CN111499900A - Two-dimensional polymer film based on disc-shaped tri-boron nuclear molecules and preparation and application thereof - Google Patents
Two-dimensional polymer film based on disc-shaped tri-boron nuclear molecules and preparation and application thereof Download PDFInfo
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- 229920006254 polymer film Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 28
- 238000010898 silica gel chromatography Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000002294 plasma sputter deposition Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- VZXFEELLBDNLAL-UHFFFAOYSA-N dodecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCC[NH3+] VZXFEELLBDNLAL-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000010410 layer Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 20
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000003990 capacitor Substances 0.000 description 12
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000010329 laser etching Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000011245 gel electrolyte Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 210000004271 bone marrow stromal cell Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
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- C23C14/5833—Ion beam bombardment
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/48—Conductive polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
- C08J2385/04—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing boron
Abstract
The invention relates to a two-dimensional polymer film based on a disc-shaped tri-boron nuclear molecule, and preparation and application thereof, and a preparation method thereofThe body is as follows: (a) mixing 6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene with alkylamine, stirring and refluxing in nitrogen atmosphere, cooling to obtain a mixture, precipitating the mixture in glacial ethanol, and purifying to obtain 3 (NHN); (b) sequentially adding the 3(NHN), triethylamine and BF obtained in the step (a) into toluene3·Et2O, stirring and mixing uniformly, then carrying out heating reaction under the nitrogen atmosphere, then cooling, decompressing and removing toluene, and purifying to obtain 3B (NF)2(ii) a (c) Subjecting the 3B (NF) obtained in step (b)2Dissolving in chlorobenzene to give 3B (NF)2Compared with the prior art, the discoid triboron nuclear molecule prepared by the invention has very rich optical characteristics and low L UMO energy level, and the obtained two-dimensional polymer film also has rich optical properties and optical activity characteristics.
Description
Technical Field
The invention relates to the field of materials, in particular to a two-dimensional polymer film based on a disc-shaped tri-boron nuclear molecule and preparation and application thereof.
Background
As the transition dependence and consumption of fossil energy by human beings cause serious environmental problems and energy crisis, the development and research of sustainable energy has gradually attracted the wide attention of scientists. Among them, with the development of portable electronic devices, micro supercapacitors having the advantages of fast charge and discharge rate, high power density, long cycle life, etc. are attracting more and more interest of researchers.
The important composition of the micro super capacitor is an electrode material, wherein the element composition, the atom arrangement and the dimension are important factors determining the performance of the electrode material. Therefore, two-dimensional porous materials (such as self-supporting two-dimensional films) having excellent properties in structural characteristics, spatial defects, specific surface area, and charging properties have become hot materials in the fields of electrochemistry, catalysis, optics, and magnetism. Two-dimensional porous materials consist of repeating monomers with covalent bonds in a single or multi-layer plane in the vertical direction, and thus the synthesis of 2D polymer-based nanosheets involves periodic covalent bonding of the monomer to a multifunctional group in two or more orthogonal directions. However, due to the relatively free twisted conformation of the polymer chains and the rotation of chemical bonds, bulk/powder porous polymeric materials are typically obtained using conventional polymerization methods. Therefore, the development of a new preparation method of the 2D polymer-based nanomaterial is very urgent.
Photopolymerization technology is an environment-friendly green technology developed in recent decades, and refers to a process of irreversibly converting each substance in a system from a liquid state to a solid state under irradiation of ultraviolet light or visible light, and is also called "photoinduced polymerization". Compared with the traditional thermal-induced polymerization technology, the photopolymerization technology has many unique advantages, such as low energy consumption, no solvent, high polymerization rate, low polymerization temperature, wide applicability, controllable appearance of a cured product and the like, so that the photopolymerization technology is widely applied to the traditional fields and emerging fields of microelectronics, solar cells, biomedicine and the like. At present, the two-dimensional porous polymer prepared by photopolymerization has a good application prospect, but few reports exist.
Disclosure of Invention
The invention aims to solve the problems and provide a two-dimensional polymer film based on a discotic triboron core molecule and preparation and application thereof, wherein the discotic triboron core molecule has a unique conjugated structure, has very rich optical characteristics and a low L UMO energy level, can be used for realizing molecular crosslinking through simple ultraviolet light to obtain the two-dimensional polymer film based on the discotic triboron core molecule, has rich optical properties and optical activity characteristics, and is applied to a micro supercapacitor.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a two-dimensional polymer film based on a discoid tri-boron nuclear molecule specifically comprises the following steps:
(a) synthesis of 3 (NHN): mixing 6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene with alkylamine, stirring and refluxing under nitrogen atmosphere, cooling to obtain a mixture, precipitating the mixture in glacial ethanol, and purifying to obtain 3(NHN) shown in formula (I):
(b)3B(NF)2the synthesis of (2): sequentially adding the 3(NHN), triethylamine and BF obtained in the step (a) into toluene3·Et2O, stirring and mixing uniformly, then carrying out heating reaction under the nitrogen atmosphere, then cooling, decompressing and removing toluene, and purifying to obtain 3B (NF)2(i.e., a discotic triboronic core molecule, it can be seen that there are three boron atoms in the compound as the core, forming a discotic molecule), as shown in formula (ii):
(c) preparation of 2D-3 BN: subjecting the 3B (NF) obtained in step (b)2Dissolving in chlorobenzene to give 3B (NF)2The chlorobenzene solution is dripped on the surface of the surfactant, and then the ultraviolet light is utilized for irradiation, so that the two-dimensional polymer film is obtained.
