CN106698430A - Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof - Google Patents
Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as a transition layer and a preparation method thereof. The method includes the steps that Ti3C2 nano-powder and dopamine hydrochloride are dispersed into ultrapure water respectively, even mixing is conducted, and stirring is conducted under the shading condition; a Tris- buffer solution is added, and stirring continues under the shading condition; the obtained mixed solution is subjected to separation, washing and drying, and Ti3C2@PDA nano-powder is obtained; the Ti3C2@PDA nano-powder is added into ultrapure water, Co(NO3)2.6H2O is added after uniform dispersion, and stirring is conducted for a reaction; urea is added after the reaction is finished, stirring is continuously conducted under a constant temperature to evaporate water, and precursor powder is obtained; the precursor powder is subjected to heat treatment, and the titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as the transition layer is obtained. The Ti3C2@PDA@CNTs three-dimensional composite is successfully prepared through a simple pyrolysis method.
Description
【Technical field】
The invention belongs to the preparing technical field of nano-functional material, particularly a kind of poly-dopamine is used as transition zone
Titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof.
【Background technology】
Recently, a class is referred to as the discovery of the material of MXene and extends the group of two-dimensional material, i.e. transition metal carbide
Or carbonitride, its structure is similar with Graphene.MXene materials by corroding the A layers of element removed in MAX phases, and can keep
MX structures originally are constant and obtain, such as Ti3C2、Ti2C etc..MXene is with its high conductivity, bigger serface, sandwich construction, good
Good chemical stability and environment friendly, have very in fields such as lithium ion battery, ultracapacitor, photocatalysis and sensors
Big application potential.In adsorbing domain, the research such as Peng shows the Ti of alkali metal intercalation3C2To toxic heavy metal Pb2+Have excellent
Absorption property, can be used for effectively purifying drinking water.Ti3C2The activated hydroxyl groups that enrich of absorption property and its surface and big
Specific surface area is closely related, big with adsorbance, and the rate of adsorption is fast, and sensitivity is high and the characteristics of reversible adsorption.Ti3C2To Pb2 +Adsorption capacity will not be subject to solution in other high concentration ions (such as Ca2+、Mg2+Deng) influence.Ti3C2With the layer of its uniqueness
Shape structure is expected to give play to huge effect at aspects such as improvement harmful ion, heavy metal and organic pollutions.As new storage
Energy material, on lithium ion battery and ultracapacitor, the research for MXenes in recent years also has a lot.Naguib etc. will
Ti2CTxIt is applied on LIBs electrodes, under the multiplying power of C/25, its specific capacity is 225mAh/g；80 cycle charge discharges are carried out with 1C
After electricity, it fills specific capacity for 110mAh/g；After carrying out 120 cycle charge-discharges with 3C, its specific capacity is 80mAh/g；Entered with 10C
After 200 cycle charge-discharges of row, its charging capacity is 70mAh/g.The good electric conductivity of MXene nano materials itself and two-dimensional layer
Shape structure is the source of its electrochemical performance.But Ti3C2Nano material self-conductive and specific capacity are relatively low, cause it
Chemical property is not good enough, and the application of MXene based electrochemical capacitors also needs further to be probed into.
CNT is typical One-dimensional Quantum material, with good conduction, mechanics, thermal property and very high
Environmental stability (resistance to strong acid, alkali corrosion) and structural stability, make its lithium ion battery, ultracapacitor, sensor and
The fields such as ripple are inhaled to have a wide range of applications.Because CNT has superior electricity and mechanical property, it is considered to be composite wood
The preferable addition phase of material.CNT has huge application to dive as strengthening phase and conductive phase in field of nanocomposite materials
Power.
Zhao etc. prepares flexible sandwich-like MXene/CNT extrusion coating papers by alternately filtering MXene and CNT dispersion system
Electrode, contrasts the MXene/CNT paper that pure MXene is mixed to get with CNT arbitrary proportions, and the chemical property of the electrode is significantly carried
It is high.Yan etc. is by Ti3C2It is immersed in dimethyl sulfoxide (DMSO) through magnetic agitation, interval be ultrasonically treated etc. that a series of processes obtain Ti3C2
Thin slice, commercial CNTs is obtained stablizing suspension by ultrasonically treated, then by Ti3C2Thin slice is with CNTs by ultrasonically treated with not
Homogenous quantities ratio is sufficiently mixed, and then filters mixed liquor, is dried to obtain Ti3C2/ CNT composites；But the price of commercialization CNTs
Compare high.
