CN110845392B - Amino fullerene, preparation method and method for preparing modified titanium carbide nanosheets by using amino fullerene - Google Patents
Amino fullerene, preparation method and method for preparing modified titanium carbide nanosheets by using amino fullerene Download PDFInfo
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- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 89
- -1 Amino fullerene Chemical compound 0.000 title claims abstract description 85
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical class C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002135 nanosheet Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- TYEYBOSBBBHJIV-UHFFFAOYSA-M 2-oxobutanoate Chemical compound CCC(=O)C([O-])=O TYEYBOSBBBHJIV-UHFFFAOYSA-M 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 238000005055 short column chromatography Methods 0.000 claims 1
- RVZPDKXEHIRFPM-UHFFFAOYSA-N tert-butyl n-(6-aminohexyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCCCCCN RVZPDKXEHIRFPM-UHFFFAOYSA-N 0.000 claims 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000654 additive Substances 0.000 abstract description 9
- 230000000996 additive effect Effects 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 10
- 229940126214 compound 3 Drugs 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2604/00—Fullerenes, e.g. C60 buckminsterfullerene or C70
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
An amino fullerene, a preparation method and a method for preparing a modified titanium carbide nano-sheet by using the amino fullerene relate to the technical fields of functional organic molecule design and synthesis and preparation of nano-modified additives. Under the action of lithium fluoride and hydrochloric acid, generating titanium carbide precipitate through etching reaction, then adding deionized water, and obtaining titanium carbide nanosheet suspension through ultrasonic centrifugation; introducing primary amine active groups on fullerene spheres, and then adjusting the pH to weak acidity to enable amino fullerene to generate ammonium salt; the amino fullerene ammonium salt acts on titanium carbide through electrostatic attraction to generate the amino fullerene modified titanium carbide nano-sheet. The amino fullerene modified titanium carbide nano-sheet utilizes the electrostatic attraction effect of the fullerene ammonium salt with positive charges and titanium carbide to enable the fullerene ammonium salt to be effectively adsorbed on the surface of the titanium carbide and prevent the fullerene ammonium salt from agglomerating. Can be applied to the fields of photocatalysis organic reaction, lubricating oil additive, metal processing liquid additive, flame retardant material additive and the like.
Description
Technical Field
The application relates to the technical field of functional organic molecule design and synthesis and preparation of nano modified additives, in particular to an amino fullerene, a preparation method and a method for preparing a modified titanium carbide nano sheet by using the amino fullerene.
Background
Because of the special cage structure, the fullerene can capture a large amount of free radicals, which are called free radical sponge, so that the derivative is hopeful to become a new flame retardant and heat stabilizer, and meanwhile, because the fullerene has good hardness, the fullerene can be used as an additive to improve the mechanical property of the composite material. Yue Fengshu and the like can greatly improve the photocatalysis performance of the material (Yue Feng Tree, yue Shuwei, li Shicheng and the like) by using carboxylated fullerene to modify the ultrathin titanium dioxide nanosheets, the efficient photocatalysis performance of the carboxylated fullerene modified ultrathin titanium dioxide nanosheets is in Guangdong chemical industry, 2018,45 (18): 56-58-70]. Wang Ting et al first synthesized AZO-C in aqueous phase 60 The composite material is characterized by finding that the composite material has good light response, heat stability and excellent cycle stability [ Wang Ting, gold, chen Zhifeng and the like ], and the water phase synthesis and the performance research of the light response azobenzene-fullerene nanocomposite [ J ]]Functional material. 