CN106145951B - Porous two-dimentional transition metal carbide of one kind and preparation method thereof - Google Patents
Porous two-dimentional transition metal carbide of one kind and preparation method thereof Download PDFInfo
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- CN106145951B CN106145951B CN201510164821.3A CN201510164821A CN106145951B CN 106145951 B CN106145951 B CN 106145951B CN 201510164821 A CN201510164821 A CN 201510164821A CN 106145951 B CN106145951 B CN 106145951B
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Abstract
The present invention provides a kind of porous two-dimentional transition metal carbides, by the way that hole is arranged in MXenes material, be conducive to improve the specific surface area of MXenes material and the absorption of MXenes material and the ability for transmitting particle, have a good application prospect in fields such as electronics, energy storage.In addition, the present invention, which is used, adulterates the MAX phase solid-solution material of Cr element at M as presoma, pass through selective etch, hole configurations is formed from the method that at least partly Cr atom is also etched from MAX phase solid solution to abjection while etching abjection forms MXenes lamellar structure in MAX phase solid solution in Al atom, this method is simple and easy, the MXenes sheet layer material with hole configurations is made in one step, and the number of hole can be regulated and controled with aperture by the doping of etch period, Cr element.
Description
Technical field
The present invention relates to transition metal carbides laminate ceramic technical fields, and in particular to a kind of porous two-dimentional mistake
Cross metal carbides and preparation method thereof.
Background technique
Graphene (graphene) is the two dimensional crystal of current most study, from 2004 by Geim, Novoselov et al.
Since it was found that, had been a great concern during the decade short.Graphene be one kind by carbon atom with sp2Single original of hydridization connection
The New Two Dimensional atomic crystal that sublayer is constituted, for the most thin a kind of material (single layer 0.335nm) being currently known, valence band with
Conduction band intersects in fermi level, energy gap zero；Carrier shows a kind of linear dispersion relation at fermi level, has surprise
Special property: thermal conductivity is up to 5150J/ (mK), carrier mobility reaches 1.5 × 104cm2·V-1·s-1, and compare table
Area theoretical value is 2630m2/ g etc. is shown in numerous areas such as electronics, electromagnetism, optics, sensor, catalysis, energy storage
Huge application potential is gone out.
Punching can be further improved the specific surface area of graphene on the surface of graphene, and suitable hole can also become small
The space in channel or storage that particle shuttles.Wen etc. has found that porous graphene is a kind of good electrode material for super capacitor,
It is especially still able to maintain very high specific capacitance (there is 200F/g in 1V/s) under the conditions of fast charging and discharging and structure is steady
Qualitative (after circulation 5000 times, specific capacitance stills remain in 97% of initial value or more) (Wen, Z.H., et al.,
Adv.Mater.,2012,24,5610).Sint etc. be found to have different functional groups modification graphene hole can to difference from
Son plays selective effect, for example the hole of electronegative F-N modification is conducive to passing through for cation, and positively charged H is repaired
The hole of decorations is then the good channel of anion (Sint, K.et al., J.Am.Chem.Soc., 2008,130,16448).