Poly-dopamine (PDA) is by a kind of DOPA amine monomers environment friend that autoxidation polymerization is obtained in the environment of alkalescent
Good type biomacromolecule product.Research is shown, be may be implemented in using the autoxidation polymerization of dopamine many organic or inorganic
Matrix surface forms poly-dopamine clad, and it is with matrix (such as：Ceramics, metal oxide, polymer etc.) adhesion it is very strong,
And due to containing substantial amounts of nitrogen-containing group and phenolic hydroxyl group in its structure, poly-dopamine can be used as good second order reaction platform.
【The content of the invention】
It is an object of the invention to overcome problems of the prior art, there is provided a kind of poly-dopamine is used as transition zone carbon
Change titanium growth in situ CNTs three-dimensional composite materials and preparation method thereof, using dopamine in Ti3C2Thin PDA layers of Surface coating, then
It is catalyst to use Co, and using lower-cost urea as carbon source, obtained three-dimensional composite material chemical property is good.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Preparation method of the invention is comprised the following steps：
Comprise the following steps：
(1) by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are well mixed respectively, in dark conditions
0.5~2h of lower stirring；Tris- buffer solutions are added, continues to stir 12~48h under dark conditions；By gained mixed solution point
From, washing and dry, obtain Ti3C2@PDA nano-powders；Wherein Ti3C2Nano-powder, Dopamine hydrochloride and Tris- buffer solutions
The ratio between be (300~500) mg：(0.1~1.0) g：(10~100) mL；
(2) by the Ti obtained by step (1)3C2@PDA nano-powders are added in ultra-pure water, and Co is added after being uniformly dispersed
(NO3)2·6H2O, 2~6h of stirring reaction；Reaction adds urea after terminating, and lasting stirring at a constant temperature evaporates water
Point, obtain precursor powder, wherein Ti3C2@PDA nano-powders, Co (NO3)2·6H2The ratio between O and urea are (0.2~0.5)：
(0.1~0.4)：(3.0~30.0)；Precursor powder is heat-treated, poly-dopamine is obtained former as transition zone titanium carbide
Position growth CNTs three-dimensional composite materials.
Further, every 300~500mg Ti in step (1)3C2Nano-powder ultrasonic disperse is in 30~300mL ultra-pure waters
In, every 0.1~1.0g Dopamine hydrochlorides are dissolved in 10~100mL ultra-pure waters.
Further, the Tris- buffer concentrations for being added in step (1) are 50mmolL-1, pH value is 8.5.
Further, in step (2) every 200~500mg Ti3C2@PDA nano-powders are added to the super of 100~400mL
In pure water.
Further, the steady temperature in step (2) is between 60~100 DEG C.
Further, the heat treatment in step (2) is carried out under the protection of Ar.
Further, heat treatment temperature is 600~1000 DEG C, and the time is 0.5~2h.
Further, the heating rate of heat treatment is 3~5 DEG C/min.
It is a kind of by the use of poly-dopamine obtained in preparation method as described above as transition zone titanium carbide growth in situ CNTs
Three-dimensional composite material.