2019, 50 (02): 2115-2128]. Fang Zheng of Zhejiang university is combined to form C 60 -d-PDBPP and mixing it with PP to form PP/C 60 The thermal stability of the d-PDBPP composite material is obviously improved compared with that of pure PP. The subject group is to synthesize C 60 PP/C formed by mixing d-CNT with PP 60 Rise in thermal stability of d-CNT composite [ Ma Haiyun, song Pingan, fang Zhengping: current situation, problems and hopes scientific China 2011,2 (41), 314-327]. Zhou Xuchen et al disperse C by solution 60 Uniformly dispersing into PPS to prepare PPS/C 60 Composite material and composite fiber, as C 60 The mechanical properties [ circumference ] of the composite material and the composite fiber can be effectively improved when the content is not more than 40 percentPreparation of polyphenylene sulfide/Fullerene Complex fiber and Performance study [ J]Synthetic fiber industry, 2015,38 (05): 5-8]. Feng Lin Feilong preparation C 60 Compared with the NR/rubber nanocomposite, the NR/rubber nanocomposite has certain improvement in stretching, ageing resistance, thermal stability and the like [ Lin Feilong ] the preparation of the graphene and fullerene/rubber nanocomposite and the performance research [ D ]]University of Beijing chemical industry 2016]。
Titanium carbide (Ti) 3 C 2 ) Is a novel two-dimensional transition metal carbide, and is prepared from ternary lamellar carbide Ti by using hydrofluoric acid in 2011 by Barsoum et al in the United states 3 AlC 2 The Al atomic layer is stripped off to obtain [ M.Naguib, M.Kurtoglu.V.Presser, J.Lu, JJ Niu, M.Heon, L Hultman, Y.Gogotsi, M.W.Barsoum, two-dimensional nanocrystals produced by exfoliation of Ti ] 3 AlC 2 ,Adv,Mater,23(2011)42484253]. The metal carbide and metal nitride materials of this two-dimensional layered structure are in turn referred to as Mxene materials. Titanium carbide has been widely used in the fields of supercapacitors, catalysis, water treatment, composite materials, lithium ion batteries, and the like, because of its excellent structural stability and good electrical conductivity. However, the titanium carbide prepared by the current chemical method is easy to generate agglomeration phenomenon due to larger surface energy, and the use of the titanium carbide is influenced. It is necessary to modify it by selecting an appropriate compound.
The application aims to provide an amino-containing fullerene compound which is prepared into ammonium salt and is adsorbed on the surface of titanium carbide through the action of electrostatic attraction with the surface of the titanium carbide to form an amino fullerene modified titanium carbide nano-sheet.
Disclosure of Invention
The application aims to provide an amino fullerene, a preparation method and a method for preparing a modified titanium carbide nano-sheet by using the amino fullerene, and the prepared amino fullerene modified titanium carbide nano-sheet can overcome the defect of easy agglomeration phenomenon and can combine the advantages of titanium carbide and fullerene materials.
In order to achieve the purpose, the application adopts the following technical scheme:
an amino fullerene has a molecular structural formula shown as follows:
the fullerene moiety in the formula may be selected from C 60 、C 70 An isopullerene family member;
r in the general formula 1 、R 2 Selected from-COOR 3 or-H, wherein R is 3 Selected from substituted aryl or heterocyclic aryl, alkyl with 2-6 carbon atoms, R 1 And R is R 2 May be the same or different;
wherein A is selected from aryl, substituted aryl or heterocyclic aryl, alkyl with 3-12 carbon atoms, and flexible chain radical with 3-12 carbon atoms containing O or S atoms.
The preparation method of the amino fullerene comprises the following steps:
the method sequentially comprises the following steps:
step (1): the compound 1 and halogenated acetic acid or halogenated acetate undergo nucleophilic substitution reaction under the catalysis of alkali (such as potassium carbonate, sodium carbonate, triethylamine and the like) to prepare a compound 2, wherein the molar ratio of the compound 1 to the alkali to the halogenated acetic acid or halogenated acetate is 0.8-1.2: 1.6 to 3.6:1.0 to 1.5, the reaction temperature is 10 ℃ to 35 ℃ and the reaction time is 10 to 24 hours;
step (2): the fullerene and the compound 2 react with aldehyde to prepare the compound 3, wherein the molar ratio of the fullerene to the compound 2 to the aldehyde is 0.8-1.2: 1.6 to 3.6:4.0 to 12, the reaction temperature is 100 to 170 ℃ and the reaction time is 0.5 to 5 hours;
step (3): removing Boc protecting groups from the compound 3 in the presence of trifluoroacetic acid to prepare a compound 4, wherein the molar ratio of the compound 3 to the trifluoroacetic acid is 0.8-1.2: 100-240, the reaction temperature is 10-30 ℃ and the reaction time is 0.5-5 h.
