CN114653405B - Vase-like polyacid-based three-dimensional metal organic framework material and preparation method and application thereof - Google Patents
Vase-like polyacid-based three-dimensional metal organic framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 150000003568 thioethers Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- -1 sulfoxide compound Chemical class 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- FEOIYPLRWRCSMS-UHFFFAOYSA-N 1-ethyl-1,2,4-triazole Chemical compound CCN1C=NC=N1 FEOIYPLRWRCSMS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 150000001879 copper Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 38
- 230000003647 oxidation Effects 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000013078 crystal Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000002178 crystalline material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- MJEPOVIWHVRBIT-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfanylbenzene Chemical compound C1=CC(Cl)=CC=C1SC1=CC=C(Cl)C=C1 MJEPOVIWHVRBIT-UHFFFAOYSA-N 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001907 polarising light microscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a vase-like polyacid-based three-dimensional metal organic framework material, and a preparation method and application thereof. The material has the following chemical formula: [ Cu ] 3 (bty) 5 ][α‑BW 12 O 40 ]·4H 2 O; wherein bty =1-ethyl-1, 2, 4-triazole. The material has stable structure and high catalytic activity and selectivity, the selectivity and the conversion rate of the material in the reaction of synthesizing the sulfoxide compound by using the thioether compound through catalytic oxidation can reach more than 99 percent, the catalyst can be repeatedly utilized for a plurality of times, the use cost is low, and in addition, the material has simple preparation process and low cost, and is beneficial to large-scale production and application.
Description
Technical Field
The invention relates to a catalytic material, in particular to a vase-like polyacid-based three-dimensional metal organic frame material, a preparation method of the vase-like polyacid-based three-dimensional metal organic frame material and application of the vase-like polyacid-based three-dimensional metal organic frame material as a catalyst for oxidizing and converting a thioether compound into a sulfoxide compound, and belongs to the technical field of catalytic chemistry.
Background
The selective oxidation of thioether has been the subject of research, and on the one hand, as a sulfide oxidation product, sulfoxide and sulfone compounds have important application in the fields of medicine, pesticide, organic synthesis and the like, and the selective oxidation of organic sulfide is an effective way for providing sulfoxide and sulfone compounds. On the other hand, thioether compounds widely exist in oil products such as gasoline, diesel oil and the like, are the most main sulfur-containing substances in the oil products, and SOx generated by high-temperature combustion can cause acid rain and acid mist, so that environmental pollution is caused to cause harm to human beings. The sulfur-containing compounds in the oil products can be catalyzed and oxidized to generate sulfone or sulfoxide with larger polarity, and then the sulfone or sulfoxide is extracted by an extracting agent, so that the products are transferred from the oil phase to the extracting agent, thereby achieving the desulfurization effect, and the oxidation desulfurization process is widely researched and practically used in recent years. Compared with other desulfurization technologies, the deep oxidation desulfurization has excellent potential, low cost and simple operation (kukukushkin v.y. Coordin. Chem. Rev,1995,139,375-407; yang Y., zhang B., wang Y., et al J.am.chem.Soc,2013,135,14500-14503; dong J., hu J., chi Y.N., et al Angew.chem.int.ed,2017, 56:4473-4477). At present, a large amount of volatile organic solvents, chemical oxidants and some noble metal catalysts used in the oxidation reaction process of thioether compounds seriously harm the environment. Therefore, the development of relatively mild, clean thioether oxidation technologies is of great research importance.
Polyoxometallate (POMs) is an important polynuclear cluster compound, has redox property, acid-base property and controllable structural composition, and has wide application prospect in the field of catalysis. Although the polyacids at present show good catalytic activity and selectivity in the catalytic oxidation reaction of thioether, the polyacids also face the difficult problems of separation and recycling. In view of this, various supported materials such as silica, zeolite or polymer are used for synthesizing composite materials of polyacids to perform heterogeneous catalytic oxidation reaction, but such systems often face problems of undefined structural composition, low loading rate, deactivation of active sites or leaching of polyacids. Therefore, the polyacid is taken as a building block to design and synthesize the heterogeneous crystal catalyst, so that the polyacid has important theoretical and practical significance for the oxidation of the thioether compound with high activity and high selectivity.
