CN108014850A - A kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst - Google Patents
A kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst Download PDFInfo
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- CN108014850A CN108014850A CN201711210324.8A CN201711210324A CN108014850A CN 108014850 A CN108014850 A CN 108014850A CN 201711210324 A CN201711210324 A CN 201711210324A CN 108014850 A CN108014850 A CN 108014850A
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- Prior art keywords
- supermolecule
- photochemical catalyst
- phenyl porphyrin
- tetracarboxylic
- tetracarboxylic phenyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005286 illumination Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000010865 sewage Substances 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 206010028980 Neoplasm Diseases 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 201000011510 cancer Diseases 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002504 physiological saline solution Substances 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000004032 porphyrins Chemical class 0.000 claims description 6
- 238000002513 implantation Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 238000011109 contamination Methods 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- RCEXBQFQNWFTDN-UHFFFAOYSA-N N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(C(=O)O)=C2C1=CC=CC=C1 Chemical compound N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(C(=O)O)=C2C1=CC=CC=C1 RCEXBQFQNWFTDN-UHFFFAOYSA-N 0.000 claims 3
- 239000011941 photocatalyst Substances 0.000 claims 3
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 abstract description 47
- 239000000463 material Substances 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000192 social effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 210000004881 tumor cell Anatomy 0.000 abstract 1
- 230000001093 anti-cancer Effects 0.000 description 22
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000000338 in vitro Methods 0.000 description 10
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 239000001963 growth medium Substances 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000001429 visible spectrum Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
- A61K41/0071—PDT with porphyrins having exactly 20 ring atoms, i.e. based on the non-expanded tetrapyrrolic ring system, e.g. bacteriochlorin, chlorin-e6, or phthalocyanines
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The present invention relates to a kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, belong to technical field of nano material.Preparation method is：TCPP raw materials are dissolved by heating using certain density KOH aqueous solutions, under rapid stirring, dilute hydrochloric acid are added dropwise while hot into solution, natural cooling, makes solid fully separate out, and is collected by filtration, vacuum drying.TCPP supermolecules photochemical catalyst good biocompatibility produced by the present invention, spectrum efficiency are high, aqueous phase dispersibility protrudes, widely used, have important social effect and application value.The material quickly can kill tumour cell under red light irradiation, have greatly medical meaning；The material efficient degradation can handle organic pollution under light illumination, have the great value of environmental protection；The material can also efficient-decomposition water under light illumination, discharge hydrogen and oxygen, there is great industrial value.
Description
Technical field
The present invention relates to a kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, belong to nanometer
Field of material technology.
Background technology
Tetracarboxylic phenyl porphyrin (tetracarboxylphenyl porphyrin, hereinafter referred to as TCPP) is that one kind has
The organic conjugated molecule of excellent hydrophilic, biocompatibility.Due to the conjugation delocalization structure that intramolecular is larger, TCPP is in visible ray
In the range of have strong absorption, absorption region (400~700nm) substantially covers whole visible spectrums.Therefore, TCPP exists
Organic photoelectric field is widely used.The big π systems of TCPP molecules so that its is intermolecular there are strong pi-pi accumulation effect, then
Add the hydrogen bond action between the position carboxyl of end, assemble to form supramolecular structure for TCPP molecules, there is provided the guarantee of active force.
The content of the invention
The purpose of the present invention is to propose to a kind of preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst,
By simple crystallization of the dissolution and precipitation technique, the TCPP supermolecule photochemical catalysts of hydrophilic, bio-compatible, high activity are prepared, to utilize
The visible light-responded performance of the material, can be widely used in the technology necks such as medical treatment, sewage disposal, clean energy resource production
Domain.And point out its purposes having now been found that.