As a further improvement of the preparation method of the amino fullerene:
the step (1) is specifically performed as follows: compound 1 was taken as 1:1.5 to 2.5 (g: mL) of the mixture is dissolved in a polar solvent (such as DMF, tetrahydrofuran or acetone, etc.), and then alkali is added; the reaction mixture was let N at room temperature 2 Or Ar is protected for 10-30 min, then haloacetic acid or haloacetate is rapidly added, ventilation is continued for 5-10 min, and the reaction bottle is sealed; the reaction mixture was stirred at room temperature for 10 to 24 hours, the solvent was removed, and the mixture was passed through a column to obtain compound 2.
The step (2) is specifically performed as follows: fullerene was prepared by mixing 1: 40-50 (g: mL) of the mixture is dissolved in a solvent (such as o-dichlorobenzene, chlorobenzene or toluene, etc.), and compound 2 is added; the reaction mixture was N-charged at room temperature 2 Or Ar is protected for 20-30 min, then aldehyde is added, ventilation is continued for 5-10 min, and the reaction mixture is put into a preheated oil bath pot for reaction; stopping the reaction when the amount of the fullerene is 20% -30%; then removing the solvent in the reaction system; the reaction mixture is dissolved by carbon disulfide and separated by column chromatography, the unreacted fullerene is removed by taking carbon disulfide as an eluent, and then the eluent with high polarity is used to obtain the compound 3.
The step (3) is specifically performed as follows: compound 3 was isolated as 1: 100-120 (g: mL) of the reaction mixture is dissolved in a solvent (such as chloroform, THF, etc.), and the reaction mixture is N 2 Or stirring for 10-20 min at room temperature under the protection of Ar, then adding trifluoroacetic acid, stirring the reaction solution for reaction for 0.5-5 h, tracking by using thin layer chromatography, and stopping the reaction after the compound 3 completely disappears; the solvent was dried by spin-drying and filtered through a silica gel column to give compound 4 as a tan color.
A method for preparing modified titanium carbide nanosheets by using amino fullerenes includes introducing primary amine active groups on fullerene spheres, obtaining fullerene ammonium salt by acidification, generating amino fullerene modified titanium carbide nanosheets by electrostatic attraction and action of titanium carbide, and adsorbing the introduced fullerene ammonium salt on the surfaces of titanium carbide nanosheets and layers;
the method sequentially comprises the following steps:
step a: under the action of lithium fluoride and acid, the carbon aluminum titanium generates titanium carbide sediment through etching reaction, wherein the mass ratio of the carbon aluminum titanium to the lithium fluoride is 0.8-1.2: 0.8 to 1.2, the pH value of the system is 1 to 3, the reaction temperature is 30 to 50 ℃, and the reaction time is 40 to 50 hours;
step b: adding deionized water into titanium carbide precipitate, repeatedly performing ultrasonic centrifugal washing until the pH value is about 7 to obtain titanium carbide nanosheet suspension, and performing film drawing to obtain dry titanium carbide;
step c: acidifying an amino fullerene compound 4 with acid, adjusting pH=4-6, and acidifying at room temperature; the acidified product is dried for 10 to 12 hours at the temperature of 40 to 60 ℃ to obtain the fullerene ammonium salt compound;
step d: and c, mixing the fullerene ammonium salt compound with the titanium carbide prepared in the step b in a mass ratio of 0.8-1.2: 0.8 to 1.2 dissolved in H 2 In the mixed solution of O and THF (the volume ratio of the O to the THF is 1:2), stirring and reacting at room temperature; and then, repeatedly washing with THF to remove water through centrifugation, and dispersing with DMF to obtain the amino fullerene modified titanium carbide nano-sheet.
