CN114073922B - Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof - Google Patents
Porphyrin-based metal-organic framework nanosphere and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 85
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 65
- 239000002077 nanosphere Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 26
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 50
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 38
- 239000005711 Benzoic acid Substances 0.000 claims description 19
- 235000010233 benzoic acid Nutrition 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- YMIJUYZSODEEOV-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Fe] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Fe] YMIJUYZSODEEOV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 3
- AMSPFPGYHIGWQE-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Zn] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Zn] AMSPFPGYHIGWQE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- HDLNBDOSVAALHG-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Co] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.C(=O)(O)C2=CC=C(C=C2)[Co] HDLNBDOSVAALHG-UHFFFAOYSA-N 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- 238000003384 imaging method Methods 0.000 abstract description 5
- 206010028980 Neoplasm Diseases 0.000 abstract description 3
- 201000011510 cancer Diseases 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 27
- 239000002904 solvent Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 description 5
- RSKDYRKXGSFNKK-UHFFFAOYSA-N C(=O)(O)C1=CC=C(C=C1)[Zn] Chemical compound C(=O)(O)C1=CC=C(C=C1)[Zn] RSKDYRKXGSFNKK-UHFFFAOYSA-N 0.000 description 5
- YCACADGRMVEVPP-UHFFFAOYSA-N OC(=O)C1=CC=C([Mn])C=C1 Chemical compound OC(=O)C1=CC=C([Mn])C=C1 YCACADGRMVEVPP-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- DTKKSWSQNRKYOS-UHFFFAOYSA-N C(=O)(O)C1=CC=C(C=C1)[Co] Chemical compound C(=O)(O)C1=CC=C(C=C1)[Co] DTKKSWSQNRKYOS-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/025—Applications of microcapsules not provided for in other subclasses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a porphyrin-based metal-organic framework nanosphere and a preparation method and application thereof. The preparation method comprises the following steps: reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerator, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure microchip; and adding polyethylenimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at the temperature of 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres. According to the invention, a chiffon-shaped micron large-size sheet is obtained by adjusting the proportion of porphine to metal ions, and then porphyrin-based metal-organic framework nanospheres with uniform-scale micropores and mesopores are prepared by further reaction; meanwhile, the porphyrin-based metal-organic framework nanospheres prepared by the invention have wide application prospects in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework nano materials, in particular to a porphyrin-based metal-organic framework nano ball and a preparation method and application thereof, and particularly relates to a porphyrin-based metal-organic framework nano ball which is formed by constructing a chiffon-shaped micro-sheet in a manner of condensation by using polyethyleneimine and has micro-pores and mesopores coexistent, and a preparation method and application thereof.
Background
The large specific surface area and ordered pore structure of the metal-organic framework material endow the metal-organic framework material with various applications in the aspects of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like. Although metal-organic framework materials are being prepared and studied in large quantities, there are few synthetic gauze-like metal-organic framework micro-sheets of size 1-20 μm, and further condensation of such gauze-like micro-sized metal-organic framework sheets into micro-and mesoporous coexisting nanospheres has not been mentioned. The nanosphere obtained by condensing the chiffon-shaped sheet metal-organic framework has a micropore and mesopore coexisting structure, can effectively load one or more substances such as small molecules, macromolecules, proteins, nano large particles and the like, and has wider application prospect, so that the development of a simple and effective method for synthesizing the micropore and mesopore coexisting porphyrin-based metal-organic framework nanosphere has important significance.
Disclosure of Invention
The invention mainly aims to provide a porphyrin-based metal-organic framework nanosphere as well as a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of porphyrin-based metal-organic framework nanospheres, which comprises the following steps:
reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerator, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure microchip;
and adding polyethylenimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at the temperature of 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres.
The embodiment of the invention also provides the porphyrin-based metal-organic framework nanospheres prepared by the method, wherein the porphyrin-based metal-organic framework nanospheres have a micropore and mesoporous structure, and the diameter of the porphyrin-based metal-organic framework nanospheres is 50-200 nm.
