CN110559949A - Phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and preparation method thereof - Google Patents
Phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and preparation method thereof Download PDFInfo
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000001338 self-assembly Methods 0.000 title claims abstract description 42
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002086 nanomaterial Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 77
- 239000000243 solution Substances 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000012043 crude product Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 10
- 239000013460 polyoxometalate Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 229910009112 xH2O Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 19
- 238000004626 scanning electron microscopy Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- -1 phthalocyanine compound Chemical class 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000527 sonication Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012874 electrostatic modification Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The invention belongs to the technical field of functional material preparation, and provides a self-assembly nano material of a phthalocyanine derivative modified surfactant and polyoxometallate compound and a preparation method thereof, aiming at the defects that polyoxometallate is easy to dissolve in water and difficult to separate and recycle as a catalyst, and the photoresponse range is narrow when the polyoxometallate is used as a photocatalyst. The phthalocyanine derivative modified surfactant is prepared by covalent bonding of a phthalocyanine derivative and a double-chain cationic surfactant, and then is combined with polyoxometallate in an electrostatic manner to form a compound, and the compound is self-assembled in a solution to form a nano material with a certain morphology structure. The surfactant is made to have the spectroscopic properties of phthalocyanine. Not only improves the dispersibility of the phthalocyanine in the solution and enhances the photocatalytic activity of the phthalocyanine, but also enables the photocatalytic activity of the phthalocyanine and the photocatalytic function of the POM to play a synergistic role. The nano materials with different morphologies are obtained by self-assembly in the solution, and the method has important significance in the fields of photoelectric materials, photocatalysis and the like.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and a preparation method thereof. The material is formed by self-assembling a compound of a phthalocyanine derivative modified surfactant and polyoxometallate in a solution; the phthalocyanine derivative modified surfactant is prepared by covalently bonding a phthalocyanine derivative and a surfactant, and the phthalocyanine derivative modified surfactant and a polyoxometallate compound are combined through electrostatic interaction.
Background
Polyoxometalates (abbreviated as POM) are inorganic metal oxygen cluster compounds formed by connecting high-valence early transition metals (V, Nb, Ta, Mo, W, etc.) and oxygen atoms through oxygen coordination bridges. The polyoxometalate cluster consists of two parts, namely an oxygen-enriched anion cluster and a counter cation. Polyoxometallate is a compound with a structure smaller than that of virus molecules, the size is about 0.5-5 nm, and the polyoxometallate can be dissolved in polar solvents such as water and the like. It possesses excellent chemical properties such as redox, electron transfer, ion exchange, etc. due to its unique and steric framework. Other characteristics such as exhibiting a stronger acidity than conventional inorganic oxyacids are considered to be solid superacids which have a higher acid strength than concentrated sulfuric acid in non-polar organic solvents and a very high thermal stability. The polyoxometallate also has strong oxidizability and reducibility, has good storage capacity for electrons and protons, can absorb ultraviolet light and the like, and is an ideal raw material for preparing functional materials. However, the use of polyacids is limited by the disadvantages of small specific surface area, high solubility in polar solvents such as water, difficulty in separation and recovery, etc.
Researches find that the controllable self-assembly of the POM is beneficial to the materialization use of the POM.self-assembly of polyoxometalate clusters in solution was first discovered by A.M ü ller and T.B. Liu et al, who discovered a wheel in 2003 { Mo154The anion cluster can self-assemble in aqueous solution to form an assembly body with a hollow monolayer vesicular blackberry structure, and the polymetallic oxygen cluster with larger size can basically form the assembly body spontaneously in aqueous solution, but the assembled form and structure are relatively single. Therefore, in order to obtain a functionally-rich and structurally-diverse assembly, researchers have organically modified POM and induced its self-assembly. Functional organic groups are modified on polyoxometallate through a physical or chemical method to obtain functional organic-inorganic hybrid composite molecules, and the composite molecules can be self-assembled to generate aggregates with various structures and rich functions. The organic cationic surfactant is utilized to carry out electrostatic modification on the POM, so that the amphipathy of the compound is improved, the controllable aggregation of the compound is facilitated, the flexibility of self-assembly of the organic-inorganic hybrid compound in a solution is greatly improved, and the organic cationic surfactant is a research hotspot in the field of current material science.
