CN106698430B - A kind of poly-dopamine is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof - Google Patents
A kind of poly-dopamine is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of poly-dopamines as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof, by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are uniformly mixed respectively, are stirred under dark conditions；Tris- buffer solutions are added, continue to stir under dark conditions；By the separation of gained mixed solution, washing and drying, Ti is obtained3C2@PDA nano-powders；By Ti3C2@PDA nano-powders are added in ultra-pure water, and Co (NO are added after being uniformly dispersed3)2·6H2O is stirred to react；Urea is added after reaction, and lasting stirring at a constant temperature evaporates moisture, obtains precursor powder；Precursor powder is heat-treated, obtains poly-dopamine as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials.The present invention successfully prepares Ti by simple pyrolysismethod3C2@PDA@CNTs three-dimensional composite materials.
Description
【Technical field】
The invention belongs to the preparing technical fields of nano-functional material, and particularly a kind of poly-dopamine is as transition zone
Titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof.
【Background technology】
Recently, the discovery of a kind of material for being referred to as MXene extends the group of two-dimensional material, i.e. transition metal carbide
Or carbonitride, structure are similar with graphene.MXene materials can remove the A layer elements in MAX phases by corrosion, and keep
MX structures originally are constant and obtain, such as Ti3C2、Ti2C etc..MXene is with its high conductivity, bigger serface, multilayered structure, good
Good chemical stability and environment friendly, has very in fields such as lithium ion battery, ultracapacitor, photocatalysis and sensors
Big application potential.In adsorbing domain, Peng etc. research shows that alkali metal intercalation Ti3C2To toxic heavy metal Pb2+Have excellent
Absorption property, can be used for effectively purifying drinking water.Ti3C2Absorption property and the abundant activated hydroxyl groups in its surface and greatly
The characteristics of specific surface area is closely related, has large amount of adsorption, and the rate of adsorption is fast, high sensitivity and reversible adsorption.Ti3C2To Pb2 +Adsorption capacity will not be by other high concentration ions (such as Ca in solution2+、Mg2+Deng) influence.Ti3C2With its unique layer
Shape structure is expected to play huge effect in improvement harmful ion, heavy metal and organic pollution etc..As novel storage
Energy material in recent years also has much the research of MXenes on lithium ion battery and ultracapacitor.Naguib etc. will
Ti2CTxApplied on LIBs electrodes, under the multiplying power of C/25, specific capacity 225mAh/g；80 cycle charge discharges are carried out with 1C
After electricity, it is 110mAh/g to fill specific capacity；After 120 cycle charge-discharges being carried out with 3C, specific capacity 80mAh/g；With 10C into
After 200 cycle charge-discharges of row, charging capacity 70mAh/g.The good electric conductivity of MXene nano materials itself and two-dimensional layer
Shape structure is the source of its electrochemical performance.However Ti3C2Nano material self-conductive and specific capacity are relatively low, lead to it
Chemical property is not good enough, and the application of MXene based electrochemical capacitors also needs further to be probed into.
Carbon nanotube is typical One-dimensional Quantum material, has 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 wave are inhaled to have a wide range of applications.Since carbon nanotube has superior electricity and mechanical property, it is considered to be composite wood
The ideal addition phase of material.Carbon nanotube has huge application latent 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, compares the MXene/CNT paper that pure MXene is mixed to get with CNT arbitrary proportions, and the chemical property of the electrode significantly carries
It is high.Yan etc. is by Ti3C2It is immersed in dimethyl sulfoxide (DMSO) and obtains Ti through a series of processes such as magnetic agitation, interval supersound process3C2
Thin slice obtains by supersound process commercial CNTs to stablize suspension, then by Ti3C2Thin slice is with CNTs by being ultrasonically treated with not
Homogenous quantities ratio is sufficiently mixed, and is then filtered mixed liquor, is dried to obtain Ti3C2/ CNT composite materials；But the price of commercialization CNTs
It is relatively high.