Compared with prior art, the present invention has following beneficial technique effect：
First with dopamine, autoxidation is aggregated in Ti to the present invention in weakly alkaline environment3C2Very thin PDA layers of Surface coating
Obtain Ti3C2@PDA composites, clad PDA can protect Ti3C2The integrality of structure, by controlling reaction condition (such as hydrochloric acid
Dopamine concentration etc.), the PDA clads of different-thickness can be prepared；Then with Ti3C2@PDA are matrix, and it is catalysis to use Co
Agent, adds urea as carbon source, and Ti is prepared using simple pyrolysismethod3C2@PDA@CNTs three-dimensional composite materials, and by control
Urea content in presoma, is capable of achieving the regulation and control of carbon nano tube growth length and density；This method can low cost, it is quick,
Environmental protection, the content by changing urea in presoma of safety, so as to realize Ti3C2The controllable life of surface C NTs length and density
It is long.Than directly in Ti3C2Superficial growth goes out CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2After Surface coating PDA layers again
Growth CNTs, is more easy to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite materials, and the CNTs mass for growing is higher, Ti3C2
It is stronger with CNTs adhesions, so that Ti3C2The performances such as chemical property, absorbing property, the photocatalysis of@CNTs are also that it enters more preferably
Application of one step in fields such as lithium ion battery, photocatalysis, suction ripples is laid a good foundation.Additionally, this simple pyrolysismethod is due to it
The advantage such as low for equipment requirements, easy to operate, with low cost, is advantageously implemented industrialization large-scale production.
Three-dimensional composite material of the present invention is by two-dimensional layer Ti3C2, transition zone poly-dopamine and be grown on Ti3C2Surface
Distribution density multi-walled carbon nano-tubes composition high, in Ti3C2Superficial growth goes out CNT, and providing electronics using CNT passes
Defeated passage, the conductance of raising material, and Ti3C2The transmittability between CNT can be improved, so as to efficiently solve one-dimensional carbon
Nanotube and two dimension Ti3C2Heat and conductibility outside the directional dependence of electric transmission and relatively low face, make composite in three-dimensional
Space all has good electrical property.The present invention prepare three-dimensional composite material is in electrochemical energy storage materials, absorbing material and urges
Agent carrier etc. is upper to have important use value.Search document, it is found that not yet someone is in Ti so far3C2Surface in situ grows
CNT, and realize Ti3C2The controllable growth of surface CNT.
【Brief description of the drawings】
Fig. 1 is Ti prepared by embodiment 33C2SEM figures (a) and XRD (b) of@PDA@CNTs three-dimensional composite materials.
Fig. 2 is Ti prepared by embodiment 33C2@PDA@CNTs6.0Three-dimensional composite material (a) sweeps speed (0.002V/s- in difference
CV curve maps under 0.1V/s)；B () is its capacity with the change curve for sweeping speed.
Fig. 3 is Ti prepared by embodiment 1-43C2The SEM figures of@PDA@CNTs three-dimensional composite materials, wherein (a)-(d) is respectively
It is situation when Dopamine hydrochloride content is 1.0g, 0.5g, 0.25g, 0.1g.
【Specific embodiment】
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
Step one, ternary layered Ti3AlC2The preparation of ceramic powder；
According to the method synthesis of ternary stratiform Ti of patent ZL201310497696.93AlC2Ceramic powder：First, will test
Raw material TiC, Ti, Al powder are TiC according to mol ratio：Ti：Al=2.0：1.0：1.2 carry out batch mixing；Secondly, by batch mixing, oxidation
Aluminium ball stone is with absolute ethyl alcohol according to 1：3：, in ball milling is carried out in corundum ball grinder, wherein absolute ethyl alcohol is used as ball milling for 1 mass ratio
Auxiliary agent, aluminum oxide ballstone is abrasive media, and drum's speed of rotation is 300r/min, in 40 DEG C of freeze-day with constant temperature baking ovens after wet ball grinding 4h
In dry 24h；Then, dry batch mixing is put into corundum crucible, with the heating rate of 8 DEG C/min in vacuum hotpressing carbon shirt-circuiting furnace
Vacuum non-pressure sintering is carried out, 1350 DEG C are heated to, 1h, vacuum ＜ 10 is incubated-2Pa, insulation cools to room temperature with the furnace after terminating；
Finally, to the powder dry method high-energy ball milling 2h after sintering, rotating speed is 400r/min, and powder is 1 with ballstone ratio：10, will be levigate
Powder carries out 400 mesh sievings, you can obtain Ti of the particle diameter less than 38 μm3AlC2Ceramic powder.
