CN108298585A - Micro/nano-scale wave structure and preparation method thereof in a kind of macrocomposite - Google Patents
Micro/nano-scale wave structure and preparation method thereof in a kind of macrocomposite Download PDFInfo
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- C01G39/00—Compounds of molybdenum
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses micro/nano-scale wave structures in a kind of macrocomposite and preparation method thereof, belong to functional composite material technical field.Two-dimension nano materials dispersion liquid is self-assembly of the macrostructures such as film, gel, carboritride is generated using thermal chemical reaction and regulates and controls Two-dimensional Composites state, forms micro/nano-scale wave structure.The present invention has preparation process simple, the size and shape of composite material are easy to regulate and control, the mechanics elasticity of material, the features such as electronic structure or surface state are adjustable, research and application for the macroscopic material that is assembled into the fields such as fexible conductor, micromechanics electronics and flexible energy storage device, catalytic carrier are laid a good foundation.
Description
Technical field：
The present invention relates to functional composite material technical fields, and in particular to micro/nano-scale wave in a kind of macrocomposite
Unrestrained structure and preparation method thereof is suitable for the two-dimensional materials structures such as mechanical property changes, electron valence state is adjusted, surface chemical state modification
At composite construction preparation.
Background technology：
Wave structure is as a kind of appearance structure for typically having and greatly deforming, and especially two-dimension nano materials are in sub-micro
The wave structure that metrical scale is formed, can be changed flexibility, electronic structure, the surface chemistry conditions etc. of material, thus receive wide
General concern.Currently, preparing the wave structure of micro/nano-scale, there is the side such as substrate prestrain method, directional deformation method, quick quenching method
Method, obtained wave structure usually have mono-oriented or can not be integrated in macroscopic material, and it is numerous to exist simultaneously preparation process
The drawbacks such as trivial, regulation and control complexity.
As a kind of novel nano material, two-dimensional material presents all in fields such as mechanics, electricity, optics, photoelectrons
More novel and excellent performances, illustrate extensively in fields such as electrochemical energy storage, adsoption catalysis, electromagnetic shielding, de-noising, bio-sensings
Wealthy application prospect.Typical two-dimension nano materials, as graphene, boron nitride nanosheet, transition metal oxide nano-slice,
MXene, transient metal sulfide nanometer sheet etc. have excellent flexible, unique surface texture, adjustable electron valence state etc..
In practical applications, the intrinsic Van der Waals'attractive force of two-dimension nano materials piece interlayer makes the composite material controllability being assembled into drop
Low, mechanical property drastically declines, thus what assembles high quality, multi-functional using preparation process that is simple, being easy to amplification
Wave structure composite material still has challenge.
Invention content：
In order to solve current micro/nano-scale wave structure preparation process it is complicated, there are orientation, can not integrate the problems such as, this
Invention is designed to provide micro/nano-scale wave structure and preparation method thereof in a kind of macrocomposite, and this method is simply high
Effect, can in the macroscopic material that two-dimensional material is assembled into in-situ preparation micro/nano-scale wave structure, for two-dimensional material assembling obtain
The shortcomings of macroscopic material obtained has poor flexibility, destructible, be difficult in practical applications provides a kind of solution.
To achieve the goals above, the technical solution adopted in the present invention is as follows：
The preparation method of micro/nano-scale wave structure in a kind of macrocomposite, this method will include two-dimensional nano first
Material and the presoma composite solution of cyanamide substance are self-assembly of fiber, film or gel macrostructure, then utilize
Thermal chemical reaction generates sheet carboritride, while regulating and controlling composite construction (two wieners using piece interlayer model ylid bloom action power
Rice material and carboritride be combined) form, to obtain that there is the macrocomposite of micro/nano-scale wave structure.