As a further improvement of the preparation method of the amino fullerene modified titanium carbide nano-sheet,
the specific operation of the step a is as follows: respectively measuring hydrochloric acid and deionized water by using a pipette, placing the solution into a centrifuge tube, adjusting the pH to be proper, placing the centrifuge tube into a constant-temperature water bath at 41 ℃ and stirring the solution by using a magnet, then weighing lithium fluoride and aluminum titanium carbide by using an electronic balance, and adding the lithium fluoride and the aluminum titanium carbide into the centrifuge tube according to the sequence, wherein the concentration of the lithium fluoride in the solution is 1: 15-25 (g: mL), adding titanium aluminum carbide slowly, avoiding danger caused by violent reaction, stirring at 41 ℃ for 48h, and stopping the reaction.
The specific operation of the step b is as follows: taking out the centrifuge tube in the step a, placing the centrifuge tube in a table type high-speed centrifuge to adjust the rotating speed to 9500rpm for centrifugation for 5min, pouring out clarified liquid after centrifugation, adding 2/3 of deionized water into the centrifuge tube for cleaning, and adjusting the pH value to a proper value after the centrifugal tube is fully washed to obtain etched preliminary titanium carbide nano-sheets; fully dispersing titanium carbide nano-sheets in deionized water, centrifuging at 4000rpm for 5min to retain the liquid at the upper layer, and removing impurity heavy objects at the bottom layer to obtain stripped titanium carbide nano-sheet suspension; and taking 10g of titanium carbide nanosheet suspension, and performing film drawing to measure the solid content.
The specific operation of the step c is as follows: amino fullerene compound 4 was prepared as a 1: 250-350 (g: mL) of the fullerene ammonium salt is dissolved in a mixed solution of chloroform and ethanol (the volume ratio of the chloroform to the ethanol is 2:1), the chloroform and the ethanol are placed on a magnetic stirrer for stirring after being fully dissolved, 1mol/L hydrochloric acid is added dropwise while stirring to adjust the pH to be weak acidity, stirring is continued for 20min, and the adjusted liquid is placed in a constant-temperature drying oven for drying for standby, so that the fullerene ammonium salt compound is obtained.
The specific operation of the step d is as follows: the fullerene ammonium salt compound and titanium carbide are mixed according to the following ratio of 1: 200-350 (g: mL) of the mixed solution of water and THF, stirring for 30-50 min at room temperature, and centrifuging to pour out the upper liquid; and then THF is used for washing for 3 to 4 times to remove water, and DMF is used for dispersing to obtain the amino fullerene modified titanium carbide nano-sheet.
Compared with the prior art, the application has the beneficial effects that:
1) According to the application, fullerene with a unique structure is used as a modifier of titanium carbide, so that titanium carbide agglomeration can be effectively prevented.
2) The application utilizes the electrostatic attraction effect of the fullerene ammonium salt with positive charges and the titanium carbide to ensure that the fullerene ammonium salt can be effectively adsorbed on the surface of the titanium carbide to prevent the fullerene ammonium salt from agglomerating.
3) The amino fullerene modified titanium carbide nano-sheet can be applied to the fields of photocatalysis organic reaction, lubricating oil additive, metal processing liquid additive, flame retardant material additive and the like.
Drawings
Fig. 1 is a route diagram for the preparation of amino fullerenes.
FIG. 2 is a flow chart of the preparation of an amino fullerene modified titanium carbide nanoplatelet.
FIG. 3 is a fullerene derivative 3-1 prepared in example 1 H NMR。
FIG. 4 shows the fullerene derivative 3-1 prepared in example 13 C NMR。
Fig. 5 is an XRD pattern of an amino fullerene-derived modified titanium carbide nanoplatelet prepared in the example.
Detailed Description
This example takes an amino fullerene 4-1 and a modified titanium carbide nanosheet prepared by using the same as an example, and the structure and a specific preparation method thereof are described in connection with the preparation route patterns (shown in fig. 1 and 2).
The preparation method of the intermediate 2-1 comprises the following steps:
2.17g of t-butyl N- (6-aminohexyl) carbamate 1-1 and 4.2mL of triethylamine are weighed into a 100mL single neck round bottom flask and 25mL of tetrahydrofuran is added to make it fully dissolved. 1.11g of ethyl bromoacetate was dissolved in 25mL of tetrahydrofuran, and the mixture was slowly dropped into a round-bottomed flask through a constant pressure dropping funnel, and the reaction was stopped after stirring at room temperature for 12 hours. The solvent was removed by distillation under reduced pressure, and after filtration through a short column, the solvent was removed by distillation to give 2-1 as a yellow liquid product in 82.9% yield.