The embodiment of the invention also provides application of the porphyrin-based metal-organic framework nanospheres in the fields of gas storage and separation, fuel cell performance conversion or biomedical imaging.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, by utilizing the characteristic that meso-tetra (4-carboxyphenyl) porphin or metal porphin and metal ions thereof coordinate under a certain condition, a micrometer-sized two-dimensional metal-organic framework structure micrometer sheet like a chiffon is obtained by adjusting the proportion and performing an oil bath heating method, and then polyethyleneimine is added for controllable condensation, so that the porphyrin-based metal-organic framework nanospheres with uniform particle size and coexisting micropores and mesopores are obtained;
(2) The invention firstly utilizes the metal-organic framework sheet condensation of the gauze micron size to form the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, and meanwhile, the porphyrin-based metal-organic framework nanospheres prepared by the invention have larger specific surface area and pore structure, can effectively load one or more substances such as small molecules, macromolecules, proteins, nano large particles and the like, have wide application prospects in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging, cancer treatment and the like, and in addition, the network structure of the micropores and mesopores can further promote energy or electron transition, enhance the light conversion efficiency and improve the yield of active oxygen.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron micrograph of a two-dimensional metal-organic framework micro-plate according to example 10 of the present invention;
FIG. 2 is a transmission electron micrograph of porphyrin-based metal-organic framework nanospheres of example 10 of the present invention;
FIG. 3 is a graph showing nitrogen adsorption-desorption curves for porphyrin-based metal-organic framework nanospheres in example 10 of the present invention;
FIG. 4 is a pore size distribution curve of porphyrin-based metal-organic framework nanospheres according to example 10 of the present invention.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
One aspect of the embodiments of the present invention provides a method for preparing a porphyrin-based metal-organic framework nanosphere, comprising:
reacting a mixed reaction system containing meso-tetra (4-carboxyphenyl) porphin and/or metal porphin, metal ions, an accelerator, an organic solvent and water at 50-130 ℃ for 1-5 h to obtain a two-dimensional metal-organic framework structure microchip;
and adding polyethylenimine into the mixed reaction system, and carrying out condensation reaction for 2-10 h at the temperature of 10-60 ℃ to obtain the porphyrin-based metal-organic framework nanospheres.
In some more specific embodiments, the metallic porphins include, but are not limited to, any one or a combination of two or more of meso-tetra (4-carboxyphenyl) iron porphin, meso-tetra (4-carboxyphenyl) copper porphin, meso-tetra (4-carboxyphenyl) zinc porphin, meso-tetra (4-carboxyphenyl) cobalt porphin, meso-tetra (4-carboxyphenyl) manganese porphin.
Further, the metal ion includes any one or a combination of two or more of copper ion, cobalt ion and nickel ion, preferably copper ion.
Further, the accelerator comprises any one or more than two of benzoic acid, polyvinylpyrrolidone and biphenyl dicarboxylic acid, and is preferably benzoic acid.
In the invention, the benzoic acid has the functions of promoting the metal coordination of porphyrin centers, forming metalloporphyrin, reducing H-accumulation and J-aggregation between sheets, and having the same effect as polyvinylpyrrolidone (PVP) and biphenyl dicarboxylic acid.
In the invention, the long-chain high molecular polymer with branched chains can also have the same effect as polyethyleneimine.
In some more specific embodiments, the preparation method specifically comprises: dissolving meso-tetra (4-carboxyphenyl) porphin and/or metal porphin in an organic solvent to form a meso-tetra (4-carboxyphenyl) porphin solution and/or metal porphin solution, and mixing the meso-tetra (4-carboxyphenyl) porphin solution and the metal ions, the accelerator, the organic solvent and water to form the mixed reaction system.
Further, the concentration of the meso-tetra (4-carboxyphenyl) porphin solution and/or the metal porphin solution is 0.1-10.0 mmol/L.
In some more specific embodiments, the metal ions are derived from a salt solution containing metal ions.
Further, the salt solution includes any one or a combination of two or more of nitrate, chloride, sulfate, acetate and phosphate, and is not limited thereto.
Further, the concentration of the metal ions in the salt solution containing the metal ions is 0.1 to 10.0mmol/L.
Further, the concentration of the benzoic acid is 1.0-30.0 g/L.
In some more specific embodiments, the molar ratio of mid-tetra (4-carboxyphenyl) porphine and/or metallic porphine, metal ion to accelerator is from 1 to 10:1 to 10.
Further, the organic solvent includes any one or a combination of two or more of N, N-dimethylformamide, dimethylsulfoxide, methanol, ethanol, and chloroform, and is not limited thereto.
In some more specific embodiments, the two-dimensional metal-organic framework structure micro-sheet is a tissue-like two-dimensional metal-organic framework structure micro-sheet, having a size of 1 to 20 μm and a thickness of 1 to 20nm.
Further, the molecular weight of the polyethyleneimine is 600-25000 g/mol.
Further, the polyethyleneimine is derived from a polyethyleneimine solution with a concentration of 1-1000 mg/L.
