CN106145951A - A kind of porous two dimension transition metal carbide and preparation method thereof - Google Patents
A kind of porous two dimension transition metal carbide and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of porous two dimension transition metal carbide, by arranging hole in MXenes material, the beneficially specific surface area of raising MXenes material, and the absorption of MXenes material and the ability of transmission particle, have a good application prospect in the field such as electronics, energy storage.Additionally, the present invention uses the MAX phase solid-solution material of the Cr element that adulterates in M position as presoma, pass through selective etch, from MAX phase solid solution, the method formation pore space structure that while abjection forms MXenes lamellar structure, at least part of Cr atom is also etched from MAX phase solid solution abjection is etched at Al atom, the method is simple, one step prepares the MXenes sheet layer material with pore space structure, and the number of hole can be regulated and controled by etch period, the doping of Cr element with aperture.
Description
Technical field
The present invention relates to transition metal carbides laminate ceramic technical field, be specifically related to a kind of porous two
Dimension transition metal carbide and preparation method thereof.
Background technology
Graphene (graphene) is the two dimensional crystal of current most study, from 2004 by Geim,
Since Novoselov et al. finds, have been a great concern during the decade short.Graphene is a kind of by carbon
Atom is with sp2The New Two Dimensional atomic crystal that the monoatomic layer that hydridization connects is constituted is the thinnest for be currently known
A kind of material (monolayer is 0.335nm), its valence band intersects at fermi level with conduction band, and energy gap is zero；Current-carrying
Son presents a kind of linear dispersion relation at fermi level, has peculiar character: thermal conductivity is up to
5150J/ (m K), carrier mobility reach 1.5 × 104cm2·V-1·s-1, and specific surface area theoretical value
2630m2/ g etc., open up at numerous areas such as electronics, electromagnetism, optics, sensor, catalysis, energy storage
Show huge application potential.
Can improve the specific surface area of Graphene further in graphenic surface punching, suitable hole can also become
The passage shuttled back and forth for small particles or the space of storage.Wen etc. find that porous graphene is a kind of good super electricity
Container electrode material, especially still can keep the highest specific capacitance (at 1V/s under the conditions of fast charging and discharging
Time there is 200F/g) and structural stability (after circulating 5000 times, still remain in the 97% of initial value than electric capacity
(Wen, Z.H., et al., Adv.Mater., 2012,24,5610) above).Sint etc. find have different official's energy
Different ions can be played selective effect by the Graphene hole that group modifies, and the most electronegative F-N repaiies
Passing through of the hole beneficially cation of decorations, the hole that the H of positively charged modifies is then good the leading to of anion
Road (Sint, K.et al., J.Am.Chem.Soc., 2008,130,16448).Wells etc. are then by porous graphene
It is applied in the determination of DNA sequence.They are found when DNA passes through the hole on Graphene by simulation
Time, the nucleotide in DNA has ion and hinders electric current to produce, and this value is relevant with the kind of nucleotide
(Wells,D.B.,et al.,Nano Lett.,2012,12,4117)。
At present, the preparation method of porous graphene has a lot, can be divided into polymer construction method, beam-plasma,
Electron beam or photon beam etching method, template and chemical etching method etc..Bieri etc. use benzene iodide as presoma
Polymerization obtains the two dimension six side's network structure built by phenyl ring for the first time, and the aperture that this structure has is about
Aperture, and in being periodically uniformly distributed (Bieri, M., Chem.Commum., 2009,6919).
Akhavan then obtains the porous stone of about 300nm with the photocatalytic activity of ZnO nanorod at graphene oxide
Ink alkene, the advantage of this method is that hole size can be adjusted by the diameter of ZnO nanorod, but its hole
Distribution density needs to improve (Akhavan, O.ACS Nano, 2010,4,4174) further.Jung etc. utilize
Au Specific surface area, as template, utilizes AAO technique etching to obtain diameter and is about the closeest of 100nm
The porous graphene (Jung, I., et al., Appl.Phys.Lett., 2013,103,023105.) of collection distribution.The profits such as Zhu
By KOH solution, microwaved graphene oxide is performed etching, obtains the porous graphene of nanoscale,
This method is simply effective, and the specific surface area of porous graphene can be made to be increased to 3100m2/g(Zhu,Y.et al.,
Science,2011,332,1537)。
Two dimension transition metal carbide or carbonitride (MXenes) are by Gogotsi and Barsoum et al.