At present, research discovers that the polyacid-based metal organic framework material can effectively solve the catalytic problem, combines the advantages of both the polyacid and the metal organic framework material, and can also effectively improve the structural stability and the thermal stability (Du, D.Y., qin, J.S., li, S.L., et al.Chem.Soc.Rev.2014,43,4615 4632;Buru C.T, platero-Prats A.E., chica D.G., et al.J. Mater.chem.A., 2018,6,7389-7394). Therefore, the polyacid-based three-dimensional metal organic framework material with a novel structure is researched and developed, and the sulfide compound can be efficiently catalyzed and oxidized, so that the polyacid-based three-dimensional metal organic framework material has practical production and application values.
Disclosure of Invention
In view of the drawbacks of the prior art, a first object of the present invention is to provide a vase-like polyacid-based three-dimensional metal-organic framework material formed by a transition metal copper ion and a bty ligand connected to form a vase-like three-dimensional porous structure, and { BW } 12 O 40 } 5- The anions are filled in the pore canal, the structure is stable, the repeated recycling of the material is facilitated, and the { BW (b-w) with catalytic activity is provided 12 O 40 } 5- Anions and copper ions are dispersed in the three-dimensional porous structure, so that catalytic active sites can be fully exposed, the catalytic activity is improved, and the active center ions are in a special coordination environment, so that the material has high catalytic activity and catalytic selectivity.
The second aim of the invention is to provide a preparation method of the vase-like polyacid-based three-dimensional metal organic framework material, which is simple, mild in condition and low in cost, and is beneficial to mass production.
The third purpose of the invention is to provide an application of the vase-like polyacid-based three-dimensional metal organic framework material, and the application of the vase-like polyacid-based three-dimensional metal organic framework material as a catalyst for oxidizing and converting a thioether compound into a sulfoxide compound, which has the characteristics of high catalytic activity and high selectivity, and particularly has the advantages of good stability, repeated use of the catalyst for a plurality of times and contribution to reduction of use cost.
In order to achieve the technical aim, the invention provides a vase-like polyacid-based three-dimensional metal organic framework material, which has the following chemical formula: [ Cu ] 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 O; wherein bty =1-ethyl-1, 2, 4-triazole.
As a preferable scheme, the vase-like polyacid-based three-dimensional metal organic framework material belongs to a monoclinic system, and the space group is C2/C. The unit cell parameter of the vase-like polyacid-based three-dimensional metal organic framework material is a =β=128.7785(7)°,/>
The vase-like polyacid-based three-dimensional metal organic framework material has a crystal structure that: there are two halves of crystallographically independent { BW in an asymmetric cell 12 O 40 } 5- Ion, three copper ions, five 1-ethyl-1, 2, 4-triazoles (bty), one deprotonated 1-ethyl-1, 2, 4-triazoles (bty) - ) The method comprises the steps of carrying out a first treatment on the surface of the Three copper ions all adopt a hexacoordinated octahedral configuration, and the copper ions are connected through bty to form two cores { Cu } 2 (bty) 2 Three cores { Cu }, three cores 3 (bty) 4 Sum of four cores { Cu } 4 (bty) 4 Different subunit structures, two different subunits are connected to form a one-dimensional chain structure, adjacent one-dimensional chains are connected with each other through tetranuclear subunits to form a two-dimensional metal complex layer, adjacent two-dimensional layers are connected to form a one-dimensional pore canal, the three-dimensional metal complex structure presents a vase-like frame structure along an a-axis, { BW 12 O 40 } 5- And the anions are used as tetradentate ligands to be filled in the one-dimensional pore canal to form the polyacid-based three-dimensional metal organic framework material.
The invention also provides a preparation method of the vase-like polyacid-based three-dimensional metal organic framework material, which is to dissolve K 5 [BW 12 O 40 ]·xH 2 And (3) regulating the pH of the mixed solution of O, copper salt and bty ligand to be acidic, performing hydrothermal reaction, and slowly cooling to room temperature after the hydrothermal reaction is completed.
As a preferred embodiment, K 5 [BW 12 O 40 ]·xH 2 The mol ratio of O, copper salt and bty is 1:4-6:1-2.
As a preferred embodiment, the copper salt is a conventional water-soluble copper salt including at least one of copper chloride, copper nitrate, copper acetate, and copper sulfate.
As a preferred scheme, the pH of the mixed solution is in the range of 2-4, and the obtained mixed solution is mainly green strip-shaped crystal product, and the crystal phase structure is in a vase-like shape. The pH value is more than 4 and less than or equal to 6.5, the obtained product is mainly blue blocky crystal, the crystal phase structure is not vase-like, and the crystal yield is greatly reduced in the environment with the pH value more than 4, so that the production is not facilitated.
