CN110498929B - Preparation method of polyaniline covalent modified molybdenum sulfide - Google Patents
Preparation method of polyaniline covalent modified molybdenum sulfide Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 title claims 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 98
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- -1 molybdenum sulfide compound Chemical class 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 230000004048 modification Effects 0.000 claims abstract description 32
- 238000012986 modification Methods 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 72
- 239000006185 dispersion Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 35
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000004108 freeze drying Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052740 iodine Chemical group 0.000 claims description 6
- 239000011630 iodine Chemical group 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- 239000002131 composite material Substances 0.000 abstract description 29
- 239000003990 capacitor Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- CQXXYOLFJXSRMT-UHFFFAOYSA-N 5-diazocyclohexa-1,3-diene Chemical class [N-]=[N+]=C1CC=CC=C1 CQXXYOLFJXSRMT-UHFFFAOYSA-N 0.000 abstract 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052961 molybdenite Inorganic materials 0.000 description 8
- 125000005647 linker group Chemical group 0.000 description 7
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 229920000128 polypyrrole Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- MUNOBADFTHUUFG-UHFFFAOYSA-N 3-phenylaniline Chemical group NC1=CC=CC(C=2C=CC=CC=2)=C1 MUNOBADFTHUUFG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of polyaniline covalent modification molybdenum sulfide comprises the steps of using molybdenum sulfide nanosheets as templates, functionalizing amino groups of two-dimensional molybdenum sulfide with halogenated diazobenzene compounds with amino groups at end groups, then using aniline monomers to polymerize and graft amino-functionalized molybdenum sulfide, washing, filtering and drying to obtain a polyaniline covalent modification two-dimensional molybdenum sulfide compound. The invention has the advantages that the polymer is uniformly and covalently grafted on the two-dimensional molybdenum sulfide nanosheet, and the molybdenum sulfide-based composite electrode material is promoted to show excellent electrochemical performance as an electrode material of a super capacitor. The method is simple and controllable, the process is safe, and the obtained composite material has high specific surface area and specific capacitance, can be directly used as an electrode material for a super capacitor and a sodium/lithium ion battery, and has good application prospect in the field of energy storage devices.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a preparation method of a functionalized molybdenum sulfide nanosheet.
Background
Two-dimensional transition metal molybdenum disulfide (MoS)2) Due to its stable physical properties, excellent electrochemical properties and ultra-high active specific surface area, it has been widely studied in the field of electrochemical storage (e.g., lithium/sodium ion batteries, supercapacitors). In particular, have
Inter-layer MoS2The electrochemical activity and the chemical stability of the material are excellent in the energy storage device. The electrode not only has a series of oxidation states from +2 to +6, has pseudocapacitance characteristics, but also has a large specific surface area for charge desorption of an electric double layer capacitor. However, due to the original MoS2The low conductivity, low crystallinity and stacking of sheets restrict the application of the composite material in the field of supercapacitors.
Various methods have been developed to overcome the above disadvantages to improve MoS2Electrochemical performance of the pseudo-capacitance super capacitor. Wherein different nano-structures MoS2And compounding with other high specific capacitance materials, such as graphene, transition metal compounds or conductive polymers. (Adv. energy mater.2014,4(6),1301380.Adv Funct Mater 2014,24(42),6700-6707.Nanoscale 2017,9(28),10059-10066.) the advantage of using the method of synergistic recombination is obvious, which on one hand maintains the good electrochemical stability of the sulfide and on the other hand, the high specific capacitance brings excellent electrochemical performance to the compound after the action of molybdenum sulfide is strong. Tang et al, by a method that allows large scale solution preparation, grown polypyrrole (PPy) films of controlled thickness on two-dimensional molybdenum sulfide nanoplates. Based on such MoS2the/PPY-2 pseudocapacitance material can still keep about 85% of initial capacitance value after 4000 cycles of charge and discharge, and PPy and