The preparation method of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst proposed by the present invention, includes the following steps：
(1) at 50-80 DEG C, it is completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution is
0.5~5molL-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 0.1~2molL-1, it is neutrality to reaction system；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 70~90 DEG C, and drying time is
When 4-12 is small, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is obtained.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to treatment of cancer, apply
Process comprises the following steps：
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 1-500 μ gmL-1；
(2) dispersion liquid configured is directly injected into inside tumor with syringe, is 1 μ by the implantation dosage of gross tumor volume
L/mm3；
(3) tumor locus for having dispersion liquid to injection carries out positioning illumination, illumination wavelength 500-800nm, light application time
For 10 minutes.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to sewage disposal, apply
Process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl are added in the sewage that organic contamination produces
The addition mass volume ratio of porphyrin supermolecule photochemical catalyst is 0.5~5g/L；
(2) it is sufficiently stirred, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is uniformly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time reach row for sewage
Put standard.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to clean energy resource production,
Application process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin supermolecule photocatalysis are added in water
The addition mass volume ratio of agent is according to 0.05~2g/L；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is tetracarboxylic phenyl porphyrin
The 10 of supermolecule photochemical catalyst2-105Times, the sacrifice agent is any in silver nitrate, ferrous nitrate, triethanolamine or lactic acid
It is a kind of；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output hydrogen or oxygen.
The preparation method and applications of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst proposed by the present invention, its advantage are：
1st, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, compared to general organic photocatalysis
Agent, for supramolecular materials because compound with regular structure, structural approach is single, and crystallinity is high, therefore possesses more preferable photo-generated carrier separation
Effect, possesses more excellent photocatalysis performance.Using the intermolecular active forces of TCPP, make the supermolecule photochemical catalyst of TCPP have
Very high application value.And photocatalysis has the characteristics that safe and environment-friendly, efficient, to prepare present invention tetracarboxylic phenyl
The application prospect of porphyrin supermolecule photochemical catalyst is boundless.
2nd, the method for the present invention is prepared for tetracarboxylic phenyl porphyrin supermolecule photocatalysis by simple crystallization of the dissolution and precipitation technique
Agent, and preparation method is easy to operate, is easy to repeat, and solves the problems such as cumbersome preparing for organic photochemical catalyst, low output, is
Commercial applications provide good technical foundation and material guarantee.
3rd, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, has hydrophilic, bio-compatible, visible
The excellent properties such as photo absorption property, therefore there is extensive use in fields such as medical treatment, sewage disposal and clean energy resource generations, pass through
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by red light irradiation this method, has killing effect, for cancer to cancer cell
Disease has therapeutic effect；Under visible light illumination for the degradation of organic pollution, therefore have for environmental contaminants and control
Manage effect；By radiation of visible light, water can be decomposed, discharge hydrogen and oxygen, therefore can be used for production cleaning energy
Source.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of the TCPP supermolecule photochemical catalysts prepared in embodiment 1.
Fig. 2 is the high resolution transmission electron microscopy photo of the TCPP supermolecule photochemical catalysts prepared in embodiment 1.
Fig. 3 is the selective electron diffraction pattern of the TCPP supermolecule photochemical catalysts prepared in embodiment 1.
Fig. 4 is the high resolution transmission electron microscopy photo of the TCPP supermolecule photochemical catalysts prepared in embodiment 1.
Fig. 5 is the high resolution transmission electron microscopy photo of the TCPP supermolecule photochemical catalysts prepared in embodiment 2.
Fig. 6 is the selective electron diffraction pattern of the TCPP supermolecule photochemical catalysts prepared in embodiment 2.
Fig. 7 is 5 μ gmL in embodiment 3-1The feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts.
Fig. 8 is 10 μ gmL in embodiment 4-1The feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts.
Fig. 9 is 15 μ gmL in embodiment 5-1The feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts.
Figure 10 is 20 μ gmL in embodiment 6-1The feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts.
Figure 11 is 25 μ gmL in embodiment 7-1The feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts.
Figure 12 is that the feux rouges of TCPP supermolecule photochemical catalysts in embodiment 8 drives biological living anti-cancer applications.
Figure 13 is the Photocatalytic Degradation of Phenol sewage of TCPP supermolecule photochemical catalysts in embodiment 9.
Figure 14 is the photocatalytic degradation bisphenol-A sewage of TCPP supermolecule photochemical catalysts in embodiment 10.
Figure 15 is the photocatalytic degradation 2,4- Dichlorophenol sewage of TCPP supermolecule photochemical catalysts in embodiment 11.