As a preferred embodiment, the hydrothermal reaction conditions are as follows: the temperature is 120-180 ℃ and the time is 2-5 days.
K related to the invention 5 [BW 12 O 40 ]·xH 2 O is a compound reported in the prior art, and can be synthesized by reference to the prior art, for example (Deltcheff, C.R, inorg. Chem,1983,22,207-216).
The preparation method of the vase-like polyacid-based three-dimensional metal organic framework material provided by the invention comprises the following steps of: will K 5 [BW 12 O 40 ]·xH 2 O is dissolved in water and then copper salt and ligand bty are added, wherein K 5 [BW 12 O 40 ]·xH 2 The ratio of the O, copper salt and bty is 1:4-6:1-2, stirring is carried out for 0.2-0.8 h, the pH is regulated to 2-4 by nitric acid, stirring is continued for 0.2-0.8 h, then the mixture is transferred into a polytetrafluoroethylene reaction kettle, heating is carried out in an oven for 2-5 days at 120-180 ℃, the mixture is slowly cooled to room temperature, and the obtained crystal material is washed and dried to obtain the vase-like polyacid-based three-dimensional metal organic framework material.
The invention also provides application of the vase-like polyacid-based three-dimensional metal organic framework material as a catalyst for oxidizing and converting a thioether compound into a sulfoxide compound.
As a preferable scheme, the thioether compound and the vase-shaped polyacid-based three-dimensional metal organic framework material are mixed, heated to 50-70 ℃, and then added with an oxidant for oxidation reaction to obtain the sulfoxide compound.
As a preferable scheme, the molar ratio of the thioether compound to the vase-like polyacid-based three-dimensional metal organic framework material to the oxidant is 100:0.5-1.5:100-150.
As a further preferred embodiment of the present invention,
the thioether compound has the structure of formula 1:
the sulfoxide compound has the structure of formula 2:
wherein R is 1 Is a common substituent group, e.g. C 1 ~C 5 Alkyl (such as methyl, propyl, etc.), C 1 ~C 5 Alkoxy (specifically, such as methoxy, ethoxy, etc.), halogen substituents (specifically, such as fluoro substituents, chloro substituents, etc.), and the like; r is R 2 Alkyl radicals, e.g. C 1 ~C 5 Alkyl (such as methyl, propyl, etc. in particular).
As a further preferred embodiment, the oxidizing agent is hydrogen peroxide. Typically in the form of industrial hydrogen peroxide.
As a preferred scheme, the thioether compound and the vase-shaped polyacid-based three-dimensional metal organic framework material are mixed in a solvent such as methanol, acetonitrile or ethanol.
The invention also provides a method for synthesizing the sulfoxide compound by selectively catalyzing and oxidizing the thioether compound by using the vase-like polyacid-based three-dimensional metal organic framework material, which comprises the following steps: adding the thioether compound, the vase-like polyacid-based three-dimensional metal organic framework material and the internal standard naphthalene into a methanol solution, mixing, stirring and heating to 50-70 ℃, adding an oxidant, and reacting for a period of time under the stirring condition, wherein the molar ratio of the thioether compound to the vase-like polyacid-based three-dimensional metal organic framework material to the oxidant is 100:0.5-1.5:100-150, and carrying out qualitative analysis by using gas chromatography. Wherein naphthalene does not participate in the reaction, and is mainly used as an internal standard for gas chromatography detection and analysis.
Taking a vase-like polyacid-based three-dimensional metal organic framework material for catalyzing and oxidizing phenyl sulfide to be converted into phenyl methyl sulfoxide as an example, the reaction route is as follows:
the oxidation reaction of the thioether compound is difficult to control to produce sulfoxide compounds with high selectivity, generally sulfone compounds are produced, and the selectivity of the vase-like polyacid-based three-dimensional metal organic framework material for converting the thioether compounds into the sulfoxide compounds reaches more than 99 percent.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
(1) The vase-like polyacid-based three-dimensional metal organic framework material provided by the invention has high catalytic activity and catalytic selectivity, and the conversion rate and the selectivity can reach more than 99% in the reaction of synthesizing sulfoxide compounds by catalytically oxidizing thioether compounds.
