A zirconium-based metal-organic framework material, a preparation method and application thereof

Abstract

The application discloses a zirconium-based metal-organic framework material and a preparation method and application thereof. The preparation method of the zirconium-based metal-organic framework material comprises the following steps: 1) dispersing a zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin and a regulator in an organic solvent to react, so as to obtain a two-dimensional zirconium-based metal-porphyrin framework; and 2) dispersing the two-dimensional zirconium-based metal-porphyrin framework and a transition metal salt in an organic solvent to react, so as to obtain the zirconium-based metal-organic framework material. The zirconium-based metal-organic framework material has the advantages of large specific surface area, strong adsorption capacity, rich active sites, high catalytic activity, and the like, and the loaded metal is not easy to flow out, and the structure is still complete and high catalytic activity after multiple cycles, and the preparation method is simple, and is suitable for being used for the oxidation reaction of a benzyl C-H bond.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalytic oxidation, in particular to a zirconium-based metal-organic framework material and a preparation method and application thereof. BACKGROUND

[0002] Selective oxidation of hydrocarbons is of great significance in the fields of biology, environment and synthetic chemistry, and the current requirements for selective oxidation of hydrocarbons include environmentally friendly oxidants, inexpensive catalysts with high selectivity, high atomic utilization rate and the like (X. Hu, Y. Liu, H. Huang, B. Huang, G. Chai, Z. Xie, Green Chem. 2020, 22, 1291-1300; E. Paris, C. Oldani, A. S. Aricò, C. D'Urso, F. Bigi, G. Maestri, F. Pancrazzi, R. Maggi, ACS Sustainable Chem. Eng. 2019, 7, 5886-5891). Molecular oxygen (O2) is the most ideal oxidant, but it is difficult to use O2 alone as an oxidant for selective oxidation of hydrocarbons, and it is necessary to prepare a catalyst capable of activating O2 under mild conditions for direct selective oxidation of hydrocarbons.

[0003] Metal-organic frameworks (MOFs) are crystalline materials assembled by metal or metal clusters and organic ligands through coordination, which have attracted great attention due to their regular crystal structure, high porosity, and strong designability (D. Yang, B. C. Gates, ACS Catal. 2019, 9, 1779-1798; Q. Wang, D. Astruc, Chem. Rev. 2020, 120, 1438-1511; Z. X. Sun, K. Sun, M. L. Gao, O. Metin, H. L. Jiang, Angew. Chem. Int. Ed. 2022, 61, e202206108). In the past decade, researchers have designed various MOFs-based artificial enzymes that can be used to simulate single oxygenation reactions, CO2 reduction reactions, and other important reactions (X. Feng, Y. Song, J. S. Chen, Z. Xu, S. J. Dunn, W. Lin, J. Am. Chem. Soc. 2021, 143, 1107-1118; G. Liu, H. Cui, S. Wang, L. Zhang, C.-Y. Su, J. Mater. Chem. A 2020, 8, 8376-8382.; A. T. Castner, B. A. Johnson, S. M. Cohen, S. Ott, J. Am. Chem. Soc. 2021, 143, 7991-7999; P. M. Stanley, A. Y. Su, V. Ramm, P. Fink, C. Kimna, O. Lieleg, M. Elsner, J. A. Lercher, B. Rieger, J. Warnan, R. A. Fischer, Adv. Mater. 2023, 35, 2207380). However, most of the existing MOFs artificial enzyme mimics are three-dimensional structures, which have regular pore size and channels and hinder the diffusion of substrate molecules in the catalyst and their contact with active sites to some extent, ultimately directly affecting the catalytic activity of these MOFs as catalysts. In addition, the existing MOFs also have the problems of small specific surface area, limited adsorption capacity, easy loss of loaded metal, and significant decrease in catalytic activity after multiple cycles.

[0004] Therefore, it is of great significance to develop a MOF with large specific surface area, strong adsorption capacity, rich active sites, high catalytic activity, and the ability to maintain structural integrity and high catalytic activity after multiple cycles. SUMMARY

[0005] The present application aims to provide a zirconium-based metal-organic framework material and its preparation method and application.