Figure 16 is the photocatalysis hydrogen gas production using lactic acid as the TCPP supermolecule photochemical catalysts of sacrifice agent in embodiment 12.
Figure 17 is that the photocatalysis hydrogen in embodiment 13 using triethanolamine as the TCPP supermolecule photochemical catalysts of sacrifice agent is given birth to
Production.
Figure 18 is that the photocatalysis oxygen in embodiment 14 using ferrous nitrate as the TCPP supermolecule photochemical catalysts of sacrifice agent is given birth to
Production.
Figure 19 is the photocatalysis oxygen production using silver nitrate as the TCPP supermolecule photochemical catalysts of sacrifice agent in embodiment 15.
Embodiment
The preparation method of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst proposed by the present invention, includes the following steps：
(1) at 50-80 DEG C, it is completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution is
0.5~5molL-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 0.1~2molL-1, it is neutrality to reaction system；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 70~90 DEG C, and drying time is
When 4-12 is small, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is obtained.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to treatment of cancer, apply
Process comprises the following steps：
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 1-500 μ gmL-1；
(2) dispersion liquid configured is directly injected into inside tumor with syringe, is 1 μ by the implantation dosage of gross tumor volume
L/mm3；
(3) tumor locus for having dispersion liquid to injection carries out positioning illumination, illumination wavelength 500-800nm, light application time
For 10 minutes.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to sewage disposal, apply
Process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl are added in the sewage that organic contamination produces
The addition mass volume ratio of porphyrin supermolecule photochemical catalyst is 0.5~5g/L；
(2) it is sufficiently stirred, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is uniformly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time reach row for sewage
Put standard.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to clean energy resource production,
Application process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin supermolecule photocatalysis are added in water
The addition mass volume ratio of agent is according to 0.05~2g/L；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is tetracarboxylic phenyl porphyrin
The 10 of supermolecule photochemical catalyst2-105Times, the sacrifice agent is any in silver nitrate, ferrous nitrate, triethanolamine or lactic acid
It is a kind of；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output hydrogen or oxygen.
The preparation method of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst proposed by the present invention, includes the following steps：
(1) at 50-80 DEG C, it is completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution is
0.5~5molL-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 0.1~2molL-1, it is neutrality to reaction system；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 70~90 DEG C, and drying time is
When 4-12 is small, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is obtained.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to treatment of cancer, apply
Process comprises the following steps：
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 1-500 μ gmL-1；
(2) dispersion liquid configured is directly injected into inside tumor with syringe, is 1 μ by the implantation dosage of gross tumor volume
L/mm3；
(3) tumor locus for having dispersion liquid to injection carries out positioning illumination, illumination wavelength 500-800nm, light application time
For 10 minutes.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to sewage disposal, apply
Process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl are added in the sewage that organic contamination produces
The addition mass volume ratio of porphyrin supermolecule photochemical catalyst is 0.5~5g/L；
(2) it is sufficiently stirred, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is uniformly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time reach row for sewage
Put standard.
Tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared by the method for the present invention, can be applied to clean energy resource production,
Application process comprises the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin supermolecule photocatalysis are added in water
The addition mass volume ratio of agent is according to 0.05~2g/L；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is tetracarboxylic phenyl porphyrin
The 10 of supermolecule photochemical catalyst2-105Times, the sacrifice agent is any in silver nitrate, ferrous nitrate, triethanolamine or lactic acid
It is a kind of；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output hydrogen or oxygen.
The method of the present invention is illustrated by specific embodiment below in conjunction with the accompanying drawings, but the invention is not limited in
This, any modifications, equivalent replacements and improvementsmade within the spirit and principles of the invention, etc., should be included in the present invention
Protection domain within.
The materials, reagents and the like used in the following examples, is commercially available.
Embodiment 1, prepare TCPP supermolecule organic semiconductor photochemical catalysts
(1) at 60 DEG C, it is completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution is
1mol·L-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 0.5molL-1, to reaction
System is neutrality；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 60 DEG C, and drying time is small for 12
When, obtain tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst.