graphene/PPy nano composite can only keep 50% under the same cycle number work. (Adv Mater 2015,27(6), 1117-1123.). Yan et al, by combining a PANI nanoneedle array with MoS2The single-layer is compounded to form a multifunctional nano structure which is applied to the super capacitor. The specific capacitance of the composite material can reach 669F g-1Compared with a pure PANI super capacitor, the super capacitor is increased by 40% (Small 2015,11(33), 4123-4129). Liu et al designed a ternary MoS with a "pizza-like" nanostructure2a/PPy/PANI composite material, which is 0.5A g-1Specific capacitance can reach 1273F g-1And the structural design effectively improves the cycling stability of the material, and the capacitance value can still be kept about 83 percent after 3000 charge/discharge cycles (Advanced Materials Interfaces 2016,3(19), 1600665.). The above studies were all in MoS2As a template, MoS is prepared2The conductive polymer composite material greatly improves the specific capacitance of the electrode material, but due to MoS2The polymer film on the monolithic layer is directly loaded on the molybdenum sulfide layer, so that the linking force of the two is not strong enough, andand polymer accumulation phenomenon exists, so that the electrochemical reaction is not perfect in the aspects of cycle stability and rate performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of polyaniline covalent modification molybdenum sulfide. In an aqueous phase system, molybdenum sulfide nanosheets are used as templates, and halogenated diazo substituted R-based compounds with amino groups at end groups are used for covalently modifying molybdenum sulfide. Wherein the R group can be aryl, alkenyl or alkynyl. Then, the amino functionalized molybdenum sulfide is used as a template, and polyaniline is grafted in situ through polymerization to prepare the polyaniline covalent modification molybdenum sulfide composite material with excellent electrochemical performance.
The invention relates to a preparation method of polyaniline covalent modification molybdenum sulfide, which comprises the following steps:
a) under the acidic condition that the pH value is 3-5, taking a molybdenum sulfide dispersion liquid with the concentration of 0.5-2 mg/mL as a raw material, taking an amino halogenated diazo substituted R-based compound aqueous solution accounting for 4-20% of the mass fraction of molybdenum sulfide, dripping the dispersion liquid into the dispersion liquid, stirring, and reacting at 0-10 ℃ for 0.5-2 hours to obtain an amino substituted R-based compound covalent modification molybdenum sulfide solution; then sequentially washing, filtering and freeze-drying the molybdenum sulfide compound by using ethanol and water to obtain an amino substituent R group compound covalent modification molybdenum sulfide compound; weighing the product according to a volume ratio of 1: dissolving the 1 in a mixed liquid of deionized water and ethanol, and performing ultrasonic uniform dispersion to obtain an amino R-group compound covalent modification molybdenum sulfide dispersion liquid with the concentration of 0.5-3 mg/mL.
b) Putting the amino-substituted R-group compound covalent modification molybdenum sulfide dispersion liquid obtained in the step a) into a flask, adding aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at the temperature of 0-5 ℃, then gradually dropwise adding dilute HCl solution and Ammonium Persulfate (APS), reacting for 12-24 hours, finally, sequentially cleaning with ethanol, deionized water and the like, removing raw materials, performing suction filtration, and freeze drying to obtain the product.
Wherein the mass ratio of aniline monomer raw material to amino-substituted R group compound covalently modified molybdenum sulfide is 1 x 10-4～4×10-3:1. thin paperThe concentration of the hydrochloric acid is 1-2M, and the molar ratio of the amount of the ammonium persulfate to the aniline monomer is 1: 1.0-2.0.
The molecular formula of the amino halogenated diazo substituted R group compound is shown as the following formula:
wherein, when R is aryl
When n is the number of repeating phenyl units, n is an integer of 2 to 3, and X represents a halogen element such as fluorine, chlorine, bromine, or iodine.
When R is a vinyl group
When n is the number of repeating phenyl units, n is an integer of 1 to 3, and X represents a halogen element such as fluorine, chlorine, bromine, or iodine.
When R is an acetylene group
When n is the number of repeating phenyl units, n is an integer of 1 to 3, and X represents a halogen element such as fluorine, chlorine, bromine, or iodine.
Preferably, in the step a), the molybdenum sulfide is molybdenum sulfide nanosheets, the dispersion liquid is prepared by dissolving the molybdenum sulfide nanosheets in deionized water, performing ultrasonic treatment for 30-60 minutes, and uniformly mixing.