The phthalocyanine compound is a highly conjugated system with 18 pi electrons, aromatic pi electrons of the phthalocyanine compound are conjugated on the whole porphyrazine ring, the phthalocyanine compound is a conjugated macromolecule with high planarity, and the phthalocyanine compound has the characteristics of electron supply and electron donor, and the whole chemical property is very stable; the p-type semiconductor is a p-type semiconductor, has strong absorption and fluorescence emission of a B band (300-400 nm) and a Q band (600-800 nm), can perform energy transfer with a triplet state oxygen molecule under a certain excitation wavelength to generate singlet state oxygen molecules with high activity, can be effectively used as a photosensitizer or a catalyst, and is widely applied to optical materials, semiconductor materials and the like.
Disclosure of Invention
The invention provides the following defects that Polyoxometallate (POM) is easy to dissolve in water and difficult to separate and recycle as a catalyst, and has narrow photoresponse range when being used as a photocatalyst and the like: (1) a phthalocyanine derivative modified surfactant and a preparation method thereof; (2) a phthalocyanine derivative modified surfactant combined polyoxometallate compound and a preparation method thereof; (3) the prepared phthalocyanine derivative modified surfactant and polyoxometallate compound self-assembly nano material and a preparation method thereof.
Dawson type phosphotungstate K used in the present invention6 [α-P2W18O62]·14H2O according to The reference [ Graham C R, Finke R G, The classic Wells-Dawson polyoxometalate, K6[alpha-P2W18O62].14H2O. Answering an 88 year-old question: what is its preferred, optimum synthesis[J]. Inorganic Chemistry, 2008, 47(9): 3679-3686]Preparing; k used10[α-P2W17O61]·20H2O (abbreviated as P)2W17) According to the literature [ cyanine, preparation of covalently bonded polyacid/naphthalene and porphyrin hybrid materials and research on photoelectric properties [ D]Hubei: 2014: 23-24 of Hubei university]Preparing; the Waugh type phosphotungstate Na is used3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O according to the reference [ Lv H, Gao Y, Guo W, et al. Cu-based Polyoxometalate Catalyst for Efficient Catalytic Hydrogen Evolution [ J]. Inorganic Chemistry, 2016, 55(13): 6750.]Preparing; the phthalocyanine derivatives (MNPc) used are based on the simple synthesis and characterization of two tetraamino zinc phthalocyanine isomers according to the reference [ Congress, Du-tin-light, Zhao-Bao, et al. ] [ J]The higher school journal of chemistry 2002,23(12): 2221-2225.]Preparing; the 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol) is used according to the reference [ Zhang jiao. Anthracene modified surfactant/polymetallic oxygen cluster compound light-controlled self-assembly [ D]Jilin: jilin university, 2015: 19-21.]And (4) preparation.
The invention is realized by adopting the following technical scheme: a phthalocyanine derivative-modified surfactant which is a phthalocyanine derivative-modified double-stranded cationic surfactant, the phthalocyanine derivative being: a tetra-beta- (4-nitro) metal phthalocyanine MNPc, wherein NPc is tetra-beta- (4-nitro) phthalocyanine; m = any one of Fe, Co, Mn, Zn, Ni, or Cu; the double-chain cationic surfactant is 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol).
The method for preparing the phthalocyanine derivative modified surfactant comprises the following specific steps: dissolving 0.5-1.00 g of phthalocyanine derivative MNPc in 30-55 mL of DMSO, adding 20-45 mL of DMSO solution in which a certain amount of DDAB-11-ol is dissolved, and introducing N2Heating to 45-55 deg.C for 20-30 min, reacting for 0.5-1.5 hr under magnetic stirring, and mixing with 0.36-0.41 g K2CO3Adding the raw materials into the reaction system in four batches within two hours, monitoring the reaction process by a point plate, finishing the reaction after DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 400-500 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product by using ethanol, filtering to remove unreacted phthalocyanine derivatives, performing rotary evaporation on the filtrate, and drying to obtain the phthalocyanine derivative modified double-chain cationic surfactant MNPc-O-DDAB. Wherein the molar ratio of MNPc to DDAB-11-ol is 1:2-3: 1.