Step 2, two-dimensional layer Ti3C2The preparation of nano material；
Method according to patent 201410812056.7 prepares two-dimensional layer Ti3C2Nano material:By institute in 5g steps (1)
The Ti of preparation3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solutions, at room temperature magnetic agitation 24h, and rotating speed is
1200r/min, corrosion product is centrifuged, and 4500r/min ultra-pure waters eccentric cleaning to supernatant pH value is about 6,
Use washes of absolute alcohol 5 times again, the 24h drying in 40 DEG C of vacuum drying chambers, that is, obtain two-dimensional layer Ti by gained sediment3C2
Nano-powder.
Step 3, the preparation of titanium carbide@PDA composites
First, by 300~500mg Ti3C2Nano-powder ultrasonic disperse in 30~300mL ultra-pure waters, ultrasonic 30min；
0.1~1.0g Dopamine hydrochlorides are dissolved in 10~100mL ultra-pure waters, above-mentioned solution is added, is stirred at room temperature under dark conditions
0.5~2h；Or by 300~500mg Ti3C2It is 12.5~14.0mmolL that nano-powder adds 40~400mL concentration-1's
0.5~2h is stirred in room temperature shading in Dopamine hydrochloride solution；Complete liquid phase reactor；
Add 10~100mL Tris- buffer solutions (50mmolL-1, pH=8.5), it is stirred at room temperature 12 under dark conditions
~48h；By gained mixed solution centrifugation, deionized water is cleaned to supernatant clarification, is transferred in freeze drier, after 48h
Take out and can obtain Ti3C2@PDA。
Step 4, Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by 200~500mg steps (3) gained Ti3C2@PDA nano-powders are added to 100~400mL as matrix
In ultra-pure water, ultrasonic disperse 30min；Then, 0.1~0.4g Co (NO are added3)2·6H2O, is stirred at room temperature 2~6h；Or
By 200~500mg steps (3) gained Ti3C2@PDA nano-powders are added to 100~400mL concentration for 7.8~8.2mmolL-1
Co (NO3)2·6H2In O solution, 2~6h is stirred at room temperature；
Secondly, 3.0~30.0g urea is added, the lasting stirring evaporation under 60~100 DEG C of steady temperatures by above-mentioned mixed liquor
Fall moisture, obtain grey presoma；Finally, by precursor powder with agate mortar it is levigate after, be transferred in Ar atmosphere tube furnaces, with
The heating rate of 3~5 DEG C/min is heated to 600~1000 DEG C, is pyrolyzed 0.5~2h, is taken after being cooled to normal temperature under the protection of Ar
Go out, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 1
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse in 300mL ultra-pure waters, ultrasonic 30min；By 1.0g salt
Sour dopamine is dissolved in 100mL ultra-pure waters, adds above-mentioned solution, and 1h is stirred at room temperature under dark conditions；Add
100mLTris- buffer solutions (50mmolL-1, pH=8.5), 24h is stirred at room temperature under dark conditions；By the centrifugation of gained mixed solution
Separate, deionized water is cleaned to supernatant clarification, is transferred in freeze drier, taken out after 48h and can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@PDA nano-powders, are added in 200mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.29g Co (NO are added3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Lasting stirring evaporates moisture under determining temperature, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, 900 DEG C is heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, is cooled under the protection of Ar often
Taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
By 50-200mg Ti obtained as above3C2@PDA@CNTs nano-powders are with conductive carbon black and binding agent (PTFE) with 80:
15:5 mass ratio mixing, grinding 10-15min forms uniform purees in agate mortar.Secondly, above-mentioned purees is rolled into
Film, and 1cm*1cm is cut into, then it is bonded in the nickel foam of 2cm*1cm sizes, it is subsequently placed into vacuum drying chamber, 80
24h is dried at DEG C.Finally, by dried electrode slice under press, Ti is obtained in 20Mpa pressurizes 1min3C2@PDA@CNTs
Electrode.