Preferably, in step (a), the alkylamine is selected from one or more of n-propylamine, n-hexylamine or n-dodecylamine, and the equivalent ratio of 6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene to alkylamine is 1: 10.
Preferably, in the step (a), the temperature of stirring reflux is 50-255 ℃, the time of stirring reflux is 2-4d, the rotation speed of stirring is 20-40r/min, the cooling temperature is room temperature, the cooling time is 0.5-2h, the temperature of precipitation is 0 ℃, the time of precipitation is 0.5h, silica gel column chromatography is adopted for purification, the mobile phase is dichloromethane and methanol, the volume flow ratio of dichloromethane and methanol is 30:1, the temperature of purification is room temperature, and the time of purification is 1 h. Further preferably, the stirring reflux time is 3 d.
Preferably, in the step (b), the stirring speed is 20-40r/min, the stirring time is 20min, the reaction temperature is 80-100 ℃, the reaction time is 22-26h, the cooling temperature is room temperature, the cooling time is 0.5h, the purification is carried out by silica gel column chromatography, the mobile phase comprises dichloromethane and petroleum ether, the volume flow ratio of the dichloromethane to the petroleum ether is 1:1, the purification temperature is room temperature, and the purification time is 1 h. Further preferably, the reaction temperature is 90 ℃ and the reaction time is 24 h.
Preferably, in step (b), 3(NHN), triethylamine and BF3·Et2The molar ratio of O is 1:9:15, and toluene only acts as a solvent.
Preferably, in step (c), the power of the ultraviolet light is 20-40W, the irradiation time is 1h,
preferably, in step (c), the surfactant is selected from one or more of tetrabutylammonium bromide (denoted as TBAB), dodecylammonium bromide (denoted as DTAB) or sodium dodecylbenzenesulfonate (denoted as SDBS), wherein TBAB is a cationic surfactant and SDBS is an anionic surfactant.
Preferably, in step (c), the mass concentration of the surfactant is 10mg m L-1，3B(NF)2In chlorobenzene solution 3B (NF)2Has a mass concentration of 1mg m L-1，3B(NF)2The chlorobenzene solution of (a) has a volume of 50-100 mu L, a surfactant and 3B (NF)2The volume ratio of the chlorobenzene solution is 1 (50-100).
A two-dimensional polymer film prepared by the preparation method.
The application of the two-dimensional polymer film in the miniature super capacitor specifically comprises the following steps:
(i) preparing semi-solid gel electrolyte, namely adding L iCl solution into polyvinyl alcohol (marked as PVA) aqueous solution, stirring and cooling to obtain semi-solid gel PVA-L iCl electrolyte;
(ii) preparing 2D-3BN @ MSCs by placing a two-dimensional polymer film (marked as a 2D-3BN film) on a silicon chip, plating a nanogold film on the 2D-3BN film, etching interdigital patterns on the nanogold film, removing the nanogold film which is not covered by the interdigital patterns and the two-dimensional polymer film positioned below the nanogold film, finally coating the semi-solid PVA-L iCl electrolyte obtained in the step (i) on the nanogold film, drying to obtain 2D-3BN @ MSCs, placing the 2D-3BN @ MSCs in an electrochemical workstation instrument for carrying out capacitance performance test, wherein the scanning voltage interval is 0-1V, and the scanning rate is 0.1-10000V s-1。
Preferably, in step (i), the aqueous solution of polyvinyl alcohol is prepared by dissolving polyvinyl alcohol in water, heating, stirring and dissolving, wherein the heating temperature is 90-110 ℃, the stirring speed is 50-60r/min, the stirring time is 0.5h, the cooling temperature is room temperature, and the cooling time is 2 h. Further preferably, the heating temperature is 98 ℃.
Preferably, in step (i), the L iCl solution has a concentration of 0.1mg m L-1The mass addition ratio of polyvinyl alcohol and L iCl was 1: 1.
Preferably, in step (ii), the plating is performed by ion sputtering, and the vacuum degree of the plating is 10-1mbar and plating time of 3-7 min.
Preferably, in the step (ii), etching is performed by oxygen plasma sputtering, and the etching time is 20 min.
Preferably, in step (ii), the drying temperature is 40-60 ℃ and the drying time is 12-16 h.
The disc-shaped tri-boron nuclear molecule and the novel two-dimensional polymer film based on the disc-shaped tri-boron nuclear molecule are prepared, the disc-shaped tri-boron nuclear molecule can generate self photo-induced crosslinking, and the two-dimensional polymer film with rich optical properties and optical activity characteristics can be simply, conveniently and quickly prepared by utilizing ultraviolet light. In addition, since the discotic triboronic core molecule is a planar fused ring aromatic structure, the two-dimensional polymer film also exhibits excellent performance in terms of energy storage of a micro supercapacitor.
Compared with the prior art, the invention has the following advantages:
(1) the discotic triboron core molecule has a unique conjugated structure, has rich optical characteristics and a low L UMO energy level.
(2) Based on the optical activity of the disc-shaped tri-boron nuclear molecules and the triple symmetric boron nuclear structure, the two-dimensional polymer film based on the disc-shaped tri-boron nuclear molecules can be obtained by simply realizing the cross-linking of the molecules through ultraviolet light, and the two-dimensional polymer film also has rich optical/electrical characteristics.