This method comprises the following steps：
(1) configuration of presoma composite solution：Two-dimension nano materials are dispersed in water, uniform two dimension is obtained after ultrasound
Nano material dispersion liquid；The saturated aqueous solution of cyanamide substance is gradually added into two-dimension nano materials dispersion liquid, and is mixed equal
It is even, obtain the presoma composite solution containing two-dimension nano materials and cyanamide substance；
(2) liquid phase is self-assembly of macrostructure：The presoma composite solution that in a reservoir prepared by injection step (1), first
It carries out body to be mutually pre-chilled, the water in solution is changed into ice and forms self-template, is then freeze-dried, and obtains including two-dimensional nano material
Expect and load the fiber, film or gel macrostructure of cyanamide substance；
(3) in-situ preparation of micro/nano-scale wave structure：By fiber, film or the gel macroscopic view knot obtained by step (2)
Structure carries out the Low Temperature Heat Treatment under the conditions of 500-600 DEG C, and cyanamide substance pyrolytic polycondensation generates sheet carboritride, simultaneously
(cause non-under the action of existing Van der Waals'attractive force between two-dimension nano materials and evenly dispersed stratiform carboritride
Equally distributed chemically and thermally compression stress), in-situ preparation has the entirely uniformly distributed micro/nano-scale wave knot of local order
Structure, to obtain that there is the macrocomposite of micro/nano-scale wave structure.
In above-mentioned steps (1), the two-dimension nano materials are stannic oxide/graphene nano piece, boron nitride nanosheet, transition gold
Belong to oxide nano-slice, MXene nanometer sheets or transient metal sulfide nanometer sheet etc.；The number of plies of the stannic oxide/graphene nano piece
It is 1-10 layers；The cyanamide substance is dicyanodiamine, melamine or urea.
In above-mentioned steps (1), the two-dimension nano materials dispersion liquid is neutrality, a concentration of 2-20mg/ml, when ultrasonic disperse
Between be 10-120 minutes.
In above-mentioned steps (1), the mass ratio of cyanamide substance and two-dimension nano materials is in the presoma composite solution
(0.1-4)：1, preferably (2-5)：5.
In above-mentioned steps (2), first presoma composite solution is subjected to body under the conditions of -40-0 DEG C and be mutually pre-chilled, promote shape
At larger-size ice crystal；It is then freeze-dried, the temperature of freeze-drying is -100~-140 DEG C, and sublimation drying is
1-24 hours, complete porous microstructure is kept by being freeze-dried to be formed.
In above-mentioned steps (3), the low temperature heat treatment is：It is warming up to 500- with the heating rate of 1-20 DEG C/min
600 DEG C, heat treatment time is 1-24 hours, with stove natural cooling；Protective gas is passed through in heat treatment process, protective gas is argon
Gas or nitrogen, the shield gas flow rate being passed through in every milligram of sample are 5-20 ml/mins.
In above-mentioned steps (3), gained macrocomposite is fiber, foam or film, depends on container in step (2)
Structure feature (area of section and height) and processing method, the macrocomposite macro-size of acquisition is adjustable, in section and height
Degree can be cut out on direction.
Using the macrocomposite prepared by the above method of the present invention nitrogenized by two-dimension nano materials and sheet carbon
It closes object to be combined, composite construction is in micro/nano-scale wave structure；The wavelength of the micro/nano-scale wave structure is 0.01-2 μm.It should
Wave structure local order and overall distribution is uniform in the composite, (wavelength shakes for the density and deformation extent of wave structure
Width) it is adjustable.
Advantages of the present invention and advantageous effect are：
1. the side of in-situ preparation micro/nano-scale wave structure in the macrostructure that a kind of two-dimensional material of present invention proposition is formed
Method, this method have the characteristics that operating succinct, size is easy to regulate and control and be easy to largely to prepare, can integrate.
2. the method proposed by the present invention for preparing micro/nano-scale wave structure, the compression caused by thermal chemical reaction in situ
Stress and nanoscale twins Interaction Force obtain the parallel entirely uniformly distributed microcosmic wave structure of local, while wave
The density and deformation extent of structure such as wavelength, adjustable amplitude control.
3. heterogeneous reaction proposed by the present invention causes chrominance signal stress, the method for generating micro/nano-scale wave structure,
With great versatility, be applicable not only to a variety of two-dimension nano materials of good mechanical properties, including graphene, boron nitride,
Transition metal oxide nano-slice, MXene, transient metal sulfide etc., and the preparation macroscopic material for being easy to and utilizing extensively
Method as being freeze-dried, filter, hydrothermal synthesis etc. integrated.
4. the composite material that the present invention obtains has adjustable micro/nano-scale wave structure, it can be used for changing the soft of material
Toughness, electronic structure, surface chemistry conditions etc., be nanocomposite and assembling macroscopic body super light material, conductive film,
The practical application of electrochemical energy storing device, sensor, composite functional material etc. is laid a good foundation.