The preparation method of the intermediate 3-1 comprises the following steps:
2g of Compound 2-1 and 0.23g of C were weighed out 60 Mix in a 50mL single-neck flask, add 8mL o-dichlorobenzene and make it fully dissolved by ultrasound with an ultrasonic machine. The reaction mixture was purged with nitrogen at room temperature for half an hour, and 340. Mu.L of ethyl glyoxylate was added with a microsyringe after the flask had been sufficiently purged of air. Then the reaction flask is put into a preheated oil bath pot with the temperature of 165 ℃ for heating and refluxing for 1.5 hours, and the reaction is stopped. After the reaction apparatus was cooled to room temperature, the solvent was distilled off under reduced pressure. Separating with chromatographic column, and recovering unreacted C with pure carbon disulfide as eluent 60 . And then carbon disulphide is used: dichloromethane was 1:4, separating the target product by using the mixed solution as a eluting agent, and spin-drying the solvent to obtain a product 3-1, wherein the yield is 44%.
Fullerene derivative 3-1 prepared as described above 1 H NMR， 13 The C NMR is shown in FIGS. 3 and 4, respectively, to confirm the structure of the compound.
The synthesis step of the compound 4-1:
200mg of Compound 3-1 was placed in a 50mL round bottom flask, and 20mL of chloroform was added to make it fully dissolved. The flask was purged of air by passing nitrogen through the flask for 20 minutes, followed by rapid addition of 4mL of trifluoroacetic acid and sealing. After stirring at room temperature for 1.5h, the plate was tracked until the starting material point disappeared, and the reaction was stopped immediately to spin-dry the solvent. Separating with chromatographic column, vacuum drying to obtain target product 4-1 with yield of 98%.
Preparation steps of titanium carbide precipitation:
7.5mL of hydrochloric acid with the concentration of 9mol/L and 2.5mL of deionized water are respectively measured by a 5mL liquid-transfering gun and placed in a 50mL centrifuge tube, the centrifuge tube is placed in a 41 ℃ constant-temperature water bath kettle and stirred by a magnet, then 0.5g of lithium fluoride and 0.5g of aluminum titanium carbide are weighed by an electronic balance and added into the centrifuge tube in sequence (the aluminum titanium carbide is added and dropwise added slowly, so that the danger caused by severe reaction is avoided), and the reaction is stopped after stirring at 41 ℃ for 48 hours.
The preparation method of the titanium carbide nanosheet suspension comprises the following steps:
taking out the centrifuge tube after stopping the reaction, placing the centrifuge tube in a desk type high-speed centrifuge to centrifuge for 5min at the speed of 9500rpm, pouring out clarified liquid after centrifugation, adding 2/3 of deionized water into the centrifuge tube for cleaning, and adjusting the pH value to 7 after the centrifugal tube is fully washed, thus obtaining the etched preliminary titanium carbide nano-sheets. Fully dispersing titanium carbide nano-sheets in 120mL of deionized water, centrifuging at 4000rpm for 5min to retain the liquid at the upper layer, and removing impurity heavy objects at the bottom layer to obtain the stripped titanium carbide nano-sheet suspension. 10g of titanium carbide nanosheet suspension is taken out and subjected to film drawing to measure the solid content (the concentration is 3.7 mg/g).
The preparation method of the fullerene ammonium salt comprises the following steps:
500mg of an amino fullerene compound 4 was taken with chloroform and ethanol 2:1, fully dissolving 150mL of mixed solution in proportion, putting the mixed solution on a magnetic stirrer for stirring, adding a stirrer, dropwise adding 1mol/L hydrochloric acid while stirring to adjust the pH to be slightly acidic, continuously stirring for 20min, and putting the adjusted liquid into a constant-temperature drying oven for drying at 50 ℃ for later use to obtain the fullerene ammonium salt compound.
