CN112264103B - Silver-based metal organic framework material and preparation method and application thereof - Google Patents
Silver-based metal organic framework material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112264103B CN112264103B CN202011181167.4A CN202011181167A CN112264103B CN 112264103 B CN112264103 B CN 112264103B CN 202011181167 A CN202011181167 A CN 202011181167A CN 112264103 B CN112264103 B CN 112264103B
- Authority
- CN
- China
- Prior art keywords
- silver
- metal organic
- framework material
- organic framework
- based metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 50
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 40
- 239000004332 silver Substances 0.000 title claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- DLOBKMWCBFOUHP-UHFFFAOYSA-N pyrene-1-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 DLOBKMWCBFOUHP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 claims description 11
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 150000003568 thioethers Chemical class 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 6
- 239000003049 inorganic solvent Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- -1 p-bromobenzylthioate Chemical compound 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- CZLSHVQVNDDHDQ-UHFFFAOYSA-N pyrene-1,3,6,8-tetrasulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC(S(O)(=O)=O)=C(C=C3)C2=C2C3=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 CZLSHVQVNDDHDQ-UHFFFAOYSA-N 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LBVWMBBKFFQMRX-UHFFFAOYSA-N 4-chlorobenzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=C(Cl)C=C1 LBVWMBBKFFQMRX-UHFFFAOYSA-N 0.000 claims 1
- YGAPOICUMNPIPF-UHFFFAOYSA-N 4-methoxybenzenecarbothioic s-acid Chemical compound COC1=CC=C(C(S)=O)C=C1 YGAPOICUMNPIPF-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000935 solvent evaporation Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UZBIRLJMURQVMX-UHFFFAOYSA-J tetrasodium;pyrene-1,3,6,8-tetrasulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C2C(S(=O)(=O)[O-])=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 UZBIRLJMURQVMX-UHFFFAOYSA-J 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- GEMJZZWKASRCFH-UHFFFAOYSA-N pyrene-1,2,3,4-tetrasulfonic acid Chemical compound OS(=O)(=O)C1=C(S(O)(=O)=O)C(S(O)(=O)=O)=C2C(S(=O)(=O)O)=CC3=CC=CC4=CC=C1C2=C34 GEMJZZWKASRCFH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/17—Silver
Abstract
The invention provides a silver-based metal organic framework material and a preparation method and application thereof, belonging to the technical field of metal organic framework material preparation and photocatalysis. The invention uses Ag+Ions, pyridine and pyrenesulfonic acid are designed and synthesized into silver-based MOFs through a solvent evaporation method, and a large pi bond in the pyrenesulfonic acid forms a stacked two-dimensional structure to facilitate the formation of excitons, so that singlet oxygen is used as a main active species, and Ag is ensured+And (4) stabilizing ions. The preparation method has mild preparation conditions, can obtain products with higher yield at room temperature, has little environmental pollution, obviously improves the performance of the photocatalyst, is suitable for industrial production, and has good practical application value.
Description
Technical Field
The invention belongs to the technical field of metal organic framework material preparation and photocatalysis, and particularly relates to a silver-based metal organic framework material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, silver-based photocatalysts such as AgX (X ═ Cl, Br, I), Ag2CO3And Ag3PO4Etc. are effective because of having a narrow band gapThe photocatalytic performance has received a great deal of attention. Silver-based photocatalysts generally have the problem of instability during the photocatalytic process. This is mainly due to Ag+The ions are easily reduced to silver simple substance under illumination, thereby leading the photocatalyst to lose activity. Therefore, finding a suitable stable silver-based photocatalyst remains a challenge. Excitons have been reported to participate in photocatalytic processes in addition to the usual photogenerated electrons and holes. Ag is able to generate charge-neutral excitons other than electrons if silver-based photocatalysis is possible+Photo-reduction of ions will be greatly suppressed.
Metal Organic Frameworks (MOFs) materials are a class of organic-inorganic composite materials composed of metal nodes and organic ligands. Due to the various structures, the adjustable pore canal and the performance have important application in the aspects of photocatalytic water splitting and selective organic synthesis. In general, materials containing organic ligands will generally have a greater exciton binding energy and favor exciton generation relative to inorganic materials. Therefore, it is possible that the combination of silver ions and organic ligands promotes the generation of excitons, thereby securing the stability of silver ions.