According to Fig. 1 observables, the sample in Fig. 1 shows lamella packed structures, shows that material internal molecule is when assembled excellent
Gesture orientation assembling packed structures；In high resolution transmission electron microscopy photo shown in Fig. 2, it is observed that the crystallization feelings of material
Condition, it was demonstrated that strong and regular pi-pi accumulation inside supermolecule；High-resolution electronic selected area diffraction patterns shown in Fig. 3 prove super
The excellent crystal property of molecular material；High resolution transmission electron microscopy photo shown in Fig. 4 then indicates micro- inside supermolecule
The crystal grain diameter of crystalline region is conducive to the transmission and separation of photo-generated carrier in 15nm or so, is TCPP supermolecule photochemical catalysts
Performance provides guarantee.
Embodiment 2, prepare TCPP supermolecule organic semiconductor photochemical catalysts
(1) at 80 DEG C, it is completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution is
2mol·L-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 1molL-1, to reactant
It is for neutrality；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 80 DEG C, and drying time is small for 10
When, obtain tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst.
According in the high resolution transmission electron microscopy photo shown in Fig. 5, it is observed that the crystallization situation of material, it was demonstrated that
Strong and regular pi-pi accumulation and the crystal grain diameter in crystallite area are in 15nm or so inside supermolecule；High-resolution electronic shown in Fig. 6
Selected area diffraction patterns prove the excellent crystal property of supramolecular materials, are conducive to the transmission and separation of photo-generated carrier, are TCPP
The performance of supermolecule photochemical catalyst provides guarantee.
Embodiment 3, the feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 5 μ gmL-1；
(2) by the dispersion liquid configured and small Hela cancer cells co-incubation 24 when；
(3) culture medium is irradiated using the feux rouges that wavelength is 600,650,700nm, light application time is 10 minutes.
As shown in fig. 7, the material shows obvious and excellent anti-cancer properties, and the effect of anticancer is with irradiation light energy
Increase significantly improving.
Embodiment 4, the feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 10 μ gmL-1；
(2) by the dispersion liquid configured and small Hela cancer cells co-incubation 24 when；
(3) culture medium is irradiated using the feux rouges that wavelength is 600,650,700nm, light application time is 10 minutes.
As shown in figure 8, the material shows obvious and excellent anti-cancer properties, and the effect of anticancer is with irradiation light energy
Increase significantly improving.
Embodiment 5, the feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 15 μ gmL-1；
(2) by the dispersion liquid configured and small Hela cancer cells co-incubation 24 when；
(3) culture medium is irradiated using the feux rouges that wavelength is 600,650,700nm, light application time is 10 minutes.
As shown in figure 9, the material shows obvious and excellent anti-cancer properties, and the effect of anticancer is with irradiation light energy
Increase significantly improving.
Embodiment 6, the feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 20 μ gmL-1；
(2) by the dispersion liquid configured and small Hela cancer cells co-incubation 24 when；
(3) culture medium is irradiated using the feux rouges that wavelength is 600,650,700nm, light application time is 10 minutes.
As shown in Figure 10, which shows obvious and excellent anti-cancer properties, and the effect of anticancer is with irradiation luminous energy
The increase of amount is significantly improving.
Embodiment 7, the feux rouges driving in vitro anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 25 μ gmL-1；
(2) by the dispersion liquid configured and small Hela cancer cells co-incubation 24 when；
(3) culture medium is irradiated using the feux rouges that wavelength is 600,650,700nm, light application time is 10 minutes.
As shown in figure 11, which shows obvious and excellent anti-cancer properties, and the effect of anticancer is with irradiation luminous energy
The increase of amount is significantly improving.
Embodiment 8, the vital red optical drive anti-cancer applications of TCPP supermolecule photochemical catalysts
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic acid in dispersion liquid
The mass-volume concentration of base phenyl porphyrin supermolecule photochemical catalyst is 500 μ gmL-1；
(2) dispersion liquid configured is directly injected into inside tumor with syringe, implantation dosage is 1 μ L/ by gross tumor volume
mm3；
(3) tumor locus for having dispersion liquid to injection carries out positioning illumination, illumination wavelength 650, and light application time is 10 points
Clock.