Porous graphene has then been applied in the determination of DNA sequence dna by Wells etc..They are by simulation discovery when DNA passes through graphene
On hole when, the nucleotide in DNA has ion and electric current is hindered to generate, and this value is related with the type of nucleotide
(Wells,D.B.,et al.,Nano Lett.,2012,12,4117)。
Currently, the preparation method of porous graphene has very much, polymer construction method, plasma beam, electron beam can be divided into
Or photon beam etching method, template and chemical etching method etc..Bieri etc. use benzene iodide as presoma polymerization for the first time obtain by
Six side's network structure of two dimension of phenyl ring building, the aperture which has is aboutAperture, and in periodically uniformly point
Cloth (Bieri, M., Chem.Commum., 2009,6919).Akhavan then uses the photocatalytic activity of ZnO nanorod in oxidation stone
Black alkene obtains the porous graphene of 300nm or so, and the advantage of the method is that hole size can be carried out by the diameter of ZnO nanorod
Adjustment, but its pore size distribution density needs to be further increased (Akhavan, O.ACS Nano, 2010,4,4174).The benefits such as Jung
It uses Au Specific surface area as template, etches to obtain the porous of the uniform dense distribution that diameter is about 100nm using AAO technique
Graphene (Jung, I., et al., Appl.Phys.Lett., 2013,103,023105.).Zhu etc. is using KOH solution to warp
The graphene oxide of microwave treatment performs etching, and obtains the porous graphene of nanoscale, and the method is simple and effective, can make porous stone
The specific surface area of black alkene is increased to 3100m2/g(Zhu,Y.et al.,Science,2011,332,1537)。
Two-dimentional transition metal carbide or carbonitride (MXenes) were by Gogotsi and Barsoum et al. in 2011 years
The ceramic material with two-dimensional slice structure for cooperating discovery, is generally available Mn+1XnTzIt indicates, wherein M refers to magnesium-yttrium-transition metal (such as
Ti, Zr, Hf, V, Nb, Ta, Cr, Sc etc.), X refers to that C or/and N, n are generally 1-3, TzRefer to surface group (such as O2-、OH-、F-、NH3、
NH4 +Deng).Currently, MXenes is typically derived from ternary layered cermet Mn+1AXn(M is transition metal element to phase, and A is main group
Element, X are C and/or N, and n is generally 1~3, abbreviation MAX phase), by will combine weaker A bit element in MAX phase, (such as Al is former
Son) extraction obtain.
Similar with graphene, MXenes is also in two-dimensional slice structure, has high-specific surface area, high conductivity etc., in electronics
The fields such as, electromagnetism, optics, sensor, catalysis, energy storage have application potential.
For example, M.Naguib etc. reports V in terms of energy storage2CTzElectrode material as lithium ion battery has excellent
Specific discharge capacity (when cycle rate is 1C, 280mAhg-1；When cycle rate is 10C, 125mAhg-1), and in charge and discharge 140
Still good stability (M.Naguib et al, J.Am.Chem.Soc., 2013,135,15966) is able to maintain after secondary；
M.Lukatskaya etc. then has studied lamella Ti3C2TxAs the electrode active material of supercapacitor, 1M MgSO is worked as in discovery4Make
For electrolyte, 1A g is used-1The specific capacitance of the material is up to 400Fcm when testing electric current-3(M.Lukatskaya,et al,
Science,2013,341,1502)；Recently, the discovery such as M.W.Barsoum is with claylike Ti3C2TzThe supercapacitor of preparation
With 900F/cm3Volumetric capacitance, the value is very close to ruthenium oxide hydration (1000-1500F/cm3), compare activated graphene
(60-100F/cm3), the thin carbide-derived carbon electrode (180F/cm of micron3), chemical conversion graphene (260F/cm3) etc. body
Product specific capacitance is much higher (M.Ghidiu et al, Nature, 2014,516,78).
In other applications, Zhou Aiguo etc. takes the lead in having studied the Ti activated through NaOH3C2Tz nanometer sheet is to weight in sewage
The absorption behavior of metal finds that at 323K, pH=5.8~6.2, the material is reachable to the maximum adsorption capacity of Pb (II)
140mg g-1(Q.Peng et al,J.Am.Chem.Soc.,2014,136,4113)；MXenes also can be used as Pt nanoparticle
Carrier material fuel cell rise catalytic action (Y.P.Gao et al, Solid State Sciences, 2014,35,
62.), its same Cu2The composite material of O can promote ammonium perchlorate decomposition (X.H.Xie et al, Chem.Commun.,
2013,49,10112.)；In addition, this seminar expands application of the MXenes in the field of polymers, find polymethyl
Sour N, N- dimethylamino ethyl ester (PDMAEMA) branch is connected to V2CTzIn nanometer sheet, it can obtain with CO2Temperature double stimuli is rung
Answer the hybrid material (Chen, J., et al., Chem.Commun., 2015,51,314) of performance.