Pyrene and its derivatives have a large conjugated structure and have good fluorescent properties. It is reported that pyrene can generate singlet oxygen by energy transfer.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a silver-based metal organic framework material, a preparation method and application thereof+The silver-based MOFs has good photocatalytic stability and photocatalytic selective oxidation conversion rate through experimental verification, so that the silver-based MOFs has good practical application value.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a silver-based metal organic framework material, which comprises the steps of taking silver salt, pyridine and pyrenesulfonic acid as raw materials and obtaining the silver-based metal organic framework material by a solvent evaporation method.
Second of the inventionIn one aspect, the silver-based metal organic framework material obtained by the preparation method is provided. Pyrenesulfonic acid forms an Ag-O-S bond with Ag, and pyridine forms a stable Ag-N bond with Ag. The invention can simply and effectively form the Ag-based MOFs material, and can generate singlet oxygen through the energy transfer process to promote Ag+Ionic stability and efficiency of photocatalytic oxidation of thioethers.
Therefore, in a third aspect of the present invention, there is provided the use of the silver-based metal organic framework material described above for photocatalytic selective oxidation.
In a fourth aspect of the invention, there is provided a photocatalyst comprising the above silver-based metal organic framework material.
In a fifth aspect of the present invention, there is provided a method for carrying out photocatalytic selective oxidation, said method comprising adding the above silver-based metal organic framework material and/or photocatalyst to the reaction, and oxidizing thioether to sulfoxide under the total light condition.
The beneficial technical effects of one or more technical schemes are as follows:
1. the technical proposal uses Ag for the first time+The ions, pyridine and pyrenesulfonic acid are used for obtaining the photocatalyst through a solvent evaporation method, and a large pi bond in the pyrenesulfonic acid forms a stacked two-dimensional structure to be beneficial to the formation of excitons, so that singlet oxygen is used as a main active species, and Ag is ensured+And (4) stabilizing ions.
2. The preparation method of the technical scheme has mild preparation conditions, can obtain a product with higher yield at room temperature, has little environmental pollution, obviously improves the performance of the photocatalyst, is suitable for industrial production, and has good value of practical application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a simulated and experimentally measured powder X-ray diffraction pattern of Ag-based MOFs in example 1 of the present invention;
FIG. 2 is a SEM of Ag-based MOFs in example 1 of the present invention;
FIG. 3 is a graph of the UV-visible diffuse reflectance of Ag-based MOFs in example 1 of the present invention;
FIG. 4 is a histogram of the performance of photocatalytic oxidation of thioanisole in the full light range of 1,3,6, 8-pyrenetetrasulfonic acid, 4, 4-bipyridine and Ag-based MOFs in Experimental examples 1-3 of the present invention;
FIG. 5 is a histogram of the performance of photocatalytic oxidation of thioanisole in the full light range of experimental examples 3-5 of the present invention;
FIG. 6 is a bar graph of the performance of photocatalytic oxidation of thioanisole with 5 cycles in the full light range in Experimental example 3;
FIG. 7 shows Ag before and after 5 cycles of photocatalytic oxidation of thioanisole in full light range in Experimental example 3 of the present invention+XPS comparison of ions.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As described above, in the prior art, Ag-based photocatalysts are prone to suffer from insufficient photo-corrosion.
In view of the above, in a typical embodiment of the present invention, a method for preparing a silver-based metal organic framework material is provided, wherein the method comprises using silver salt, pyridine and pyrenesulfonic acid as raw materials, and performing a solvent evaporation method to obtain the silver-based metal organic framework material.
In yet another embodiment of the present invention, the silver salt may be silver nitrate or silver acetate;
in yet another embodiment of the present invention, the pyridine is 4, 4-bipyridine;
in yet another embodiment of the present invention, the pyrene sulfonic acid comprises pyrene tetrasulfonic acid and analogs thereof, more specifically, 1,3,6, 8-pyrenetetrasulfonic acid, 1-pyrenesulfonic acid and p-pyrenesulfonic acid. Pyrenetetrasulfonic acid or the like is used as an organic ligand containing rich pi electrons and is combined with Ag ions through Ag-O-S bonds to form a two-dimensional stacked structure, so that excitons are favorably formed.
In still another embodiment of the present invention, Ag is in the silver salt+The molar ratio of the ions to the pyridine to the pyrenesulfonic acid is 2:2: 0.5-2. The molar ratio can be selected from 2:2:0.5, 2:2:1, 2:2:1.5 or 2:2: 2.