The method of the invention is simple and controllable. The invention mainly obtains the polyaniline covalent modification molybdenum sulfide composite material with different thicknesses and electrochemical properties by changing the amount of amino covalent modification groups in molybdenum sulfide and polyaniline polymerized in situ. The molybdenum disulfide is used as a substrate material on one hand and is used as a template on the other hand to form an S-C covalent bond with a halogenated diazoamino substituted R group compound. Polyaniline is directionally grafted under the action of amino groups to form a novel uniform and stable polyaniline/molybdenum sulfide/polyaniline composite material. The composite material obtained by the invention has higher specific surface area and specific capacitance, thus having good application prospect in the field of energy storage devices.
Drawings
FIG. 1 shows that 4-amino-4' -bromo-diazo-biphenyl is used as the intermediate covalent linker raw material in example 1 of the present invention, and the mass ratio of the 4-amino-biphenylyl covalently modified molybdenum sulfide to the aniline monomer is 1:1.5 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 2 shows that in example 2 of the present invention, 4-amino-4' -chlorodiazo terphenyl is used as the intermediate covalent link raw material, and the mass ratio of the 4-amino terphenyl covalently modified molybdenum sulfide to aniline monomer is 1:1.5 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 3 shows that in example 3 of the present invention, 4-amino-4' -chlorodiazo-biphenyl is used as the raw material of the intermediate covalent linker, and the ratio of the 4-amino-substituted-biphenyl covalently modified molybdenum sulfide to aniline monomer is 1:3 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 4 shows that in example 4 of the present invention, 2-amino-4' -bromo-diazo-biphenyl is used as the raw material of the intermediate covalent linker, and the ratio of the 2-amino-biphenyl covalently modified molybdenum sulfide to aniline monomer is 1:1.5 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 5 shows that in example 5 of the present invention, 3-amino-4' -chlorodiazo-biphenyl is used as the raw material of the intermediate covalent linker, and the ratio of the 3-amino-substituted-biphenyl covalently modified molybdenum sulfide to aniline monomer is 1:3 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 6 shows that in example 6 of the present invention, 3-amino-4' -chlorodiazo terphenyl is used as the intermediate covalent link material, and the ratio of the 3-amino terphenyl covalently modified molybdenum sulfide to aniline monomer is 1: 1.5X 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 7 is the present inventionMing example 7 (E) -1-amino-2-chlorodiazoethylene as intermediate covalent link raw material, the ratio of (E) -1-amino vinyl covalent modified molybdenum sulfide to aniline monomer is 1: 1.5X 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 8 shows that in example 8 of the present invention, (E) -1-amino-2-chlorodiazoacetylene is used as the raw material of the intermediate covalent linker, and the ratio of (E) -1-aminoethynyl group covalent modified molybdenum sulfide to aniline monomer is 1: 1.5X 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 9 shows that in example 9 of the present invention, (1E,3E) -1-amino-4-chlorodiazo-1, 3-butanedivinyl is used as the raw material of the intermediate covalent linker, and the ratio of the (1E,3E) -1-amino-1, 3-butanedivinyl covalently modified molybdenum sulfide to aniline monomer is 1: 1.5X 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
FIG. 10 shows that in example 10 of the present invention, (1E,3E) -1-amino-4-bromodiazo-1, 3-butadiyne is used as the intermediate covalent linker raw material, and the ratio of the (1E,3E) -1-amino-1, 3-butadiyne covalently modified molybdenum sulfide to aniline monomer is 1:3 × 10-3And (3) under the condition, carrying out transmission electron microscope photo on the prepared polyaniline covalent modified molybdenum sulfide composite nanosheet.
Detailed Description
The invention will be further illustrated by the following examples.
Example 1.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to be 4 by using acid, adding 80mL of 7mmol of 4-amino-4' -chlorodiazo biphenyl aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 4-amino-substituted biphenyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, and freeze-drying to obtain the 4-amino-biphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 4-amino-substituted biphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The projection electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 1.