Description of the drawings：
Fig. 1 is two-dimension nano materials and the macrocomposite shape appearance figure of preparation；Wherein：(a) it is two dimensional oxidation molybdenum nanometer
Piece electron scanning micrograph；(b) it is the high power microstructure scanning electron microscopy of molybdenum oxide-carboritride composite material
Mirror photo；(c) it is the microstructure electron scanning micrograph of boron nitride nanosheet；(d) it is that boron nitride-carboritride is multiple
Condensation material surface topography map.
Fig. 2 is the system that the compound porous foam of graphene-carboritride with micro-nano scale wave structure is formed in situ
Standby process and microcosmic hierarchical structure change schematic diagram.
Fig. 3 is that dicyanodiamine/graphene oxide mass ratio prepared by embodiment 3 is 3:Redox graphene-carbon when 5
The compound porous foam micro-structure diagram of nitrogen compound；Wherein：(a) scanning electron microscope micro-structure diagram；(b) compound hole wall is cut
The high-resolution picture in face.
Fig. 4 is that dicyanodiamine in embodiment 3/graphene oxide mass ratio is 3:Redox graphene-carbon nitridation when 5
Close the wave structure microdeformation region of object composite porous material different orientation.
Fig. 5 is the reduction-oxidation graphite of different dicyanodiamine/graphene oxide mass ratioes in precursor solution in embodiment 3
The high power electron scanning micrograph skeleton surface topography map of alkene-carbon nitrogen compound three-dimensional porous foams comparative sample；Wherein：
(a) dicyanodiamine/graphene oxide mass ratio is 1:5；(b) dicyanodiamine/graphene oxide mass ratio is 2:5；(c) dicyan two
Amine/graphene oxide mass ratio is 3:5；(d) dicyanodiamine/graphene oxide mass ratio is 4:5；(e) dicyanodiamine/oxidation stone
Black alkene mass ratio is 8:5；All show microcosmic wave structure.
Fig. 6 is that the scanning electron microscope of the redox graphene-carbon nitrogen laminated film filtered in embodiment 4 is shone
Piece micro-structure diagram.
Specific implementation mode：
The present invention is described in detail below by way of drawings and examples.
The present invention is the method that micro/nano-scale wave structure is formed in the macrocomposite that two-dimensional material is assembled into, and is used
Liquid phase self assembly loads cyanogen amine molecule in the macrostructure that two-dimensional material stacking is formed, subsequently through Low Temperature Heat Treatment into
Row solid state reaction obtains micro-nano material-carboritride macrocomposite, while generation part has on the composite
The entirely uniformly distributed micro/nano-scale wave structure of sequence.It is as follows：
(1) configuration of presoma composite solution：Ultrasound obtains uniformly layer or single layer two-dimensional material dispersion liquid less, will be saturated
Cyanamide substance aqueous solution is gradually added into dispersion liquid, and is uniformly mixed；
Used two-dimensional material dispersion solution (including graphene oxide, boron nitride nanosheet, transition metal oxide are received
Rice piece, Mxene nanometer sheets, transient metal sulfide nanometer sheet etc.) a concentration of 2-20mg/ml, dispersion liquid is neutrality, ultrasonic disperse
Time is 10-120 minutes；Used cyanamide class presoma includes dicyan diamino, melamine, urea etc.；Cyanamide class forerunner
Body and two-dimensional material mass ratio are 0.1-5, and preferred mass ratio is 2:5-5:5, mixed solution stirring and ultrasound 10-60 minutes up to
It is uniformly mixed；
(2) liquid phase is self-assembly of macrostructure：Mixed uniformly solution is injected in a reservoir, is first carried out body and is mutually pre-chilled,
It forms self-template to be then freeze-dried, obtains the hybrid gel of appendix cyanogen amine molecule；
Used container is ceramics or corundum crucible, and volume is that 0.5~10ml is optional, and preferred volume is 1 cubic centimetre
The cylindrical ceramic crucible of high about 1cm, the mixed uniformly liquor capacity of addition are no more than the 90% of container volume；Freeze-drying
- 40-0 DEG C of precoolings of preceding progress, promote to form larger-size ice crystal, the time being then freeze-dried is 1-24 hours, has been kept
Whole porous microstructure；The composite material macro-size of acquisition is adjustable, and gel can be cut out on section and short transverse；
Composite shapes can be foam, film, fiber etc. simultaneously, depend on the container and processing method of step 2；
(3) in-situ preparation of micro/nano-scale wave structure：Hybrid gel in 500-600 DEG C of Low Temperature Heat Treatment step (2), cyanogen
Amine presoma pyrolytic polycondensation generates sheet carboritride, two-dimensional material nanometer sheet and evenly dispersed carboritride it
Between there are Van der Waals'attractive force, cause the chemically and thermally compression stress of non-uniform Distribution, and generating has local order integrally equal
The composite material of the micro/nano-scale wave structure of even distribution.