[0006] The technical scheme adopted by the present application is:

[0007] A preparation method of a zirconium-based metal-organic framework material comprises the following steps:

[0008] 1) dispersing a zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin and a regulator in an organic solvent to react, to obtain a two-dimensional zirconium-based metal-porphyrin framework;

[0009] 2) dispersing the two-dimensional zirconium-based metal-porphyrin framework and a transition metal salt in an organic solvent to react, to obtain the zirconium-based metal-organic framework material.

[0010] Preferably, a preparation method of a zirconium-based metal-organic framework material comprises the following steps:

[0011] 1) dispersing a zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin and a regulator in an organic solvent to react, and then purifying and drying the reaction product, to obtain a two-dimensional zirconium-based metal-porphyrin framework;

[0012] 2) dispersing the two-dimensional zirconium-based metal-porphyrin framework and a transition metal salt in an organic solvent to react, and then purifying and drying the reaction product, to obtain the zirconium-based metal-organic framework material.

[0013] Preferably, the molar ratio of the zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin and the regulator in step 1) is 1:0.25-0.50:36-1176.

[0014] Further preferably, the molar ratio of the zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin and the regulator in step 1) is 1:0.25-0.35:150-370.

[0015] Preferably, the zirconium salt in step 1) is at least one of ZrCl4 and ZrOCl2·8H2O.

[0016] Preferably, the regulator in step 1) is a mixture of water and at least one of formic acid, glacial acetic acid, lauric acid, oleic acid and benzoic acid.

[0017] Preferably, the organic solvent in step 1) is at least one of N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

[0018] Preferably, the reaction in step 1) is carried out at a temperature of 90-130℃, and the reaction time is 12-36h.

[0019] Preferably, the molar ratio of the two-dimensional zirconium-based metal- porphyrin framework (molecular formula: [Zr6O4(OH)4](HCOO - )4(OH - )4) to the transition metal salt in step 2) is 1:1-14.

[0020] Further preferably, the molar ratio of the two-dimensional zirconium-based metal- porphyrin framework to the transition metal salt in step 2) is 1:2-4.

[0021] Preferably, the transition metal salt in step 2) is at least one of ferrous salt, manganese salt, cobalt salt, nickel salt, copper salt, and zinc salt.

[0022] Further preferably, the transition metal salt in step 2) is at least one of FeCl2, MnCl2, CoCl2, NiCl2, CuCl2, and ZnCl2.

[0023] More preferably, the transition metal salt in step 2) is at least one of FeCl2, MnCl2, CoCl2, and CuCl2.

[0024] Preferably, the organic solvent in step 2) is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, and acetonitrile.

[0025] Preferably, the reaction in step 2) is carried out at a temperature of 50-150°C, and the reaction time is 12-36h.

[0026] A zirconium-based metal-organic framework material prepared by the above method.

[0027] Preferably, the zirconium-based metal-organic framework material has a sheet structure.

[0028] A method for selectively oxidizing a benzyl-containing compound includes the following steps:

[0029] The benzyl-containing compound, the above zirconium-based metal-organic framework material, and isobutyraldehyde are dispersed in an organic solvent, and then the mixture is placed in an oxygen atmosphere to carry out the reaction.

[0030] Preferably, the benzyl-containing compound is one of , wherein R 1 is -H or -OCH3.

[0031] Preferably, the molar ratio of the benzyl-containing compound, the zirconium-based metal-organic framework material, and isobutyraldehyde is 1:0.005-0.020:3-7.

[0032] Preferably, the organic solvent is at least one of 1,2-dichloroethane, dichloromethane, and trichloromethane.

[0033] Preferably, the reaction is carried out at a temperature of 15-60℃, and the reaction time is 6-15h.

[0034] Further preferably, the reaction is carried out at a temperature of 20-35℃, and the reaction time is 10-15h.

[0035] The zirconium-based metal-organic framework material has the advantages of large specific surface area, strong adsorption capacity, rich active sites, high catalytic activity, and the like, and the preparation method is simple, and the zirconium-based metal-organic framework material is suitable for the oxidation reaction of a benzyl C-H bond.