At the ceramic material with two-dimensional slice structure that cooperation in 2011 finds, it is generally available Mn+1XnTzRepresent,
Wherein M refers to magnesium-yttrium-transition metal (such as Ti, Zr, Hf, V, Nb, Ta, Cr, Sc etc.), X refer to C or/and
N, n are generally 1-3, TzRefer to that surface group is (such as O2-、OH-、F-、NH3、NH4 +Deng).At present, MXenes
It is typically derived from ternary layered ceramic metal Mn+1AXnPhase (M is transition metal, and A is major element,
X is C and/or N, and n is generally 1～3, is called for short MAX phase), by MAX phase combining more weak A
Bit element (such as Al atom) is extracted out and is obtained.
Being similar to Graphene, MXenes also in two-dimensional slice structure, has high-specific surface area, high conductivity etc.,
In fields such as electronics, electromagnetism, optics, sensor, catalysis, energy storage, there is application potential.
Such as, in terms of energy storage, M.Naguib etc. reports V2CTzElectrode material as lithium ion battery has
Have excellence specific discharge capacity (when cycle rate is 1C, 280mAhg-1；When cycle rate is 10C,
125mAhg-1), and still can keep good stability (M.Naguib et for 140 times in discharge and recharge later
al,J.Am.Chem.Soc.,2013,135,15966)；M.Lukatskaya etc. then have studied lamella Ti3C2Tx
As the electrode active material of ultracapacitor, find as 1M MgSO4As electrolyte, use 1A g-1
During test electric current, the ratio electric capacity of this material is up to 400Fcm-3(M.Lukatskaya,et al,Science,2013,
341,1502)；Recently, M.W.Barsoum etc. find with claylike Ti3C2TzThe ultracapacitor of preparation
There is 900F/cm3Volumetric capacitance, this value closely ruthenium oxide hydration (1000-1500F/cm3), than
Activation Graphene (60-100F/cm3), micron thin carbide-derived carbon electrode (180F/cm3), chemical conversion
Graphene (260F/cm3) etc. volumetric capacitance much higher (M.Ghidiu et al, Nature, 2014,516,78).
In other applications, Zhou Aiguo etc. take the lead in have studied the Ti through NaOH activation3C2Tz nanometer sheet pair
The absorption behavior of heavy metal in sewage, finds 323K, pH=5.8～6.2 times, and this material is to Pb (II)
Big adsorption capacity is up to 140mg g-1(Q.Peng et al,J.Am.Chem.Soc.,2014,136,4113)；
MXenes also can as the carrier material of Pt nanoparticle fuel cell rise catalytic action (Y.P.Gao et al,
Solid State Sciences, 2014,35,62.), its same Cu2The composite of O can promote dividing of ammonium perchlorate
Solve (X.H.Xie et al, Chem.Commun., 2013,49,10112.)；Additionally, this seminar expands MXenes
Application in field of polymer technology, finds polymethylacrylic acid N, N-dimethylamino ethyl ester (PDMAEMA)
Branch links V2CTzIn nanometer sheet, it is possible to obtain there is CO2The hybrid material of temperature dual stimuli responsive performance
(Chen,J.,et al.,Chem.Commun.,2015,51,314)。
On the other hand, compared with Graphene, owing to the lamellar structure of MXenes comprising carbon one element incessantly,
Hence in so that MXenes has the most flexible adjustable structure and rich and varied performance than Graphene.Logical
Cross and at present the research and development of Graphene are improved its performance, widen its application etc., it is intended that to MXenes
The structures of material etc. carry out researching and developing to improve its performance, widen its application etc..But, the research and development of current this respect
Less, the research and development result reported is only that O.Mashtalir etc. finds little molecule dimethyl sulfoxide (DMSO)
Spontaneous can be inserted into Ti3C2TzInterlayer, has good peeling effect through supersound process to MXenes,
The Ti of which floor even monolayer as Graphene can be obtained3C2TzNanometer sheet (d-Ti3C2Tz), utilize this list
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 have 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, and this material comprises transiting group metal elements and carbon, has
Lamellar structure, and its lamellar structure has some holes, is porous MXenes material, thus is conducive to
Improve the specific surface area of MXenes, and adsorb and the ability of transmission particle.