In another embodiment of the present invention, the preparation method comprises: dissolving silver salt and pyrenesulfonic acid in an inorganic solvent, dissolving pyridine in an organic solvent, mixing the two to obtain a light yellow precipitate, adding ammonia water until the precipitate is dissolved, standing, and volatilizing the crystal (light yellow needle crystal) along with the solvent to obtain the product.
In another embodiment of the present invention, the molar volume ratio of the pyrenesulfonic acid to the inorganic solvent is 0.5 to 2mmol: 1-50 mL, such as 0.5mmol:5mL, 1mmol:5mL, 1.5mmol:5mL or 2mmol:5 mL;
in another embodiment of the present invention, the inorganic solvent is water.
In another embodiment of the present invention, the molar volume ratio of pyridine to organic solvent is 2mmol: 2-10mL, such as 2mmol:2mL, 2mmol:5mL, 2mmol:8mL or 2mmol:10 mL;
in yet another embodiment of the present invention, the organic solvent is methanol.
In another embodiment of the invention, the specific standing condition is standing at 15-100 ℃ for 12-48 h; preferably, the mixture is kept still for 12-24 hours at room temperature.
In still another embodiment of the present invention, the preparation method further comprises a step of purifying the product.
In another embodiment of the present invention, the purification step is specifically: the collected product was filtered, washed and dried.
In another embodiment of the present invention, the filtering is specifically washing with deionized water and absolute ethyl alcohol for 2-3 times in sequence;
in yet another embodiment of the present invention, the drying is specifically vacuum drying. The vacuum drying condition is that the temperature is 60-150 ℃ and the time is 12-24 h. Ethanol is present in the product due to the use of ethanol in the wash, which has a lower boiling point than water and thus does not require the use of higher temperatures.
In still another embodiment of the present invention, there is provided a silver-based metal organic framework material obtained by the above-mentioned preparation method. Pyrenesulfonic acid forms an Ag-O-S bond with Ag, and pyridine forms a stable Ag-N bond with Ag. The invention can simply and effectively form the Ag-based MOFs material, and can generate singlet oxygen through the energy transfer process to promote Ag+Ionic stability and efficiency of photocatalytic oxidation of thioethers.
Therefore, in a third aspect of the present invention, there is provided the use of the silver-based metal organic framework material described above for photocatalytic selective oxidation.
In yet another embodiment of the present invention, the photocatalytic selective oxidation is a photocatalytic selective oxidation of thioether.
In still another embodiment of the present invention, there is provided a photocatalyst including the above silver-based metal organic framework material.
In yet another embodiment of the present invention, there is provided a method for carrying out photocatalytic selective oxidation, said method comprising adding the above silver-based metal organic framework material and/or photocatalyst to the reaction, and oxidizing the thioether to sulfoxide under plenoptic conditions.
In yet another embodiment of the present invention, the sulfides include, but are not limited to, mustard gas, thioanisole, p-chlorobenzenethiol, p-bromobenzylenethiol and p-methoxybenzenethiol.
The full light of the invention refers to natural light or light similar to natural light, and the light similar to natural light refers to light with full spectrum, such as full spectrum xenon lamp.
In yet another embodiment of the present invention, the method of performing photocatalytic selective oxidation is performed in a liquid environment, preferably provided by an organic solvent including, but not limited to, acetonitrile.
The technical solution of the present invention will be described below with specific examples. The starting materials used in the following examples are all commercially available.
Example 1
The preparation process of the Ag-based MOFs comprises the following steps:
(1) 0.5mmol of 1,3,6, 8-pyrenetetrasulfonic acid sodium salt (Na-PTS) and 2mmol of silver nitrate are weighed into 5mL of water, and stirred until the solution is completely dissolved.
(2) 2mmol of 4, 4-Bipyridine (BPY) was weighed out and added to 5mL of methanol, and stirred until the solution was completely dissolved.
(3) Gradually dripping the solution (1) into the solution (2), and stirring until the reaction is complete.
(4) 1.5mL of ammonia was added dropwise to the mixture of (3) until it was clear without precipitation, and left to stand at room temperature at 25 ℃ for 12 hours.
(5) And (4) collecting and filtering the product in the step (4), washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the product for 12 hours in a 60-DEG C oven to obtain Ag-based MOFs which are marked as Ag-PTS-BPY. The structural characterization is shown in figures 1-3, and the experimental and simulated X-ray diffraction patterns in figure 1 are consistent, which indicates that a sample with higher purity is obtained.
