CN111785534B - Method for immobilizing MXene by ionic liquid covalent bonding and product thereof - Google Patents
Method for immobilizing MXene by ionic liquid covalent bonding and product thereof Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000003100 immobilizing effect Effects 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000002135 nanosheet Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 230000005855 radiation Effects 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Chemical group 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- 239000011829 room temperature ionic liquid solvent Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000005865 ionizing radiation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229910009819 Ti3C2 Inorganic materials 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
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- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910019762 Nb4C3 Inorganic materials 0.000 description 1
- 229910004472 Ta4C3 Inorganic materials 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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Abstract
The invention belongs to the field of nano functional materials, and discloses a method for immobilizing MXene by ionic liquid covalent bonding and a product thereof. Adding MXene materials containing-OH, -F, -O end groups into an ionic liquid monomer solution containing unsaturated double bonds, carrying the ionic liquid on the surface of the MXene materials through covalent bonding and immobilization by an ionizing radiation technology, and washing and centrifuging to obtain a series of ionic liquid covalent bonding and immobilization MXene materials containing different structures. The preparation method provided by the invention can be used for reaction at normal temperature, does not need a catalyst, and has the advantages of fast reaction, easiness in control and low energy consumption. The method solves the problem of MXene nanosheet stacking, enriches the types of active sites of the MXene nanosheets or increases the chemical effective active area of the MXene nanosheets. The synthesized MXene composite material maintains the nano structure of the MXene material, has the advantages of MXene and ionic liquid, and has good application prospects in the aspects of energy storage, catalysis, sensing and adsorption.
Description
Technical Field
The invention belongs to the field of nano functional materials, and particularly relates to a method for immobilizing MXene by ionic liquid covalent bonding and a product thereof.
Background
The two-dimensional transition metal carbide and nitride (MXene) is obtained by selectively corroding an A atomic layer of MAX phase in a specific chemical environment, has terminal functional groups of-OH, -O, -H, -F and the like on the surface, has a structure similar to that of graphene, has a large specific surface area, excellent chemical properties, good conductivity and Lewis-acidity, and is widely applied to the aspects of energy storage/conversion, optical/electro-catalysis, chemical sensing, electrostatic shielding and adsorption. However, the MXene lamellar structure is susceptible to re-stacking, resulting in a large loss of active surface area, affecting the diffusion of ions between layers, and thus limiting its application.
Recently, chinese patent CN 109449002 a discloses the direct irradiation of aqueous Ti3C2Tx dispersions with gamma rays or electron beams for surface modification. The modified Ti3C2Tx material has a fold structure and amorphous carbon, and is beneficial to improving the active specific surface area and improving the capacitance performance. Chinese patent CN110760075A discloses a method for preparing Ti by radiation polymerization initiated by gamma rays or electron beams3C2TxComposite double-network hydrogel, wherein Ti3C2TxAs an additive, Ti is imparted with its highly strain-dependent electrical resistance characteristics3C2TxThe composite double-network hydrogel has high-sensitivity strain sensor performance. However, the modification of MXene by radiation technology in these studies is relatively single, and only MXene itself is modified and used as an additive, which cannot satisfy different purposes. The modification of MXene materials by covalent bonding with monomers with specific functions needs to be further investigated.
Ionic Liquids (ILs) are liquid substances consisting of ions only at room temperature, with negligible vapor pressure, adjustable solubility and high thermal stability. Moreover, the physicochemical properties of the anions and the cations can be modulated by changing the types or the structures of the anions and the cations to obtain the functionalized ionic liquid. The ionic liquid modified MXene material has been reported. The Chinese invention patent CN 108379876A discloses an adsorbent obtained by mixing functionalized ionic liquid and MXene materials by utilizing electrostatic action, and the method has the advantages of long reaction time, weak binding force between the ionic liquid and the MXene and easy loss. Sun Yiming et al (Energy Storage Science and Technology, 2095-3C2Tx) As an electrode material of a super capacitor. But the methodThe method has complex operation and long reaction time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for immobilizing MXene by ionic liquid covalent bonding and a product thereof, solves the technical problems that MXene materials are easy to re-accumulate and few in active sites, and overcomes the defects of high energy consumption, complex operation and the like of the existing modification method.