Embodiment 2
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse in 150mL ultra-pure waters, ultrasonic 30min；By 0.5g salt
Sour dopamine is dissolved in 50mL ultra-pure waters, adds above-mentioned solution, and 1h is stirred at room temperature under dark conditions；Add 50mLTris-
Buffer solution (50mmolL-1, pH=8.5), 24h is stirred at room temperature under dark conditions；By gained mixed solution centrifugation, go from
Sub- water is cleaned to supernatant clarification, is transferred in freeze drier, is taken out after 48h and be can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@PDA nano-powders, are added in 200mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.29g Co (NO are added3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Lasting stirring evaporates moisture under determining temperature, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, 900 DEG C is heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, is cooled under the protection of Ar often
Taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 3
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse in 75mL ultra-pure waters, ultrasonic 30min；By 0.25g salt
Sour dopamine is dissolved in 25mL ultra-pure waters, adds above-mentioned solution, and 1h is stirred at room temperature under dark conditions；Add 25mLTris-
Buffer solution (50mmolL-1, pH=8.5), 24h is stirred at room temperature under dark conditions；By gained mixed solution centrifugation, go from
Sub- water is cleaned to supernatant clarification, is transferred in freeze drier, is taken out after 48h and be can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@PDA nano-powders, are added in 200mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.29g Co (NO are added3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Lasting stirring evaporates moisture under determining temperature, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, 900 DEG C is heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, is cooled under the protection of Ar often
Taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.Fig. 1 is gained Ti3C2@PDA@CNTs three-dimensional composite materials
SEM figure and XRD spectrum, it can be seen that intensive CNTs is evenly distributed on Ti3C2Lamella both sides, significantly improve stratified material
Specific surface area and increase the distance of piece interlayer so that Ti3C2The chemical property of@PDA@CNTs three-dimensional composite materials and suction
The performances such as ripple are better than pure Ti3C2。
Ti3C2The preparation of@PDA@CNTs electrodes；
First, respectively by 100mg Ti obtained as above3C2@PDA@CNTs6.0Nano-powder and conductive carbon black and binding agent
(PTFE) with 80:15:5 mass ratio mixing, grinding 15min forms uniform purees in agate mortar.Secondly, will
Above-mentioned purees rolls into film, and is cut into 1cm*1cm, is then bonded in the nickel foam of 2cm*1cm sizes, is subsequently placed into true
In empty drying box, 24h is dried at 80 DEG C.Finally, by dried electrode slice under press, distinguish in 20Mpa pressurizes 1min
Obtain Ti3C2@PDA@CNTs6.0Electrode.
Again, using three electrode test systems, electrode slice (working electrode) and platinum electrode (to electrode), the silver-colored chlorine that will be made
Change silver electrode (reference electrode) and easy ultracapacitor is assembled into electrolytic cell, wherein electrolyte is that 6mol/L KOH are molten
Liquid, Ti is tested using Shanghai Chen Hua CHI660E electrochemical workstations3C2@PDA@CNTs6.0The chemical property of electrode, such as circulates
VA characteristic curve, constant current charge-discharge, AC impedance and cycle life.Shown in Fig. 2, (a) is Ti3C2@PDA@CNTs6.0In difference
The CV curve maps under fast (0.002V/s-0.1V/s) are swept, CV curve maps are represented close to the rectangle of standard as we can see from the figure
Its good capacitive property, (b) is its capacity with the change curve for sweeping speed, it can be seen that fast for 0.05V/s and 0.2V/s when sweeping
When, the purer Ti of its capacity3C2There is great lifting.