Anatomical results such as Figure 12 show, the mouse after being treated into TCPP supermolecule photochemical catalysts red light irradiation, in vivo not
Find obvious tumor tissues.
The Photocatalytic Degradation of Phenol sewage of embodiment 9, TCPP supermolecule photochemical catalysts
(1) in 50mL, 25mg tetracarboxylic phenyl porphyrin supermolecule photochemical catalysts are added in the sewage that phenol concentration is 5ppm；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time reach row for sewage
The standard of putting is limited.
Sewage degradation treatment effect is as shown in figure 13.
The photocatalytic degradation bisphenol-A sewage of embodiment 10, TCPP supermolecule photochemical catalysts
(1) in 50mL, 25mg tetracarboxylic phenyl porphyrin supermolecule photocatalysis is added in the sewage that bisphenol A concentration is 5ppm
Agent；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time reach row for sewage
The standard of putting is limited.
Sewage degradation treatment effect is as shown in figure 14.
The photocatalytic degradation 2,4- Dichlorophenol sewage of embodiment 11, TCPP supermolecule photochemical catalysts
(1) in 50mL, 25mg tetracarboxylic phenyl porphyrin oversubscription sub-lights are added in the sewage that 2,4- Dichlorophenols concentration is 5ppm
Catalyst；
(2) it is sufficiently stirred, makes to be uniformly dispersed in sewage in tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 350-800nm with wavelength, irradiation time reach row for sewage
The standard of putting is limited.
Sewage degradation treatment effect is as shown in figure 15.
The photocatalysis hydrogen gas production of embodiment 12, TCPP supermolecule photochemical catalysts
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin oversubscription sub-light are added in 100mL water
The addition quality of catalyst is 50mg, obtains the first solution；
(2) lactic acid is added in above-mentioned first solution, lactic acid dosage is 5mL；
(3) with 300-850nm continuous spectrums irradiation reaction system.
As shown in figure 16, using lactic acid as sacrifice agent, 6 interior hydrogen outputs when small are 1.5 μm of olg-1。
The photocatalysis hydrogen gas production of embodiment 13, TCPP supermolecule photochemical catalysts
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin oversubscription sub-light are added in 100mL water
The addition quality of catalyst is 50mg, obtains the first solution；
(2) triethanolamine is added in above-mentioned first solution, lactic acid dosage is 20mL；
(3) with 300-850nm continuous spectrums irradiation reaction system.
As shown in figure 17, using triethanolamine as sacrifice agent, 6 interior hydrogen outputs when small are 240 μm of olg-1。
The photocatalysis oxygen production of embodiment 14, TCPP supermolecule photochemical catalysts
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin oversubscription sub-light are added in 100mL water
The addition quality of catalyst is 50mg, obtains the first solution；
(2) ferrous nitrate is added in above-mentioned first solution, ferrous nitrate dosage is 20mL, 0.05molL-1Solution；
(3) with 300-850nm continuous spectrums irradiation reaction system.
As shown in figure 18, using ferrous nitrate as sacrifice agent, 6 interior oxygen outputs when small are 50 μm of olg-1。
The photocatalysis oxygen production of embodiment 15, TCPP supermolecule photochemical catalysts
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin oversubscription sub-light are added in 100mL water
The addition quality of catalyst is 50mg, obtains the first solution；
(2) silver nitrate is added in above-mentioned first solution, silver nitrate dosage is 10mL, 0.05molL-1Solution；
(3) with 300-850nm continuous spectrums irradiation reaction system.
As shown in figure 19, using silver nitrate as sacrifice agent, 6 interior oxygen outputs when small are 210 μm of olg-1。
Claims (4)
1. a kind of preparation method of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, it is characterised in that this method includes following step
Suddenly：
(1) at 50-80 DEG C, be completely dissolved tetracarboxylic phenyl porphyrin with KOH solution, the molar concentration of KOH solution for 0.5~
5mol·L-1, dilute hydrochloric acid is added dropwise in solution upon dissolution, the molar concentration of dilute hydrochloric acid is 0.1~2molL-1, to anti-
System is answered as neutrality；
(2) reaction system of above-mentioned steps (1) is sufficiently stirred, separates out the solid in reaction system, natural cooling；
(3) reaction system is filtered, collects solid, solid is fully washed with deionized water；
(4) solid of above-mentioned steps (3) is dried in vacuo, vacuum drying temperature is 70~90 DEG C, drying time 4-12
Hour, obtain tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst.