[0036] Specifically:

[0037] 1) The zirconium-based metal-organic framework material has the structural characteristics of a super-thin sheet structure, adjustable structure, large specific surface area, strong adsorption capacity, and rich catalytic active sites, the enrichment and activation of oxygen in the metal porphyrin in the framework accelerate the reaction rate between the substrate molecules and active oxygen, and the electronic state of the metal porphyrin in the framework can be retained after the reaction, so that the recycling of the catalyst is realized, at the same time, the super-thin two-dimensional structure promotes the exposure of the active sites in the catalyst and reduces the mass transfer resistance in the reaction process, which is beneficial to the rapid contact of the reactants with the active center metal porphyrin for reaction and the rapid desorption and diffusion of the subsequent products;

[0038] 2) The zirconium-based metal-organic framework material has high stability and catalytic activity in the oxidation reaction of a benzyl C-H bond, the conversion value of the unit catalyst is significantly improved compared with traditional three-dimensional materials, and has the advantages of mild reaction conditions, convenient operation, wide substrate applicability, and the like, and has good application prospect;

[0039] 3) The preparation method of the zirconium-based metal-organic framework material has the advantages of simple operation and mild conditions, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 The PXRD pattern of the two-dimensional zirconium-based metal-porphyrin framework in Examples 1-5.

[0041] Figure 2 The PXRD pattern of the zirconium-based metal-organic framework material in Examples 6-11.

[0042] Figure 3 The SEM pattern of the two-dimensional zirconium-based metal-porphyrin framework in Example 1.

[0043] Figure 4SEM image of the two-dimensional zirconium-based metallo-porphyrin framework in Example 2.

[0044] Figure 5 SEM image of the two-dimensional zirconium-based metallo-porphyrin framework in Example 3.

[0045] Figure 6 SEM image of the two-dimensional zirconium-based metallo-porphyrin framework in Example 4.

[0046] Figure 7 SEM image of the two-dimensional zirconium-based metallo-porphyrin framework in Example 5.

[0047] Figure 8 SEM image of the zirconium-based metal-organic framework material in Example 6.

[0048] Figure 9 SEM image of the zirconium-based metal-organic framework material in Example 7.

[0049] Figure 10 SEM image of the zirconium-based metal-organic framework material in Example 8.

[0050] Figure 11 SEM image of the zirconium-based metal-organic framework material in Example 9.

[0051] Figure 12 SEM image of the zirconium-based metal-organic framework material in Example 10.

[0052] Figure 13 SEM image of the zirconium-based metal-organic framework material in Example 11.

[0053] Figure 14 AFM image of the two-dimensional zirconium-based metallo-porphyrin framework in Example 1.

[0054] Figure 15 AFM image of the zirconium-based metal-organic framework material in Example 6.

[0055] Figure 16 Nitrogen adsorption-desorption isotherms of the two-dimensional zirconium-based metallo-porphyrin framework in Example 1 and the zirconium-based metal-organic framework material in Example 6.

[0056] Figure 17 XPS spectra (N 1s) of the two-dimensional zirconium-based metallo-porphyrin framework in Example 1 and the zirconium-based metal-organic framework material in Example 6.

[0057] Figure 18 XPS spectra (Fe 2p) of the zirconium-based metal-organic framework material in Example 6.

[0058] Figure 19A graph of the results of the cycle performance test for the zirconium-based metal-organic framework material in Example 6.

[0059] Figure 20 A graph of the results of the thermal filtration experiment test for the zirconium-based metal-organic framework material in Example 6. DETAILED DESCRIPTION

[0060] The application will be further explained and described with reference to the following specific examples.

[0061] Example 1:

[0062] A two-dimensional zirconium-based metal-porphyrin framework was prepared as follows:

[0063] 10 mg (0.043 mmol) of ZrCl4, 10 mg (0.013 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin, 586 mg (12.7 mmol) of formic acid, and 50 mg (2.8 mmol) of water were added to 2 mL of N,N-dimethylformamide, ultrasonically dispersed for 30 min, and then placed in an oven at 120°C for 24 h. The reaction solution was then cooled to room temperature, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone multiple times, and then placed in a vacuum drying oven at 100°C for 24 h to obtain a two-dimensional zirconium-based metal-porphyrin framework (denoted as Zr-TCPP1).