On the other hand, compared with graphene, due to including incessantly a kind of element of carbon in the lamellar structure of MXenes, make
Obtaining MXenes ratio Graphene has more flexible adjustable structure and rich and varied performance.By at present to Graphene's
Research and develop and improve its performance, widen its application etc., it is intended that being researched and developed to the structure etc. of MXenes material to improve its property
It can, widen its application etc..But the research and development of this respect are less at present, reported research and development result is only the hair such as O.Mashtalir
Existing small molecule dimethyl sulfoxide (DMSO) spontaneous can be inserted into Ti3C2TzInterlayer has MXenes by ultrasonic treatment fine
Peeling effect, the Ti of available several layers of even single layers as graphene3C2TzNanometer sheet (d-Ti3C2Tz), it utilizes
Single layer Ti3C2TzNanometer sheet reaches 410mAh g as the energy storage density of lithium ion battery anode active material-1@1C、110mAh
g-1@36C, and there is good stable circulation performance (O.Mashtalir, et al., Nat.Commun., 2013,4,1716).
Summary of the invention
The present invention provides a kind of MXenes material, which includes transiting group metal elements and carbon, has lamella knot
Structure, and its lamellar structure has several holes, as porous MXenes material, thus be conducive to improve the specific surface of MXenes
Product, and the ability of absorption and transmission particle.
Part transition metal element can be replaced by Cr element in the porous MXenes material, and chemical formula is (M1- xCrx)2C, wherein M is transition metal element, including but not limited to Ti, V******* etc., and 0≤x≤0.5.
In addition, part carbon can be replaced by N element in the porous MXenes material.
In the porous MXenes material, aperture is preferably 20nm-300nm.
The present invention also provides a kind of methods for preparing above-mentioned porous MXenes material, and this method is using M doping Cr members
The MAX phase solid-solution material of element is (M as presoma, the molecular formula of the persursor material1-xCrx)n+1AlCn, wherein M is transition
Metal, 0 < x≤0.5, n=1-3；Selective etchant, under corrosive agent effect, Al atom is deviate to be formed from the presoma
MXenes lamellar structure, while at least partly Cr atom is deviate from from MAX phase solid solution, forms hole.
The M element is transition metal element, including but not limited to Ti, V etc..
Persursor material (the M1-xCrx)n+1AlCnIn at least partly carbon can be replaced by N element, formed forerunner
Body material (M1-xCrx)n+1Al(C1-yNy)n, wherein 0≤y≤1.
The persursor material includes but is not limited to (Ti1-xCrx)2AlC、(V1-xCrx)2AlC、(Ti1-xCrx)2Al
(C0.5N0.5)、(Ti1-xCrx)3AlC2、(V1-xCrx)3AlC2、(Ti1-xCrx)4AlC3、(V1-xCrx)4AlC3One of or it is several
The combination of kind.
The etching agent is unlimited, can be single corrosive agent, such as HF aqueous solution, NH4HF2Aqueous solution etc., is also possible to
Compound corrosive agent composed by fluoride salt and customary acid.The fluoride salt includes but is not limited to LiF, NaF, KF, NH4F
Deng one of or several combinations.The acid includes but is not limited to hydrochloric acid, sulfuric acid etc..The compound corrosive agent includes
But it is not limited to the compound corrosive agent etc. of LiF and HCL aqueous solution composition.
When corrosive agent is HF aqueous solution, the mass percent concentration of the corrosive agent is preferably 10%-50%.
When corrosive agent is NH4HF2When aqueous solution, the molar concentration of the corrosive agent is preferably 1-10M.
Number and the aperture of described hole can be controlled by regulating and controlling etch period.
Doping by regulating and controlling Cr element can regulate and control the number of described hole.
Since etching reaction process is violent, preferably, etching agent is slowly added drop-wise in precursor powder dropwise.Into
One step is preferred, and the reaction vessel is placed in ice-water bath, to reduce the heat generated in reaction.
In conclusion the present invention is by being arranged hole in MXenes material, to improve the specific surface area of MXenes material,
Hole can also become the space in channel or storage that particle shuttles simultaneously, therefore be conducive to improve the conductivity of MXenes material
And absorption property etc., it has a good application prospect in fields such as electronics, energy storage.It is adulterated in addition, the present invention is used at M
The MAX phase solid-solution material of Cr element is etched from MAX phase solid solution by selective etch in Al atom as presoma
At least partly Cr atom is also etched the method shape of abjection by abjection from MAX phase solid solution while forming MXenes lamellar structure
At hole configurations, this method is simple and easy, and the MXenes sheet layer material with hole configurations, and the number of hole is made in a step
It can be regulated and controled by the doping of etch period, Cr element with aperture.