In order to achieve the aim, the invention provides a method for immobilizing MXene by ionic liquid covalent bonding, which comprises the following steps
Preparing MXene material nanosheet dispersion liquid;
carrying out ultrasonic treatment and deoxidization sealing on the MXene material nanosheet dispersion liquid, adding an ionic liquid monomer containing unsaturated double bonds for mixing, and carrying out radiation grafting reaction;
and centrifuging and washing a product obtained by the radiation grafting reaction to obtain the ionic liquid covalent bonding immobilized MXene material.
Further, the MXene material nanosheet dispersion is obtained by adding a MAX phase material into a fluorine-containing solution for etching and ultrasonic processing.
Further, the MXene material is MXene, a metal nano material @ MXene composite material or a metal oxide nano material @ MXene composite material.
Further, MXene has a general formula of Mn+1XnTxWherein M is an early transition metal, X is carbon and/or nitrogen, Tx is a surface termination group, and n is 1 or 2 or 3.
Further, the metal nano material comprises one or more of ferromagnetic metal and alloy thereof, gold, silver and copper.
Further, the mass concentration of MXene is 0.5-60 mg/mL, and the addition amount of the metal salt ensures the mass of the provided metal: the ratio of the MXene to the MXene is (1-9) to (1-30).
Furthermore, the ionic liquid is one or more of imidazole salt, pyridine salt, quaternary ammonium salt and quaternary phosphonium salt room-temperature ionic liquid containing unsaturated double bonds.
Further, the concentration of the ionic liquid is 5wt% -30 wt%, and the solvent is water, methanol, toluene, N-dimethylformamide or an emulsion system.
Furthermore, the volume ratio of the MXene material to the ionic liquid is (1-5): (1-50).
According to another aspect of the invention, the product prepared by the method is provided, and the form of the ionic liquid covalently bonded and immobilized MXene material is a lamellar structure.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the method for modifying the radiation grafting ionic liquid solves the problem of re-accumulation of the MXene nanosheets, and enriches the types of active sites of the MXene nanosheets or increases the chemical effective active area of the MXene nanosheets. The prepared ionic liquid covalent bonding MXene composite material maintains the nano structure of the MXene material, has the advantages of the ionic liquid and the MXene, and has good application prospects in the aspects of energy storage, catalysis, sensing and adsorption.
(2) Compared with the defects of complex modification operation, difficult control, long reaction time, difficult realization of mass production and the like of the traditional chemical method, the radiation grafting technology related by the invention is a modification method with mild reaction condition, fast reaction, environmental protection, simple and convenient operation and easy control. A series of ionic liquids containing unsaturated double bonds are grafted on an MXene substrate, so that the method has the advantages of low loss of the ionic liquids, no need of adding an initiator or a catalyst in the reaction, high yield and the like; moreover, modified materials with different grafting ratios can be obtained by adjusting the radiation dose and the dose ratio, and the large-scale industrial production of the ionic liquid covalently bonded MXene can be realized.
Drawings
Fig. 1 is a scanning electron microscope spectrogram of an MXene nanosheet provided by an embodiment of the present invention.
Fig. 2 is a thermogravimetric diagram of MXene nanosheets, 10%, 20%, 30% ionic liquid covalently bonded to MXene material provided by an embodiment of the present invention.
Fig. 3 is an infrared diagram of MXene nanosheet, Fe @ MXene material and 10% ionic liquid covalently bonded Fe/MXene material provided by an embodiment of the present invention.
Fig. 4 is a thermogram of MXene nanoplatelets, ionic liquid covalently bonded Fe @ MXene material and 10% ionic liquid covalently bonded Fe @ MXene material according to an embodiment of the present invention.