(3) The two-dimensional polymer film is applied to the aspect of the micro super capacitor, and the prepared micro super capacitor has high area capacitance and volume power density.
(4) The preparation method has simple steps and high repeatability, and has profound significance for development and practical application expansion of the high-performance super capacitor.
Drawings
FIG. 1 is a schematic diagram of a preparation route of a 2D-3BN two-dimensional polymer film;
FIG. 2 shows 3(NHN) and 3B (NF)2The synthetic route of (1) is simplified;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 3(NHN) obtained in example 1;
FIG. 4 shows 3B (NF) obtained in example 12Nuclear magnetic hydrogen spectrum of (a);
FIG. 5 is a schematic of a manufacturing route for a miniature ultracapacitor for 2D-3BN @ MSCs;
FIG. 6 is a scanning electron micrograph of 2D-3BN @ MSCs prepared in example 1;
FIG. 7 shows that 2D-3BN-5@ MSCs devices from 0.1 to 1000V s made in example 1-1CV curve at sweep speed;
FIG. 8 is a graph comparing the impedance of the 2D-3BN-5@ MSCs device made in example 1, the 2D-3BN-3@ MSCs device made in example 2, and the 2D-3BN-1@ MSCs device made in example 3;
FIG. 9 is a graph comparing the area capacitance of the 2D-3BN-5@ MSCs device made in example 1, the 2D-3BN-3@ MSCs device made in example 2, and the 2D-3BN-1@ MSCs device made in example 3;
FIG. 10 is a Ragon plot of the 2D-3BN-5@ MSCs device made in example 1;
FIG. 11 shows that the 2D-3BN-3@ MSCs devices obtained in example 2 are from 0.1 to 1000V s-1CV curve at sweep speed;
FIG. 12 shows that the 2D-3BN-1@ MSCs devices obtained in example 3 are from 0.1 to 1000V s-1CV curve at sweep speed.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The preparation and application of a two-dimensional polymer film based on discoid tri-boron nuclear molecules are shown in figures 1, 2 and 5, wherein the preparation comprises the synthesis of 3(NHN), 3B (NF)22D-3BN preparation, 3(NHN) structure as shown in formula (I):
the application comprises the preparation of semi-solid gel electrolyte and the preparation of 2D-3BN @ MSCs, and the steps are as follows:
(1) synthesis of 6,12, 18-tris (hexylamine) -5,11, 17-triazatrinaphthalene (3(NHN))
6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene (1.0 equivalent) was refluxed with stirring at a rate of 20 to 40R/min for 3 days in n-hexylamine (R0 in FIG. 2 is hexyl) at a temperature of 132-135 ℃ under a nitrogen atmosphere. After cooling for 1h to room temperature, the mixture was precipitated in 0 ℃ ice ethanol for 0.5 h. The residue was purified by silica gel column chromatography (dichloromethane: methanol ═ 30:1, v/v) at room temperature for 1h to give the product, noted 3(NHN) -1 (R1 in fig. 2 is hexyl) as a yellow solid powder in 50% yield, tested on 3(NHN) -1 using a Bruker Avanvce type iii-400 MHz nuclear magnetic resonance spectrometer with CDCl3As a solvent (the same applies below), the nuclear magnetic hydrogen spectrum of 3(NHN) -1 is shown in FIG. 3, 1H NMR (400MHz, CDCl)3):＝14.6(s,3H；NHCH2),8.35(d,J＝7.8Hz,3H；Ar-H),7.89(d,J＝7.8Hz,3H；Ar-H),7.65(t,J＝7.8Hz,3H；Ar-H),7.31(t,J＝7.8Hz,3H；Ar-H),4.01(s,6H；NHCH2),1.95(t,J＝7.0Hz,6H；NHCH2CH2),1.50(m,6H；CH2CH2),1.18(m,12H；CH2CH2CH3),0.86(t,J＝7.1Hz,9H；CH3)。
(2)3B(NF)2Synthesis of (2)
3(NHN) (1.0 eq) was stirred in dry toluene (30m L) at 20-40r/min for 20 minutes, and triethylamine (9.0 eq), BF, was added3·Et2O (15.0 equiv.). Mixing under nitrogen atmosphereThe reaction mixture was reacted at 90 ℃ for 24 hours. After cooling to room temperature, toluene was removed under reduced pressure, the solid was collected and purified by silica gel column chromatography (dichloromethane: petroleum ether ═ 1:1, v/v) at room temperature for 1h to give the product, reported as 3b (nf)2-1 (hexyl for R2 in FIG. 2) as a yellow solid powder in 69% yield, 3B (NF)2The nuclear magnetic hydrogen spectrum of-1 is shown in FIG. 4, 1H NMR (400MHz, CDCl)3):＝8.76(d,J＝8.8Hz,3H；Ar-H),8.20(d,J＝8.4Hz,3H；Ar-H),7.82(t,J＝7.9Hz,3H；Ar-H),7.48(t,J＝7.6Hz,3H；Ar-H),4.11(s,6H；NHCH2),2.12(t,J＝7.0Hz,6H；NHCH2CH2),1.62(m,6H；CH2CH2),1.28-1.37(m,12H；CH2CH2CH3),0.90(t,J＝7.0Hz,9H；CH3)。
(3) Preparation of 2D-3BN
An appropriate amount of TBAB (10mg m L) was added to the beaker-1) The solution was then pipetted 50. mu. L of the prepared 3B (NF)2Chlorobenzene solution (1mg m L)-1) Dropwise adding the solution on the surface of the solution, irradiating for 1 hour by using an ultraviolet lamp with the power of 20-40W, and finally taking out a film on the surface by using a silicon wafer, wherein the film is marked as 2D-3 BN.