2. a kind of application of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst as claimed in claim 1, it is characterised in that by four
Carboxyl phenyl porphyrin supermolecule photocatalyst applications comprise the following steps in treatment of cancer：
(1) with physiological saline by tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst prepared composition dispersion liquid, tetracarboxylic benzene in dispersion liquid
The mass-volume concentration of base porphyrin supermolecule photochemical catalyst is 1-500 μ gmL-1；
(2) dispersion liquid configured is directly injected into inside tumor with syringe, is 1 μ L/mm by the implantation dosage of gross tumor volume3；
(3) tumor locus for having dispersion liquid to injection carries out positioning illumination, illumination wavelength 500-800nm, light application time 10
Minute.
3. a kind of application of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst as claimed in claim 1, it is characterised in that by four
Carboxyl phenyl porphyrin supermolecule photocatalyst applications comprise the following steps in sewage disposal：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst, tetracarboxylic phenyl porphyrin are added in the sewage that organic contamination produces
The addition mass volume ratio of supermolecule photochemical catalyst is 0.5~5g/L；
(2) it is sufficiently stirred, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is uniformly dispersed in sewage；
(3) sewage for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, irradiation time reach discharge mark for sewage
It is accurate.
4. a kind of application of tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst as claimed in claim 1, it is characterised in that by four
Carboxyl phenyl porphyrin supermolecule photocatalyst applications are produced in clean energy resource, are comprised the following steps：
(1) tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst is added in water, tetracarboxylic phenyl porphyrin supermolecule photochemical catalyst
It is according to 0.05~2g/L to add mass volume ratio；
(2) sacrifice agent is added in the reaction system of above-mentioned steps (1), the addition of sacrifice agent is tetracarboxylic phenyl porphyrin oversubscription
The 10 of sub-light catalyst2-105Times, the sacrifice agent is any one in silver nitrate, ferrous nitrate, triethanolamine or lactic acid
Kind；
(3) reaction system for the light source irradiation above-mentioned steps (2) for being 300-850nm with wavelength, output hydrogen or oxygen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804190A (en) * | 2019-11-05 | 2020-02-18 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
| WO2020162030A1 (en) * | 2019-02-04 | 2020-08-13 | パナソニックＩｐマネジメント株式会社 | Photoresponsive oxygen storage material |
| CN112221541A (en) * | 2020-09-27 | 2021-01-15 | 东北师范大学 | Polyacid-porphyrin hybrid material and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537854A (en) * | 2003-04-16 | 2004-10-20 | 中国科学院上海有机化学研究所 | Method of separating, large scale preparing porphyrin from complex reaction system |
| CN101153085A (en) * | 2006-09-25 | 2008-04-02 | 中国科学院化学研究所 | Supermolecule chirality film with reversible chirality and method for preparing the same |
| CN101333437A (en) * | 2007-06-28 | 2008-12-31 | 中国医学科学院生物医学工程研究所 | Near infrared fluorescent compounds of porphyrins connected with alkynyl and preparation method |
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
| CN104151567A (en) * | 2014-07-16 | 2014-11-19 | 东北师范大学 | Preparation method of metal coordination supermolecular nanogel |
| CN104321297A (en) * | 2012-05-31 | 2015-01-28 | 伊士曼化工公司 | Catalyst and method having improved selectivity to isobutyraldehyde via catlayst induction |
| CN104588101A (en) * | 2015-01-13 | 2015-05-06 | 中国石油大学(华东) | Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof |
| CN105503886A (en) * | 2015-12-09 | 2016-04-20 | 中国科学院长春光学精密机械与物理研究所 | Nanometer photosensitizer for molecular system near-infrared light triggering water splitting and preparation method of nanometer photosensitizer |
| CN105688995A (en) * | 2016-01-21 | 2016-06-22 | 湖南科技大学 | Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature |
| CN105802609A (en) * | 2016-03-28 | 2016-07-27 | 华中科技大学 | Light-response room-temperature phosphorescent supramolecular anti-counterfeit material and preparation method thereof |
| CN106000474A (en) * | 2016-06-07 | 2016-10-12 | 河南大学 | Preparation method and application of porphyrin/titanium dioxide uniformly co-assembled nanosphere |
-
2017
- 2017-11-28 CN CN201711210324.8A patent/CN108014850B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537854A (en) * | 2003-04-16 | 2004-10-20 | 中国科学院上海有机化学研究所 | Method of separating, large scale preparing porphyrin from complex reaction system |
| CN101153085A (en) * | 2006-09-25 | 2008-04-02 | 中国科学院化学研究所 | Supermolecule chirality film with reversible chirality and method for preparing the same |
| CN101333437A (en) * | 2007-06-28 | 2008-12-31 | 中国医学科学院生物医学工程研究所 | Near infrared fluorescent compounds of porphyrins connected with alkynyl and preparation method |
| CN104321297A (en) * | 2012-05-31 | 2015-01-28 | 伊士曼化工公司 | Catalyst and method having improved selectivity to isobutyraldehyde via catlayst induction |
| CN104028308A (en) * | 2014-06-20 | 2014-09-10 | 中国科学院新疆理化技术研究所 | Nanometer photo-catalyst used in producing hydrogen by decomposing water under visible light response and application of nanometer photo-catalyst |
| CN104151567A (en) * | 2014-07-16 | 2014-11-19 | 东北师范大学 | Preparation method of metal coordination supermolecular nanogel |
| CN104588101A (en) * | 2015-01-13 | 2015-05-06 | 中国石油大学(华东) | Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof |
| CN105503886A (en) * | 2015-12-09 | 2016-04-20 | 中国科学院长春光学精密机械与物理研究所 | Nanometer photosensitizer for molecular system near-infrared light triggering water splitting and preparation method of nanometer photosensitizer |
| CN105688995A (en) * | 2016-01-21 | 2016-06-22 | 湖南科技大学 | Method for preparing metalloporphyrin-graphene nano composite material under condition of room temperature |
| CN105802609A (en) * | 2016-03-28 | 2016-07-27 | 华中科技大学 | Light-response room-temperature phosphorescent supramolecular anti-counterfeit material and preparation method thereof |
| CN106000474A (en) * | 2016-06-07 | 2016-10-12 | 河南大学 | Preparation method and application of porphyrin/titanium dioxide uniformly co-assembled nanosphere |
Non-Patent Citations (4)
| Title |
|---|
| ALBERT WAN ET AL.: ""Directed assembly of porphyrin nanofibers"", 《POLYMER PREPRINTS》 * |
| ZIJIAN ZHANG ET AL.: ""A Full‐Spectrum Metal‐Free Porphyrin Supramolecular Photocatalyst for Dual Functions of Highly Efficient Hydrogen and Oxygen Evolution"", 《ADVANCED MATERIALS》 * |
| 孟娇: ""卟啉分子聚集体光催化剂及其光催化产氧性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 黄艳琴: ""π-共轭体系超分子自组装"", 《中国科学:化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020162030A1 (en) * | 2019-02-04 | 2020-08-13 | パナソニックＩｐマネジメント株式会社 | Photoresponsive oxygen storage material |
| CN112351950A (en) * | 2019-02-04 | 2021-02-09 | 松下知识产权经营株式会社 | Light-responsive oxygen storage material |
| JP7370016B2 (en) | 2019-02-04 | 2023-10-27 | パナソニックＩｐマネジメント株式会社 | Photoresponsive oxygen storage material |
| CN110804190A (en) * | 2019-11-05 | 2020-02-18 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
| CN110804190B (en) * | 2019-11-05 | 2021-10-29 | 东莞行渡科技有限公司 | Preparation method of hydrophilic-hydrophobic water molecule self-assembled micelle embedded with aromatic amide fragment and supermolecule photocatalytic assembly |
| CN112221541A (en) * | 2020-09-27 | 2021-01-15 | 东北师范大学 | Polyacid-porphyrin hybrid material and preparation method and application thereof |
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