The phthalocyanine derivative modified surfactant is MNPc-O-DDAB prepared by the method, and the polyoxometallate POM is Keggin type phosphotungstic acid H3PW12O40·xH2O, Dawson type phosphotungstate K6 [α-P2W18O62]·14H2O, Dawson type phosphotungstate K10[α-P2W17O61]·20H2O or Waugh type phosphotungstate Na3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O。
The preparation method of the phthalocyanine derivative modified surfactant combined polyoxometallate compound comprises the following specific steps: dissolving 0.05-0.1 g of MNPc-O-DDAB in 50-70 mL of absolute ethyl alcohol, dropwise adding 40-50mL of aqueous solution containing POM under magnetic stirring, reacting for 8-12 h, centrifuging the reaction solution, successively washing for 3-5 times by using the absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the compound MNPc-O-DDAB/POM of the phthalocyanine derivative modified double-chain cationic surfactant combined with polyoxometallate. Wherein the molar ratio of MNPc-O-DDAB to POM is 1:6-3: 1.
The preparation method of the self-assembly nano material in the solution by combining the phthalocyanine derivative modified surfactant and the polyoxometallate compound comprises the following specific steps: fully dissolving 0.004 g of MNPc-O-DDAB/POM in 4-10 mL of good solvent, adding 1-8mL of poor solvent under the condition of ultrasound/oscillation, and standing for 30 min after 10-15 min of ultrasound/oscillation to obtain a self-assembly solution;
Centrifuging the self-assembly solution at 25 deg.C and 8000rpm for 10-15 min, dispersing the precipitate in 10-20 ml deionized water, standing for 60-120 min, and centrifuging at 25 deg.C and 8000rpm to obtain spindle-shaped or spherical MNPc-O-DDAB/POM self-assembly material; or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160-200 ℃ for 10-12 h to obtain the stable shuttle-shaped or spherical MNPc-O-DDAB/POM self-assembly material. Wherein the good solvent is dimethyl sulfoxide DMSO and N, N-dimethylformamide DMF treated by anhydrous magnesium sulfate; the poor solvent is water or carbon tetrachloride.
Compared with the prior art, the invention has the following remarkable advantages: (1) the invention adopts the phthalocyanine derivative to modify the double-chain cationic surfactant, and the modified surfactant keeps the spectroscopic property of the phthalocyanine; (2) the phthalocyanine derivative modified double-chain cationic surfactant is combined with polyoxometallate to form a compound, so that the aggregation of phthalocyanine in a solution can be avoided, and the dispersibility of the phthalocyanine in the solution is improved; in addition, in ZnTNPc-O-DDAB/PW12In the compound, ZnTNPc and PW12Remain unchanged and retain the respective light absorption due to ZnTNPc and PW12The compound has better photocatalytic activity, so the compound is supposed to integrate the photocatalytic activity of phthalocyanine and the photocatalytic function of POM; (3) the phthalocyanine derivative modified double-chain cationic surfactant and polyoxometallate compound are self-assembled in solution to obtain nano materials with different morphologies, and the nano materials have important significance for application as photocatalytic materials and the like.
In order to illustrate the chemical structures of the phthalocyanine derivative modified double-stranded cationic surfactant (MNPc-O-DDAB) and the phthalocyanine derivative modified double-stranded cationic surfactant and polyoxometallate complex (MNPc-O-DDAB/POM), the present invention is further illustrated with reference to the attached drawings.
Drawings
FIG. 1 is an infrared spectrum of ZnNPc, ZnNPc-O-DDAB, DDAB-11-ol. As can be seen from the spectrogram of ZnNPc, it is 1083 cm-1、837 cm-1、744 cm-1Is located at 1522 cm of the vibration peak of the skeleton of phthalocyanine-1、1337 cm-1Is a symmetric telescopic absorption peak of nitro on phthalocyanine ring, 1609 cm-1Is the stretching vibration peak of benzene ring, 1489 cm-1Is C-N stretching vibration peak. From the spectrogram of DDAB-11-ol, at 2919 cm-1And 2850 cm-11466 cm from symmetric and asymmetric absorption peak of stretching vibration due to methylene-1Shear mode vibration absorption peak at 724 cm of methylene-1And an in-plane bending vibration absorption peak of methylene. 1609 cm in the infrared spectrogram of ZnNPc-O-DDAB-1、1486 cm-1、746 cm-1Respectively shows an absorption peak on a phthalocyanine ring, 2924 cm-1、2852 cm-1An absorption peak of DDAB-11-ol appeared, indicating that ZnNPc has been bonded to DDAB-11-ol to form ZnNPc-O-DDAB.