Example 2
The preparation process of the Ag-based MOFs comprises the following steps:
(1) 1mmol of 1,3,6, 8-pyrenetetrasulfonic acid sodium salt (Na-PTS) and 2mmol of silver nitrate are weighed into 5mL of water, and stirred until the solution is completely dissolved.
(2) 2mmol of 4, 4-Bipyridine (BPY) was weighed out and added to 5mL of methanol, and stirred until the solution was completely dissolved.
(3) Gradually dripping the solution (1) into the solution (2), and stirring until the reaction is complete.
(4) 2mL of aqueous ammonia was added dropwise to the mixture of (3) until it was clear without precipitation, and left to stand at 25 ℃ for 12 hours.
(5) And (4) collecting and filtering the product in the step (4), washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the product for 12 hours in an oven at the temperature of 60 ℃.
Example 3
The preparation process of the Ag-based MOFs comprises the following steps:
(1) 1.5mmol of 1,3,6, 8-pyrenetetrasulfonic acid sodium salt (Na-PTS) and 2mmol of silver nitrate are weighed into 5mL of water, and stirred until the solution is completely dissolved.
(2) 2mmol of 4, 4-Bipyridine (BPY) was weighed out and added to 5mL of methanol, and stirred until the solution was completely dissolved.
(3) Gradually dripping the solution (1) into the solution (2), and stirring until the reaction is complete.
(4) 2mL of aqueous ammonia was added dropwise to the mixture of (3) until it was clear without precipitation, and left to stand at 25 ℃ for 12 hours.
(5) And (4) collecting and filtering the product in the step (4), washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the product for 12 hours in an oven at the temperature of 60 ℃.
Example 4
The preparation process of the Ag-based MOFs comprises the following steps:
(1) 2mmol of 1,3,6, 8-pyrenetetrasulfonic acid sodium salt (Na-PTS) and 2mmol of silver nitrate are weighed and added to 5mL of water, and stirred until the dissolution is complete.
(2) 2mmol of 4, 4-Bipyridine (BPY) was weighed out and added to 5mL of methanol, and stirred until the solution was completely dissolved.
(3) Gradually dripping the solution (1) into the solution (2), and stirring until the reaction is complete.
(4) 2mL of aqueous ammonia was added dropwise to the mixture of (3) until it was clear without precipitation, and left to stand at 25 ℃ for 12 hours.
(5) And (4) collecting and filtering the product in the step (4), washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the product for 12 hours in an oven at the temperature of 60 ℃.
Example 5
The preparation process of the Ag-based MOFs comprises the following steps:
(1) 0.5mmol of 1,3,6, 8-pyrenetetrasulfonic acid sodium salt (Na-PTS) and 2mmol of silver acetate are weighed out and added to 5mL of water, and stirred until the dissolution is complete.
(2) 2mmol of 4, 4-Bipyridine (BPY) was weighed out and added to 5mL of methanol, and stirred until the solution was completely dissolved.
(3) Gradually dripping the solution (1) into the solution (2), and stirring until the reaction is complete.
(4) 1.5mL of ammonia was added dropwise to the mixture of (3) until it was clear without precipitation, and left to stand at room temperature at 25 ℃ for 12 hours.
(5) And (4) collecting and filtering the product in the step (4), washing the product for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the product for 12 hours in a drying oven at the temperature of 60 ℃ to obtain the Ag-based MOFs.
Experimental example 1
40mg of 1,3,6, 8-pyrene tetrasulfonic acid sodium salt (Na-PTS) dried for 12 hours at 120 ℃ in a vacuum drying oven was weighed, added to 2mL of acetonitrile solution (containing 1.2. mu.L of thioanisole), subjected to photocatalytic oxidation experiment under full light (supplied by a xenon lamp) after bubbling oxygen for 15min, and sampled after one hour, and the results are shown in FIG. 4.
Experimental example 2
40mg of 4, 4-Bipyridine (BPY) dried in a vacuum oven at 120 ℃ for 12 hours was weighed, added to 2mL of acetonitrile solution (containing 1.2. mu.L of thioanisole), subjected to photocatalytic oxidation test under full light (supplied by a xenon lamp) after bubbling oxygen for 15min, and sampled after one hour, the results are shown in FIG. 4.