[0064] Example 2:

[0065] A two-dimensional zirconium-based metal-porphyrin framework was prepared as follows:

[0066] 10 mg (0.043 mmol) of ZrCl4, 10 mg (0.013 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin, 252 mg (4.2 mmol) of glacial acetic acid, and 50 mg (2.8 mmol) of water were added to 2 mL of N,N-dimethylformamide, ultrasonically dispersed for 30 min, and then placed in an oven at 120°C for 24 h. The reaction solution was then cooled to room temperature, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone multiple times, and then placed in a vacuum drying oven at 100°C for 24 h to obtain a two-dimensional zirconium-based metal-porphyrin framework (denoted as Zr-TCPP2).

[0067] Example 3:

[0068] A two-dimensional zirconium-based metal-porphyrin framework was prepared as follows:

[0069] ZrCl4, 10 mg (0.013 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin, 1.18 g (4.2 mmol) of oleic acid and 50 mg (2.8 mmol) of water were added into 2 mL of N,N-dimethylformamide, ultrasonic dispersion for 30 min, then placed in an oven at 120 °C for 24 h, then the reaction solution was cooled to room temperature, filtered, the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying oven at 100 °C for 24 h to obtain a two-dimensional zirconium-based metal-porphyrin framework (denoted as Zr-TCPP4).

[0070] Example 4:

[0071] A two-dimensional zirconium-based metal-porphyrin framework was prepared by the following method:

[0072] ZrCl4, 10 mg (0.013 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin, 1.18 g (4.2 mmol) of oleic acid and 50 mg (2.8 mmol) of water were added into 2 mL of N,N-dimethylformamide, ultrasonic dispersion for 30 min, then placed in an oven at 120 °C for 24 h, then the reaction solution was cooled to room temperature, filtered, the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying oven at 100 °C for 24 h to obtain a two-dimensional zirconium-based metal-porphyrin framework (denoted as Zr-TCPP4).

[0073] Example 5:

[0074] A two-dimensional zirconium-based metal-porphyrin framework was prepared by the following method:

[0075] ZrCl4, 10 mg (0.013 mmol) of 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin, 1.18 g (4.2 mmol) of oleic acid and 50 mg (2.8 mmol) of water were added into 2 mL of N,N-dimethylformamide, ultrasonic dispersion for 30 min, then placed in an oven at 120 °C for 24 h, then the reaction solution was cooled to room temperature, filtered, the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying oven at 100 °C for 24 h to obtain a two-dimensional zirconium-based metal-porphyrin framework (denoted as Zr-TCPP4).

[0076] Example 6:

[0077] A zirconium-based metal-organic framework material was prepared by the following method:

[0078] A two-dimensional zirconium metal-organic framework (Zr-TCPP1) and 0.15 mmol of FeCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 h, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying box at 100°C for 24 h to obtain a zirconium metal-organic framework material (denoted as Zr-TCPP(Fe)).

[0079] Example 7:

[0080] A zirconium metal-organic framework material was prepared by the following method:

[0081] A two-dimensional zirconium metal-organic framework (Zr-TCPP1) and 0.15 mmol of MnCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 h, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying box at 100°C for 24 h to obtain a zirconium metal-organic framework material (denoted as Zr-TCPP(Mn)).

[0082] Example 8:

[0083] A zirconium metal-organic framework material was prepared by the following method:

[0084] A two-dimensional zirconium metal-organic framework (Zr-TCPP1) and 0.15 mmol of CoCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 h, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying box at 100°C for 24 h to obtain a zirconium metal-organic framework material (denoted as Zr-TCPP(Co)).