The whole uniform micro/nano-scale wave structure of local order is formed in situ using thermal chemical reaction, without accurate complicated
Reaction controlling step；Heating rate is 5-10 DEG C/min, and reaction temperature is 500-600 DEG C, protective atmosphere such as argon gas, nitrogen
Deng every milligram of sample flow is about 5-20 ml/mins, and with stove natural cooling, it is simple, efficiently that Low Temperature Heat Treatment controls process.
The present invention obtains functional composite material, tool by regulating and controlling micro-nano structure in the macrostructure that two-dimensional material is assembled into
There is a generated in-situ local order and entirely uniformly distributed micro/nano-scale wave structure, wavelength is 0.01-2 μm, wave structure
Density and deformation extent (wavelength, amplitude) it is controllable.
Embodiment 1：
The present embodiment is that two-dimentional transition metal oxide nano-slice assembles the answering with micro-nano scale wave structure to be formed
Condensation material, with molybdenum oxide MoO3For nanometer sheet, specifically carry out according to the following steps：
1, the dicyanodiamine aqueous solution (40mg/ml, 80 DEG C of heat preservations) of configuration saturation；Oxidation prepared by chemical vapour deposition technique
The electron scanning micrograph of molybdenum nanometer sheet such as Fig. 1 (a), it can be seen that its smooth surface；Abrasive chemical vapour deposition process
(CVD) the molybdenum oxide nanometer sheet synthesized makes its transversal dimensions become smaller, and is then dispersed within 10-20 minutes with 80% power ultrasonic dense
Degree is the emulsion of 2-10mg/ml；
2, it is 5 according to mass ratio：The 4 saturation dicyanodiamine aqueous solutions for measuring 3 milliliters inject 30 milliliters of a concentration of 5mg/ml
In molybdenum oxide emulsion, vibrates and ultrasound is mixed for 10-30 minutes with obtaining evenly dispersed molybdenum oxide nanometer sheet-dicyanodiamine
Liquid；
3, it measures 9 milliliters of molybdenum oxides-dicyanodiamine mixed dispersion liquid to inject in 10 milliliters of cylindrical ceramic crucibles, in -40-
0 DEG C carries out precooling in 2-4 hours and forms interconnection ice crystal, and freeze-drying in 1-24 hours is then carried out at -100~-140 DEG C, is obtained
Load has the aeroge of dicyanodiamine molecule on hole wall, and then slightly grinding forms powder；
4, molybdenum oxide-cyanamid dimerization aerogel powder that step 3 obtains is put into boiler tube, in 550 DEG C of every milligram of sample flows
2-4 hours, which are kept the temperature, under the amount about argon gas atmosphere of 5-20 ml/mins is heat-treated (heating rate is 5-10 DEG C/min) simultaneously
With stove natural cooling, molybdenum oxide-carboritride composite material is obtained, surface is a mass of nanoscale chevron shape wave knot
Structure (fold), such as Fig. 1 (b).