FIG. 5 is an XRD pattern of an ionic liquid covalently bonded Fe @ MXene material and a 10% ionic liquid covalently bonded Fe @ MXene material according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of MXene immobilized by ionic liquid covalent bonding, which comprises the following steps:
step one, preparing MXene nano-sheets: adding MAX phase materials into a fluorine-containing solution for etching and ultrasonic treatment to obtain MXene nanosheet dispersion.
And step two, taking MXene nanosheet dispersion liquid with a certain concentration, ultrasonically dispersing uniformly, introducing inert gas, sealing, and adding an ionic liquid monomer containing unsaturated double bonds to perform radiation grafting reaction with MXene.
And step three, centrifuging and washing the product obtained in the step two to obtain the ionic liquid covalent bonding immobilized MXene material.
The general formula of MXene in the first step is Mn+1XnTx(n-1-3) wherein M is an early transition metal (Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, etc.), X is carbon and/or nitrogen, and Tx is a surface termination group (e.g., OH, O, or F).
Preferably, MXene is Ti2CTx、Ti3C2Tx、Ti3CNTx、Ta4C3Tx、Nb2CTx、V2CTxOr Nb4C3Tx。
In the first step, the MXene nano sheet material is in a sheet structure, and the sheet structure is formed by a single layer or multiple layers of Mn+1XnFormed of, or consisting of, single or multiple layers Mn+1And X. Preferably, the transverse dimension of the lamellar structure is 5 nm-50 mu m, and the thickness of each single sheet is 0.5-100 nm.
In the first step, the MXene material can also be a composite material of a metal nano material @ MXene or a composite material of a metal oxide nano material @ MXene.
Preferably, the metal nanomaterial comprises one or more of ferromagnetic metals and alloys thereof, gold, silver, copper. The metal oxide nano material comprises one or more of ferric oxide, zinc oxide, magnesium oxide, copper oxide, nickel oxide, praseodymium oxide, tin dioxide, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, aluminum oxide, manganese oxide, zinc ferrite, nickel ferrite and cobalt ferrite.
Preferably, the mass concentration of MXene is 0.5-60 mg/mL, and the addition amount of the metal salt ensures the mass of the metal provided by the MXene: the ratio of the MXene to the MXene is (1-9) to (1-30).
And the kind of the ionic liquid in the second step is one or more of imidazole salt, pyridine salt, quaternary ammonium salt and quaternary phosphonium salt room-temperature ionic liquids containing unsaturated double bonds.
Preferably, the ionic liquid species selected are vinyl and allyl with cations containing unsaturated double bonds and the anion X is Cl, Br, I, BF4,PF6And NTF2One or more of the alkenyl functional ionic liquid(s).
Preferably, the concentration of the ionic liquid in the second step is 5wt% -30 wt%, and the solvent is water, methanol, toluene, N-dimethylformamide or an emulsion system.
The ratio of the MXene material to the ionic liquid in the second step is (1-5) to (1-50).
Preferably, the radiation grafting dose in the second step is 5 kGy-300 kGy, and the grafting rate of the graft polymerization is 3% -100%.
In addition, according to the material obtained by the preparation method, the ionic liquid is immobilized on the MXene material by the radiation grafting technology, the grafting rate is 3% -100%, and the obtained ionic liquid is in a lamellar structure in a covalent bonding mode; the transverse size of the lamellar structure is 5 nm-200 mu m, and the thickness of each single piece is 0.5-1 mu m.
Example one
The preparation method of the ionic liquid covalent immobilized MXene comprises the following steps:
step one, preparing MXene nano-sheets: adding 1g of LiF into a 50mL polytetrafluoroethylene container, adding 20mL of 9M HCl, stirring at room temperature for 30min to obtain a colorless and transparent solution, weighing 1g of Ti3AlC2, slowly adding the solution in batches, stirring at 35 ℃ for 48h, centrifuging the obtained reaction solution (3500rpm, 5min), washing until the pH value of the supernatant poured out after centrifugation is more than 5, preferably 5-7, and taking the precipitate. Adding 80mL H2O to carry out ice bath ultrasound (600W, 20min), collecting the upper-layer black Zongzi color liquid, namely a few-layer Ti3C2Tx dispersion liquid, repeatedly adding water in a multilayer Ti3C2Tx to shake up the ultrasound and collect the upper-layer black Zongzi color liquid in order to obtain more few-layer Ti3C2Tx, preferably, repeating for 3-5 times, and combining the collected black Zongzi color liquid. Obtaining Ti with a concentration of about 7.5mg/mL in a single layer or in a few layers3C2TxAnd (3) dispersing the mixture.