[0085] Example 9:

[0086] A zirconium metal-organic framework material was prepared by the following method:

[0087] A two-dimensional zirconium metal-organic framework (Zr-TCPP1) and 0.15 mmol of NiCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 h, filtered, and the obtained solid was washed with N,N-dimethylformamide and acetone for several times, and then placed in a vacuum drying box at 100°C for 24 h to obtain a zirconium metal-organic framework material (denoted as Zr-TCPP(Ni)).

[0088] Example 10:

[0089] A zirconium metal-organic framework material was prepared by the following method:

[0090] 0.05 mmol of two-dimensional zirconium-based metal-porphyrin framework (Zr-TCPP1) and 0.15 mmol of CuCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 hours, filtered, and the filtered solid was washed with N,N-dimethylformamide and acetone several times, and then placed in a vacuum drying oven at 100°C for 24 hours to obtain a zirconium-based metal-organic framework material (denoted as Zr-TCPP(Cu)).

[0091] Example 11:

[0092] A zirconium-based metal-organic framework material, the preparation method of which is as follows:

[0093] 0.05 mmol of two-dimensional zirconium-based metal-porphyrin framework (Zr-TCPP1) and 0.15 mmol of ZnCl2 were added to 1 mL of N,N-dimethylformamide, stirred at 100°C for 24 hours, filtered, and the filtered solid was washed with N,N-dimethylformamide and acetone several times, and then placed in a vacuum drying oven at 100°C for 24 hours to obtain a zirconium-based metal-organic framework material (denoted as Zr-TCPP(Zn)). Performance test:

[0094] 1) The powder X-ray diffraction (PXRD) patterns of the two-dimensional zirconium-based metal-porphyrin frameworks (Zr-TCPP1, Zr-TCPP2, Zr-TCPP3, Zr-TCPP4, and Zr-TCPP5) in Examples 1 to 5 are shown in FIG. Figure 1 As shown, the PXRD patterns of the zirconium-based metal-organic framework materials (Zr-TCPP(Fe), Zr-TCPP(Mn), Zr-TCPP(Co), Zr-TCPP(Ni), Zr-TCPP(Cu) and Zr-TCPP(Zn)) in Examples 6 to 11 are as follows: Figure 2 shown.

[0095] Depend on Figure 1 It can be seen that: Zr-TCPP x Three obvious peaks appear at (x=1,2,3,4,5), which are attributed to the (0,0,1), (2,0,2) and (3,-1,1) crystal planes respectively. This is consistent with the reported PCN-222 single crystal, and the characteristic peaks are wider than those of conventional crystalline materials, which is consistent with the characteristics of 2D nanosheets, that is, the growth of the material in a certain direction is inhibited, thus exhibiting an ultra-thin layered structure.

[0096] Depend on Figure 2It can be seen that the PXRD patterns of Zr-TCPP(M) (M = Fe, Mn, Co, Ni, Cu, Zn) are consistent with Zr-TCPP1, indicating that the introduction of metal active centers does not destroy the original two-dimensional zirconium metal- porphyrin framework (MOF) crystal structure, and the finally prepared zirconium metal-organic framework material has a complete structure.

[0097] 2) The scanning electron microscope (SEM) images of the two-dimensional zirconium metal- porphyrin frameworks (Zr-TCPP1, Zr-TCPP2, Zr-TCPP3, Zr-TCPP4 and Zr-TCPP5) in Examples 1-5 are shown in Figures 3-7 , and the SEM images of the zirconium metal-organic framework materials (Zr-TCPP(Fe), Zr-TCPP(Mn), Zr-TCPP(Co), Zr-TCPP(Ni), Zr-TCPP(Cu) and Zr-TCPP(Zn)) in Examples 6-11 are shown in Figures 8-13 .

[0098] It can be seen from Figures 3-13 that Zr-TCPP x (x = 1, 2, 3, 4, 5) and Zr-TCPP(M) (M = Fe, Mn, Co, Ni, Cu, Zn) are all petal-shaped structures composed of ultrathin layered structures, and have uniform sizes.

[0099] 3) The atomic force microscope (AFM) image of the two-dimensional zirconium metal- porphyrin framework (Zr-TCPP1) in Example 1 is shown in Figure 14 , and the AFM image of the zirconium metal-organic framework material (Zr-TCPP(Fe)) in Example 6 is shown in Figure 15 .