Embodiment 2：
The present embodiment be prepare with micro/nano-scale wave structure boron nitride-base composite material method, specifically press with
What lower step carried out：
1, the dicyanodiamine aqueous solution (40mg/ml, 80 DEG C of heat preservations) of configuration saturation；Boron nitride nanosheet such as Fig. 1 (c),
Surface is smooth；With 80% 10-30 minutes dispersion boron nitride powders of power ultrasonic at the emulsion of a concentration of 2-10mg/ml；
2, it is 5 according to mass ratio：The 3 saturation dicyanodiamine aqueous solutions for measuring 2.25 milliliters inject 30 milliliters of a concentration of 5mg/
In the boron nitride emulsion of ml, vibrates and ultrasound 10-30 minutes is to obtain relatively uniform boron nitride-dicyanodiamine mixed liquor；
3,9 milliliters of boron nitride-dicyanodiamine mixed dispersion liquid are measured to inject in 10 milliliters of cylindrical ceramic crucibles, first-
40-0 DEG C carries out precooling in 2-4 hours and forms interconnection ice crystal, and freeze-drying in 1-24 hours is then carried out at -100~-140 DEG C, is obtained
Obtaining load on hole wall has the aeroge of dicyanodiamine molecule, and then slightly grinding forms powder；
4, the boron nitride for obtaining step 4-cyanamid dimerization powder (5-10 DEG C/min of heating under 550 DEG C of argon gas atmospheres
Rate, every milligram of sample gas flow are about 5-20 ml/mins) it is heat-treated, heat preservation 4 hours and with stove natural cooling,
Boron nitride-carboritride composite material is obtained, surface is dispersed with the almost parallel strip wave structure of nanoscale, such as schemes
Shown in 1 (d).
Embodiment 3：
The present embodiment is the graphene-based of micro/nano-scale wave structure of the preparation with different distortion degree and different densities
The method of porous composite foam, preparation process and microcosmic wave structure change process such as Fig. 2；Specifically carry out according to the following steps
's：
1, the dicyanodiamine aqueous solution (40mg/ml, 80 DEG C of heat preservations) of configuration saturation, while supersonic density is 2-8mg/ml's
Neutral alumina graphene solution, ultrasonic 10-120 minutes obtains few layer or single-layer graphene oxide nanometer sheet solution；
2, it is 5 according to mass ratio:1,5:2,5:3,5:4 and 5:8 measure 0.25,0.5,0.75,1 and 2 milliliter of dicyan respectively
Diamine solution is injected in the graphene oxide solution of 10 milliliters of a concentration of 5mg/ml, vibrates and ultrasound 15-60 minutes is equal to mix
It is even；
3, the mixed solution for taking out 0.9 milliliter of step 2 injects in 1 milliliter of cylindrical ceramic crucible, is first carried out at -40-0 DEG C
Precooling in 2-4 hours forms interconnection ice crystal, and freeze-drying in 1-24 hours is then carried out at -120 DEG C, and obtaining load on hole wall has two
The graphite oxide alkenyl aeroge of two amine molecule of cyanogen；
4, graphene oxide-cyanamid dimerization porous aerogel that step 3 obtains is put into boiler tube, in 550 DEG C of every milligram of samples
Product flow be about 5-20 ml/mins argon gas atmosphere under keep the temperature 2-6 hours and be heat-treated that (heating rate is 5-10 DEG C/minute
Clock) and with stove natural cooling, thermal polycondensation dicyanodiamine molecule generates sheet carboritride to redox graphene simultaneously, obtains
The compound porous foam of redox graphene-carboritride, be dispersed on hole wall amplitude less, wavelength be several microns,
The slightly larger micro/nano-scale wave structure of spacing distance.
Fig. 3 (a) is the scanning electron microscope micro-structure diagram of compound porous foam, the porous size of three-dimensional interconnection about 1-
100 μm, high power illustration shows that film surface is dispersed with almost parallel microcosmic wave structure；Fig. 3 (b) is the height in compound hole wall section
Times pattern phase, film surface spreads all over the micro/nano-scale wave structure that local order's wavelength is 0.01-2 μm, and (focused ion beam is cut
It cuts).
Fig. 4 is the micro-nano of different orientation on the film skeleton of the compound porous foam of redox graphene-carboritride
Scale wave structure deformed region, region inner folds are almost parallel, show that wave structure is integrally uniformly distributed.