Example 2.
a) Taking 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to be 5 by using acid, adding 80mL of 7mmol of 4-amino-4' -chlorodiazo terphenyl aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 4-amino terphenyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the 4-amino terphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 4-amino terphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The projection electron micrograph of the polyaniline covalently modified molybdenum sulfide complex is shown in figure 2.
Example 3.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to be 4 by using acid, adding 80mL of 7mmol of 4-amino-4' -diazo-biphenyl chloride aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 4-amino-biphenyl covalent modified molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, and freeze-drying to obtain the 4-amino-biphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 4-amino-substituted biphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 300 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially cleaning with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and carrying out freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 3.
Example 4.
a) Taking 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to be 4 by using acid, adding 80mL of 7mmol of 2-amino-4' -bromo-diazo-biphenyl aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 2-amino-substituted-biphenyl covalent modified molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, and freeze-drying to obtain the 2-amino-biphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 2-amino-substituted biphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 300 dispersed aniline monomers into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomers, reacting for 24 hours, finally, sequentially cleaning with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and carrying out freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 4.
Example 5.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to be 5 by using acid, adding 80mL of 7mmol of 3-amino-4' -chlorodiazo biphenyl aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 3-amino-substituted biphenyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, and freeze-drying to obtain the 3-amino-biphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 3-amino-substituted biphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 5.
Example 6.
a) Taking 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to 3 by using acid, adding 80mL of 7mmol of 3-amino-4' -chlorodiazo terphenyl aqueous solution dropwise into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a 3-amino terphenyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the 3-amino terphenyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a 3-amino terphenyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 6.
Example 7.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to 3 by using acid, dropwise adding 80mL of 7mmol of (E) -1-amino-2-chlorodiazoethylene aqueous solution into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain (E) -1-amino vinyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the (E) -1-amino vinyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain (E) -1-amino vinyl covalent modification molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 7.
Example 8.
a) Using 100mL of molybdenum sulfide nanosheet dispersion liquid with the concentration of 1mg/mL as a raw material, adjusting the pH value of the solution to 3 by using acid, dropwise adding 80mL of 7mmol of (E) -1-amino-2-chlorodiazoacetylene water solution into the dispersion liquid, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain the (E) -1-aminoethynyl covalent modification molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the (E) -1-amino ethynyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain (E) -1-aminoethynyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 8.
Example 9.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to 3 by using an acid, dropwise adding 80mL of 7mmol of (1E,3E) -1-amino-4-chlorodiazo-1, 3-butyldivinyl aqueous solution into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain a (1E,3E) -1-aminobutyldivinyl covalent modified molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the (1E,3E) -1-amino divinyl butane covalently modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment on the mixture of deionized water and ethanol for 30 minutes, and uniformly dispersing to obtain (1E,3E) -1-aminobutyldivinyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 150 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially washing with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 9.
Example 10.
a) Using 100mL of 1mg/mL molybdenum sulfide nanosheet dispersion as a raw material, adjusting the pH value of the solution to 3 by using acid, dropwise adding 80mL of 7mmol of (1E,3E) -1-amino-4-bromodiazo-1, 3-butyne aqueous solution into the dispersion, reacting and stirring at 5 ℃, and reacting for 12 hours to obtain (1E,3E) -1-aminobutynyl covalent modified molybdenum sulfide solution. And then sequentially washing with ethanol and water, filtering, freezing and drying to obtain the (1E,3E) -1-aminobutadiynyl covalent modified molybdenum sulfide compound.
b) 100mg of the above product is weighed out and dissolved in 100mL of a solution with a volume ratio of 1:1, performing ultrasonic treatment for 30 minutes in a mixed liquid of deionized water and ethanol, and uniformly dispersing to obtain a (1E,3E) -1-aminobutadiynyl covalent modified molybdenum sulfide dispersion liquid.
c) Putting the dispersion liquid obtained in the step a) into a flask, adding 300 mu L of aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at 0 ℃, gradually dropwise adding 10mL of 2M HCl solution dissolved with ammonium persulfate with the molar ratio of 1:1.5 to the aniline monomer, reacting for 24h, finally, sequentially cleaning with ethanol, deionized water and the like, removing raw materials, carrying out suction filtration, and carrying out freeze drying to obtain the product polyaniline covalent modification molybdenum sulfide compound.
d) The transmission electron micrograph of the polyaniline covalently modified molybdenum sulfide composite is shown in figure 10.