In described porous MXenes material, part transition metal can be replaced by Cr element, chemical formula
For (M1-xCrx)2C, wherein M is transition metal, includes but not limited to Ti, V******* etc., and
0≤x≤0.5。
It addition, part carbon can be replaced by N element in described porous MXenes material.
In described porous MXenes material, aperture is preferably 20nm-300nm.
Present invention also offers a kind of method preparing above-mentioned porous MXenes material, the method uses M position
The MAX phase solid-solution material of doping Cr element as presoma, the molecular formula of this persursor material is
(M1-xCrx)n+1AlCn, wherein M is transition metal, 0 ＜ x≤0.5, n=1-3；Selective etchant, in corruption
Under erosion agent effect, Al atom is deviate to form MXenes lamellar structure from this presoma, the most at least partly
Cr atom is deviate from from MAX phase solid solution, forms hole.
Described M element is transition metal, includes but not limited to Ti, V etc..
Described persursor material (M1-xCrx)n+1AlCnIn at least partly carbon can be replaced by N element,
Form persursor material (M1-xCrx)n+1Al(C1-yNy)n, wherein 0≤y≤1.
Described persursor material includes but 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)4AlC3In one or several combination.
Described etching agent does not limits, and can be single caustic, such as HF aqueous solution, NH4HF2Aqueous solution
Deng, it is also possible to the compound caustic that to be fluoride salt formed with customary acid.Described fluoride salt include but not
It is limited to LiF, NaF, KF, NH4One or several combination in F etc..Described acid includes but does not limits
In hydrochloric acid, sulphuric acid etc..Described compound caustic includes but not limited to answering of LiF and HCl/water solution composition
Close caustic etc..
When caustic is HF aqueous solution, the mass percent concentration of this caustic is preferably 10%-50%.
When caustic is NH4HF2During aqueous solution, the molar concentration of this caustic is preferably 1-10M.
Number and the aperture of described hole can be controlled by regulation and control etch period.
The number of described hole can be regulated and controled by the doping of regulation and control Cr element.
Owing to etching reaction process is violent, as preferably, etching agent is added drop-wise to the most lentamente precursor powder
In.Further preferably, described reaction vessel is placed in ice-water bath, to reduce the heat produced in reaction.
In sum, the present invention is by arranging hole, to improve MXenes material in MXenes material
Specific surface area, hole can also become passage or the space of storage that particle shuttles back and forth simultaneously, is thus advantageous to improve
The electrical conductivity of MXenes material and absorption property etc., have good application in the field such as electronics, energy storage
Prospect.It addition, present invention employing is adulterated in M position, the MAX phase solid-solution material of Cr element is as presoma,
By selective etch, from MAX phase solid solution, etch abjection at Al atom and form MXenes lamella knot
The method that at least part of Cr atom also etches while structure from MAX phase solid solution abjection forms hole knot
Structure, the method is simple, and a step prepares the MXenes sheet layer material with pore space structure, and hole
Number can be regulated and controled by etch period, the doping of Cr element with aperture.
Accompanying drawing explanation
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 quality
Mark be 40% Fluohydric acid. in etching before XRD diffraction pattern；
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 quality
Mark be 40% Fluohydric acid. in etch the XRD diffraction pattern after 7 days；
Fig. 2 is (V in the embodiment of the present invention 11-xCrx)2AlC (x=0,0.01,0.10) solid solution is respectively in matter
Measure the SEM figure after etching 7 days in the Fluohydric acid. that mark is 40%；
Fig. 3 is (V in the embodiment of the present invention 20.90Cr0.10)2AlC solid solution is the Fluohydric acid. of 40% at mass fraction
XRD diffraction pattern after middle etching different time；
Fig. 4 is (V in the embodiment of the present invention 20.90Cr0.10)2AlC solid solution is the Fluohydric acid. of 40% at mass fraction
SEM figure after middle etching different time；
Fig. 5 is (V in the embodiment of the present invention 31-xCrx)2AlC (x=0,0.01,0.10) solid solution divides in quality
Number be 40% Fluohydric acid. in etch the ultracapacitor that the sheet layer material obtained after 5 days prepares as raw material and exist
Sweep speed is cyclic voltammetry curve during 100mV/s.