Poly-dopamine (PDA) is a kind of environment friend that autoxidation polymerize in the environment of alkalescent by DOPA amine monomers
Good type biomacromolecule product.Studies have shown that may be implemented in using the autoxidation polymerization of dopamine many organic or inorganic
Matrix surface forms poly-dopamine clad, (such as with matrix：Ceramics, metal oxide, polymer etc.) binding force it is very strong,
And due to containing a large amount of nitrogen-containing group and phenolic hydroxyl group in its structure, poly-dopamine can be used as good second order reaction platform.
【Invention content】
It is an object of the invention to overcome problems of the prior art, a kind of poly-dopamine is provided as transition zone carbon
Change titanium growth in situ CNTs three-dimensional composite materials and preparation method thereof, using dopamine in Ti3C2Surface coats thin PDA layers, then
Use Co for catalyst, using lower-cost urea as carbon source, three-dimensional composite material chemical property obtained is good.
In order to achieve the above object, the present invention adopts the following technical scheme that：
The preparation method of the present invention includes the following steps：
Include the following steps：
(1) by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are uniformly mixed respectively, in dark conditions
0.5~2h of lower stirring；Tris- buffer solutions are added, continue 12~48h of stirring under dark conditions；By gained mixed solution point
From, washing and dry, Ti is obtained3C2@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 is stirred to react 2~6h；Urea is added after reaction, 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, it is former as transition zone titanium carbide to obtain poly-dopamine
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 being added in step (1) are 50mmolL-1, pH value 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) carries 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 using poly-dopamine made from 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 technique effect beneficial below：
The invention firstly uses dopamines in weakly alkaline environment, and autoxidation is aggregated in Ti3C2Surface coats very thin PDA layers
Obtain Ti3C2@PDA composite materials, 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, use Co for catalysis
Agent is added urea as carbon source, Ti is prepared using simple pyrolysismethod3C2@PDA@CNTs three-dimensional composite materials, and pass through control
Urea content in presoma, it can be achieved that carbon nano tube growth length and density regulation and control；This method can low cost, it is quick,
Environmental protection, the safe content by changing urea in presoma, to realize Ti3C2The controllable life of surface C NTs length and density
It is long.Compared with directly in Ti3C2Surface grows CNTs and prepares Ti3C2The method of@CNTs, in Ti3C2After PDA layers of surface cladding again
CNTs is grown, is more easy to realize Ti3C2The controllable preparation of@CNTs three-dimensional composite materials, and grow CNTs mass higher, Ti3C2
It is stronger with CNTs binding forces, to Ti3C2The performances such as chemical property, absorbing property, the photocatalysis of@CNTs also more preferably, be it into
Application of one step in fields such as lithium ion battery, photocatalysis, suction waves is laid a good foundation.In addition, this simple pyrolysismethod is due to it
The advantages such as low for equipment requirements, easy to operate, of low cost, are 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
The high multi-walled carbon nanotube composition of distribution density, in Ti3C2Surface grows carbon nanotube, and providing electronics using carbon nanotube passes
Defeated channel, improves the conductivity of material, and Ti3C2The transmittability between carbon nanotube can be improved, to efficiently solve one-dimensional carbon
Nanotube and two dimension Ti3C2Heat and conductibility outside the directional dependence of electron-transport and lower face, make composite material in three-dimensional
Space all has good electrical property.Three-dimensional composite material prepared by the present invention is in electrochemical energy storage materials, absorbing material and urges
Agent carrier etc. is upper to have important use value.Document is searched for, it is found that not yet someone is in Ti so far3C2Surface in situ is grown
Carbon nanotube, and realize Ti3C2The controllable growth of surface carbon nanotube.
【Description of the drawings】
Fig. 1 is Ti prepared by embodiment 33C2The SEM figures (a) and XRD diagram (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 graphs under 0.1V/s)；(b) be its capacity with sweep speed change curve.