Detailed description of the invention
Fig. 1 a is (V in the embodiment of the present invention 11-xCrx)2AlC (x=0,0.01,0.10) solid solution is in mass fraction
XRD diffraction pattern before being etched in 40% hydrofluoric acid；
Fig. 1 b is (V in the embodiment of the present invention 11-xCrx)2AlC (x=0,0.01,0.10) solid solution is in mass fraction
XRD diffraction pattern after being etched 7 days in 40% hydrofluoric acid；
Fig. 2 is (V in the embodiment of the present invention 11-xCrx)2AlC (x=0,0.01,0.10) solid solution is in mass fraction respectively
SEM figure after being etched 7 days in 40% hydrofluoric acid；
Fig. 3 is (V in the embodiment of the present invention 20.90Cr0.10)2AlC solid solution is carved in the hydrofluoric acid that mass fraction is 40%
XRD diffraction pattern after losing different time；
Fig. 4 is (V in the embodiment of the present invention 20.90Cr0.10)2AlC solid solution is carved in the hydrofluoric acid that mass fraction is 40%
SEM figure after losing different time；
Fig. 5 is (V in the embodiment of the present invention 31-xCrx)2AlC (x=0,0.01,0.10) solid solution is 40% in mass fraction
Hydrofluoric acid in etch 5 days after obtained sheet layer material as supercapacitor made from raw material be 100mV/s in sweep speed
When cyclic voltammetry curve.
Specific embodiment
Present invention is further described in detail for embodiment with reference to the accompanying drawing, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, two-dimentional transition metal carbide is (V1-xCrx)2C, 0≤x < 0.1, and the metal carbides piece
There are several holes in layer structure, be in porous structure.
The preparation step of the two-dimentional transition metal carbide with porous structure is as follows:
(1) MAX phase solid-solution material (V is selected1-xCrx)2AlC is as presoma, and wherein x is respectively 0,0.01,0.10, should
The preparation method and document of presoma: V described in Chen, J., et al., Chem.Commun., 2015,51,3142The system of AlC
Preparation Method is identical, and material rate and the sintering temperature for preparing presoma are as shown in table 1 below, and three kinds of different presoma materials are made
Material；Table 1:(V1-xCrx)2The raw material proportioning and sintering temperature of AlC (x=0,0.01 or 0.10) solid solution
(2) three kinds of persursor materials made from step (1) are crushed respectively, are ground to 300 mesh, obtain three kinds of size distributions
Uniform presoma powder；
(3) selecting concentration is the hydrofluoric acid aqueous solution of 40wt.% as corrosive agent；For the sake of comparison, every kind of presoma powder
Weigh 1g be respectively placed in three plastic containers, by each plastic containers impregnate in water, corrosive agent is slowly added to dropwise it is each before
It drives in body powder；For every kind of presoma powder, the time for adding of corrosive agent is greater than or equal to 5 minutes, and each corrosive agent
Drop rate, time for adding and dripping quantity it is identical；After being added dropwise uniformly mixing, stand 7 days, and every cross 12h gently
Ground is sufficiently stirred；
(4) seperation film is used as using polyvinyladine floride miillpore filter (PVDF, aperture are 0.45 μm), filtered through step (3)
Then obtained product is sufficiently cleaned, then through ethyl alcohol with separating every kind of presoma powder and hydrofluoric acid aqueous solution with deionized water
Room temperature vacuum drying after cleaning.
Detect the object phase and crystalline substance for corroding the every kind of presoma powder in front and back through step (3) respectively using X-ray diffraction spectrum (XRD)
The variation of body structure, Fig. 1 a are the XRD diagram through every kind of presoma powder before step (3) corrosion, and Fig. 1 b is to corrode through step (3)
The XRD diagram of every kind of presoma powder afterwards, from, Fig. 1 a and Fig. 1 b it can be seen that
(1) for every kind of presoma powder, under the selective corrosion effect of corrosive agent, Al atom is solid from MAX phase
Abjection forms MXenes lamellar structure in solution；
(2) powder after comparing three kinds of difference Cr doping corrosion, the corresponding characteristic peak of MXenes is all at about 7.4 °, therefore
The doping of Cr does not influence the spacing of the MXenes lamella eventually formed.