FIG. 2 is a view of ZnNPc-O-DDAB1H-NMR spectrum, shift of hydrogen protons on the methyl group at the end of ZnNPc-O-DDAB chain at δ =0.86 (b), on the two methyl groups on the nitrogen atom of the quaternary amine at δ =2.96 (c), δ =3.36 (d) on the methylene group adjacent to O, δ =1.63 (e) on the two methylene groups adjacent to the methylene group connected to the end O, δ =3.19 (f) on the two methylene groups on the nitrogen atom of the quaternary amine. g. h and i are chemical shifts on a long alkyl chain, which are attributed to the shift of hydrogen protons on DDAB-11-ol, and besides, the shift of hydrogen protons j-u on a phthalocyanine ring appears in a range of delta =6.0-8.5, thereby also indicating that ZnNPc-O-DDAB has been successfully synthesized.
FIG. 3 shows ZnNPc-O-DDAB, PW12、ZnNPc-O-DDAB/PW12Infra-red spectrograms, PW12At 1080, 982, 889 and 805 cm-1The absorption at four positions is P-Oa (tetrahedral oxygen) stretching vibration, W = Od (terminal oxygen)The antisymmetric stretching vibration peak of W-Ob-W (oxygen shared by the tops of different trimetal clusters) and W-Oc-W (oxygen shared by the same trimetal cluster). At 1609, 1487, 745cm-1Is the absorption peak of the phthalocyanine ring. When PW is generated12After forming a complex with ZnNPc-O-DDAB, due to PW12Electrostatic interaction exists between the outer negatively charged O atom and the N atom of the positively charged quaternary ammonium salt of ZnNPc-O-DDAB, which causes PW12The characteristic absorption peak of (A) slightly shifts to 1089 cm respectively-1、978 cm-1、894 cm-1And 817 cm-1。ZnNPc-O-DDAB/PW12In the compound, both PW and beta-cyclodextrin are retained12The basic framework structure of the ZnNPc-O-DDAB is not damaged at the same time, which shows that the ZnNPc-O-DDAB/PW is formed12And (c) a complex.
FIG. 4 shows that different concentrations of PW are added into ZnTNPc-O-DDAB solution12Fluorescence emission spectrum of (a). As can be seen from the fluorescence spectrum of ZnTNPc-O-DDAB in FIG. 4, the fluorescence emission intensity of ZnTNPc-O-DDAB at 700 nm varies with PW12The increase in concentration is substantially in an increasing trend. The increase in fluorescence intensity is probably due to the fact that when PW is used12When the concentration is increased, the nano-particles and ZnTNPc-O-DDAB have electrostatic interaction, thus reducing aggregation caused by accumulation of the ZnTNPc-O-DDAB pi-pi, improving the dispersibility of the nano-particles in a solution and increasing the fluorescence emission of the ZnTNPc.
FIG. 5 shows ZnTNPc, ZnTNPc-O-DDAB, PW12、ZnTNPc-O-DDAB/PW12In DMSO and H2O mixed solvent (V)DMSO : VH2OElectron absorption spectrum in =4: 1). From PW12Can be seen in the spectrogram, PW12O in (1)dThe → W characteristic charge shift is caused by its absorption peak transition at 266 nm, which has no absorption in the visible range; the absorption peaks of ZnTNPc at 256 nm and 347 nm are a1uTo egThe characteristic absorption peak of B band caused by (pi) low-energy transition is a2uTo eg(π) characteristic absorption peak of Q band due to high energy transition. While the electron absorption spectrum of ZnTNPc-O-DDAB is almost the same as that of ZnTNPc, and characteristic absorption peaks of the B band and the Q band of ZnTNPc appear at 347 nm and 693 nm.ZnTNPc-O-DDAB/PW12The absorption spectrum of the compound shows both the absorption peak of ZnTNPc and PW12absorption peak of, i.e. broadening PW12Absorption into the visible region.
In order to illustrate the self-assembly behavior of the phthalocyanine derivative modified double-chain cationic surfactant and the polyoxometalate complex in the solution, the invention is further illustrated with reference to the attached drawings.
FIG. 6 shows ZnNPc-O-DDAB/PW12Field emission Scanning Electron Microscopy (SEM) of self-assemblies of the composites. In the figure: a, b are ZnNPc-O-DDAB/PW12Complex in DMSO/H2Structure of assembly in O (V: V =4: 1); c, d is a secondary assembly structure of the centrifugal precipitation of the primary self-assembly liquid and 10ml of water; e and f are assembly structures of the secondary assembly through hydrothermal reaction for 10 hours at 180 ℃.