Detailed description of the invention
The present invention is described in further detail by embodiment below in conjunction with the accompanying drawings, it should be pointed out that the following stated
Embodiment is intended to be easy to the understanding of the present invention, and it does not play any restriction effect.
Embodiment 1:
In the present embodiment, two dimension transition metal carbide is (V1-xCrx)2C, 0≤x ＜ 0.1, and this metal carbon
There is some holes, in loose structure in compound lamellar structure.
The preparation process of this two-dimentional transition metal carbide with loose structure is as follows:
(1) MAX phase solid-solution material (V is selected1-xCrx)2AlC as presoma, wherein x be respectively 0,
0.01,0.10, the preparation method of this presoma and document: Chen, J., et al., Chem.Commun., 2015,51,
V described in 3142The preparation method of AlC is identical, prepares material rate and the sintering temperature such as table 1 below of presoma
Shown in, prepare three kinds of different persursor materials；Table 1:(V1-xCrx)2AlC (x=0,0.01 or 0.10) is solid
The proportioning raw materials of solution and sintering temperature
(2) three kinds of persursor materials that step (1) prepares are crushed respectively, be ground to 300 mesh, obtain three
Plant the presoma powder body of even particle size distribution；
(3) selecting concentration is that the hydrofluoric acid aqueous solution of 40wt.% is as caustic；For the sake of contrast, every kind of forerunner
Body powder metage 1g is respectively placed in three plastic containers, is immersed in water by each plastic containers, by caustic
Dropwise it is slowly added in each presoma powder body；For every kind of presoma powder body, the time for adding of caustic is more than
Or equal to 5 minutes, and the drop rate of each caustic, time for adding and dripping quantity are identical；Drip complete
Rear uniformly mixing, stand 7 days, and often cross 12h and be sufficiently stirred for lightly；
(4) use polyvinyladine floride microporous filter membrane (PVDF, aperture is 0.45 μm) as separating film, mistake
The product that filter obtains through step (3), to separate every kind of presoma powder body and hydrofluoric acid aqueous solution, then spends
Ionized water fully cleans, then room temperature vacuum drying after ethanol purge.
X-ray diffraction spectrum (XRD) is utilized to detect every kind of presoma powder body before and after step (3) is corroded respectively
Thing phase and the change of crystal structure, Fig. 1 a is the XRD of every kind of presoma powder body before step (3) is corroded
Figure, Fig. 1 b is the XRD figure of every kind of presoma powder body after step (3) is corroded, from, Fig. 1 a and figure
In 1b it can be seen that
(1) for every kind of presoma powder body, under the selective corrosion effect of caustic, Al atom from
In MAX phase solid solution, abjection forms MXenes lamellar structure；
(2) powder body after three kinds of different Cr dopings corrosion of contrast, MXenes characteristic of correspondence peak is all about
7.4 °, therefore the spacing of the doping of the Cr MXenes lamella on eventually forming does not affects.
Lattice paprmeter c value change according to above-mentioned XRD figure spectrum change calculations MXenes is as shown in table 2 below.
Table 2:(V1-xCrx)2The change of the AlC (x=0,0.01,0.10) lattice paprmeter c value after solid solution is etched
The spacing base of MXenes in powder body from table 2 it is also seen that after three kinds of different Cr dopings corrosion
Originally it is identical.That is, the lamella obtained after mixing the MXenes lamella obtained after Cr corrodes and not mixing Cr corrosion
The most consistent.
Scanning electron microscope (SEM) is utilized to observe what each presoma powder body obtained after step (3) is corroded
The shape appearance figure of powder body, as in figure 2 it is shown, display utilizes said method all to obtain two-dimensional layer nanometer sheet；Pass through
In Fig. 2, (a), (b), the contrast of (c) figure find, as doping Cr in x ＞ 0, i.e. presoma, and each nanometer
Lamellar structure has hole and occurs, size is at about 200nm；Further, under identical etching condition, Cr mixes
The hole that miscellaneous amount obtains the most greatly is the most.
Embodiment 2:
In the present embodiment, identical with embodiment 1, two dimension transition metal carbide is (V1-xCrx)2C, 0
There is some holes, in loose structure on≤x ＜ 0.1, and this metal carbides lamellar structure.
The preparation of this two-dimensional slice material with loose structure is identical with the preparation method in embodiment 1,
Except that the present embodiment is paid close attention to for identical presoma powder body, the etch period impact on its etching effect,
This preparation method is as follows:
(1) MAX phase solid-solution material (V is selected0.90Cr0.10)2AlC is as presoma, the preparation of this presoma
Method and document: V described in Chen, J., et al., Chem.Commun., 2015,51,3142The preparation side of AlC
Method is identical, wherein prepares the corresponding parameter of the material rate of presoma and sintering temperature and the x=0.10 in table 1
Identical；
(2) persursor material that step (1) prepares is crushed respectively, be ground to 300 mesh, obtain granularity and divide
Cloth uniform presoma powder body；
(3) selecting concentration is that the hydrofluoric acid aqueous solution of 40wt.% is as caustic；For the sake of contrast, weigh 1g
Presoma powder body four parts, every part is respectively placed in four identical plastic containers as sample one, two, three,
Four；Then, each plastic containers are immersed in water, caustic is dropwise slowly added in each sample；To various kinds
For product, the time for adding of caustic is more than or equal to 5 minutes, and instills dripping of caustic in each sample
Rate of acceleration, time for adding and dripping quantity are identical；Uniformly mix after dropping, stand respectively 1d, 3d,
5d, 7d, and often 12h excessively is sufficiently stirred for lightly, i.e. and the sample one after dropping stands 1d, dropping
After sample and stand 3d, the sample three after dropping stands 5d, and the sample four after dropping stands 7d；
(4) use polyvinyladine floride microporous filter membrane (PVDF, aperture is 0.45 μm) as separating film, mistake
The product that filter obtains through step (3), to separate every kind of sample and hydrofluoric acid aqueous solution, then uses deionized water
Fully clean, then room temperature vacuum drying after ethanol purge.
Utilize X-ray diffraction spectrum (XRD) detect respectively through step (3) corrode before and after each sample thing phase and
The change of crystal structure is as can be seen from Figure 3:
(1) for each presoma powder body, under the selective corrosion effect of caustic, Al atom from
In MAX phase solid solution, abjection forms MXenes lamellar structure；
(2) prolongation of etch time contributes to more presoma powder body and is transformed into MXenes.
Scanning electron microscope (SEM) is utilized to observe the powder body that each sample obtains after step (3) is corroded
Shape appearance figure, as shown in Figure 4, display utilizes said method all to obtain two-dimensional layer nanometer sheet, and each nanometer
Lamellar structure is respectively provided with hole to be occurred, pore size increases over time and increases, respectively etch 1 day
39nm, 3 days 50nm, 5 days 85nm, 7 days 140nm.By (a), (b), (c), (d) in Fig. 2
Figure contrast also is able to find, under identical etching condition, the hole obtained along with the increase of etch period increases.
Embodiment 3:
In the present embodiment, identical with embodiment 1, two dimension transition metal carbide is (V1-xCrx)2C, 0
There is some holes, in loose structure on≤x ＜ 0.1, and this metal carbides lamellar structure.
The preparation of this two-dimensional slice material with loose structure is identical with the preparation method in embodiment 1,
Except that etch period is chosen as 5 days in the present embodiment, this preparation method is as follows:
(1) MAX phase solid-solution material (V is selected1-xCrx)2AlC as presoma, wherein x be respectively 0,
0.01,0.10, the preparation method of this presoma and document: Chen, J., et al., Chem.Commun., 2015,51,
V described in 3142The preparation method of AlC is identical, wherein prepares material rate and the sintering temperature such as table of presoma
Shown in 1, prepare three kinds of different persursor materials.
(three kinds of persursor materials that step (1) prepares are crushed by 2 respectively, are ground to 300 mesh, obtain three
Plant the presoma powder body of even particle size distribution；
(3) selecting concentration is that the hydrofluoric acid aqueous solution of 40wt.% is as caustic；For the sake of contrast, every kind of forerunner
Body powder metage 1g is respectively placed in three plastic containers, is immersed in water by each plastic containers, by caustic
Dropwise it is slowly added in each presoma powder body；For every kind of presoma powder body, the time for adding of caustic is more than
Or equal to 5 minutes, and the drop rate of each caustic, time for adding and dripping quantity are identical；Drip complete
Rear uniformly mixing, stand 5 days, and often cross 12h and be sufficiently stirred for lightly；
(4) use polyvinyladine floride microporous filter membrane (PVDF, aperture is 0.45 μm) as separating film, mistake
The product that filter obtains through step (3), to separate every kind of presoma powder body and hydrofluoric acid aqueous solution, then spends
Ionized water fully cleans, then room temperature vacuum drying after ethanol purge, obtains three kinds of two-dimentional transition metal carbides.
Same as in Example 1, utilize X-ray diffraction spectrum (XRD) to detect respectively before step (3) is corroded
Thing phase in every kind of presoma powder body and the change of crystal structure afterwards, utilizes scanning electron microscope (SEM) to see
Examine the shape appearance figure of the powder body that each presoma powder body obtains after step (3) is corroded.Find, for every kind of forerunner
For body powder body, under the selective corrosion effect of caustic, Al atom deviates from shape from MAX phase solid solution
Becoming MXenes lamellar structure, as x ＞ 0, at least part of Cr atom is deviate from from MAX phase solid solution simultaneously,
Form hole, and along with the increase hole number of x increases.
Being utilized respectively above-mentioned every kind of prepared two-dimentional transition metal carbide is the electricity that raw material makes ultracapacitor
Pole piece, specific as follows:
By above-mentioned every kind of prepared two-dimentional transition metal carbide, super carbon (Super P), Kynoar
(PVDF) ratio of 8.5:1.0:0.5 in mass ratio spreads upon foam after mixing in METHYLPYRROLIDONE
On nickel, it is pressed into electrode slice after drying, concrete preparation method such as document (Cao, H.L.et al., Carbon, 2013,
56,218.) described.
Method same as described above is used to prepare activated carbon electrodes sheet, using this activated carbon electrodes sheet as to electrode,
Reference electrode selects Ag/AgCl, and its standard electrode EMF is 0.2224V.
The chemical property of the ultracapacitor that above-mentioned three electrodes are constituted is tested: use 1470E type electricity
Its cyclic voltammetry curve, set scanning speed are tested in pond test system (Solartron analytical, USA)
Rate 100mV/s, voltage window is with open-circuit voltage as the upper limit, to prevent ultracapacitor by oxygen in experimentation
Change.Being C=S/ (V × U × m) than the computing formula of electric capacity, wherein C is ratio electric capacity, and S is cyclic voltammetry curve
Integral area, V is sweep speed, and U is voltage window, and m is the quality of active substance.
Fig. 5 is sweep speed when being 100mV/s, the cyclic voltammetry curve of this ultracapacitor.From Fig. 5
It can be seen that the ratio electric capacity that (when the amount Han hole is most), ultracapacitor has as x=0.10 is obvious
Higher than other two kinds；And (during without hole), the ratio electric capacity of ultracapacitor is minimum during x=0.It is computed
The ratio electric capacity of the three kinds of capacitors obtained when x=0,0.01,0.10 is respectively 16.2F/g, 18.3F/g and 22.1F/g.
This shows that the MXenes with pore space structure has higher electrical conductivity, promoting ultracapacitor ratio
The field of electric capacity possesses advantage.
Technical scheme has been described in detail by embodiment described above, it should be understood that above institute
State the specific embodiment of the only present invention, be not limited to the present invention, all institutes in the spirit of the present invention
Any amendment made and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a porous two dimension transition metal carbide, comprises transiting group metal elements and carbon, has sheet
Rotating fields, is characterized in that: its lamellar structure has some holes.
2. porous two dimension transition metal carbide as claimed in claim 1, is characterized in that: section transitions gold
Belonging to element to be replaced by Cr element, chemical formula is (M1-xCrx)2C, wherein M is transition metal, and
0≤x≤0.5。
3. porous two dimension transition metal carbide as claimed in claim 1, is characterized in that: at least partly carbon
Element is replaced by N element.
4. porous two dimension transition metal carbide as claimed in claim 1, is characterized in that: described transition
Metallic element is the one in Ti, V.
5. the porous two dimension transition metal carbide as described in any claim in Claims 1-4, its
Feature is: the aperture of described hole is 20-300nm.
6. prepare porous two dimension transition metal carbide as claimed in claim 5, it is characterized in that: use M
The MAX phase solid-solution material of position doping Cr element as presoma, the molecular formula of this persursor material is
(M1-xCrx)n+1AlCn, wherein M is transition metal, 0 ＜ x≤0.50, n=1-3；
Selective etchant, under caustic effect, Al atom deviates to be formed two dimension transition metal from presoma
Carbide platelets Rotating fields, the most at least partly Cr atom is deviate from from MAX phase solid solution, forms hole.
7. the method preparing porous two dimension transition metal carbide as claimed in claim 6, is characterized in that:
Described persursor material is (Ti1-xCrx)2AlC、(V1-xCrx)2AlC、(Ti1-xCrx)2Al(C0.5N0.5)、
(Ti1-xCrx)3AlC2、(V1-xCrx)3AlC2、(Ti1-xCrx)4AlC3、(V1-xCrx)4AlC3In one or several
The combination planted.
8. the method preparing porous two dimension transition metal carbide as claimed in claim 6, is characterized in that:
Described etching agent is the compound caustic that single caustic or fluoride salt are formed with customary acid；
As preferably, described fluoride salt is LiF, NaF, KF, NH4In F one or several
Combination, described acid is the one in hydrochloric acid, sulphuric acid；
As preferably, described caustic is HF aqueous solution, and the mass percent concentration of this caustic is
10%-50%；
As preferably, described caustic is NH4HF2During aqueous solution, the molar concentration of this caustic is 1-10M.
9. the method preparing porous two dimension transition metal carbide as claimed in claim 6, is characterized in that:
By number and the aperture of etch period regulation and control described hole.
10. the method preparing porous two dimension transition metal carbide as claimed in claim 6, is characterized in that:
The number of described hole is regulated and controled by the doping of Cr element.
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| CN109650391A (en) * | 2019-01-29 | 2019-04-19 | 武汉科技大学 | The preparation method of two-dimentional vanadium carbide MXene |
| CN109928393A (en) * | 2019-03-12 | 2019-06-25 | 郜明文 | A kind of preparation method and applications of porous two-dimentional transition metal carbide |
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| CN108793166A (en) * | 2018-07-10 | 2018-11-13 | 中国科学院宁波材料技术与工程研究所 | Composite material, its preparation method and the application of the compound MXenes of B metal |
| CN110357666A (en) * | 2018-10-08 | 2019-10-22 | 湖南德智新材料有限公司 | A kind of ceramic composite coating and preparation method thereof |
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| CN109650391A (en) * | 2019-01-29 | 2019-04-19 | 武汉科技大学 | The preparation method of two-dimentional vanadium carbide MXene |
| CN109928393A (en) * | 2019-03-12 | 2019-06-25 | 郜明文 | A kind of preparation method and applications of porous two-dimentional 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 |
| CN110698204A (en) * | 2019-11-12 | 2020-01-17 | 中国工程物理研究院核物理与化学研究所 | Preparation method of MAX phase ceramic |
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| CN112225221A (en) * | 2020-06-05 | 2021-01-15 | 上海大学 | I-MAX phase material with core-shell structure and preparation method thereof |
| CN111634914A (en) * | 2020-06-12 | 2020-09-08 | 陕西科技大学 | Preparation method of M-site vanadium-doped MXene |
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| CN114408873A (en) * | 2021-12-08 | 2022-04-29 | 中国科学院宁波材料技术与工程研究所 | Method for etching MXene material |
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