The lattice constant c value variation for changing calculating MXenes according to above-mentioned XRD spectrum is as shown in table 2 below.
Table 2:(V1-xCrx)2The variation of lattice constant c value of the AlC (x=0,0.01,0.10) after solid solution is etched
From in table 2 it is also seen that the spacing of MXenes is substantially identical in powder after the corrosion of three kinds of difference Cr dopings
's.It is totally consistent that is, mixing the MXenes lamella obtained after Cr corrosion with the lamella obtained after Cr corrosion is not mixed.
The shape for the powder that each presoma powder obtains after step (3) corrosion is observed using scanning electron microscope (SEM)
Looks figure, as shown in Fig. 2, display has obtained two-dimensional layer nanometer sheet using the above method；(a), (b), (c) figure in Fig. 2
Comparison discovery, when adulterating Cr as x > 0, i.e., in presoma, each nano-lamellar structure occurs with hole, and size is on the left side 200nm
It is right；Also, under identical etching condition, the hole that Cr doping obtains more greatly is more.
Embodiment 2:
Identical with embodiment 1 in the present embodiment, two-dimentional transition metal carbide is (V1-xCrx)2C, 0≤x < 0.1,
And there are several holes in the metal carbides lamellar structure, be in porous structure.
The preparation of the two-dimensional slice material with porous structure is identical with the preparation method in embodiment 1, and institute is not
Same is that the present embodiment is paid close attention to for identical presoma powder, influence of the etch period to its etching effect, the preparation method
It is as follows:
(1) MAX phase solid-solution material (V is selected0.90Cr0.10)2AlC is as presoma, the preparation method and text of the presoma
It offers: V described in Chen, J., et al., Chem.Commun., 2015,51,3142The preparation method of AlC is identical, wherein preparing
The material rate and sintering temperature of presoma are identical as the correspondence parameter of x=0.10 in table 1；
(2) persursor material made from step (1) is crushed respectively, 300 mesh is ground to, before obtaining even particle size distribution
Drive body powder；
(3) selecting concentration is the hydrofluoric acid aqueous solution of 40wt.% as corrosive agent；For the sake of comparison, the presoma of 1g is weighed
Four parts of powder, every part is respectively placed in four identical plastic containers as sample one, two, three, four；Then, by each plastics
Container impregnates in water, and corrosive agent is slowly added in each sample dropwise；For each sample, the time for adding of corrosive agent is greater than
Or it is equal to 5 minutes, and the drop rate, time for adding and the dripping quantity that instill corrosive agent in each sample are identical；It drips
Uniformly mixing after finishing, stands 1d, 3d, 5d, 7d respectively, and every 12h that crosses lightly is sufficiently stirred, that is, the sample one after dropwise addition
Stand 1d, sample after dropwise addition and stand 3d, the sample three after dropwise addition stands 5d, and the sample four after dropwise addition stands 7d；
(4) seperation film is used as using polyvinyladine floride miillpore filter (PVDF, aperture are 0.45 μm), filtered through step (3)
Then obtained product is sufficiently cleaned, then after ethyl alcohol cleans with separating every kind of sample and hydrofluoric acid aqueous solution with deionized water
Room temperature in vacuo drying.
Detect the object phase and crystal structure for corroding front and back each sample through step (3) respectively using X-ray diffraction spectrum (XRD)
Change as can be seen from Figure 3:
(1) for each presoma powder, under the selective corrosion effect of corrosive agent, Al atom is dissolved from MAX phase
Abjection forms MXenes lamellar structure in body；
(2) extension of etch time facilitates more presoma powders and is transformed into MXenes.
The shape appearance figure for the powder that each sample obtains after step (3) corrosion is observed using scanning electron microscope (SEM), such as
Shown in Fig. 4, display has obtained two-dimensional layer nanometer sheet using the above method, and each nano-lamellar structure all has hole and goes out
Existing, pore size increases as time increases, respectively 1 day 39nm of etch, 3 days 50nm, 5 days 85nm, 7 days 140nm.It is logical
Cross (a) in Fig. 2, (b), (c), (d) figure comparison also it can be found that, under identical etching condition, with increasing for etch period
To hole increase.