Embodiment 4：
The present embodiment be prepare with micro/nano-scale wave structure graphene-based laminated film method, specifically press with
What lower step carried out：
1, the dicyanodiamine aqueous solution (40mg/ml, 80 DEG C of heat preservations) of configuration saturation, while supersonic density is 2-8mg/ml's
Neutral alumina graphene solution, ultrasonic 10-120 minutes obtains few layer or single-layer graphene oxide nanometer sheet solution；
2, it is 5 according to mass ratio:3 measure the oxidation that 0.75 milliliter of dicyanodiamine solution injects 10 milliliters of a concentration of 5mg/ml
In graphene solution, vibrates and ultrasound 15-60 minutes is with uniformly mixed；
3, it takes out in the mixed solution injection vacuum filtration container of step 2, uses aperture for 20 μm of water system filter membrane, filter
2-8 hours and load on hole walls is obtained within dry 1-6 hours at 60 DEG C there is the graphene oxide base film of dicyanodiamine molecule；
4, graphene oxide-cyanamid dimerization film that step 3 obtains is put into boiler tube, in 550 DEG C of every milligram of sample flows
4 hours, which are kept the temperature, about under the argon gas atmosphere of 5-20 ml/mins is heat-treated (heating rate is 5-10 DEG C/min) and with stove
Natural cooling, thermal polycondensation dicyanodiamine molecule generates sheet carboritride to redox graphene simultaneously, obtains oxygen reduction
Graphite alkene-carboritride laminated film is dispersed with the micro/nano-scale wave structure that wavelength is 2-40 μm thereon.Fig. 6 is this
The dicyanodiamine that embodiment filters/graphene oxide mass ratio is 3:5 graphene-carboritride laminated film it is micro-
Shape appearance figure is seen, surface equally exists micro/nano-scale wave structure.
Effect and applicability of the method for micro/nano-scale wave structure to two-dimensional nano piece is formed in situ in the present invention：
The nitridation boron-carbon nitridation that the molybdenum oxide obtained to embodiment 1-carboritride composite material and embodiment 2 obtain
Compound composite material carries out microscopic appearance SEM map analysis, and Fig. 1 shows the compound carboritride of two-dimentional micro-nano structure, surface topography
Become from smooth rich in micro/nano-scale wave structure.The three-dimensional grapheme that the embodiment 3-4 is obtained-compound porous foam of carbon nitrogen
Carry out Fig. 3-5 analyses of microscopic appearance SEM figures, it can be deduced that in situ generated the nanoscale of local order on porous foam skeleton
Wave structure.
Fig. 5 is that redox graphene-carbon nitrogen of different dicyanodiamine/graphene oxide mass ratioes in precursor solution is multiple
Close the high power electron scanning micrograph skeleton surface topography map of object three-dimensional porous foams comparative sample, it can be seen that presoma
Dicyanodiamine is different from graphene oxide mass ratio in solution, generates the graphene and carboritride of different content, hot therebetween
Chemical stress interacts to form the micro-nano scale wave structure (fold) of different densities and different distortion degree (wavelength).Dicyan
The variation of diamines ratio generates the carboritride of different content, bonding action power (covalent bond and hydrogen in carboritride lamella
Key) change therewith.It is 3 in dicyanodiamine/graphene oxide mass ratio:5 or 4:When 5, the bonding in carboritride lamella is made
It is firmly sufficiently large to generate certain compression internal stress, while graphene and carboritride thermal stress are bigger, thus generate and cause
The wave structure of close and deformation extent big (wavelength is 0.01-2 μm).The almost parallel microdeformation region of wave structure takes in region
To random distribution, surface microscopic wave structure overall distribution is uniform.
The above results show the present invention by adding cyanamide class presoma, in two-dimensional material surface original when heat treatment is reacted
Position thermal polymerization forms the sheet carboritride of Dispersed precipitate.Since there are Van der Waals suctions between two-dimensional material and carboritride
Gravitation, thermal strain non_uniform response between two-dimension nano materials and carboritride in reaction process, carbon nitrogenizes in temperature-fall period
It closes object and shrinks generation compression；Covalent bond and hydrogen bond action in carboritride lamella generate compression, while reduction-oxidation
Graphene and carboritride dot matrix, which mismatch, generates compression in situ, and synergistic effect generation deformation degree is big, local order is whole
The equally distributed micro/nano-scale wave structure of body.Moreover, this original position thermal chemical reaction causes compression and generates micro/nano-scale wave
Unrestrained structure has great versatility, is suitable for a variety of two-dimension nano materials such as graphene, transition metal oxide nano-slice etc.；
This quadrat method is easy to be integrated with the method that existing two-dimension nano materials assemble simultaneously, and it is 3 such as to filter mass ratio:5 dicyan
Diamines/graphene oxide solution, the graphene obtained subsequently through low temperature hot material-its surface of carboritride laminated film
There are micro/nano-scale wave structures.