Embodiment 4
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse in 30mL ultra-pure waters, ultrasonic 30min；By 0.1g hydrochloric acid
Dopamine is dissolved in 10mL ultra-pure waters, adds above-mentioned solution, and 1h is stirred at room temperature under dark conditions；10mL Tris- are added to delay
Fliud flushing (50mmolL-1, pH=8.5), 24h is stirred at room temperature under dark conditions；By gained mixed solution centrifugation, deionization
Water is cleaned to supernatant clarification, is transferred in freeze drier, is taken out after 48h and be can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 300mg3C2@PDA nano-powders, are added in 200mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.29g Co (NO are added3)2·6H2O, is stirred at room temperature 4h；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Lasting stirring evaporates moisture under determining temperature, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, 900 DEG C is heated to the heating rate of 4 DEG C/min, be pyrolyzed 1h, is cooled under the protection of Ar often
Taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 5
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 300mg3C2Nano-powder ultrasonic disperse in 200mL ultra-pure waters, ultrasonic 30min；By 0.6g salt
Sour dopamine is dissolved in 60mL ultra-pure waters, adds above-mentioned solution, and 0.5h is stirred at room temperature under dark conditions；Add
30mLTris- buffer solutions (50mmolL-1, pH=8.5), 12h is stirred at room temperature under dark conditions；By the centrifugation of gained mixed solution
Separate, deionized water is cleaned to supernatant clarification, is transferred in freeze drier, taken out after 48h and can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 200mg3C2@PDA nano-powders, are added in 100mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.1g Co (NO are added3)2·6H2O, is stirred at room temperature 2h；Secondly, 3.0g urea is added, above-mentioned mixed liquor is constant at 60 DEG C
At a temperature of lasting stirring evaporate moisture, obtain grey presoma；Finally, by precursor powder with agate mortar it is levigate after, turn
Enter in Ar atmosphere tube furnaces, 600 DEG C are heated to the heating rate of 3 DEG C/min, be pyrolyzed 2h, normal temperature is cooled under the protection of Ar
After take out, you can Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 6
(1)Ti3C2The preparation of@PDA composites；
First, by the Ti of 400mg3C2Nano-powder ultrasonic disperse in 250mL ultra-pure waters, ultrasonic 30min；By 0.8g salt
Sour dopamine is dissolved in 90mL ultra-pure waters, adds above-mentioned solution, and 2h is stirred at room temperature under dark conditions；Add 80mLTris-
Buffer solution (50mmolL-1, pH=8.5), 48h is stirred at room temperature under dark conditions；By gained mixed solution centrifugation, go from
Sub- water is cleaned to supernatant clarification, is transferred in freeze drier, is taken out after 48h and be can obtain Ti3C2@PDA。
(2)Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by the Ti of 500mg3C2@PDA nano-powders, are added in 400mL ultra-pure waters, ultrasonic disperse 30min；So
Afterwards, 0.4g Co (NO are added3)2·6H2O, is stirred at room temperature 6h；Secondly, 30.0g urea is added, by above-mentioned mixed liquor in 100 DEG C of perseverances
Lasting stirring evaporates moisture under determining temperature, obtains grey presoma；Finally, by precursor powder with agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, 1000 DEG C is heated to the heating rate of 5 DEG C/min, be pyrolyzed 0.5h, is cooled down under the protection of Ar
Taken out after to normal temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 7
Control presoma in urea content be respectively 3.0g, 6.0g ... .30.0g, other conditions are with embodiment 1.
Result proves, the present invention is capable of achieving Ti by controlling urea content in presoma3C2Surface length of carbon nanotube and
The regulation and control of density, Ti3C2Surface length of carbon nanotube is in 100~900nm.
In addition, obtained by embodiment 1-4, with the reduction of Dopamine hydrochloride content, Ti3C2Surface coated poly-dopamine
Layer is gradually thinning, as shown in figure 3, it is 1.0g, 0.5g, 0.25g, 0.1g that wherein Fig. 3 (a)-(d) is respectively Dopamine hydrochloride content
When situation.