(4) Preparation of semi-solid gel electrolyte
Firstly, 3g of polyvinyl alcohol (PVA) is dissolved in 30m L deionized water, the mixture is heated to 98 ℃ on a stirring table at the rotating speed of 50-60r/min to fully dissolve the PVA, and after the PVA is completely dissolved, 3g of diluted PVA with the mass concentration of 0.1mg m L-1Slowly dripping the L iCl solution into the polyvinyl alcohol solution, continuously stirring to completely dissolve the polyvinyl alcohol solution, and cooling the solution for 2h to room temperature to obtain the semi-solid gel PVA-L iCl electrolyte.
(5) Preparation of 2D-3BN-5@ MSCs
As shown in FIG. 5, the 2D-3BN-5@ MSCs are prepared by simple magnetron sputtering coating and laser etching technology, and the specific operation steps are as follows: firstly, putting 5 layers of completely dried 2D-3BN films into a magnetron sputtering coating machine, vacuumizing until the vacuum degree is stabilized at 10-1mbar, opening ion target for ion sputtering for 5min, slowly increasing to atmospheric pressure, and coatingTaking out a sample, drawing a certain size of mutually staggered interdigital patterns by utilizing CAD software, guiding the mutually staggered interdigital patterns onto a laser etching instrument, etching the interdigital patterns on the film-plated sample by utilizing laser etching, and then putting the device into an oxygen plasma sputtering instrument for processing for 20min to remove the nano gold film which is not etched by the laser and is not covered by the interdigital patterns and the 2D-3BN-5 positioned below the nano gold film, so that the whole device is in an open circuit state. And finally, uniformly coating the prepared gel electrolyte on the surface of the device by using a fine needle-shaped object, and drying at the temperature of 40-60 ℃ for 12-16h to finally obtain the 2D-3BN-5@ MSCs. FIG. 6 is a SEM cross-sectional view of the prepared 2D-3BN-5@ MSCs, from which it can be clearly seen that the prepared MSCs have a membrane-nanogold-electrolyte triple-layer structure, and from FIG. 6, the thickness of a single layer of 2D-3BN is around 45 nm.
An electrochemical workstation (CHI660 e; CH instruments, Chenhua Co., China) is adopted for testing the capacitor performance of the material, the scanning voltage interval is 0-1V, and the scanning speed is 0.1-10000V s-1(the same below), the test was carried out on the micro-supercapacitor prepared from the 2D-3BN-5@ MSCs film by using cyclic voltammetry and constant current charging and discharging methods in the CHI660e electrochemical workstation. The 2D-3BN-5@ MSCs device is in the range of 0.1 to 1000V s-1The CV plot at sweep speed is shown in detail in FIG. 7, which can be seen at 1000V s-1The CV characteristic curve of the prepared micro super capacitor at the sweep speed is very close to a rectangle, and the stability and the rapid charge and discharge performance of the material are shown. The impedance diagram is shown in fig. 8 (wherein, the small diagram at the lower right corner of fig. 8 is an enlarged diagram under the low frequency curve), from which it can be seen that the curve of the material at the low frequency curve is close to a straight line, which shows that the device has good capacitance effect, and it can be seen that the device prepared by 5 layers of films has smaller impedance, which may be due to the improvement of the conductivity of the whole device caused by the increase of the number of layers of polymer films. The area capacitance plot is shown in FIG. 9 at 1000V s-1At an ultra-high sweep rate of (2), the prepared miniature supercapacitor has a capacitance of 107.032 [ mu ] F cm-2Area capacitance of (d). The Ragon diagram is shown in FIG. 10, which is at 1000V s-1The energy density at the ultrahigh sweeping speed of the brush is 0.514mWh cm-3Volume power density of 1850.168Wcm-3。
Example 2
The 2D-3BN prepared in example 1 was used to prepare 2D-3BN-3@ MSCs, the preparation route is also shown in FIG. 5, and the specific steps are as follows:
(i) preparation of semi-solid gel electrolyte
Firstly, 3g of polyvinyl alcohol (PVA) is dissolved in 30m L deionized water, the mixture is heated to 98 ℃ on a stirring table at the rotating speed of 50-60r/min to fully dissolve the PVA, and after the PVA is completely dissolved, 3g of diluted PVA with the mass concentration of 0.1mg m L-1Slowly dripping the L iCl solution into the polyvinyl alcohol solution, continuously stirring to completely dissolve the polyvinyl alcohol solution, and cooling the solution for 2 hours to room temperature to obtain the semi-solid gel PVA-L iCl electrolyte.
(ii) Preparation of 2D-3BN-3@ MSCs
The 2D-3BN-3@ MSCs are prepared by simple magnetron sputtering coating and laser etching technology, and the specific operation steps are as follows: firstly, putting 3 layers of completely dried 2D-3BN films into a magnetron sputtering coating machine, vacuumizing until the vacuum degree is stabilized at 10-1mbar, opening an ion target for ion sputtering, wherein the sputtering time is 5min, slowly raising the pressure to atmospheric pressure after the sputtering is finished, taking out the film-plated sample, then drawing a certain size of mutually staggered interdigital pattern by using CAD software, guiding the interdigital pattern onto a laser etching instrument, using laser etching to punch the interdigital pattern on the film-plated sample, and then putting the device into an oxygen plasma sputtering instrument for processing for 20min to remove the nano gold film which is not etched by laser and is not covered by the interdigital pattern and 2D-3BN-3 positioned under the nano gold film, so that the whole device is in an open circuit state. And finally, uniformly coating the prepared gel electrolyte on the surface of the device by using a fine needle-shaped object, and drying at the temperature of 40-60 ℃ for 12-16h to finally obtain the 2D-3BN-3@ MSCs. 2D-3BN-3@ MSCs were tested by CHI660e electrochemical workstation using cyclic voltammetry and constant current charging and discharging, the test conditions being the same as in example 1. The impedance diagram is shown in fig. 8 (wherein, the small diagram at the lower right corner in fig. 8 is an enlarged diagram under the low frequency curve), and the curve of the material at the low frequency curve can be seen from the diagramApproaching a straight line, this indicates that the device has good capacitive effects, and it can be seen that the 5-layer film produced a device with less resistance, probably due to the increased conductivity of the device as a whole due to the increased number of polymer film layers. The area capacitance graph is shown in fig. 9, and it can be seen that the area capacitance measured for the device fabricated with 3 layers of film is less than that measured for the device fabricated with 5 layers of film. The results of cyclic voltammograms at different scan speeds are shown in FIG. 11, which can be seen at 1000V s-1The CV characteristic curve of the prepared micro super capacitor at the sweep speed is very close to a rectangle, and the stability and the rapid charge and discharge performance of the material are shown.
Example 3
The 2D-3BN prepared in example 1 was used to prepare 2D-3BN-1@ MSCs, the preparation route is also shown in FIG. 5, and the specific steps are as follows:
(i) preparation of semi-solid gel electrolyte
Firstly, 3g of polyvinyl alcohol (PVA) is dissolved in 30m L deionized water, the mixture is heated to 98 ℃ on a stirring table at the rotating speed of 50-60r/min to fully dissolve the PVA, and after the PVA is completely dissolved, 3g of diluted PVA with the mass concentration of 0.1mg m L-1Slowly dripping the L iCl solution into the polyvinyl alcohol solution, continuously stirring to completely dissolve the polyvinyl alcohol solution, and cooling the solution for 2 hours to room temperature to obtain the semi-solid gel PVA-L iCl electrolyte.
(ii) Preparation of 2D-3BN-1@ MSCs
The 2D-3BN-1@ MSCs are prepared by simple magnetron sputtering coating and laser etching technology, and the specific operation steps are as follows: firstly, putting 1 layer of completely dried 2D-3BN film into a magnetron sputtering coating machine, vacuumizing until the vacuum degree is stabilized at 10-1mbar, opening an ion target for ion sputtering for 5min, slowly raising the pressure to atmospheric pressure after the sputtering is finished, taking out the film-plated sample, drawing a certain size of mutually staggered interdigital pattern by using CAD software, guiding the interdigital pattern to a laser etching instrument, using laser etching to punch the interdigital pattern on the film-plated sample, and then putting the device into an oxygen plasma sputtering instrument for processing for 20min to remove the nano gold film which is not etched by the laser and is not covered by the interdigital patternAnd 2D-3BN-1 positioned under the nano gold film to ensure that the whole device is in an open circuit state. And finally, uniformly coating the prepared gel electrolyte on the surface of the device by using a fine needle-shaped object, and drying at the temperature of 40-60 ℃ for 12-16h to finally obtain the 2D-3BN-1@ MSCs. 2D-3BN-1@ MSCs were tested by CHI660e electrochemical workstation using cyclic voltammetry and constant current charging and discharging, and the test conditions were the same as in example 1. The impedance plot is shown in fig. 8 (where the lower right hand plot in fig. 8 is an enlarged view of the curve at low frequency), from which it can be seen that the curve of the material at low frequency curve is close to a straight line, which illustrates the good capacitive effect of the device, and it can be seen that the device made of 5 layers of film has a lower impedance, which may be due to the increased conductivity of the device as a whole due to the increased number of layers of polymer film. The area capacitance graph is shown in fig. 9, and it can be seen that the area capacitance of the device prepared by 5 layers of film is better than the device performance of 1 layer of film, so the increase of the number of layers can improve the capacitor performance of the material. The cyclic voltammogram results at different scan speeds are shown in detail in FIG. 12, and can be seen at 1000V s-1The CV characteristic curve of the prepared micro super capacitor at the sweep speed is very close to a rectangle, and the stability and the rapid charge and discharge performance of the material are shown.