Claims (10)
1. the preparation method of micro/nano-scale wave structure in a kind of macrocomposite, it is characterised in that：This method first will packet
Presoma composite solution containing two-dimension nano materials and cyanamide substance is self-assembly of fiber, film or gel macroscopic view knot
Then structure utilizes thermal chemical reaction in-situ preparation sheet carboritride, while utilizing two-dimension nano materials and sheet carbon
The form of active force regulation and control composite construction between nitrogen compound, to form micro/nano-scale wave in gained macrocomposite
Unrestrained structure.
2. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 1, it is characterised in that：
This method comprises the following steps：
(1) configuration of presoma composite solution：Two-dimension nano materials are dispersed in water, uniform two-dimensional nano is obtained after ultrasound
Material dispersion liquid；The saturated aqueous solution of cyanamide substance is gradually added into two-dimension nano materials dispersion liquid, and is uniformly mixed, is obtained
Obtain the presoma composite solution containing two-dimension nano materials and cyanamide substance；
(2) liquid phase is self-assembly of macrostructure：The presoma composite solution that in a reservoir prepared by injection step (1), first carries out
Body is mutually pre-chilled, and the water in solution is changed into ice and forms self-template, is then freeze-dried, and obtains comprising two-dimension nano materials simultaneously
Load fiber, film or the gel macrostructure of cyanamide substance；
(3) in-situ preparation of micro/nano-scale wave structure：Fiber, film or gel macrostructure obtained by step (2) are carried out
Low Temperature Heat Treatment under the conditions of 500-600 DEG C, cyanamide substance pyrolytic polycondensation generate sheet carboritride, and in two wieners
(cause non-uniform Distribution under the action of existing Van der Waals'attractive force between rice material and evenly dispersed stratiform carboritride
Chemically and thermally compression stress), in-situ preparation have the entirely uniformly distributed micro/nano-scale wave structure of local order, to
To the macrocomposite with micro/nano-scale wave structure.
3. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (1), the two-dimension nano materials are stannic oxide/graphene nano piece, boron nitride nanosheet, transition metal oxide nano
Piece, MXene nanometer sheets or transient metal sulfide nanometer sheet；The number of plies of the stannic oxide/graphene nano piece is 1-10 layers；It is described
Cyanamide substance is dicyanodiamine, melamine or urea.
4. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (1), the two-dimension nano materials dispersion liquid is neutrality, and a concentration of 2-20mg/ml, the ultrasonic disperse time is 10-120 points
Clock.
5. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (1), the mass ratio of cyanamide substance and two-dimension nano materials is (0.1-4) in the presoma composite solution：1, it is excellent
Choosing is ranging from (2-5)：5.
6. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (2), first presoma composite solution is subjected to body under the conditions of -40-0 DEG C and is mutually pre-chilled, promote surface formed size compared with
Big ice crystal；It is then freeze-dried, the temperature of freeze-drying is -100~-160 DEG C, and sublimation drying is that 1-24 is small
When, keep complete porous microstructure by being freeze-dried to be formed.
7. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (3), the low temperature heat treatment is：It is warming up to 500-600 DEG C with the heating rate of 1-20 DEG C/min, when heat treatment
Between be 1-24 hours, with stove natural cooling；Protective gas is passed through in heat treatment process, protective gas is argon gas or nitrogen, per milli
The shield gas flow rate being passed through in gram sample is 5-20 ml/mins.
8. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
In step (3), gained macrocomposite is foam, film or fiber, can be cut out on section and short transverse.
9. the preparation method of micro/nano-scale wave structure in macrocomposite according to claim 2, it is characterised in that：
The macrocomposite is combined by two-dimension nano materials and sheet carboritride, and the composite construction formed is in
Micro/nano-scale wave pattern；The wavelength of the micro/nano-scale wave structure is 0.01-2 μm.
10. the preparation method of micro/nano-scale wave structure, feature exist in macrocomposite according to claim 2
In：The wave structure local order and overall distribution is uniform, the density and deformation extent of wave structure are adjustable.
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| CN115610050A (en) * | 2022-09-22 | 2023-01-17 | 重庆交通大学 | Preparation method of designable layered nano composite film |
| CN115504471B (en) * | 2022-09-22 | 2023-07-11 | 重庆交通大学 | Preparation method of micro-nano material large-area film |
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| CN115610050B (en) * | 2022-09-22 | 2023-08-18 | 重庆交通大学 | Method for preparing designable layered nano composite film |
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