From fig. 6 (a, b) it is seen that the composite assembled in mixed solvent forms a multi-layer densely packed network 100 nm wide. FIG. 6 (c, d) is an SEM image of a self-assembly liquid centrifugally precipitated solid dispersed in an aqueous solution, and the aggregates formed small spheres and fusiform aggregates in the aqueous solution. Fig. 6 (e, f) is an SEM image of the self-assembled pellet and spindle shaped aggregate after hydrothermal treatment, still pellet and spindle shaped aggregate.
Detailed Description
The preparation method of the phthalocyanine derivative modified surfactant combined polyoxometallate composite is illustrated by the following example.
Example 1: preparation of phthalocyanine derivative modified surfactant: the phthalocyanine derivative modified surfactant is a double-chain cationic surfactant modified by a phthalocyanine derivative, and the phthalocyanine derivative is: a tetra-beta- (4-nitro) metal phthalocyanine MNPc, wherein NPc is tetra-beta- (4-nitro) phthalocyanine; m = any one of Fe, Co, Mn, Zn, Ni, or Cu; the double-chain cationic surfactant is 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol).
The specific method comprises the following steps: 1 g (1.34 mmol) of MnNPc is dissolved in 30mL of DMSO, filtered through a filter membrane and added to a reactor, and then a solution of 0.21 g (0.45 mmol) of DDAB-11-ol in 20 mL of DMSO is added, and N is introduced2 Heating to 45 deg.C for 20 min, reacting for 0.5 h under magnetic stirring, and mixing with 0.36 g K2CO3Adding the mixture into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction when DDAB-11-ol in the system completely reacts, pouring the reaction liquid into 400 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted MnNPc, performing rotary evaporation on the filtrate, and drying to obtain the MnNPc-O-DDAB product.
Preparing a phthalocyanine derivative modified surfactant combined polyoxometallate compound: 0.09 g (0.08 mmol) MnNPc-O-DDAB is dissolved in 50mL absolute ethanol, and 40 mL of a solution containing 0.19 g (0.04mmol) K is added dropwise with magnetic stirring6 [α-P2W18O62]·14H2Reacting the O water solution for 12 hours, centrifuging the reaction solution, washing the reaction solution for 3 times by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain MnNPc-O-DDAB/P2W18And (c) a complex.
Example 2: 0.8 g (1.06 mmol) of CoNPc was dissolved in 40 mL of DMSO, filtered through a filter and added to the reactor, and a solution of 0.27 g (0.59 mmol) of DDAB-11-ol in 30mL of DMSO was added thereto, followed by N-sparging2 Heating to 49 deg.C for 24 min, reacting for 1 h under magnetic stirring, and mixing with 0.38 g K2CO3Adding the reaction solution into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction after DDAB-11-ol in the system completely reacts, pouring the reaction solution into 450mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted CoNPc, performing rotary evaporation on the filtrate, and drying to obtain a CoNPc-O-DDAB product.
0.07 g (0.06 mmol) of CoNPc-O-DDAB was dissolved in 60 mL of anhydrous ethanol, and 50mL of a solution containing 0.58 g (0.12 mmol) of K was added dropwise with magnetic stirring10[α-P2W17O61]·20H2Reacting the aqueous solution of O for 10 hours, centrifuging the reaction solution, washing the reaction solution for 5 times by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain CoNPc-O-DDAB/P2W17And (c) a complex.
Example 3: 0.9 g (1.20 mmol) of FeNPc is dissolved in 35 mL of DMSO, filtered through a filter membrane, added to the reactor, and addedA solution of 0.28 g (0.60 mmol) DDAB-11-ol in 25 mL DMSO and N was passed through2 Heating to 47 deg.C for 22 min, reacting for 1 hr under magnetic stirring, and mixing with 0.37 g K2CO3Adding the mixture into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction when DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 430mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted FeNPc, performing rotary evaporation on the filtrate, and drying to obtain a FeNPc-O-DDAB product.
0.1 g (0.09 mmol) of FeNPc-O-DDAB are dissolved in 55 mL of absolute ethanol and 45 mL of a solution containing 0.09 g (0.03mmol) of H are added dropwise with magnetic stirring3PW12O40·xH2Reacting the O aqueous solution for 11 hours, centrifuging the reaction solution, washing the reaction solution for 4 times by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain FeNPc-O-DDAB/PW12And (c) a complex.
Example 4: 0.5 g (0.67 mmol) of NiNPc was dissolved in 45 mL of DMSO, filtered through a filter and added to the reactor, and a solution of 0.62 g (1.34 mmol) of DDAB-11-ol in 35 mL of DMSO was added thereto, followed by N-sparging2 Heating to 51 deg.C for 26 min, reacting for 1.5 h under magnetic stirring, and mixing with 0.39 g K2CO3Adding the mixture into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction when DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 470 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted NiNPc, performing rotary evaporation on the filtrate, and drying to obtain the NiNPc-O-DDAB product.
0.06 g (0.05 mmol) of NiNPc-O-DDAB is dissolved in 65 mL of absolute ethanol and 50mL of a solution containing 0.58 g (0.20 mmol) of H are added dropwise with magnetic stirring3PW12O40·xH2Reacting the aqueous solution of O for 9 h, centrifuging the reaction solution, washing with anhydrous ethanol and deionized water for 4 times, and drying to obtain NiNPc-O-DDAB/PW12And (c) a complex.
Example 5: 0.6 g (0.79 mmol) of CuNPc is dissolved in 50mL of DMSO, filtered through a filter and added to the reactor, and a solution of 0.37 g (0.79 mmol) of DDAB-11-ol in 45 mL of DMSO is added, and N is added2 Heating to 53 deg.C for 28 min, reacting for 1.5 h under magnetic stirring, and mixing with 0.40 g K2CO3Adding the mixture into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction when DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 490 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted CuNPc, performing rotary evaporation on the filtrate, and drying to obtain a CuNPc-O-DDAB product.
0.08 g (0.07 mmol) of CuNPc-O-DDAB is dissolved in 70 mL of absolute ethanol, and 40 mL of a solution containing 0.38 g (0.07 mmol) of Na is added dropwise with magnetic stirring3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2Reacting the water solution of O for 8 hours, centrifuging the reaction solution, washing the reaction solution for 3 times by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain CuNPc-O-DDAB/Na3K7-Cu4P2And (c) a complex.
Example 6: 0.73 g (0.96 mmol) of ZnNPc is dissolved in 30mL of DMSO, filtered through a filter membrane and added to the reactor, a solution of 0.30 g (0.65 mmol) of DDAB-11-ol in 20 mL of DMSO is added, and N is added2 Heating to 55 deg.C for 30 min, reacting for 1.5 hr under magnetic stirring, and mixing the obtained mixture with 0.41 g K2CO3Adding the mixture into a reactor in four batches within two hours, monitoring the reaction process through a point plate, finishing the reaction after DDAB-11-ol in the system completely reacts, pouring the reaction liquid into 500 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product with ethanol, filtering to remove unreacted ZnNPc, performing rotary evaporation on the filtrate, and drying to obtain a ZnNPc-O-DDAB product.
0.05 g (0.04mmol) ZnNPc-O-DDAB is dissolved in 50mL absolute ethanol and 45 mL H containing 0.69 g (0.24 mmol) is added dropwise with magnetic stirring3PW12O40·xH2Reacting the O aqueous solution for 12 hours, centrifuging the reaction solution, washing the reaction solution for 3 times by using absolute ethyl alcohol and deionized water in sequence, and drying to obtain ZnNPc-O-DDAB/PW12And (c) a complex.
The results are shown in FIGS. 3, 4 and 5, in ZnTNPc-O-DDAB/PW12In the compound, ZnTNPc and PW12Remains unchanged and remainsrespective light absorption is due to ZnTNPc and PW12Since the compound itself has a good photocatalytic activity, it is presumed that the photocatalytic activity of phthalocyanine and the photocatalytic function of POM are integrated.
The self-assembly behavior of MNPc-O-DDAB/POM in solution is illustrated by way of example below.
Example 7: 0.004 g of ZnNPc-O-DDAB/PW12After being well dissolved in 8ml of DMSO, 2 ml of H was added under sonication/shaking2And O, standing for 30 min after ultrasonic/oscillation for 15 min to obtain a self-assembly solution, and observing that the assembly forms a multi-layer densely-packed net structure with the width of about 100 nm by a Scanning Electron Microscope (SEM). Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 15 min, dispersing the precipitate in 10ml deionized water, standing for 60 min, and centrifuging to obtain spindle or spherical ZnNPc-O-DDAB/PW12The self-assembly material is observed by a Scanning Electron Microscope (SEM) that the secondary assembly of the assembly gradually forms a fusiform structure of about 6 mu m and a spherical structure of about 300 nm. Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 180 ℃ for 10 h to obtain ZnNPc-O-DDAB/PW with a fusiform structure of about 1 mu m and a spherical structure of about 200 nm12A self-assembling material.