The preparation method of the amino fullerene modified titanium carbide nanosheets comprises the following steps:
the above-mentioned dried fullerenic ammonium salt compound (210 mg) was taken, and 57g of a titanium carbide suspension was added with 43mL of water and 86mL of THF, and after stirring at room temperature for 40min, the supernatant was centrifuged off. And then THF is used for washing for 3 to 4 times to remove the water. And dispersing the prepared modified titanium carbide by using 200mL of DMF to obtain the amino fullerene modified titanium carbide nanosheets.
The XRD patterns of the prepared amino fullerene modified titanium carbide nano-sheet, carbon aluminum titanium, acidified titanium carbide, peeled titanium carbide and amino fullerene 4-1 are shown in figure 5. Investigation of modified Ti by XRD diffraction peaks 3 C 2 Crystalline phase characteristics of original Ti 3 AlC 2 The XRD of (a) shows stronger diffraction peaks at a and b, then is etched by lithium fluoride and hydrochloric acid, and is subjected to a series of stripping treatment, ti 3 C 2 The diffraction peak of (b) starts to disappear at b, indicating that the etching processes out Ti 3 AlC 2 Al atoms in (C), ti in etching and stripping 3 C 2 The same diffraction peak appears at 6.65 deg. with a lower 2 theta angle, wherein the peak height of the exfoliation indicates a much more crystalline phase. The amino fullerene itself showed many diffraction peaks, but the titanium carbide modified with the amino fullerene did not show these diffraction peaks, indicating that less crystal had disappeared in the modified titanium carbide. The diffraction peak appears in the modified titanium carbide at 6.35 degrees, and the movement of the peak position shows that the interlayer spacing of the titanium carbide nano-sheet is increased due to the addition of the amino fullerene into the titanium carbide nano-sheet, the crystal lattice is subjected to stress to elongate, and the reduction of the peak value means the reduction of the crystal phase.
The structural formula of the prepared amino fullerene compound 4-1 is shown as follows:
for those skilled in the art, with different choices of R, A in the general formula of the amino fullerene compound 4 (the general structural formula is shown below), several amino fullerene compounds with different structures can be prepared, and the molecular structural general formula is as follows:
example 1 (amino fullerene compound 4-2):
in the general formula, R 1 Is H, R 2 Is CO 2 Et, A is
Example 2 (amino fullerene compound 4-3):
in the general formula, R 1 ,R 2 Is H, A is
Example 3 (amino fullerene compound 4-4):
in the general formula, R 1 ,R 2 Is CO 2 Et, a is butyl.
Example 4 (amino fullerene compound 4-5):
in the general formula, R 1 Is H, R 2 Is CO 2 Ph, A is n-octyl.
The preparation methods and reaction mechanisms of the different amino fullerene compounds (4-2-4-5) are similar to those of the amino fullerene compound (4-1), and meanwhile, the preparation methods of the amino fullerene modified titanium carbide nano-sheets are similar to those of the amino fullerene compound (4-1) modified titanium carbide nano-sheets, and are not repeated herein.