Embodiment 3:
Identical with embodiment 1 in the present embodiment, two-dimentional transition metal carbide is (V1-xCrx)2C, 0≤x < 0.1,
And there are several holes in the metal carbides lamellar structure, be in porous structure.
The preparation of the two-dimensional slice material with porous structure is identical with the preparation method in embodiment 1, and institute is not
Be that etch period is selected as 5 days in the present embodiment, should the preparation method is as follows:
(1) MAX phase solid-solution material (V is selected1-xCrx)2AlC is as presoma, and wherein x is respectively 0,0.01,0.10, should
The preparation method and document of presoma: V described in Chen, J., et al., Chem.Commun., 2015,51,3142The system of AlC
Preparation Method is identical, wherein prepare presoma material rate and sintering temperature it is as shown in table 1, be made three kinds of different presoma materials
Material.
(2 are crushed three kinds of persursor materials made from step (1) respectively, are ground to 300 mesh, obtain three kinds of size distributions
Uniform presoma powder；
(3) selecting concentration is the hydrofluoric acid aqueous solution of 40wt.% as corrosive agent；For the sake of comparison, every kind of presoma powder
Weigh 1g be respectively placed in three plastic containers, by each plastic containers impregnate in water, corrosive agent is slowly added to dropwise it is each before
It drives in body powder；For every kind of presoma powder, the time for adding of corrosive agent is greater than or equal to 5 minutes, and each corrosive agent
Drop rate, time for adding and dripping quantity it is identical；After being added dropwise uniformly mixing, stand 5 days, and every cross 12h gently
Ground is sufficiently stirred；
(4) seperation film is used as using polyvinyladine floride miillpore filter (PVDF, aperture are 0.45 μm), filtered through step (3)
Then obtained product is sufficiently cleaned, then through ethyl alcohol with separating every kind of presoma powder and hydrofluoric acid aqueous solution with deionized water
Room temperature vacuum drying after cleaning obtains three kinds of two-dimentional transition metal carbides.
It is same as Example 1, it is detected respectively using X-ray diffraction spectrum (XRD) and corrodes the every kind of presoma in front and back through step (3)
The variation of object phase and crystal structure in powder observes each presoma powder through step (3) using scanning electron microscope (SEM)
The shape appearance figure of the powder obtained after corrosion.It was found that being acted on for every kind of presoma powder in the selective corrosion of corrosive agent
Under, Al atom is deviate to form MXenes lamellar structure from MAX phase solid solution, while as x > 0 at least partly Cr atom from
Deviate from MAX phase solid solution, forms hole, and as the increase hole number of x increases.
Being utilized respectively every kind obtained above two-dimentional transition metal carbide is the electrode slice that raw material makes supercapacitor,
It is specific as follows:
Every kind obtained above two-dimentional transition metal carbide, super carbon (Super P), Kynoar (PVDF) are pressed
The ratio of mass ratio 8.5:1.0:0.5 is applied in nickel foam after mixing in n-methyl-2-pyrrolidone, is pressed into after dry
Electrode slice, specific preparation method such as document (Cao, H.L.et al., Carbon, 2013,56,218.) are described.
Activated carbon electrodes piece is prepared using method same as described above, using the activated carbon electrodes piece as to electrode, reference
Electrode selects Ag/AgCl, standard electrode EMF 0.2224V.
Test can be carried out to the electrochemistry for the supercapacitor that above-mentioned three electrode is constituted: using 1470E type battery testing
System (Solartron analytical, USA) tests its cyclic voltammetry curve, set sweep speed 100mV/s, voltage
Window is using open-circuit voltage as the upper limit, to prevent supercapacitor to be oxidized during the experiment.The calculation formula of specific capacitance is C=
S/ (V × U × m), wherein C is specific capacitance, and S is the integral area of cyclic voltammetry curve, and V is sweep speed, and U is voltage window, m
It is the quality of active material.