Example 8: 0.004 g of MnNPc-O-DDAB/P2W18After fully dissolving in 10ml of DMSO, 1 ml of H was added under sonication/shaking2And O, standing for 30 min after ultrasonic/oscillation for 14 min to obtain a self-assembly solution, and observing assembly through a Scanning Electron Microscope (SEM) to form regular and uniform spherical aggregates with the size of about 300 nm. Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 14 min, dispersing the precipitate in 20 ml deionized water, standing for 120 min, and centrifuging to obtain spindle or spherical MnNPc-O-DDAB/P2W18The self-assembled material is observed to form relatively uniform small spheres of about 10 nm by a Scanning Electron Microscope (SEM). Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160 ℃ for 12 h to obtain more stable spherical MnNPc-O-DDAB/P with the particle size of about 10 nm2W18A self-assembling material.
Example 9: 0.004 g of NiNPc-O-DDAB/PW12Fully dissolved in 4 ml of DMSO, then 8ml of H was added under sonication/shaking2And O, standing for 30 min after performing ultrasonic/oscillation for 13 min to obtain a self-assembly solution, and observing assembly through a Scanning Electron Microscope (SEM) to form a sticky large ball with the diameter of about 200 nm. Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 13 min, dispersing the precipitate in 15 ml deionized water, standing for 100 min, and centrifuging to obtain shuttle-shaped or spherical NiNPc-O-DDAB/PW12The self-assembled material was observed by Scanning Electron Microscopy (SEM) to form dispersed beads of about 50 nm. Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 170 ℃ for 11 h to obtain more stable spherical NiNPc-O-DDAB/PW with the particle size of about 30 nm12A self-assembling material.
Example 10: 0.004 g of CoNPc-O-DDAB/P2W17After fully dissolving in 8ml of DMF, 2 ml of CCl were added under sonication/shaking4Standing for 30 min after 12 min of ultrasonic/oscillation to obtain a self-assembly solution, and observing and assembling the self-assembly solution into a sticky spherical structure with the size of about 500 nm by a Scanning Electron Microscope (SEM). Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 12 min, dispersing the precipitate in 10ml deionized water, standing for 90 min, and centrifuging to obtain spindle or spherical CoNPc-O-DDAB/P2W17The self-assembly material is observed to form a bead structure which is adhered by about 50nm through a Scanning Electron Microscope (SEM). Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 200 ℃ for 10 h, and observing that the assembly forms CoNPc-O-DDAB/P with a dispersed globular structure of about 40 nm through a Scanning Electron Microscope (SEM)2W17A self-assembling material.
Example 11: 0.004 g of CuNPc-O-DDAB/Na3K7-Cu4P2Fully dissolved in 8ml of DMSO, then added with 2 ml of CCl under sonication/shaking4And standing for 30 min after ultrasonic/oscillation for 15 min to obtain a self-assembly solution, and observing assembly through a Scanning Electron Microscope (SEM) to form spherical and blocky aggregates with regular shapes. Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 12 min, dispersing the precipitate in 15 ml deionized water, standing for 90 min, and centrifuging to obtain fusiform orSpherical CuNPc-O-DDAB/Na3K7-Cu4P2The self-assembled material was observed to form a sphere of about 100 nm by Scanning Electron Microscopy (SEM). Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160 ℃ for 10 h, and observing that the assembly forms CuNPc-O-DDAB/Na with a spherical structure of about 50nm through a Scanning Electron Microscope (SEM)3K7-Cu4P2A self-assembling material.
Example 12: 0.004 g of FeNPc-O-DDAB/PW12After being fully dissolved in 8ml of DMF, 2 ml of H was added under sonication/shaking2And O, standing for 30 min after ultrasonic/oscillation for 10 min to obtain a self-assembly solution, and observing assembly through a Scanning Electron Microscope (SEM) to form a spherical aggregate which is adhered at about 150 nm. Centrifuging the self-assembly solution at 8000rpm (25 deg.C) for 10 min, dispersing the precipitate in 20 ml deionized water, standing for 80 min, and centrifuging to obtain spindle or spherical FeNPc-O-DDAB/PW12The self-assembled material was observed by Scanning Electron Microscopy (SEM) to form small spheres dispersed at about 60 nm. Or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 180 ℃ for 12 h, and observing that the assembly forms FeNPc-O-DDAB/PW with a dispersed globular structure of about 40 nm through a Scanning Electron Microscope (SEM)12A self-assembling material.