Step two, preparing an ionic liquid covalent immobilized MXene material: 5mL of the Ti layer of small thickness obtained in the first step3C2TxThe suspension is put into a polyethylene bag and spread flat, and is vacuumized and sealed, 5mL of 10 wt% 1-vinyl ethyl imidazole chloride ionic liquid solution which is aerated with nitrogen and deoxidized is injected and sealed, radiation grafting is carried out under accelerator beams, the radiation dose rate is 20kGy/pass, and the absorption dose is 160 kGy.
Step three: and (5) washing the product obtained in the step two with ethanol and water or performing soxhlet extraction with toluene, and then centrifuging and freezing to obtain the needed MXene immobilized by the ionic liquid.
SEM test of the product of the first step in example one, as shown in FIG. 1, is a SEM image of Ti3C2Tx with a single layer or few layers, and it can be seen that Ti3C2Tx is in the form of thin yarn, indicating that MXene was successfully exfoliated.
Example two
An improvement was made over the process provided in example one, except that the ionic liquid concentration was 20 wt%.
EXAMPLE III
An improvement was made over the process provided in example one, except that the ionic liquid concentration was 30 wt%.
The products from examples one to three were subjected to thermogravimetric testing. As shown in fig. 2, a thermogravimetric analysis diagram of MXene, 10%, 20%, 30% ionic liquid covalently bonded immobilized MXene is shown, the grafting rate of 10% ionic liquid covalently bonded immobilized MXene is about 22%, and the grafting rate of 20% ionic liquid and 30% ionic liquid covalently bonded immobilized MXene is about 50%. The grafting rate is gradually increased along with the increase of the ion concentration, and the grafting rate is kept unchanged after the MXene surface is increased to a certain concentration due to the limited surface area of the MXene surface.
Example four
A method for preparing an ionic liquid covalent immobilization-magnetic metal/MXene composite material comprises the following steps:
s1, preparation of MXene nanosheets: the same procedure as in example one.
S2, preparation of MXene nano-sheets loaded with magnetic Fe nano-particles: 1g of FeSO is taken47H2O in a beaker, 20mL of water are added, after complete dissolution, the flask is transferred to a three-neck flask, and 20mL of ultrasonically dispersed, less-layered Ti are added3C2TxSuspending the mixture in a sealed environment at room temperature under N2Protecting and stirring for 24h, adding 10mL of 2mol/L sodium borohydride solution by using an injector, reacting for 30min, and quickly filtering out the reaction solution. Washing with anhydrous ethanol and oxygen-free deionized water, centrifuging (10000W, 10min) for multiple times, preferably 3-8 times, and drying in vacuum drying oven to obtain black powder as Fe/Ti3C2And (c) a complex.
S3, ionic liquid covalent immobilization Fe/Ti3C2Of compositesPreparation:
s31, taking 2mg of the few-layer Ti obtained in the step 23C2TxPlacing the suspension into a polyethylene bag, paving the polyethylene bag, vacuumizing and sealing the polyethylene bag, injecting 5mL of 10 wt% 1-vinyl ethyl imidazole chloride ionic liquid solution which is filled with nitrogen and deoxidized, sealing the polyethylene bag, and carrying out radiation grafting under an accelerator beam, wherein the radiation dose rate is 20kGy/pass, and the absorption dose is 160 kGy;
s32, washing the product obtained in the step S31 with ethanol and water or performing soxhlet extraction with toluene, and centrifuging to obtain the required ionic liquid covalently immobilized Fe/Ti3C2A composite material.