The invention provides a kind of poly-dopamine as transition zone Ti3C2The preparation side of@PDA@CNTs three-dimensional composite materials
Method, including：The ternary layered Ti of high-purity fine grain3AlC2The synthesis of powder；Ti is processed by HF solution corrosions3AlC2Selectivity
Etch away ternary layered Ti3AlC2In Al layers prepare two-dimensional layer Ti3C2Nano material；With Ti3C2As carrier, first
Using dopamine, autoxidation is aggregated in Ti in weakly alkaline environment3C2Very thin PDA layers of Surface coating obtains Ti3C2@PDA are combined
Material, clad PDA can protect Ti3C2The integrality of structure, by controlling reaction condition (such as Dopamine hydrochloride concentration), can
To prepare the PDA clads of different-thickness；Then with Ti3C2@PDA are matrix, and it is catalyst to use Co, nitrogenous in PDA structures
Group and phenolic hydroxyl group can be by the Co in solution2+Absorption is in Ti3C2@PDA surfaces, while will be adsorbed using the week reduction of PDA
The Co of matrix surface2+It is reduced into Co nano-particles and is uniformly fixed to Ti3C2@PDA surfaces and as catalysis activity point, and cladding
Layer PDA can protect Ti3C2The integrality of structure；Part Co2+Ion by with Ti3C2The ion exchange of surface oxygen functional group is made
With absorption in Ti3C2Surface, adds urea as carbon source, urea by with Ti3C2The Co on surface2+Ion forms complex
And insert Ti3C2Lamella in；It is pyrolyzed under argon atmosphere, with the rising of temperature, Co2+It is reduced to Co nano particle conducts
The catalyst of CNTs growths, and urea is decomposed into carbonitride, carbonitride is grown to CNTs under the catalysis of Co, by controlling forerunner
Urea content in body, is capable of achieving the regulation and control of carbon nano tube growth length and density.The present invention is prepared using simple pyrolysismethod
Ti3C2@PDA@CNTs three-dimensional composite materials, this method can low cost, quick, environmental protection, safety by changing presoma in
The content of urea, so as to realize Ti3C2The controllable growth of surface C NTs length and density.Than directly in Ti3C2Superficial growth goes out
CNTs prepares Ti3C2The method of@CNTs, in Ti3C2Regrowth CNTs after Surface coating PDA layers, is more easy to realize Ti3C2@CNTs
The controllable preparation of three-dimensional composite material, and the CNTs mass for growing is higher, Ti3C2It is stronger with CNTs adhesions, so that Ti3C2@
Also more preferably, this is for extension Ti for the performances such as chemical property, absorbing property, the photocatalysis of CNTs3C2Material ultracapacitor,
The application in the fields such as lithium ion battery, nano adsorber and suction ripple, has important practical significance.Compared to report other prepare
Method, the experiment condition needed for this method is fairly simple, and low cost is easy to operate.
The present invention improves Ti3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., from
And extend Ti3C2Application of the material in fields such as ultracapacitor, lithium ion battery, nano adsorber and suction ripples.
Claims (9)
1. a kind of poly-dopamine as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials preparation method, its feature exists
In comprising the following steps：
(1) by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are well mixed respectively, are stirred under dark conditions
Mix 0.5~2h；Tris- buffer solutions are added, continues to stir 12~48h under dark conditions；By the separation of gained mixed solution, water
Wash and dry, obtain Ti3C2@PDA nano-powders；Wherein Ti3C2The ratio between nano-powder, Dopamine hydrochloride and Tris- buffer solutions are
(300~500) mg：(0.1~1.0) g：(10~100) mL；
(2) by the Ti obtained by step (1)3C2@PDA nano-powders are added in ultra-pure water, and Co is added after being uniformly dispersed
(NO3)2·6H2O, 2~6h of stirring reaction；Reaction adds urea after terminating, and lasting stirring at a constant temperature evaporates water
Point, obtain precursor powder, wherein Ti3C2@PDA nano-powders, Co (NO3)2·6H2The ratio between O and urea are (0.2~0.5)：
(0.1~0.4)：(3.0~30.0)；Precursor powder is heat-treated, poly-dopamine is obtained former as transition zone titanium carbide
Position growth CNTs three-dimensional composite materials.
2. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that every 300~500mg Ti in step (1)3C2Nano-powder ultrasonic disperse is super in 30~300mL
In pure water, every 0.1~1.0g Dopamine hydrochlorides are dissolved in 10~100mL ultra-pure waters.
3. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the Tris- buffer concentrations added in step (1) are 50mmolL-1, pH value is 8.5.
4. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the Ti of every 200~500mg in step (2)3C2@PDA nano-powders are added to 100~400mL
Ultra-pure water in.
5. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the steady temperature in step (2) is between 60~100 DEG C.
6. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the heat treatment in step (2) is carried out under the protection of Ar.
7. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that heat treatment temperature be 600~1000 DEG C, the time be 0.5~2h.
8. a kind of poly-dopamine according to claim 1 is used as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, it is characterised in that the heating rate of heat treatment be 3~5 DEG C/min.
9. poly-dopamine obtained in a kind of preparation method by the use of described in claim 1 is used as transition zone titanium carbide growth in situ
CNTs three-dimensional composite materials.
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