(2) The vase-like polyacid-based three-dimensional metal organic framework material provided by the invention has good structural stability, can be repeatedly used for many times, and can keep higher catalytic activity, for example, more than 95% of catalytic activity can be still kept after 5 times of cyclic utilization
(3) The preparation method of the vase-like polyacid-based three-dimensional metal organic framework material provided by the invention is simple, mild in condition and low in cost, and is beneficial to mass production.
(4) The vase-like polyacid-based three-dimensional metal organic framework material provided by the invention has mild reaction conditions in the process of catalytically oxidizing thioether compounds, and can react at 60 ℃ under normal pressure.
Drawings
In fig. 1 (a) is an asymmetric unit of a vase-like polyacid-based three-dimensional metal organic framework material; (b) Is a trinuclear subunit of a vase-like polyacid-based three-dimensional metal organic framework material; (c) Is a dinuclear subunit of a vase-like polyacid-based three-dimensional metal organic framework material; (d) Is a tetranuclear subunit of a vase-like polyacid-based three-dimensional metal organic framework material; (e) Is a two-dimensional layer of vase-like polyacid-based three-dimensional metal organic framework material.
FIG. 2 is a crystalline structure of a vase-like polyacid-based three-dimensional metal organic framework material.
Fig. 3 (a) shows a three-dimensional metal-organic framework structure; (b) a connection mode of polyacid and copper; (c) Is a vase-like polyacid-based three-dimensional metal organic framework material.
Fig. 4 is a vase-like polyacid-based three-dimensional metal organic framework material synthesized at ph=5.
FIG. 5 shows the results of selective catalytic oxidation of various thioether compounds by vase-like polyacid-based three-dimensional metal organic framework materials.
FIG. 6 shows the results of a cyclic use of vase-like polyacid-based three-dimensional metal organic framework materials.
FIG. 7 is a XRD contrast plot of vase-like polyacid-based three-dimensional metallo-organic framework material before and after catalytic reaction.
FIG. 8 is a graph showing the catalytic efficiency of vase-like polyacid-based three-dimensional metal-organic framework materials in different solvents.
FIG. 9 is a graph comparing catalytic efficiencies of different materials.
FIG. 10 is a diagram of the catalytic mechanism of a vase-like polyacid-based three-dimensional metal-organic framework material.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but are not intended to limit the scope of the claims.
The chemical reagents referred to in the following examples are commercially available, unless otherwise specified.
Example 1
Multi-acid-base three-dimensional metal organic framework crystal material [ Cu 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 The preparation method of O comprises the following specific steps:
(1) Obtaining a precursor K by a conventional aqueous solution method 5 [BW 12 O 40 ]·xH 2 O(Deltcheff,C.R,Inorg.Chem,1983,22,207-216);
(2)K 5 [BW 12 O 40 ]·xH 2 O (0.15 g,0.05 mmol) was dissolved in 10ml water and then CuCl was added 2 ·2H 2 O(00341g,0.20 mmol) and bty (0.082 g,0.05 mmol), the pH was adjusted to 2.5 with dilute nitric acid at room temperature for 30min, stirring was continued at room temperature for 30min, the mixed solution was transferred to a 20ml polytetrafluoroethylene reaction vessel, heated in an oven at 120℃for 5 days, and then cooled slowly to room temperature to give a green strand-like crystalline material in a yield of 41% (based on W).
(3) The implementation steps of the selective catalytic oxidation of thioether include: adding 0.5mmol of phenyl sulfide into a 2ml glass reaction bottle, adding 0.005mmol of the catalyst synthesized in the step 2 into 1ml of methanol solvent, heating to 60 ℃, stirring for 5min, adding 0.5mmol of oxidant hydrogen peroxide, reacting for 1h, quantitatively analyzing by a gas chromatography internal standard method, and obtaining that the conversion rate and the selectivity can reach more than 99%, wherein the catalyst can be recycled by simple filtration and can be reused by washing and drying.
In this example, when a pH adjustment of 5 was used instead of pH 2.5, a blue bulk crystalline material with a crystal structure as shown in FIG. 4 was obtained.
In this example, when CuCl 2 ·2H 2 O is composed of equal amounts of CuSO 4 ·5H 2 O、Cu(NO 3 ) 2 ·3H 2 O or Cu (OAc) 2 ·H 2 O is replaced, and the crystals obtained are the same.
In this example, the methanol solvent may be replaced by acetonitrile or ethanol, and the catalytic reaction effect is shown in fig. 8.
In this example, the phenyl sulfide may be replaced by p-methoxy phenyl sulfide, p-fluoro phenyl sulfide and p-chloro phenyl sulfide, and the catalytic reaction effect is shown in fig. 5.