Fig. 5 is sweep speed when being 100mV/s, the cyclic voltammetry curve of the supercapacitor.From figure 5 it can be seen that
The specific capacitance that supercapacitor has (when amount containing hole is most) as x=0.10 will be apparently higher than other two kinds；And x=0
When hole (be free of) supercapacitor specific capacitance it is minimum.The three kinds of capacitors obtained when being computed x=0,0.01,0.10
Specific capacitance be respectively 16.2F/g, 18.3F/g and 22.1F/g.It can be seen that the MXenes with hole configurations has more
High conductivity has advantage in the field for promoting supercapacitor specific capacitance.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
It for specific embodiments of the present invention, is not intended to restrict the invention, all any modifications made in spirit of the invention
With improve etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of porous two-dimentional transition metal carbide, includes transiting group metal elements and carbon, has lamellar structure, special
Sign is: its lamellar structure has several holes；
For the MAX phase solid-solution material for adulterating Cr element using M as presoma, the molecular formula of the persursor material is (M1- xCrx)n+1AlCn, wherein M is one of transition metal Ti, V, 0 < x≤0.5, n=1-3；Selective etchant is made in corrosive agent
Under, Al atom is deviate from from the presoma forms MXenes lamellar structure, while at least partly Cr atom is from MAX phase solid solution
Middle abjection forms hole.
2. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: at least partly carbon is by N element
Replace.
3. porous two-dimentional transition metal carbide as claimed in claim 1 or 2, it is characterized in that: the aperture of described hole is 20-
300nm。
4. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: the persursor material is
(Ti1-xCrx)2AlC、(V1-xCrx)2AlC、(Ti1-xCrx)3AlC2、(V1-xCrx)3AlC2、(Ti1-xCrx)4AlC3、(V1-xCrx)4AlC3One of or several combinations.
5. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: the corrosive agent is single corrosion
Compound corrosive agent composed by agent either fluoride salt and customary acid.
6. porous two-dimentional transition metal carbide as claimed in claim 5, it is characterized in that: the fluoride salt be LiF,
NaF、KF、NH4One of F or several combinations, the acid are one of hydrochloric acid, sulfuric acid.
7. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: the corrosive agent is that HF is water-soluble
Liquid, the mass percent concentration of the corrosive agent are 10%-50%.
8. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: the corrosive agent is NH4HF2Water
When solution, the molar concentration of the corrosive agent is 1-10M.
9. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: regulating and controlling the hole by etching time
The number in hole and aperture.
10. porous two-dimentional transition metal carbide as described in claim 1, it is characterized in that: passing through the doping tune of Cr element
Control the number of described hole.
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| US11554961B2 (en) * | 2017-12-22 | 2023-01-17 | Drexel University | Crumpled mesoporous MXene powders synthesized by acid-, base-, or salt-induced crumpling |
| CN108793166B (en) * | 2018-07-10 | 2020-06-19 | 中国科学院宁波材料技术与工程研究所 | Composite material of subgroup metal composite MXenes, preparation method and application thereof |
| CN110357666B (en) * | 2018-10-08 | 2021-12-28 | 湖南德智新材料有限公司 | Ceramic composite coating and preparation method thereof |
| CN109650391B (en) * | 2019-01-29 | 2022-03-18 | 武汉科技大学 | Preparation method of two-dimensional vanadium carbide MXene |
| CN109928393B (en) * | 2019-03-12 | 2021-03-30 | 宝晟(苏州)能源科技有限公司 | Preparation method and application of porous two-dimensional transition metal carbide |
| CN110394449A (en) * | 2019-08-27 | 2019-11-01 | 西安交通大学 | A kind of quaternary MAX phase enhances nickel-base high-temperature Oxidation Resistance Composites and its synthetic method |
| CN110698204B (en) * | 2019-11-12 | 2022-06-07 | 中国工程物理研究院核物理与化学研究所 | Preparation method of MAX phase ceramic |
| CN112225221B (en) * | 2020-06-05 | 2023-02-10 | 上海大学 | I-MAX phase material with core-shell structure and preparation method thereof |
| CN111634914B (en) * | 2020-06-12 | 2021-10-22 | 陕西科技大学 | Preparation method of M-site vanadium-doped MXene |
| CN113115581B (en) * | 2021-04-13 | 2022-12-02 | 郑州大学 | Ti 3 C 2 T x Composite material and preparation method thereof |
| CN114408873B (en) * | 2021-12-08 | 2023-09-26 | 中国科学院宁波材料技术与工程研究所 | Etching method of MXene material |
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