Claims (2)
1. A preparation method of polyaniline covalent modification molybdenum sulfide is characterized by comprising the following steps:
a) under the acidic condition that the pH value is 3-5, taking a molybdenum sulfide dispersion liquid with the concentration of 0.5-2 mg/mL as a raw material, taking an amino halogenated diazo substituted R-based compound aqueous solution accounting for 4-20% of the mass fraction of molybdenum sulfide, dripping the dispersion liquid into the dispersion liquid, stirring, and reacting at 0-10 ℃ for 0.5-2 hours to obtain an amino substituted R-based compound covalent modification molybdenum sulfide solution; then sequentially washing, filtering and freeze-drying the molybdenum sulfide compound by using ethanol and water to obtain an amino substituent R group compound covalent modification molybdenum sulfide compound; weighing the product according to a volume ratio of 1: dissolving the 1 in a mixed liquid of deionized water and ethanol, and performing ultrasonic uniform dispersion to obtain an amino-substituted R-group compound covalent modification molybdenum sulfide dispersion liquid with the concentration of 0.5-3 mg/mL;
b) putting the amino-substituted R-group compound obtained in the step a) into a flask, adding aniline monomer into the flask, then putting the flask into a low-temperature reaction tank, stirring until the reaction system is at the temperature of 0-5 ℃, then gradually dropwise adding dilute HCl solution and ammonium persulfate, reacting for 12-24 hours, finally, sequentially cleaning with ethanol and deionized water, removing raw materials, performing suction filtration, and performing freeze drying to obtain a product;
wherein the mass ratio of aniline monomer raw material to amino-substituted R group compound covalently modified molybdenum sulfide is 1 x 10-4~4×10-3: 1; the concentration of the dilute hydrochloric acid is 1-2M, and the molar ratio of the amount of ammonium persulfate to the aniline monomer is 1: 1.0-2.0;
the molecular formula of the amino halogenated diazo substituted R group compound is shown as the following formula:
wherein, when R is aryl, n is the repeated number of phenyl units, n is an integer of 2-3, and X represents fluorine, chlorine, bromine or iodine;
when R is a vinyl group, n is the number of repeating vinyl units, n is an integer of 1 to 3, and X represents fluorine, chlorine, bromine or iodine;
when R is an ethynyl group, n is the number of repeating ethynyl units, n is an integer from 1 to 3, and X represents fluorine, chlorine, bromine or iodine.
2. The method for preparing polyaniline-covalently modified molybdenum sulfide as claimed in claim 1, wherein in the step a), the molybdenum sulfide is a molybdenum sulfide nanosheet, the dispersion liquid is a two-dimensional molybdenum sulfide nanosheet dissolved in deionized water, and the ultrasonic treatment is carried out for 30-60 minutes and the mixture is uniformly mixed.
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| CN105384693A (en) * | 2015-10-21 | 2016-03-09 | 盐城工学院 | Compound containing benzoxazole ring bis(azo) structure, synthetic method for compound and use of compound |
| CN105885410A (en) * | 2016-05-17 | 2016-08-24 | 东华大学 | Molybdenum sulfide/polypyrrole/polyaniline ternary composite material as well as preparation method and application thereof |
| CN106887347A (en) * | 2017-03-22 | 2017-06-23 | 浙江大学 | The preparation method of Graphene molybdenum bisuphide polyaniline ternary composite electrode material |
| CN107778642A (en) * | 2017-11-10 | 2018-03-09 | 湖南辰砾新材料有限公司 | A kind of semiconductor composite based on two-dimentional molybdenum disulfide and preparation method and application |
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| CN105885410A (en) * | 2016-05-17 | 2016-08-24 | 东华大学 | Molybdenum sulfide/polypyrrole/polyaniline ternary composite material as well as preparation method and application thereof |
| CN106887347A (en) * | 2017-03-22 | 2017-06-23 | 浙江大学 | The preparation method of Graphene molybdenum bisuphide polyaniline ternary composite electrode material |
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