Experimental example 3
40mg of Ag-PTS-BPY prepared in example 1 was weighed and added to 2mL of acetonitrile solution (containing 1.2. mu.L of thioanisole), and after blowing oxygen for 15min, a photocatalytic oxidation experiment was performed under full light (supplied by a xenon lamp), and samples were taken after one hour, and the results are shown in FIGS. 4 and 5.
Experimental example 4
40mg of Ag-PTS-BPY prepared in example 1 was weighed, added to 2mL (containing 1.2. mu.L of thioanisole) of acetonitrile solution, nitrogen was blown for 15min, and then a photocatalytic oxidation experiment was performed under full light (provided by a xenon lamp), and after one hour, sampling was performed, the result is shown in FIG. 5.
Experimental example 5
40mg of Ag-PTS-BPY prepared in example 1 was weighed and added to 2mL (containing 1.2. mu.L of thioanisole) of acetonitrile, and after blowing air for 15min, a photocatalytic oxidation experiment was performed under full light (supplied by a xenon lamp), and after one hour, a sample was taken, and the result is shown in FIG. 5.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (16)
1. The silver-based metal organic framework material is characterized in that the preparation method of the silver-based metal organic framework material comprises the following steps:
dissolving silver salt and pyrenesulfonic acid in an inorganic solvent, dissolving pyridine in an organic solvent, mixing the two to obtain a light yellow precipitate, adding ammonia water until the precipitate is dissolved, standing, and volatilizing and crystallizing along with the solvent to obtain the compound;
the silver salt is silver nitrate or silver acetate;
the pyridine is 4, 4-bipyridine;
the pyrenesulfonic acid comprises 1,3,6, 8-pyrenetetrasulfonic acid, 1-pyrenesulfonic acid and p-pyrenesulfonic acid;
ag in the silver salt+The molar ratio of ions to pyridine to pyrenesulfonic acid is 2:2: 0.5-2;
the molar volume ratio of the pyrenesulfonic acid to the inorganic solvent is 0.5-2 mmol: 1-50 mL;
the molar volume ratio of the pyridine to the organic solvent is 2mmol: 2-10 mL.
2. The silver-based metal organic framework material according to claim 1, wherein the inorganic solvent is water.
3. The silver-based metal organic framework material of claim 1, wherein the organic solvent is methanol.
4. The silver-based metal organic framework material according to claim 1, wherein the specific conditions of standing are 15-100 ℃ for 12-48 h.
5. The silver-based metal organic framework material according to claim 4, wherein the material is allowed to stand at room temperature for 12-24 hours.
6. The silver-based metal organic framework material of claim 1, wherein the method of preparation further comprises a step of purifying the product.
7. The silver-based metal organic framework material according to claim 6, wherein the purification step is specifically: the collected product was filtered, washed and dried.
8. The silver-based metal organic framework material according to claim 7, wherein the filtration is performed by washing with deionized water and absolute ethyl alcohol sequentially for 2 to 3 times.
9. The silver-based metal organic framework material according to claim 7, wherein the drying is in particular vacuum drying; the vacuum drying condition is that the temperature is 60-150 ℃ and the time is 12-24 h.
10. Use of the silver-based metal organic framework material according to any of claims 1 to 9 for photocatalytic selective oxidation.
11. The use of claim 10, wherein the photocatalytic selective oxidation is a photocatalytic selective oxidation of a thioether.
12. A photocatalyst, characterized in that it comprises a silver-based metal organic framework material according to any one of claims 1 to 9.
13. A method for carrying out photocatalytic selective oxidation, which comprises adding the silver-based metal organic framework material according to any one of claims 1 to 9 and/or the photocatalyst according to claim 12 to a reaction, and oxidizing thioether to sulfoxide under all light conditions.
14. The method of claim 13, wherein the sulfide includes mustard gas, thioanisole, p-chlorobenzenethioate, p-bromobenzylthioate, and p-methoxybenzenethioate.
15. The method of claim 14, wherein the method of performing photocatalytic selective oxidation is performed in a liquid environment.