Fig. 3 is Ti prepared by embodiment 1-43C2The SEM of@PDA@CNTs three-dimensional composite materials schemes, wherein (a)-(d) is respectively
Be Dopamine hydrochloride content be 1.0g, 0.5g, 0.25g, 0.1g when the case where.
【Specific implementation mode】
The present invention is described in further details with embodiment below in conjunction with the accompanying drawings.
Step 1, ternary layered Ti3AlC2The preparation of ceramic powder；
According to the method synthesis of ternary stratiform Ti of patent ZL201310497696.93AlC2Ceramic powder：First, it will test
Raw material TiC, Ti, Al powder are TiC according to molar 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 1：3：1 mass ratio is in carrying out ball milling in corundum ball grinder, wherein absolute ethyl alcohol is as ball milling
Auxiliary agent, aluminium oxide ballstone are abrasive media, in 40 DEG C of freeze-day with constant temperature baking ovens after drum's speed of rotation 300r/min, wet ball grinding 4h
Middle drying is for 24 hours；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, is heated to 1350 DEG C, keeps the temperature 1h, vacuum degree < 10-2Pa cools to room temperature with the furnace after heat preservation；
Finally, to sintered powder dry method high-energy ball milling 2h, rotating speed 400r/min, powder is 1 with ballstone ratio：10, it will be levigate
Powder carries out 400 mesh sievings, you can obtains the Ti that grain size is less than 38 μm3AlC2Ceramic powder.
Step 2, two-dimensional layer Ti3C2The preparation of nano material；
Two-dimensional layer Ti is prepared according to the method for patent 201410812056.73C2Nano material:By institute in 5g steps (1)
The Ti of preparation3AlC2Powder is slowly immersed in 100mL 40wt.% hydrofluoric acid solutions, and for 24 hours, rotating speed is magnetic agitation at room temperature
Corrosion product is centrifuged 1200r/min, and 4500r/min is about 6 with ultra-pure water eccentric cleaning to supernatant pH value,
Washes of absolute alcohol 5 times is used again, gained sediment is dried in 40 DEG C of vacuum drying chambers for 24 hours to get to two-dimensional layer Ti3C2
Nano-powder.
Step 3, the preparation of titanium carbide@PDA composite materials
First, by 300~500mg Ti3C2Nano-powder ultrasonic disperse is 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, are stirred at room temperature under dark conditions
0.5~2h；Either by 300~500mg Ti3C2A concentration of 12.5~14.0mmolL of 40~400mL are added in nano-powder-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；Gained mixed solution is centrifuged, deionized water is cleaned to supernatant and clarified, and is transferred in freeze drier, after 48h
Taking-up can be obtained Ti3C2@PDA。
Step 4, Ti3C2The preparation of@PDA@CNTs three-dimensional composite materials；
First, by Ti obtained by 200~500mg steps (3)3C2@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)2·6H22~6h is stirred at room temperature in O；Either
By Ti obtained by 200~500mg steps (3)3C2@PDA nano-powders are added to a concentration of 7.8~8.2mmolL of 100~400mL-1
Co (NO3)2·6H2In O solution, 2~6h is stirred at room temperature；
Secondly, 3.0~30.0g urea is added, the persistently stirring evaporation under 60~100 DEG C of steady temperatures by above-mentioned mixed liquor
Fall moisture, obtains grey presoma；Finally, by precursor powder 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 room temperature is cooled under the protection of Ar
Go out, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 1
(1)Ti3C2The preparation of@PDA composite materials；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse is in 300mL ultra-pure waters, ultrasonic 30min；By 1.0g salt
Sour dopamine is dissolved in 100mL ultra-pure waters, and above-mentioned solution is added, and 1h is stirred at room temperature under dark conditions；It adds
100mLTris- buffer solutions (50mmolL-1, pH=8.5), it is stirred at room temperature for 24 hours under dark conditions；Gained mixed solution is centrifuged
Separation, deionized water are cleaned to supernatant and are clarified, be transferred in freeze drier, are taken out after 48h and be can be obtained 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)2·6H24h is stirred at room temperature in O；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Determine persistently to stir at temperature and evaporate moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, be cooled under the protection of Ar often
It is 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 binder (PTFE) with 80:
15:5 mass ratio mixing grinds 10-15min and forms uniform purees in the agate mortar.Secondly, above-mentioned purees is rolled into