Referring to FIGS. 7-12, the present invention is based on a polymer film made of miniature supercapacitors, no matter how many layers of film are made, at 1000V s-1The CV characteristic curves under the sweeping speed are all very close to rectangles, the stability of the material and the performance of quick charge and discharge are shown, and the difference of area capacitance is not large. It can be seen from fig. 8 that the curves of the low frequency curves of the three materials are all close to a straight line, which indicates that the device has good capacitance effect, and that the device prepared by 5 layers of films has smaller impedance, which is probably because the conductivity of the whole device is improved due to the increase of the number of layers of polymer films. The area capacitance, volume capacitance, energy density and power density of the different materials can be obtained from fig. 9, from which it can be seen that the device prepared with the same 5-layer film has the highest area capacitance, further illustrating that the increase in the number of layers improves the capacitor performance of the material, calculated at 0.1V s-1Under the sweeping speed, the area capacitance of the 2D-3BN-5@ MSCs is 107.032 mu F cm-2And as the sweep rate increases, the capacitance drops more slowly, at 1000V s-1The material still can provide 16.652 mu F cm at the sweeping speed-2Area capacitance of (d). From the area of the CV plot, the micro-supercapacitors made from the 5-layer film had higher capacitance, an order of magnitude higher than typical activated carbon supercapacitors. This is because the polymer film has a thickness of a nanometer size, and electrons can be rapidly conducted on the surface by the pi-pi stacking effect between films, thereby enabling the capacitor to have excellent electrical properties.
Example 4
A two-dimensional polymer film based on discoid tri-boron nuclear molecules is prepared as shown in figure 1 and figure 2, and comprises synthesis of 3(NHN), 3B (NF)2-C3 synthesis and 2D-3BN-C3 preparation, 3(NHN) structure as shown in formula (I):
the steps are as follows:
(1) synthesis of 6,12, 18-tris (propylamine) -5,11, 17-triazatrinaphthalene (3(NHN) -2)
6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene (1.0 equivalent) was stirred and refluxed at a rotation speed of 20 to 40R/min for 3 days in n-propylamine (R0 in FIG. 2 is propyl) at a temperature of 48 to 55 ℃ under a nitrogen atmosphere. After cooling for 0.5h to room temperature, the mixture was precipitated in 0 ℃ ice ethanol for 0.5 h. The residue was purified by silica gel column chromatography (dichloromethane: methanol ═ 30:1, v/v) at room temperature for 1h to give the product as a yellow solid powder, noted 3(NHN) -2 (R1 in figure 2 is propyl),1H NMR(400MHz,CDCl3):＝14.6,8.35,7.89,7.65,7.31,4.01,1.95,0.86。
(2)3B(NF)2-C3 Synthesis of
3(NHN) -2(1.0 equiv.) was stirred in dry toluene (30m L) at 20-40r/min for 20 minutes, and triethylamine (9.0 equiv.) and BF were added3·Et2O (15.0 equiv.). The mixture was reacted at 90 ℃ for 24 hours under nitrogen atmosphere. After cooling to room temperature, toluene was removed under reduced pressure, the solid was collected and purified by silica gel column chromatography (dichloromethane: petroleum ether ═ 1:1, v/v) at room temperature for 1h to give the product, reported as 3b (nf)2-2 (in FIG. 2R 2 is propyl) as a yellow solid powder,1H NMR(400MHz,CDCl3):＝8.76,8.20,7.82,7.48,4.11,2.12,1.62,0.90。
(3) preparation of 2D-3BN-C3
An appropriate amount of TBAB (10mg m L) was added to the beaker-1) The solution was then pipetted 50. mu. L of the prepared 3B (NF)2-2 Chlorobenzene solution (1mg m L)-1) Dropwise adding the solution on the surface of the solution, irradiating for 1 hour by using an ultraviolet lamp with the power of 20-40W, and finally fishing out a film on the surface by using a silicon wafer, wherein the film is marked as 2D-3 BN.
Example 5
A two-dimensional polymer film based on discoid tri-boron nuclear molecules is prepared as shown in figure 1 and figure 2, and comprises synthesis of 3(NHN), 3B (NF)2-C12 synthesis and 2D-3BN-C12 preparation, 3(NHN) structure as shown in formula (I):
the steps are as follows:
(1) synthesis of 6,12, 18-tris (dodecylamine) -5,11, 17-triazatrinaphthalene (3(NHN) -3)
6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene (1.0 equivalent) was reacted under nitrogen atmosphere in n-dodecylamine (R0 in FIG. 2 is dodecyl) at a temperature of 250-255 ℃,stirring and refluxing for 3 days at the rotating speed of 20-40 r/min. After cooling for 2h to room temperature, the mixture was precipitated in 0 ℃ ice ethanol for 0.5 h. The residue was purified by silica gel column chromatography (dichloromethane: methanol ═ 30:1, v/v) at room temperature for 1h to give the product as 3(NHN) -3 (dodecyl R1 in fig. 2) as a yellow solid powder.1H NMR(400MHz,CDCl3):＝14.6,8.35,7.89,7.65,7.31,4.01,1.95,1.50,1.18,0.86。
(2)3B(NF)2Synthesis of (E) -3
3(NHN) -3(1.0 eq) was stirred in dry toluene (30m L) at 20-40r/min for 20 minutes, and triethylamine (9.0 eq) and BF were added3·Et2O (15.0 equiv.). The mixture was reacted at 90 ℃ for 24 hours under nitrogen atmosphere. After cooling to room temperature, toluene was removed under reduced pressure, the solid was collected and purified by silica gel column chromatography (dichloromethane: petroleum ether ═ 1:1, v/v) at room temperature for 1h to give the product, reported as 3b (nf)2-3 (R2 in FIG. 2 is dodecyl) as a yellow solid powder.1H NMR(400MHz,CDCl3):＝8.76,8.20,7.82,7.48,4.11,2.12,1.62,1.28-1.37,0.90。
(3) Preparation of 2D-3BN
An appropriate amount of TBAB (10mg m L) was added to the beaker-1) The solution was then pipetted 50. mu. L of the prepared 3B (NF)2Chlorobenzene solution (1mg m L)-1) Dropwise adding the solution on the surface of the solution, irradiating for 1 hour by using an ultraviolet lamp with the power of 20-40W, and finally fishing out a film on the surface by using a silicon wafer, wherein the film is marked as 2D-3 BN.