Another aspect of the embodiments of the present invention also provides a porphyrin-based metal-organic framework nanosphere prepared by the foregoing method, the porphyrin-based metal-organic framework nanosphere having a microporous and mesoporous structure, the porphyrin-based metal-organic framework nanosphere having a diameter of 50 to 200nm and a specific surface area of 500 to 1500m 2 /g。
Further, the pore size of the micropore structure of the porphyrin-based metal-organic framework nanospheres is 0.8-1.5 nm, and the pore size of the mesopore structure of the porphyrin-based metal-organic framework nanospheres is 5-40 nm.
In some more specific embodiments, the method of making comprises:
(1) Mixing meso-tetra (4-carboxyphenyl) porphin or its metal porphin, copper metal ions, benzoic acid, an organic solvent, and water to form a solution;
(2) Adjusting the mole ratio of porphine, copper metal ions and benzoic acid in the mixed solution, and reacting in an oil bath heating mode to obtain a tissue-like two-dimensional metal-organic framework structure micrometer sheet with the size of 1-20 micrometers;
(3) Adding polyethylenimine and chiffon-shaped micron sheets into the mixed solution, and condensing under stirring to obtain the porphyrin-based metal-organic framework nanospheres with micropores and mesopores coexisting.
Another aspect of the embodiments of the present invention also provides the use of the porphyrin-based metal-organic framework nanospheres described above in the fields of gas storage and separation, fuel cell performance conversion, biomedical imaging.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
The mid-tetra (4-carboxyphenyl) porphine used in this example was purchased from tokyo chemical industry co reagent company; copper nitrate and N, N-dimethylformamide were purchased from the national drug group.
1.0mmol/L of medium-tetra (4-carboxyphenyl) porphine solution is prepared by taking N, N-dimethylformamide as a solvent, 10.0mmol/L of copper nitrate solution is prepared by taking water as a solvent, 2mL of medium-tetra (4-carboxyphenyl) porphine solution and 1mL of copper nitrate solution are added into a 100mL round bottom flask, 10mL of N, N-dimethylformamide is added, 0.05g of benzoic acid is added, the mixture is uniformly stirred, the uniformly mixed solution is subjected to oil bath heating reaction under stirring, the temperature is 90 ℃, the reaction time is 4h, and the reaction is cooled to room temperature after the reaction is completed. Then adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 60 nm.
Example 2
In this example, 0.1mmol/L of a meso-tetra (4-carboxyphenyl) porphine solution was prepared using N, N-dimethylformamide as a solvent, and then 0.1mmol/L of a cupric chloride solution was prepared using water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) porphine and 1mL of copper chloride, followed by 10mL of N, N-dimethylformamide, 0.05g of benzoic acid, and stirring was performed. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 50 ℃, the reaction time is 5h, and cooling to room temperature after the reaction is finished. Then adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 2 hours at 60 ℃ under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 60 nm.
Example 3
In this example, 10.0mmol/L of a meso-tetra (4-carboxyphenyl) porphine solution was prepared using N, N-dimethylformamide as a solvent, and then 10.0mmol/L of a copper sulfate solution was prepared using water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) porphine and 1mL of copper sulfate, followed by 10mL of N, N-dimethylformamide, 0.05g of benzoic acid, and stirring was uniform. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 130 ℃, the reaction time is 1h, and cooling to room temperature after the reaction is finished. Then adding 1mL of polyethyleneimine with the concentration of 1mg/L and the molecular weight of 25000g/mol, and condensing for 10 hours at the temperature of 10 ℃ under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 60 nm.
Example 4
In the embodiment, firstly, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metallic iron to obtain the meso-tetra (4-carboxyphenyl) iron porphin, 1.0mmol/L of the meso-tetra (4-carboxyphenyl) iron porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 10.0mmol/L of cobalt nitrate solution is prepared by taking water as a solvent. 2mL of meso-tetra (4-carboxyphenyl) iron porphine solution and 1mL of cobalt nitrate solution are added into a 100mL round bottom flask, 10mL of N, N-dimethylformamide is added, 0.02g of benzoic acid is added, the mixture is stirred uniformly, the solution which is uniformly mixed is subjected to oil bath heating reaction under stirring, the temperature is 90 ℃, the reaction time is 4 hours, and the mixture is cooled to room temperature after the reaction is completed. Then adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 2000g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 50 nm.
Example 5
In the embodiment, first, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metal zinc to obtain the meso-tetra (4-carboxyphenyl) zinc porphin, 10.0mmol/L of the meso-tetra (4-carboxyphenyl) zinc porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 1.0mmol/L of the nickel nitrate solution is prepared by taking water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) zinc porphine and 1mL of a solution of nickel nitrate, followed by 10mL of N, N-dimethylformamide, 0.02g of benzoic acid, and stirring was uniform. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then adding 1mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 70 nm.