Film, and it is cut into 1cm*1cm, it is then sticked in the nickel foam of 2cm*1cm sizes, is subsequently placed into vacuum drying chamber, 80
It is dried for 24 hours 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 composite materials；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse is in 150mL ultra-pure waters, ultrasonic 30min；By 0.5g salt
Sour dopamine is dissolved in 50mL ultra-pure waters, and above-mentioned solution is added, and 1h is stirred at room temperature under dark conditions；Add 50mLTris-
Buffer solution (50mmolL-1, pH=8.5), it is stirred at room temperature for 24 hours under dark conditions；Gained mixed solution is centrifuged, go from
Sub- water is cleaned to supernatant and is clarified, and is transferred in freeze drier, is taken out after 48h and be can be obtained 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)2·6H24h is stirred at room temperature in O；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Determine persistently to stir at temperature and evaporate moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, be cooled under the protection of Ar often
It is taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 3
(1)Ti3C2The preparation of@PDA composite materials；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse is in 75mL ultra-pure waters, ultrasonic 30min；By 0.25g salt
Sour dopamine is dissolved in 25mL ultra-pure waters, and above-mentioned solution is added, and 1h is stirred at room temperature under dark conditions；Add 25mLTris-
Buffer solution (50mmolL-1, pH=8.5), it is stirred at room temperature for 24 hours under dark conditions；Gained mixed solution is centrifuged, go from
Sub- water is cleaned to supernatant and is clarified, and is transferred in freeze drier, is taken out after 48h and be can be obtained 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)2·6H24h is stirred at room temperature in O；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Determine persistently to stir at temperature and evaporate moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, be cooled under the protection of Ar often
It is 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 wave 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 binder
(PTFE) with 80:15:5 mass ratio mixing, in the agate mortar grinding grind 15min and form uniform purees.Secondly, will
Above-mentioned purees rolls into film, and is cut into 1cm*1cm, is then sticked in the nickel foam of 2cm*1cm sizes, is subsequently placed into true
In empty drying box, dried for 24 hours 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, by the electrode slice (working electrode) of making and platinum electrode (to electrode), silver-colored chlorine
Change silver electrode (reference electrode) and be assembled into easy ultracapacitor in electrolytic cell, wherein electrolyte is that 6mol/L KOH are molten
Liquid tests Ti using Shanghai Chen Hua CHI660E electrochemical workstations3C2@PDA@CNTs6.0The chemical property of electrode such as recycles
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 graphs under fast (0.002V/s-0.1V/s) are swept, CV curve graphs are indicated close to the rectangle of standard as we can see from the figure
Its good capacitive property, (b) be its capacity with sweep speed change curve, it can be seen that when sweep speed be 0.05V/s and 0.2V/s
When, the purer Ti of capacity3C2There is great promotion.
Embodiment 4
(1)Ti3C2The preparation of@PDA composite materials；
First, by the Ti of 500mg3C2Nano-powder ultrasonic disperse is in 30mL ultra-pure waters, ultrasonic 30min；By 0.1g hydrochloric acid
Dopamine is dissolved in 10mL ultra-pure waters, and above-mentioned solution is added, and 1h is stirred at room temperature under dark conditions；It is slow to add 10mL Tris-
Fliud flushing (50mmolL-1, pH=8.5), it is stirred at room temperature for 24 hours under dark conditions；Gained mixed solution is centrifuged, deionization
Water is cleaned to supernatant and is clarified, and is transferred in freeze drier, is taken out after 48h and be can be obtained 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)2·6H24h is stirred at room temperature in O；Secondly, 6.0g urea is added, by above-mentioned mixed liquor in 80 DEG C of perseverances
Determine persistently to stir at temperature and evaporate moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, is heated to 900 DEG C with the heating rate of 4 DEG C/min, is pyrolyzed 1h, be cooled under the protection of Ar often
It is taken out after temperature, you can obtain Ti3C2@PDA@CNTs three-dimensional composite materials.
Embodiment 5
(1)Ti3C2The preparation of@PDA composite materials；
First, by the Ti of 300mg3C2Nano-powder ultrasonic disperse is in 200mL ultra-pure waters, ultrasonic 30min；By 0.6g salt
Sour dopamine is dissolved in 60mL ultra-pure waters, and above-mentioned solution is added, and 0.5h is stirred at room temperature under dark conditions；It adds
30mLTris- buffer solutions (50mmolL-1, pH=8.5), 12h is stirred at room temperature under dark conditions；Gained mixed solution is centrifuged
Separation, deionized water are cleaned to supernatant and are clarified, be transferred in freeze drier, are taken out after 48h and be can be obtained 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)2·6H22h is stirred at room temperature in O；Secondly, 3.0g urea is added, above-mentioned mixed liquor is constant at 60 DEG C
At a temperature of persistently stirring evaporate moisture, obtain grey presoma；Finally, by precursor powder agate mortar it is levigate after, turn
Enter in Ar atmosphere tube furnaces, is heated to 600 DEG C with the heating rate of 3 DEG C/min, is pyrolyzed 2h, room 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 composite materials；
First, by the Ti of 400mg3C2Nano-powder ultrasonic disperse is in 250mL ultra-pure waters, ultrasonic 30min；By 0.8g salt
Sour dopamine is dissolved in 90mL ultra-pure waters, and above-mentioned solution is added, 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；Gained mixed solution is centrifuged, go from
Sub- water is cleaned to supernatant and is clarified, and is transferred in freeze drier, is taken out after 48h and be can be obtained 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)2·6H26h is stirred at room temperature in O；Secondly, 30.0g urea is added, by above-mentioned mixed liquor in 100 DEG C of perseverances
Determine persistently to stir at temperature and evaporate moisture, obtains grey presoma；Finally, by precursor powder agate mortar it is levigate after,
It is transferred in Ar atmosphere tube furnaces, is heated to 1000 DEG C with the heating rate of 5 DEG C/min, is pyrolyzed 0.5h, it is cooling under the protection of Ar
It is taken out after to room 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 the same as embodiment 1.
The results show that the present invention by control presoma in urea content, it can be achieved that Ti3C2Surface length of carbon nanotube and
The regulation and control of density, Ti3C2Surface length of carbon nanotube is in 100~900nm.
In addition, being 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), which is Dopamine hydrochloride content respectively,
When the case where.
The present invention provides a kind of poly-dopamines 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 handled by HF solution corrosions3AlC2Selectivity
Etch away ternary layered Ti3AlC2In Al layers two-dimensional layer Ti is prepared3C2Nano material；With Ti3C2As carrier, first
Using dopamine, autoxidation is aggregated in Ti in weakly alkaline environment3C2Surface coats very thin PDA layers and obtains Ti3C2@PDA are compound
Material, clad PDA can protect Ti3C2The integrality of structure can by controlling reaction condition (such as Dopamine hydrochloride concentration)
To prepare the PDA clads of different-thickness；Then with Ti3C2@PDA are matrix, use Co for catalyst, nitrogenous in PDA structures
Group and phenolic hydroxyl group can be by the Co in solution2+It is adsorbed on Ti3C2The surfaces@PDA, while will be adsorbed on using the week reduction of PDA
The Co of matrix surface2+It is reduced into Co nano-particles and is uniformly fixed to Ti3C2Surfaces@PDA and as catalytic activity point, and coat
Layer PDA can protect Ti3C2The integrality of structure；Part Co2+Ion by with Ti3C2The ion exchange of surface oxygen functional group is made
With being adsorbed on Ti3C2Surface, is added urea as carbon source, urea by with Ti3C2The Co on surface2+Ion forms complex
And it is inserted into Ti3C2Lamella in；It is pyrolyzed under argon atmosphere, with the raising 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, it can be achieved that carbon nano tube growth length and density regulation and control.The present invention is prepared using simple pyrolysismethod
Ti3C2@PDA@CNTs three-dimensional composite materials, this method can be inexpensive, quick, environmentally friendly, safety by changing in presoma
The content of urea, to realize Ti3C2The controllable growth of surface C NTs length and density.Compared with directly in Ti3C2Surface is grown
CNTs prepares Ti3C2The method of@CNTs, in Ti3C2Regrowth CNTs after surface coats PDA layers is more easy to realize Ti3C2@CNTs
The controllable preparation of three-dimensional composite material, and grow CNTs mass higher, Ti3C2It is stronger with CNTs binding forces, to Ti3C2@
Also more preferably, this is for extending Ti for the performances such as chemical property, absorbing property, the photocatalysis of CNTs3C2Material ultracapacitor,
Lithium ion battery, nano adsorber and the application for inhaling the fields such as wave, have important practical significance.Compared to report other prepare
Method, the experiment condition needed for this method is fairly simple, at low cost, easy to operate.
The present invention improves Ti3C2Electric conductivity, expand Ti3C2Specific surface area, improve Ti3C2Self stability etc., from
And extend Ti3C2Material is in ultracapacitor, lithium ion battery, nano adsorber and the application for inhaling the fields such as wave.
Claims (9)
1. a kind of preparation method of poly-dopamine as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials, feature exist
In including the following steps：
(1) by Ti3C2Nano-powder and Dopamine hydrochloride are scattered in ultra-pure water and are uniformly mixed respectively, are stirred under dark conditions
Mix 0.5~2h；Tris- buffer solutions are added, continue 12~48h of stirring under dark conditions；By the separation of gained mixed solution, water
It washes and dries, 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 is stirred to react 2~6h；Urea is added after reaction, and lasting stirring at a constant temperature evaporates water
Point, obtain precursor powder, wherein Ti3C2@PDA nano-powders, Co (NO3)2·6H2The mass ratio of O and urea be (0.2~
0.5)：(0.1~0.4)：(3.0~30.0)；Precursor powder is heat-treated, poly-dopamine is obtained and is carbonized as transition zone
Titanium growth in situ CNTs three-dimensional composite materials.
2. a kind of poly-dopamine according to claim 1 is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized 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 as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized in that the Tris- buffer concentrations being added in step (1) are 50mmolL-1, pH value 8.5.
4. a kind of poly-dopamine according to claim 1 is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized 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 as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized 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 as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized in that the heat treatment in step (2) carries out under the protection of Ar.
7. a kind of poly-dopamine according to claim 1 is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized 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 as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials
Preparation method, which is characterized in that the heating rate of heat treatment be 3~5 DEG C/min.
9. a kind of using poly-dopamine made from preparation method described in claim 1 as transition zone titanium carbide growth in situ
CNTs three-dimensional composite materials.
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| CN108417406A (en) * | 2018-01-30 | 2018-08-17 | 哈尔滨工业大学 | A kind of Ti3C2MXene-Co composite material and preparation methods |
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| CN111420649A (en) * | 2020-05-11 | 2020-07-17 | 山东省淄博生态环境监测中心 | PDA modified high-adsorbability TiO2Preparation method and application of fiber catalyst |
| CN112072126A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof |
| CN112490019A (en) * | 2020-12-09 | 2021-03-12 | 桂林电子科技大学 | Polydopamine-coated MXene-based composite material and preparation method and application thereof |
| CN114335576B (en) * | 2021-12-30 | 2023-02-10 | 河北工业大学 | CoN/Ti with foamed nickel as substrate 3 C 2 Material preparation method and application |
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