Example 6
A two-dimensional polymer film based on discoid tri-boron nuclear molecules is prepared as shown in figure 1 and figure 2, and comprises synthesis of 3(NHN), 3B (NF)2The structure of 3(NHN) is shown as the formula (I):
the steps are as follows:
(1) synthesis of 6,12, 18-tris (hexylamine) -5,11, 17-triazatrinaphthalene (3(NHN))
6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene (1.0 equivalent) was refluxed with stirring at a rate of 20 to 40R/min for 3 days in n-hexylamine (R0 in FIG. 2 is hexyl) at a temperature of 132-135 ℃ under a nitrogen atmosphere. After cooling for 1h to room temperature, the mixture was precipitated in 0 ℃ ice ethanol for 0.5 h. The residue was purified by silica gel column chromatography (dichloromethane: methanol ═ 30:1, v/v) at a temperature of 0 ℃ for 1h to give the product (R1 in fig. 2 is hexyl) as a yellow solid powder in 50% yield.1H NMR(400MHz,CDCl3):＝14.6,8.35,7.89,7.65,7.31,4.01,1.95,1.50,1.18,0.86。
(2)3B(NF)2Synthesis of (2)
3(NHN) (1.0 eq) was stirred in dry toluene (30m L) at 20-40r/min for 20min, and triethylamine (9.0 eq) and BF were added3·Et2O (15.0 equiv.). The mixture was reacted at 90 ℃ for 24 hours under nitrogen atmosphere. After cooling to room temperature, toluene was removed under reduced pressure, the solid was collected and purified by silica gel column chromatography (dichloromethane: petroleum ether ═ 1:1, v/v) at 0 ℃ for 1h to give 3b (nf)2(R2 in FIG. 2 is hexyl) as a yellow solid powder in 69% yield.1H NMR(400MHz,CDCl3):＝8.76,8.20,7.82,7.48,4.11,2.12,1.62,1.28-1.37,0.90。
(3) Preparation of 2D-3BN-DTAB
An appropriate amount of dodecyl ammonium bromide (DTAB,10mg m L) was added to the beaker-1) The solution was then pipetted 50. mu. L of the prepared 3B (NF)2Chlorobenzene solution (1mg m L)-1) Dropwise adding the solution on the surface of the solution, irradiating for 1 hour by using an ultraviolet lamp with the power of 20-40W, and finally fishing out the 2D-3BN-DTAB film on the surface by using a silicon wafer. Due to the fact that DTAB is stronger in hydrophobicity and weaker in water solubility, the prepared 2D-3BN-DTAB also has corresponding characteristics.
Example 7
A two-dimensional polymer film based on discoid tri-boron nuclear molecules is prepared as shown in figure 1 and figure 2, and comprises synthesis of 3(NHN), 3B (NF)2The structure of 3(NHN) is shown as the formula (I):
the steps are as follows:
(1) synthesis of 6,12, 18-tris (hexylamine) -5,11, 17-triazatrinaphthalene (3(NHN))
6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene (1.0 equivalent) was refluxed with stirring at a rate of 20 to 40R/min for 3 days in n-hexylamine (R0 in FIG. 2 is hexyl) at a temperature of 132-135 ℃ under a nitrogen atmosphere. After cooling for 1h to room temperature, the mixture was precipitated in 0 ℃ ice ethanol for 0.5 h. The residue was purified by silica gel column chromatography (dichloromethane: methanol ═ 30:1, v/v) at room temperature for 1h to give the product (R1 in fig. 2 is hexyl) as a yellow solid powder in 50% yield.1HNMR(400MHz,CDCl3):＝14.6,8.35,7.89,7.65,7.31,4.01,1.95,1.50,1.18,0.86。
(2)3B(NF)2Synthesis of (2)
3(NHN) (1.0 eq) was stirred in dry toluene (30m L) at 20-40r/min for 20min, and triethylamine (9.0 eq) and BF were added3·Et2O (15.0 equiv.). The mixture was reacted at 90 ℃ for 24 hours under nitrogen atmosphere. After cooling to room temperature, toluene was removed under reduced pressure, the solid was collected and purified by silica gel column chromatography (dichloromethane: petroleum ether ═ 1:1, v/v) at room temperature for 1h to give 3b (nf) R2 in fig. 2 as hexyl) as a yellow solid powder with a yield of 69%.1H NMR(400MHz,CDCl3):＝8.76,8.20,7.82,7.48,4.11,2.12,1.62,1.28-1.37,0.90。
(3) Preparation of 2D-3BN-SDBS
An appropriate amount of sodium dodecylbenzenesulfonate (SDBS,10mg m L) was added to the beaker-1) The solution was then pipetted 50. mu. L of the prepared 3B (NF)2Chlorobenzene solution (1mg m L)-1) Dropwise adding the solution on the surface of the solution, irradiating for 1 hour by using an ultraviolet lamp with the power of 20-40W, and finally fishing out the 2D-3BN-SDBS film on the surface by using a silicon wafer.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a two-dimensional polymer film based on a discoid tri-boron nuclear molecule is characterized by specifically comprising the following steps:
(a) mixing 6,12, 18-trichloro-5, 11, 17-triazatrinaphthalene with alkylamine, stirring and refluxing under nitrogen atmosphere, cooling to obtain a mixture, precipitating the mixture in glacial ethanol, and purifying to obtain 3(NHN) shown in formula (I):
(b) sequentially adding the 3(NHN), triethylamine and BF obtained in the step (a) into toluene3·Et2O, stirring and mixing uniformly, then carrying out heating reaction under the nitrogen atmosphere, then cooling, decompressing and removing toluene, and purifying to obtain 3B (NF)2As shown in formula (II):
(c) subjecting the 3B (NF) obtained in step (b)2Dissolving in chlorobenzene to give 3B (NF)2The chlorobenzene solution is dripped on the surface of the surfactant, and then the ultraviolet light is utilized for irradiation, so that the two-dimensional polymer film is obtained.