Example 6
In the embodiment, first, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metal zinc to obtain the meso-tetra (4-carboxyphenyl) zinc porphin, 1.0mmol/L of the meso-tetra (4-carboxyphenyl) zinc porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 10.0mmol/L of copper chloride solution is prepared by taking water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) zinc porphine and 1mL of copper chloride, then 10mL of N, N-dimethylformamide was added, 0.10g of benzoic acid was added, and the mixture was stirred well. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then adding 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 100 nm.
Example 7
In the embodiment, firstly, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metal manganese to obtain the meso-tetra (4-carboxyphenyl) manganese porphin, 1.0mmol/L of the meso-tetra (4-carboxyphenyl) manganese porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 10.0mmol/L of copper nitrate solution is prepared by taking water as a solvent. 2mL of meso-tetra (4-carboxyphenyl) manganese porphine solution and 1mL of copper nitrate solution are added into a 100mL round bottom flask, 10mL of N, N-dimethylformamide is added, 0.05g of benzoic acid is added, the mixture is stirred uniformly, the solution which is uniformly mixed is subjected to oil bath heating reaction under stirring, the temperature is 90 ℃, the reaction time is 4 hours, and the mixture is cooled to room temperature after the reaction is completed. Then adding 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 150 nm.
Example 8
In the embodiment, firstly, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metal manganese to obtain the meso-tetra (4-carboxyphenyl) manganese porphin, 1.0mmol/L of the meso-tetra (4-carboxyphenyl) manganese porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 10.0mmol/L of copper chloride solution is prepared by taking water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) manganese porphine and 1mL of copper chloride, followed by 10mL of N, N-dimethylformamide, 0.05g of benzoic acid, and stirring was uniform. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then adding 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 150 nm.
Example 9
In the embodiment, firstly, the meso-tetra (4-carboxyphenyl) porphin is inserted into central metallic iron to obtain the meso-tetra (4-carboxyphenyl) iron porphin, 1.0mmol/L of the meso-tetra (4-carboxyphenyl) iron porphin solution is prepared by taking N, N-dimethylformamide as a solvent, and then 10.0mmol/L of copper nitrate solution is prepared by taking water as a solvent. Adding 4mL of meso-tetra (4-carboxyphenyl) iron porphine solution and 1mL of copper nitrate solution into a 100mL round bottom flask, adding 10mL of N, N-dimethylformamide, adding 0.15g of benzoic acid, uniformly stirring, carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then adding 2mL of polyethyleneimine with the concentration of 1000mg/L and the molecular weight of 1800g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 200nm.
Example 10
In this example, first, meso-tetra (4-carboxyphenyl) porphin was inserted into a central metal iron to obtain meso-tetra (4-carboxyphenyl) iron porphin. Preparing 2.0mmol/L of medium-tetra (4-carboxyphenyl) iron porphine solution by taking N, N-dimethylformamide as a solvent, and preparing 5.0mmol/L of copper nitrate solution by taking water as a solvent. Into a 100mL round bottom flask was added 2mL of a solution of meso-tetra (4-carboxyphenyl) iron porphine and 1mL of copper nitrate, followed by 10mL of N, N-dimethylformamide, 0.02g of benzoic acid, and stirring was uniform. And (3) carrying out oil bath heating reaction on the uniformly mixed solution under stirring, wherein the temperature is 90 ℃, the reaction time is 4 hours, and cooling to room temperature after the reaction is finished. Then adding 1mL of polyethyleneimine with the concentration of 500mg/L and the molecular weight of 600g/mol, and condensing for 5 hours at room temperature under stirring to obtain the porphyrin-based metal-organic framework nanospheres with coexisting micropores and mesopores, wherein the diameter size of the porphyrin-based metal-organic framework nanospheres is about 60 nm.
FIG. 1 is a transmission electron micrograph of a meso-tetra (4-carboxyphenyl) iron porphine and copper ions formed into a microscale two-dimensional metal-organic framework structure microsheet like a chiffon with dimensions of 1-20 μm and a thickness of 1-20 nm in example 10 of the present invention; FIG. 2 is a transmission electron micrograph of a porphyrin-based metal-organic framework nanosphere formed by condensing meso-tetra (4-carboxyphenyl) iron porphine and copper ions with polyethyleneimine and coexisting with micropores and mesopores, wherein the particle size distribution is uniform, and the diameter size is about 60 nm; FIG. 3 is a graph showing the nitrogen adsorption-desorption curves of porphyrin-based metal-organic framework nanospheres according to example 10 of the present invention, showing approximate IV Langmuir isotherms, having a specific surface area of about 692.6m 2 /g; FIG. 4 is a graph showing the pore size distribution of porphyrin-based metal-organic framework nanospheres according to example 10 of the present invention, wherein micropores and mesopores exist simultaneously, the micropores are about 1.2nm, and the mesopores are distributed between 5 and 30 nm.