Claims (8)
1. A phthalocyanine derivative-modified surfactant characterized by: the phthalocyanine derivative modified surfactant is a double-chain cationic surfactant modified by a phthalocyanine derivative, and the phthalocyanine derivative is: a tetra-beta- (4-nitro) metal phthalocyanine MNPc, wherein NPc is tetra-beta- (4-nitro) phthalocyanine; m = any one of Fe, Co, Mn, Zn, Ni, or Cu; the double-chain cationic surfactant is 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol).
2. A method of preparing a phthalocyanine derivative-modified surfactant according to claim 1, comprising: the method comprises the following steps: dissolving 0.5-1.00 g of MNPc in 30-55 mL of DMSO, adding 20-45 mL of DMSO solution containing DDAB-11-ol, and introducing N2Heating for 20-30 min to 45-55Reacting at 0.5-1.5 hr under magnetic stirring, and mixing at 0.36-0.41 g K deg.C2CO3Adding the raw materials into the reaction system in four batches within two hours, monitoring the reaction process by a point plate, finishing the reaction after DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 400-500 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product by using ethanol, filtering to remove unreacted phthalocyanine derivatives, performing rotary evaporation on the filtrate, and drying to obtain the phthalocyanine derivative modified double-chain cationic surfactant MNPc-O-DDAB.
3. The method for producing a phthalocyanine derivative-modified surfactant according to claim 2, wherein: the molar ratio of MNPc to DDAB-11-ol is 1:2-3: 1.
4. A phthalocyanine derivative-modified surfactant-bound polyoxometalate complex, the phthalocyanine derivative-modified surfactant being MNPc-O-DDAB prepared according to claim 2, characterized in that: the polyoxometallate POM is Keggin type phosphotungstic acid H3PW12O40·xH2O, Dawson type phosphotungstate K6 [α-P2W18O62]·14H2O, Dawson type phosphotungstate K10[α-P2W17O61]·20H2O or Waugh type phosphotungstate Na3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O。
5. A method of preparing a phthalocyanine derivative-modified surfactant-bound polyoxometalate complex as claimed in claim 4, wherein: the method comprises the following specific steps: dissolving 0.05-0.1 g of MNPc-O-DDAB in 50-70 mL of absolute ethyl alcohol, dropwise adding 40-50mL of aqueous solution containing POM under magnetic stirring, reacting for 8-12 h, centrifuging the reaction solution, successively washing for 3-5 times by using the absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the compound MNPc-O-DDAB/POM of the phthalocyanine derivative modified double-chain cationic surfactant combined with polyoxometallate.
6. The method of preparing a phthalocyanine derivative-modified surfactant-bound polyoxometalate complex as claimed in claim 5, wherein: the molar ratio of the MNPc-O-DDAB to the POM is 1:6-3: 1.
7. The method for preparing a self-assembly material in solution from a phthalocyanine derivative modified surfactant-bound polyoxometalate complex prepared in claim 5, characterized in that: the specific method comprises the following steps: fully dissolving 0.004 g of MNPc-O-DDAB/POM in 4-10 mL of good solvent, adding 1-8mL of poor solvent under the condition of ultrasound/oscillation, and standing for 30 min after 10-15 min of ultrasound/oscillation to obtain a self-assembly solution;
Centrifuging the self-assembly solution at 25 deg.C and 8000rpm for 10-15 min, dispersing the precipitate in 10-20 ml deionized water, standing for 60-120 min, and centrifuging at 25 deg.C and 8000rpm to obtain spindle-shaped or spherical MNPc-O-DDAB/POM self-assembly material; or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160-200 ℃ for 10-12 h to obtain the stable shuttle-shaped or spherical MNPc-O-DDAB/POM self-assembly material.
8. The method for preparing the self-assembly material of the phthalocyanine derivative modified surfactant-bound polyoxometalate complex in solution according to claim 7, wherein: the good solvent is dimethyl sulfoxide DMSO and N, N-dimethylformamide DMF processed by anhydrous magnesium sulfate; the poor solvent is water or carbon tetrachloride.
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Cited By (2)
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| CN114891346A (en) * | 2022-05-16 | 2022-08-12 | 吉林大学 | Polylysine compound based on molybdic acid and application of polylysine compound in antibacterial field |
| CN114891346B (en) * | 2022-05-16 | 2023-12-19 | 吉林大学 | Polylysine compound based on molybdenum polyacid and application thereof in antibacterial field |
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