2. The method of claim 1, wherein in step (a), the alkylamine is selected from one or more of n-propylamine, n-hexylamine and n-dodecylamine.
3. The method for preparing a two-dimensional polymer film based on discotic triboron core molecule according to claim 1, wherein in the step (a), the temperature of stirring reflux is 50-255 ℃, the time of stirring reflux is 2-4d, the rotation speed of stirring is 20-40r/min, the temperature of cooling is room temperature, the time of cooling is 0.5-2h, the temperature of precipitation is 0 ℃, the time of precipitation is 0.5h, silica gel column chromatography is adopted for purification, the temperature of purification is room temperature, and the time of purification is 1 h.
4. The method for preparing a two-dimensional polymer film based on discotic triboron core molecules according to claim 1, wherein in the step (b), the rotation speed of stirring is 20-40r/min, the stirring time is 20min, the reaction temperature is 80-100 ℃, the reaction time is 22-26h, the cooling temperature is room temperature, the cooling time is 0.5h, and the purification is performed by silica gel column chromatography, the purification temperature is room temperature, and the purification time is 1 h.
5. The method for preparing a two-dimensional polymer film based on discotic triboronic core molecules according to claim 1, wherein in the step (c), the power of the ultraviolet light is 20-40W, and the irradiation time is 1 h.
6. The method for preparing a two-dimensional polymer film based on discoid triboronic core molecules as claimed in claim 1, wherein in step (c), the surfactant is selected from one or more of tetrabutylammonium bromide, dodecylammonium bromide or sodium dodecylbenzene sulfonate.
7. A two-dimensional polymer film produced by the production method according to any one of claims 1 to 6.
8. Use of a two-dimensional polymer film according to claim 7 in a micro supercapacitor, in particular comprising the steps of:
(i) adding L iCl solution into polyvinyl alcohol aqueous solution, stirring and cooling to obtain semi-solid gel PVA-L iCl electrolyte;
(ii) placing the two-dimensional polymer film of claim 7 on a silicon wafer, plating a nanogold film on the two-dimensional polymer film, etching an interdigital pattern on the nanogold film, removing the nanogold film which is not covered by the interdigital pattern and the two-dimensional polymer film positioned below the nanogold film, finally coating the semi-solid PVA-L iCl electrolyte obtained in the step (i) on the nanogold film, drying to obtain 2D-3BN @ MSCs, and placing the 2D-3BN @ MSCs in an electrochemical workstation for capacitance performance test.
9. The use of a two-dimensional polymer film in a micro supercapacitor according to claim 8, wherein in step (i), the aqueous solution of polyvinyl alcohol is obtained by dissolving polyvinyl alcohol in water, heating and stirring, the heating temperature is 90-110 ℃, the stirring speed is 50-60r/min, the stirring time is 0.5h, the cooling temperature is room temperature, and the cooling time is 2 h.
10. The use of a two-dimensional polymer film in a miniature supercapacitor according to claim 8, wherein in step (ii), the plating is performed by ion sputtering under a vacuum of 10 ° f-1mbar, and plating time is 3-7 min;
etching by oxygen plasma sputtering for 20 min;
the drying temperature is 40-60 ℃, and the drying time is 12-16 h;
the scanning voltage interval of the capacitance performance test is 0-1V, and the scanning speed is 0.1-10000V s-1。
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| CN103030788A (en) * | 2012-12-06 | 2013-04-10 | 南京邮电大学 | Conjugated polymer gelling agent poly(phenylene ethynylene) and preparation method thereof |
| CN106478627A (en) * | 2016-08-30 | 2017-03-08 | 华东师范大学 | A kind of 6,12,18 triaryl, 5,11,17 benzo three quinoline and its synthetic method |
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| CN103030788A (en) * | 2012-12-06 | 2013-04-10 | 南京邮电大学 | Conjugated polymer gelling agent poly(phenylene ethynylene) and preparation method thereof |
| CN106478627A (en) * | 2016-08-30 | 2017-03-08 | 华东师范大学 | A kind of 6,12,18 triaryl, 5,11,17 benzo three quinoline and its synthetic method |
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