In summary, by the technical scheme of examples 1-10, the invention utilizes the characteristic that meso-tetra (4-carboxyphenyl) porphine or metal porphine thereof coordinates with copper metal ions under certain conditions, obtains micron-sized two-dimensional metal-organic framework micro-sheets like tissue by adjusting the proportion and performing an oil bath heating method, and then adds polyethyleneimine to perform controllable condensation to obtain the porphyrin-based metal-organic framework nanospheres with uniform particle size and coexisting micropores and mesopores.
In addition, the present inventors have also conducted experiments in the manner of examples 1 to 10 with other raw materials, conditions, etc. listed in the present specification, and have also succeeded in producing porphyrin-based metal-organic framework nanospheres in which micropores and mesopores having uniform particle diameters coexist.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of porphyrin-based metal-organic framework nanospheres is characterized by comprising the following steps:
reacting a mixed reaction system containing metal porphin, metal ions, an accelerator, an organic solvent and water for 1-5 hours at 50 ℃ to obtain a two-dimensional metal-organic framework structure microchip; the metal porphine is selected from any one or more than two of meso-tetra (4-carboxyphenyl) iron porphine, meso-tetra (4-carboxyphenyl) zinc porphine, meso-tetra (4-carboxyphenyl) cobalt porphine and meso-tetra (4-carboxyphenyl) manganese porphine; the metal ions are selected from any one or the combination of two of cobalt ions and nickel ions; the promoter is selected from any one or more than two of benzoic acid, polyvinylpyrrolidone and biphenyl dicarboxylic acid; the two-dimensional metal-organic framework structure micron sheet is a gauze-shaped two-dimensional metal-organic framework structure micron sheet, the size is 1-20 mu m, and the thickness is 1-20 nm;
adding polyethyleneimine into the mixed reaction system, and carrying out condensation reaction for 2-10 hours at the temperature of 10-60 ℃ to obtain porphyrin-based metal-organic framework nanospheres;
the porphyrin-based metal-organic framework nanospheres have a micropore and mesoporous structure, the diameter of the porphyrin-based metal-organic framework nanospheres is 50-200 nm, and the specific surface area is 500-1500 m 2 /g; the pore size of the micropore structure of the porphyrin-based metal-organic framework nanospheres is 0.8-1.5 nm, and the pore size of the mesopore structure of the porphyrin-based metal-organic framework nanospheres is 5-40 nm.
2. The method of manufacturing according to claim 1, characterized in that: the promoter is benzoic acid.
3. The preparation method according to claim 1, characterized in that it comprises in particular: dissolving metal porphin in an organic solvent to form a metal porphin solution, and mixing the metal porphin solution with the metal ions, the accelerator, the organic solvent and water to form the mixed reaction system; wherein the concentration of the metal porphine solution is 0.1-10.0 mmol/L.
4. The method of manufacturing according to claim 1, characterized in that: the metal ions are derived from a salt solution containing metal ions; wherein the salt solution is selected from any one or more than two of nitrate, chloride, sulfate, acetate and phosphate; the concentration of metal ions in the salt solution containing the metal ions is 0.1-10.0 mmol/L.
5. The method of manufacturing according to claim 1, characterized in that: the concentration of the benzoic acid is 1.0-30.0 g/L.
6. The method of manufacturing according to claim 1, characterized in that: the molar ratio of the metal porphine to the metal ion to the accelerator is 1:10:1-10:1:10.
7. The method of manufacturing according to claim 1, characterized in that: the organic solvent is selected from any one or more than two of N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol and chloroform.
8. The method of manufacturing according to claim 1, characterized in that: the molecular weight of the polyethyleneimine is 600-25000 g/mol; the polyethyleneimine is derived from polyethyleneimine solution with the concentration of 1-1000 mg/L.
9. A porphyrin-based metal-organic framework nanosphere prepared by the method of any one of claims 1-8.
10. Use of the porphyrin-based metal-organic framework nanospheres of claim 9 in gas storage and separation or fuel cell performance conversion.
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