The prepared vase-like polyacid-based three-dimensional metal organic framework material is shown in figures 1-3.
For the polyacid-based metal organic framework material [ Cu ] having the same crystal structure in example 1 described above 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 O, bty =1-ethyl-1, 2, 4-triazole, the specific crystal material structure is shown in FIGS. 1,2 and 3, and by way of comparison, another blue block crystal, the crystal structure of which is shown in FIG. 4, is prepared at pH around 5, and is not flowerA bottle-like crystal structure.
The results of selective catalytic oxidation of the crystalline material prepared in example 1 were examined by gas chromatography, and fig. 5 summarizes the corresponding catalytic results, in which the conversion and selectivity of p-methyl phenyl sulfide can be more than 99%, and the conversion and selectivity of p-methyl phenyl sulfide, p-methoxy phenyl sulfide, p-fluoro phenyl sulfide and p-chloro phenyl sulfide are 94% -99%.
Multiple cycle catalytic experiments were performed on the crystalline material prepared in example 1 using gas chromatography, and fig. 6 shows that the catalytic efficiency did not significantly decrease for 5 cycles, and fig. 7 shows that XRD and analog comparison show that the structure of the crystalline material did not change before and after catalytic reaction.
The catalytic experiments were performed on the crystalline material prepared in example 1 using gas chromatography in different solvents, and fig. 8 shows catalytic efficiency among different solvents, and the results show that methanol is the optimal solvent. In addition, the catalytic performance research is carried out by using different precursor copper chloride and polyacid raw materials as catalysts, and the comparison of the catalytic efficiency of FIG. 9 shows that copper ions and polyacid modules have catalytic effects in the catalytic process. It is therefore inferred that the possible catalytic mechanism is shown in fig. 10, in which tungsten ions and copper ions in the crystalline material can form peroxides and thus thioether compounds undergo catalytic oxidation.
Example 2
Multi-acid-base three-dimensional metal organic framework crystal material [ Cu 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 The preparation method of O comprises the following specific steps:
(1) Obtaining a precursor K by a conventional aqueous solution method 5 [BW 12 O 40 ]·xH 2 O(Deltcheff,C.R,Inorg.Chem,1983,22,207-216);
(2)K 5 [BW 12 O 40 ]·xH 2 O (0.3 g,0.2 mmol) was dissolved in 10ml water and then CuCl was added 2 ·2H 2 O (0.0682 g,0.40 mmol) and bty (0.0164 g,0.1 mmol), stirring at room temperature for 30min, adjusting pH to 2.5 with dilute nitric acid, continuing stirring at room temperature for 30min, transferring the mixed solution to 20mlHeating the mixture in a polytetrafluoroethylene reaction kettle in an oven at 120 ℃ for about 5 days, and slowly cooling the mixture to room temperature to obtain green strip crystals with the yield of 36% (based on W);
(3) The implementation steps of the selective catalytic oxidation of thioether include: 0.5mmol of phenyl sulfide is added into a 2ml glass reaction bottle, 0.005mmol of the catalyst synthesized in the step 2 is added into 1ml of methanol solvent, the mixture is heated to 60 ℃, the mixture is stirred for 5min, 0.5mmol of oxidant hydrogen peroxide is added, after the reaction is carried out for 1h, the conversion rate and the selectivity can reach more than 99% through quantitative analysis of gas chromatography, the catalyst is recovered through simple filtration, and the catalyst can be reused through washing and drying.
Example 3
Multi-acid-base three-dimensional metal organic framework crystal material [ Cu 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 The preparation method of O comprises the following specific steps:
(1) Obtaining a precursor K by a conventional aqueous solution method 5 [BW 12 O 40 ]·xH 2 O(Deltcheff,C.R,Inorg.Chem,1983,22,207-216);
(2)K 5 [BW 12 O 40 ]·xH 2 O (0.15 g,0.1 mmol) was dissolved in 10ml water and then CuCl was added 2 ·2H 2 O (0.0341 g,0.20 mmol) and bty (0.082 g,0.05 mmol), stirring at room temperature for 30min, adjusting pH to 2.5 with dilute nitric acid, continuing stirring at room temperature for 30min, transferring the mixed solution into a 20ml polytetrafluoroethylene reaction kettle, heating at 150 ℃ for 3 days in an oven, and slowly cooling to room temperature to obtain a green strip-like crystal material with a yield of 37% (based on W);
(3) The implementation steps of the selective catalytic oxidation of thioether include: adding 0.5mmol of phenyl sulfide into a 2ml glass reaction bottle, adding 0.005mmol of the catalyst synthesized in the step 2 into 1ml of methanol solvent, heating to 60 ℃, stirring for 5min, adding 0.5mmol of oxidant hydrogen peroxide, reacting for 1h, quantitatively analyzing by gas chromatography, and obtaining the conversion rate and selectivity reaching more than 99%, wherein the catalyst can be recycled by simple filtration, washed and dried, and can be reused.
Example 4
Multi-acid-base three-dimensional metal organic framework crystal material [ Cu 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 The preparation method of O comprises the following specific steps:
(1) Obtaining a precursor K by a conventional aqueous solution method 5 [BW 12 O 40 ]·xH 2 O(Deltcheff,C.R,Inorg.Chem,1983,22,207-216);
(2)K 5 [BW 12 O 40 ]·xH 2 O (0.3 g,0.2 mmol) was dissolved in 10ml water and then CuCl was added 2 ·2H 2 O (0.0682 g,0.40mmol and bty (0.0164 g,0.1 mmol), stirring at room temperature for 30min, adjusting pH to 2.5 with dilute nitric acid, continuing stirring at room temperature for 30min, transferring the mixed solution into a 20ml polytetrafluoroethylene reaction kettle, heating at 150deg.C in an oven for 3 days, slowly cooling to room temperature, green bar-like crystals with 34% yield (based on W);
(3) The implementation steps of the selective catalytic oxidation of thioether include: adding 0.5mmol of phenyl sulfide into a 2ml glass reaction bottle, adding 0.005mmol of the catalyst synthesized in the step 2 into 1ml of methanol solvent, heating to 60 ℃, stirring for 5min, adding 0.5mmol of oxidant hydrogen peroxide, reacting for 1h, quantitatively analyzing by gas chromatography, and obtaining the conversion rate and selectivity reaching more than 99%, wherein the catalyst can be recycled by simple filtration, washed and dried, and can be reused.
For each of the above examples 1 to 4, a polyacid-based metal-organic framework material [ Cu ] having the same crystal structure was obtained 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 O, bty = 1-ethyl-1, 2, 4-triazole, see fig. 1,2 and 3 for specific crystalline material structures.
Claims (9)
1. The application of the vase-like polyacid-based three-dimensional metal organic framework material is characterized in that: as a catalyst for the oxidative conversion of thioether compounds to sulfoxide compounds;
the vase-like polyacid-based three-dimensional metal organic framework material has the following chemical formula:
[Cu 3 (bty) 5 ][α-BW 12 O 40 ]·4H 2 O;
wherein,
bty =1-ethyl-1, 2, 4-triazole.
2. The use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 1, characterized in that:
belongs to monoclinic system, and the space group is C2/C; the unit cell parameters are as follows β=128.7785(7)°,/>
3. Use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 1 or 2, characterized in that: the vase-like polyacid-based three-dimensional metal organic framework material is prepared by the following method: will dissolve K 5 [BW 12 O 40 ]·xH 2 And (3) regulating the pH of the mixed solution of O, copper salt and bty ligand to be acidic, performing hydrothermal reaction, and slowly cooling to room temperature after the hydrothermal reaction is completed.
4. Use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 3, characterized in that: k (K) 5 [BW 12 O 40 ]·xH 2 The mol ratio of O, copper salt and bty ligand is 1:4-6:1-2.
5. The use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 4, characterized in that: the copper salt comprises at least one of copper chloride, copper nitrate, copper acetate and copper sulfate.
6. Use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 3, characterized in that: the pH of the mixed solution is adjusted to 2-4.
7. Use of a vase-like polyacid-based three-dimensional metal-organic framework material according to any one of claims 3 to 6, characterized in that: conditions of the hydrothermal reaction: the temperature is 120-180 ℃ and the time is 2-5 days.
8. The use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 1, characterized in that: after mixing the thioether compound and the vase-shaped polyacid-based three-dimensional metal organic framework material, heating to 50-70 ℃, and then adding an oxidant for oxidation reaction to obtain the sulfoxide compound.
9. The use of a vase-like polyacid-based three-dimensional metalorganic framework material according to claim 1, characterized in that: the molar ratio of the thioether compound to the vase-like polyacid-based three-dimensional metal organic framework material to the oxidant is 100:0.5-1.5:100-150.
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