The product from example four was tested by infrared. As shown in FIG. 3, an infrared image of MXene, MXene @ Fe and 10% ionic liquid covalently bonded immobilized MXene @ Fe is shown, and as can be seen from the figure, MXene has a distinct infrared characteristic peak, and 10% ionic liquid covalently bonded immobilized MXene @ Fe also appears at 1228cm-1、1560cm-1C-N, C ═ N peak of imidazole of (2), 1506cm-1C ═ C, indicating that the vinylimidazole ionic liquid was successfully immobilized on MXene @ Fe.
The product from example four was subjected to thermogravimetric testing. Referring to FIG. 4, a thermogravimetric analysis of covalent bonding of MXene, MXene @ Fe and 10% ionic liquid to immobilized MXene @ Fe is shown, and the grafting rate of the ionic liquid is 45% calculated from thermogravimetric weight data.
XRD testing was performed on the product obtained in example four. Referring to FIG. 5, an XRD pattern of MXene @ Fe and 10% ionic liquid covalently bonded to immobilized MXene @ Fe is shown, and it can be seen that: the XRD peak of the MXene @ Fe composite material has the reported characteristic peak of few or single MXene, the characteristic peak of Fe is displayed at the 2 theta-44 degrees, and the characteristic peak of Fe in MXene @ Fe is not obvious when the 10% ionic liquid is covalently bonded and immobilized, so that the Fe content is reduced and the detection is difficult. And the change of XRD spectrogram before and after grafting is small, which shows that the crystallinity and the structure change of MXene are small in the radiation grafting process.
Comparative example 1
Different from the method in the embodiment, the irradiation dose is 20kGy, the grafting rate of the ionic liquid is very low, and the requirement of MXene material modification cannot be met.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The method for immobilizing MXene by ionic liquid covalent bonding is characterized by comprising the following steps
Preparing single-layer or few-layer MXene material nanosheet dispersion liquid;
carrying out ultrasonic treatment and deoxidization sealing on the MXene material nanosheet dispersion liquid, adding an ionic liquid monomer containing unsaturated double bonds for mixing, and carrying out radiation grafting reaction; the ionic liquid is one or more of imidazole salt, pyridine salt, quaternary ammonium salt and quaternary phosphonium salt room-temperature ionic liquid containing unsaturated double bonds;
the selected ionic liquid is vinyl and allyl with cation containing unsaturated double bond, and anion X is Cl, Br, I, BF4,PF6And NTF2One or more of the alkenyl functional ionic liquid;
and centrifuging and washing a product obtained by the radiation grafting reaction to obtain the ionic liquid covalent bonding immobilized MXene material.
2. The method of claim 1, wherein the MXene material nanoplatelet dispersion is obtained by adding MAX phase material to a fluorine-containing solution for etching and sonication.
3. The method of claim 2, wherein the MXene material is MXene, a metal nanomaterial @ MXene composite, or a metal oxide nanomaterial @ MXene composite.
4. The method of claim 3, wherein the MXene has the formula Mn+1XnTxWherein M is an early transition metal, X is carbon and/or nitrogen, Tx is a surface termination group, and n is 1 or 2 or 3.
5. The method of claim 3, wherein the metallic nanomaterial comprises one or more of a ferromagnetic metal and alloys thereof, gold, silver, and copper.
6. The method according to claim 5, wherein the MXene has a mass concentration of 0.5-60 mg/mL, and the metal salt is added in an amount that ensures the mass of the metal provided by the MXene: the ratio of MXene to MXene is (1-9): (1-30).
7. The method of claim 1, wherein the ionic liquid has a concentration of 5wt% to 30wt% and the solvent is water, methanol, toluene, N-dimethylformamide, or an emulsion system.
8. The method according to claim 1, wherein the ratio of the MXene material to the ionic liquid by volume is (1-5): (1-50).
9. The product prepared by the method according to any one of claims 1 to 8, wherein the ionic liquid covalently bonded supported MXene material is in a lamellar structure.
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