Claims (1)
1. The method for preparing the modified titanium carbide nano-sheet by using the amino fullerene is characterized by comprising the following steps in sequence:
1. preparation of amino Fullerene Compound 4-1
(1) The preparation method of the intermediate 2-1 comprises the following steps:
2.17g of tert-butyl N- (6-aminohexyl) carbamate 1-1 and 4.2mL of triethylamine are weighed into a 100mL single-neck round-bottom flask, and 25mL of tetrahydrofuran is added to make the three materials fully dissolved; then 1.11g of ethyl bromoacetate is taken and dissolved in 25mL of tetrahydrofuran, and is slowly added into a round bottom flask by a constant pressure dropping funnel in a dropwise manner, and the reaction is stopped after stirring for 12 hours at room temperature; distilling under reduced pressure to remove solvent, filtering with short column chromatography, and removing solvent to obtain yellow liquid product 2-1 with yield of 82.9%;
(2) the preparation method of the intermediate 3-1 comprises the following steps:
2g of Compound 2-1 and 0.23g of C were weighed out 60 Mixing the materials into a 50mL single-neck flask, adding 8mL o-dichlorobenzene, and fully dissolving the materials by ultrasonic waves; the reaction mixture was purged with nitrogen at room temperature for half an hour, and after sufficient air was removed from the flask, 340 μl of ethyl glyoxylate was added using a microsyringe; then placing the reaction bottle into a preheated 165 ℃ oil bath pot for heating reflux for 1.5 hours, and stopping the reaction; after the reaction device is cooled to room temperature, the solvent is removed by reduced pressure distillation; separating with chromatographic column, and recovering unreacted C with pure carbon disulfide as eluent 60 The method comprises the steps of carrying out a first treatment on the surface of the And then carbon disulphide is used: dichloromethane was 1:4, separating the target product by using the mixed solution as a eluting agent, and spin-drying the solvent to obtain a product 3-1 with the yield of 44%;
(3) the synthesis step of the compound 4-1:
200mg of Compound 3-1 was placed in a 50mL round bottom flask, and 20mL of chloroform was added to make it fully dissolved; introducing nitrogen for 20min to exhaust air in the flask, rapidly adding 4mL of trifluoroacetic acid, and sealing to seal the flask; stirring for 1.5h at room temperature, tracking the spot plate until the point of the raw material disappears, and immediately stopping the reaction to spin-dry the solvent; separating with chromatographic column, vacuum drying to obtain target product 4-1 with yield of 98%;
2. preparation steps of titanium carbide precipitation:
respectively measuring 7.5mL of hydrochloric acid with the concentration of 9mol/L and 2.5mL of deionized water by using a 5mL liquid-transfering gun, placing the centrifuge tube into a 50mL centrifuge tube, placing the centrifuge tube into a constant-temperature water bath at 41 ℃ and stirring by using a magnet, then weighing 0.5g of lithium fluoride and 0.5g of aluminum titanium carbide by using an electronic balance, adding the lithium fluoride and the 0.5g of aluminum titanium carbide into the centrifuge tube according to the sequence, slowly dripping the solution when adding the aluminum titanium carbide, avoiding danger caused by severe reaction, stirring the solution at 41 ℃ for 48 hours, and stopping the reaction;
3. the preparation method of the titanium carbide nanosheet suspension comprises the following steps:
taking out the centrifuge tube after stopping the reaction, placing the centrifuge tube in a table type high-speed centrifuge to centrifuge for 5min at the speed of 9500rpm, pouring out clarified liquid after centrifugation, adding 2/3 of deionized water into the centrifuge tube for cleaning, and adjusting the pH value to 7 after the centrifuge tube is fully washed to obtain etched preliminary titanium carbide nano-sheets; fully dispersing titanium carbide nano-sheets in 120mL of deionized water, centrifuging at 4000rpm for 5min to retain the liquid at the upper layer, and removing impurity heavy objects at the bottom layer to obtain stripped titanium carbide nano-sheet suspension; taking 10g of titanium carbide nanosheet suspension, and performing film drawing to measure the solid content;
4. the preparation method of the fullerene ammonium salt comprises the following steps:
500mg of an amino fullerene compound 4-1 was taken with chloroform and ethanol 2:1, fully dissolving 150mL of mixed solution in proportion, putting the mixed solution on a magnetic stirrer for stirring, adding a stirrer, dropwise adding 1mol/L hydrochloric acid while stirring to adjust the pH to be slightly acidic, continuing stirring for 20min, and putting the adjusted liquid into a constant-temperature drying oven for drying at 50 ℃ for later use to obtain the fullerene ammonium salt compound;
5. the preparation method of the amino fullerene modified titanium carbide nanosheets comprises the following steps:
taking 210mg of the dried fullerene ammonium salt compound, adding 43mL of water and 86mL of THF into 57g of titanium carbide suspension, stirring for 40min at room temperature, and centrifuging to remove upper liquid; washing with THF for 3-4 times to remove water; and dispersing the prepared modified titanium carbide by using 200mL of DMF to obtain the amino fullerene modified titanium carbide nanosheets.
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