16. The method of claim 14, wherein the liquid environment is provided by an organic solvent comprising acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011181167.4A CN112264103B (en) | 2020-10-29 | 2020-10-29 | Silver-based metal organic framework material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011181167.4A CN112264103B (en) | 2020-10-29 | 2020-10-29 | Silver-based metal organic framework material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112264103A CN112264103A (en) | 2021-01-26 |
| CN112264103B true CN112264103B (en) | 2022-01-25 |
Family
ID=74344464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011181167.4A Active CN112264103B (en) | 2020-10-29 | 2020-10-29 | Silver-based metal organic framework material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112264103B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413917A (en) * | 2021-06-02 | 2021-09-21 | 贵州师范大学 | Preparation and application of Tb-MOF nanosheet based on pyrenetetracarboxylic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN107955177A (en) * | 2017-10-24 | 2018-04-24 | 齐鲁工业大学 | A kind of Ag coordinated polymer containing p-aminobenzene sulfonic acid and preparation method thereof |
| CN109810030A (en) * | 2019-02-19 | 2019-05-28 | 曲阜师范大学 | A kind of visible light promotes the preparation method of asymmetric sulfoxide compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179262B (en) * | 2016-07-08 | 2018-07-20 | 苏州大学 | Composite material and preparation method and purposes with absorption-visible light photocatalytic degradation synergistic effect |
-
2020
- 2020-10-29 CN CN202011181167.4A patent/CN112264103B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744105A (en) * | 2011-04-18 | 2012-10-24 | 韩国化学研究院 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN107955177A (en) * | 2017-10-24 | 2018-04-24 | 齐鲁工业大学 | A kind of Ag coordinated polymer containing p-aminobenzene sulfonic acid and preparation method thereof |
| CN109810030A (en) * | 2019-02-19 | 2019-05-28 | 曲阜师范大学 | A kind of visible light promotes the preparation method of asymmetric sulfoxide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112264103A (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110194730B (en) | Application of DUT-67(Zr) in preparation of methyl phenyl sulfoxide through photocatalytic oxidation of methyl phenyl sulfide | |
| CN112264103B (en) | Silver-based metal organic framework material and preparation method and application thereof | |
| CN108101918A (en) | A kind of green general-purpose preparation method of pyridyl group porphyrin metallic | |
| CN109261188A (en) | A kind of adjustable cuprous oxide-copper oxide of Lacking oxygen/carbonitride composite oxides, preparation method and applications | |
| CN113663731B (en) | Preparation method and application of FL @ MOF composite photocatalyst | |
| CN104307519A (en) | Gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution and preparation method of gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution | |
| CN105749978A (en) | Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance | |
| CN109201113A (en) | A kind of functional metal organic framework composite material and preparation method thereof | |
| CN112718008A (en) | Heterogeneous photosensitizer based on metal organic framework material as carrier and preparation method and application thereof | |
| CN112500580B (en) | Preparation method and application of cobalt-based metal organic framework catalyst for activating oxygen molecules | |
| JP5532776B2 (en) | Photocatalyst and method for producing photocatalyst | |
| CN108855190A (en) | The Ag-g-C that a kind of copper chlorophyll trisodium and eosin are sensitized altogether3N4The preparation method and applications of catalysis material | |
| US20140046064A1 (en) | Process for the Synthesis of Precursor Complexes of Titanium Dioxide Sensitization Dyes Based on Ruthenium Polypyridine Complexes | |
| CN108080028B (en) | Preparation method of 8-hydroxyquinoline iron organic dye photodegradation catalyst | |
| CN115028849B (en) | Preparation method and application of metal triangle supermolecule with room temperature fluorescence | |
| CN104876976B (en) | Meso-5, 10, 15, 20-tetra- (p-carboxyphenyl) porphyrin bimetal coordination polymer and synthetic method thereof | |
| CN114367312B (en) | Ag + -Ag 0 Graphite-phase-doped carbon nitride coupled cobalt oxime molecule composite photocatalyst and preparation method and application thereof | |
| CN108997591B (en) | Visible-light response hafnium-based metal organic framework material and preparation method thereof | |
| Jiang et al. | N-heterocyclic carbene-ligated metal complexes and clusters for photocatalytic CO2 reduction | |
| CN111303216B (en) | Preparation method and application of metal organic ternary cyclic compound | |
| Mondal et al. | Shedding light on hydroxyquinoline-based ruthenium sensitizers with a long-lived charge carrier to boost photocatalytic H 2 evolution | |
| CN103012491B (en) | Method for synthesizing ruthenium complex through one-pot method | |
| CN109851811B (en) | Preparation method and application of bipyridyl ruthenium MOF material | |
| CN114950485B (en) | NiS/VS synthesized with assistance of eutectic solvent 2 Composite material and use thereof | |
| CN112679541B (en) | Preparation method and application of metal organic ternary cyclic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |