W, to ultrasound
Resulting solution carries out low-speed centrifugal afterwards, collects supernatant, and after the supernatant high speed centrifugation, will collect solid precipitation, described
Solid precipitation is vacuum dried, obtains the black phosphorus nanometer sheet.
Alternatively, the ratio between cumulative volume of the quality of the black phosphorus 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-dimentional black phosphorus match, and there are certain phase interaction therebetween
The required energy of bulk black phosphorus is peeled off with balancing.Wherein, the organic solvent be selected from 1-methyl-2-pyrrolidinone (NMP),
In dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), n-cyclohexyl-2-pyrrolidone (CHP) and isopropanol (IPA)
One or more, 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/black phosphorus nanometer sheet composite hydrogel is：1) first, using hydroxide
The low-temperature alkali mixed solvent of sodium, urea and water dissolves cellulose, can by the hydrogen bond network quilt 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 urinates
Plain molecule hydrate prevents the self-association of cellulose molecular chain again, and final cellulose molecular chain is molten in the form of channel inclusion compound
Solution is dissolved in including water in aqueous solution, which overcome high crystalline and intramolecular/intermolecular are more difficult compared with the cellulose of strong hydrogen bonding
The problem of usual vehicle including solvent.In addition, alkaline solution also contributes to improve the stability of black phosphorus nanometer sheet, protection black phosphorus
Aoxidized to prevent it.2) when cellulose aqueous solution is mixed under high velocity agitation with black phosphorus nanometer sheet, crosslinking agent, ultrasound after,
Under certain temperature, necleophilic reaction occurs for cellulose molecular chain and crosslinking agent, while black phosphorus nanometer sheet is fitted together into, black phosphorus is received
Rice piece is in extremely stable state, forms cellulose/crosslinking agent/black phosphorus nanometer sheet/sodium hydroxide/urine of tridimensional network
The hydrogel of element.3) hydrogel of the cellulose/crosslinking agent/black phosphorus nanometer sheet/sodium hydroxide/urea is molten by dilute sulfuric acid
After the immersion of liquid, orthogenesis occurs for cellulose, i.e. precipitation phenomenon occurs for cellulose molecular chain, is taken easy to the hydrogel after regenerating
Go out, after the immersion of water, sodium hydroxide and urea can be removed, and finally obtain cellulose/black phosphorus nanometer sheet composite hydrogel.
In the cellulose/black phosphorus nanometer sheet composite hydrogel, black phosphorus nanometer sheet is by steady load in cellulose and crosslinking
In the three-dimensional net structure that agent is cross-linked into, due to the obstruction of cellulose macromolecule chain, black phosphorus nanometer sheet is in extremely stable shape
State, is not susceptible to sedimentation of reuniting so that the composite hydrogel has photo-thermal effect that is more uniform, stablizing, its photo-thermal effect is several
Region gender gap is not present.Secondly, the moisture of abundance is contained in the composite hydrogel, is readily dispersed in aqueous solution or biology
In body body fluid, there is excellent compatibility with body fluid, this can improve the black phosphorus nanometer sheet and biological cell and organize viscous
Attached property.Furthermore due to the gelation of the composite hydrogel, when as anticancer therapy system, " intratumor injection " can be passed through
Mode, be injected directly into tumor locus.In addition, the gel frame in the composite hydrogel based on cellulose may be used also
To fix other hydrophily cancer therapy drugs, targeted therapy, photo-thermal therapy and chemotherapy of its realization to tumour cell are assigned
Multi-mode complex treatment.Finally, due to the cellulose, black phosphorus nanometer sheet are degradable, good biocompatibility material,
Make the composite hydrogel that also there is the excellent specific properties such as complete biodegradability, complete biocompatibility, biological safety.
The preparation method for cellulose/black phosphorus nanometer sheet composite hydrogel that second aspect of the present invention provides, technique is simple, green
Colour circle is protected, 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 transmission electron microscope (TEM) photo of the black phosphorus nanometer sheet used in the embodiment of the present invention：(a) low point
Distinguish photo (scale 100nm)；(b) high-resolution pattern photo (scale 10nm).
Fig. 2 is atomic force microscope (AFM) photo of black phosphorus nanometer sheet used in the embodiment of the present invention, including AFM high
The thickness (right side) of degree figure (left side) and corresponding three different size black phosphorus nanometer sheets.
Fig. 3 is the grand of cellulose aquagel (comparative example 4) and cellulose/black phosphorus nanometer sheet composite hydrogel (embodiment 4)
See photo in kind.
Fig. 4 is the freeze-dried rear gained aeroge of cellulose/black phosphorus nanometer sheet composite hydrogel in the embodiment of the present invention 4
Scanning electron microscope (SEM) photo；Wherein (b) is the amplification in region in (a).
Fig. 5 is the SEM photograph of the freeze-dried rear gained aeroge of cellulose aquagel in comparative example 4；Wherein (b) is
(a) amplification in region in.
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, raw material and other chemical reagent are all commercial goods used by the embodiment of the present invention.
Embodiment 1
A kind of preparation of cellulose/black phosphorus nanometer sheet composite hydrogel, including：
Step (1) prepares the black phosphorus nanometer sheet solid of size uniformity by liquid phase stripping method, it is comprised the following steps that：
1-a):Block black phosphorus and 1-methyl-2-pyrrolidinone (NMP) are added to agate by solid content ratio for 500mg/10mL
Mechanical lapping is carried out in mortar, the time is 30 minutes；The compound of black phosphorus/1-methyl-2-pyrrolidinone (NMP) is moved to after grinding
In 100mL reaction bulbs, and the NMP of 90mL is added, obtain dispersion liquid, solid content of the final black phosphorus in total NMP is 5mg/mL.
1-b):Above-mentioned dispersion liquid is subjected to probe sonication, ultrasonic power 600W, when the time is 50 small, obtains containing black phosphorus
The solution of nanometer sheet, it is stand-by.
1-c):Low-speed centrifugal, rotating speed 7000rpm are carried out to above-mentioned black phosphorus nanometer sheet solution, the time is 25 minutes, slowly
Take out 3/4 supernatant.
1-d):High speed centrifugation, rotating speed 17000rpm are carried out to above-mentioned supernatant, the time is 35 minutes, is slowly poured out
Clear liquid, collects black phosphorus nanometer sheet solid.
1-e):When by above-mentioned black phosphorus nanometer sheet solid, drying 20 is small in vacuum drying chamber, temperature is 75 DEG C, is finally obtained
Dry black phosphorus nanometer sheet solid, it is stand-by.
After tested, the lateral dimension of gained black phosphorus nanometer sheet is 200-400nm, and the number of plies is 15 layers, thickness 9nm.
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 the composite hydrogel of cellulose/black phosphorus nanometer sheet, it is comprised the following steps that：
3-a):The cellulose solution 5mL in step (2) is taken, takes the black phosphorus nanometer sheet solid in step (1), wherein fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：0.0001, take epoxychloropropane 0.05mL, i.e. cellulose solution and epoxy
The ratio between volume of chloropropane is 100：1；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/black phosphorus is received
The mixed solution of rice piece/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/black phosphorus nanometer sheet/sodium hydroxide/urea/deionized water
Hydrogel.
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/black phosphorus nanometer sheet
Composite hydrogel.
The composite hydrogel of cellulose made from the embodiment of the present invention 1/black phosphorus nanometer sheet, including cellulosic molecule and crosslinking
The three-dimensional net structure that agent is cross-linked into, and the black phosphorus nanometer sheet being supported in the three-dimensional net structure.
Embodiment 2
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：0.01.
Embodiment 3
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：0.03.
Embodiment 4
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：0.05.
Embodiment 5
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：5.
Embodiment 6
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：10.
Embodiment 7
The composite hydrogel of cellulose/black phosphorus nanometer sheet is prepared, difference lies in step 3-a with embodiment 1) in, fiber
The mass ratio of element and black phosphorus nanometer sheet solid is 100：50.
For prominent beneficial effects of the present invention, present invention also offers 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 0.01mL, i.e. cellulose solution and epoxy
The ratio between volume of chloropropane is 100：0.2；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/hydrogen-oxygen
Change 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 hydrogel (the referred to as cellulose water-setting of cellulose/epoxychloropropane
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 100：0.4.
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 100：0.6.
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 100：1.0.
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 100：1.4.
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 100：2.0.
Fig. 1 is the transmission electron microscope microscopic appearance figure of the black phosphorus nanometer sheet used in the embodiment of the present invention, and (a) is
Low resolution photo；(b) it is high-resolution photo.
The microscopic appearance test condition of black phosphorus nanometer sheet is as follows：Instrument and equipment：High resolution transmission electron microscopy；Model：
FEI Tecnai G2F30；Testing high voltage：300kV.
In Fig. 1 (a), about 100 nanometers × 400 nanometers of the size of black phosphorus nanometer sheet；From Fig. 1 b, black phosphorus nanometer
Piece shows obvious lattice fringe, shows that the black phosphorus nanometer sheet in the present invention has preferable crystal structure；Its lattice ruler
Very little is 0.223 nanometer, corresponding to (014) diffraction surfaces.
Fig. 2 is the atomic force microscopy of the black phosphorus nanometer sheet used in the present invention.The height map of black phosphorus nanometer sheet
Test condition it is as follows：Instrument and equipment：High-resolution atomic force microscope；Model：Brooker scanning probe microscopy；Scan mould
Formula：Intelligent scanning pattern.
As shown in Figure 2, the thickness of these black phosphorus nanometer sheets is in the distribution of 1.4-25nm.
Fig. 3 provides cellulose aquagel (comparative example 4) and the macroscopic view of cellulose/black phosphorus nanometer sheet (embodiment 4) is in kind
Photo.From the figure 3, it may be seen that it is in semi-transparent clear shape " jelly type " macro morphology that pure cellulose hydrogel (comparative example 4) is overall；And
After black phosphorus nanometer sheet is successfully introduced into, the composite hydrogel (embodiment 4) of gained cellulose/black phosphorus nanometer sheet is in integrally coffee color,
The two has strikingly color contrast.
Fig. 4 and Fig. 5 each provides cellulose/black phosphorus nanometer sheet composite hydrogel (embodiment 4) and cellulose aquagel
The electron scanning micrograph of the corresponding aeroge of (comparative example 4) gained after freeze-drying.
Test condition is as follows：
To retain the macromolecular loose structure in cellulose aquagel, hydrogel (the cellulose water-setting of comparative example 4 of test
Glue and the cellulose of embodiment 4/black phosphorus nanometer sheet composite hydrogel) first pass around freeze-drying process and obtain corresponding aeroge
Structure, wherein the experiment condition being freeze-dried is：Temperature：-80℃；Time：72 it is small when.Then the test of microscopic appearance is carried out,
The instrument and equipment used for：Cold field emission scanning electron microscope；Model：SEM-Hitachi SU8010；Test voltage：3kV；
The sample surfaces silver-plated time：20 seconds.
From the contrast of Fig. 4 and Fig. 5, this two aerogel-like shows obvious porosity, this is by cellulose
Three dimensional gell network structure is determined.But it is significantly the composite hydrogel of cellulose produced by the present invention/black phosphorus nanometer sheet
The cavernous structure distribution uniform of corresponding aeroge, aperture are 80-280 μm, and the porosity is about 85%.
By answering for cellulose aquagel made from comparative example 1-6 and the cellulose prepared by embodiment 1-7/black phosphorus nanometer sheet
Heshui gel 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
(i.e. comparative example 4) and 100：When 2 when (comparative example 6), its corresponding compression modulus increases to 60.8kPa and 79.1kPa respectively,
This is because caused by more content of crosslinking agent make it that the chemical crosslinking degree of cellulose aquagel greatly improves.However, pure fiber
Hydrogel lacks any feature, it does not show any photo-thermal effect, its photo-thermal equilibrium temperature is 25 DEG C, with room temperature base
This is identical.
However, as striking contrast, in the Compound Water of embodiment 1-7, that is, cellulose/epoxychloropropane/black phosphorus nanometer sheet
In gel, due to the introducing of black phosphorus nanometer sheet, its final photo-thermal equilibrium temperature significantly raises.For example, when cellulose with it is black
The mass ratio 100 of phosphorus nanometer sheet：When 0.0001 (i.e. embodiment 1), the final light thermal equilibrium temperature of composite hydrogel is in 0.5 He
1.0W/cm2When be able to reach 43.5 DEG C and 49.7 DEG C, compared with pure cellulose hydrogel, be about respectively increased 18.5 DEG C
With 24.7 DEG C.When the quality of black phosphorus nanometer sheet in the composite hydrogel for continuing increased fiber element/epoxychloropropane/black phosphorus nanometer sheet
During fraction, this photo-thermal equilibrium temperature significantly increases the detection range for being even more than thermal imaging system.For example, when cellulose with
The mass ratio 100 of black phosphorus nanometer sheet：When 5 (i.e. embodiment 5), the final light thermal equilibrium temperature of composite hydrogel is in 0.5 and 1.0W/
cm2When respectively 110 and 130.4 DEG C；When cellulose and the mass ratio 100 of black phosphorus nanometer sheet：10 (i.e. embodiments 6) and 100：50
When (i.e. embodiment 7), the final light thermal equilibrium temperature of composite hydrogel is higher than 150 DEG C, has exceeded the detection range of thermal imaging system.
Result above shows that the introducing of black phosphorus nanometer sheet not only significantly improves the mechanical strength of cellulose aquagel, and
And can actually assign cellulose aquagel excellent Photothermal characterisation, and this characteristic can by the content of black phosphorus nanometer sheet into
Row is adjusted.And when using the black phosphorus nanometer sheet of lower quality, balanced with regard to the composite hydrogel can be made to reach higher photo-thermal
Temperature.
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/black phosphorus nanometer sheet composite hydrogel, it is characterised in that it is three-dimensional that the composite hydrogel includes cellulose
Network structure and the black phosphorus nanometer sheet being supported in the cellulose three-dimensional net structure.
2. 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.
3. composite hydrogel as claimed in claim 1 or 2, it is characterised in that the cellulose three-dimensional net structure has hole
Footpath is 30-300 μm of pore structure.
4. composite hydrogel as claimed in claim 1 or 2, it is characterised in that the fibre in the cellulose three-dimensional net structure
Dimension element and the mass ratio of black phosphorus nanometer sheet are 100：(0.0001-50).
5. 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).
6. the preparation method of a kind of cellulose/crosslinking agent/black phosphorus nanometer sheet composite hydrogel, it is characterised in that including following step
Suddenly：
(1) prepare the mixed solvent containing highly basic, urea and water, and by its it is pre- be cooled to -15~-5 DEG C, cellulose powder is added to
The in the mixed solvent after precooling, is vigorously stirred, obtains cellulose solution；
(2) under the conditions of high-speed stirred, black phosphorus nanometer sheet, 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；
(3) add cellulose regenerated liquid into the cross-linking reaction thing and carry out immersion 30-60min, afterwards by the crosslinking after regeneration
Reactant, which is placed in water, dialyses, and obtains cellulose/black phosphorus nanometer sheet composite hydrogel.
7. preparation method as claimed in claim 6, 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%.
8. preparation method as claimed in claim 6, it is characterised in that in the cellulose solution, mixed solvent and cellulose
Mass ratio be 100：(1-4)；The mass ratio of the quality of the cellulose solution and the crosslinking agent is 100：(0.212-
2.12)。
9. preparation method as claimed in claim 6, it is characterised in that in step (3), the cellulose regenerated liquid is quality point
Number is the dilution heat of sulfuric acid of 5%-10%；The volume ratio of the cross-linking reaction thing and the dilution heat of sulfuric acid is 1：(2-3).
10. preparation method as claimed in claim 5, it is characterised in that the rotating speed of the high-speed stirred for 7000~
10000rpm, the time of the high-speed stirred is 1-3 minutes.
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