[0100] It can be seen from Figure 14 that Zr-TCPP1 is a sheet structure with a thickness of 2.5 nm, and it is speculated that Zr-TCPP1 is a double-layer ultrathin structure, which is consistent with the theoretical height of 1.2 nm of the single-layer Zr node of the material.

[0101] It can be seen from Figure 15 that the thickness of Zr-TCPP(Fe) does not change compared with Zr-TCPP1, which is still 2.5 nm, indicating that the sheet structure does not accumulate during the loading of Fe, and the structure remains intact.

[0102] 4) The nitrogen adsorption-desorption isotherm curves of the two-dimensional zirconium metal- porphyrin framework (Zr-TCPP1) in Example 1 and the zirconium metal-organic framework material (Zr-TCPP(Fe)) in Example 6 are shown in Figure 16 .

[0103] It can be seen from Figure 16It can be seen that the specific surface areas of Zr-TCPP1 and Zr-TCPP(Fe) are 320.2 m 2 / g and 315.5m 2 / g, and the pore volume is 0.8406m 3 / g and 0.8050m 3 / g, and the average pore diameters were 15.2nm and 15.1nm respectively. The specific surface area and pore diameter did not change significantly before and after loading metallic iron, indicating that the material has good stability.

[0104] 5) The X-ray photoelectron spectroscopy (XPS) diagram (N 1s orbital) of the two-dimensional zirconium-based metal-porphyrin framework (Zr-TCPP1) in Example 1 and the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6 is as follows Figure 17 As shown, the XPS pattern of Zr-TCPP(Fe) (Fe 2p orbital) is as follows Figure 18 shown.

[0105] Depend on Figure 17 It can be seen that the two peaks of the N1s orbital of Zr-TCPP1 at 399.8 eV and 397.7 eV are respectively attributed to the two different nitrogen atoms, =N- and -NH-, in the porphyrin ring. After loading metallic iron, the binding energy of the =N- peak of Zr-TCPP(Fe) obtained increases to 399.9 eV, and the peak area increases significantly, while the peak area of ​​-NH- decreases significantly, indicating that the metallic iron is successfully loaded into the center of the porphyrin ring.

[0106] Depend on Figure 18 It can be seen that the Fe 2p of the iron species contained in Zr-TCPP(Fe) 3 / 2 and 2p 1 / 2 The orbital binding energies are 724.1eV and 710.7eV, respectively, indicating that iron exists mainly in the +3 valence form.

[0107] Example 12:

[0108] Catalytic performance tests of the two-dimensional zirconium-based metal-porphyrin framework (Zr-TCPP1) in Example 1 and the zirconium-based metal-organic framework materials (Zr-TCPP(Fe), Zr-TCPP(Mn), Zr-TCPP(Co), Zr-TCPP(Ni), Zr-TCPP(Cu) and Zr-TCPP(Zn)) in Examples 6 to 11:

[0109] 0.5 mmol of indane, 10 mg of catalyst, 2.5 mmol of isobutyraldehyde, and 2 mL of 1,2-dichloroethane were added to a sealed tube. The air in the tube was completely removed and oxygen was bubbled into the tube. This operation was repeated three times. The reaction was stirred at 25°C for 12 h. The filtrate and residue were separated by filtration. The yield of the product was determined by NMR, and the results are shown in Table 1.

[0110] The reaction formula is as follows:

[0111]

[0112] Table 1: Product yield catalyzed by different catalysts

[0113]

[0114] From Table 1, it can be seen that:

[0115] a) From serial numbers 1 and 2, it can be seen that the introduction of metallic iron greatly improves the reaction yield, which may be due to the fact that iron porphyrin has very high activation ability for oxygen as a heme mimic;

[0116] b) From serial numbers 2 to 7, it can be seen that iron and manganese have high catalytic activity for different active metal centers, and iron has higher activity than manganese.

[0117] In summary, the catalytic effect of Zr-TCPP(Fe) in Example 2 is the best.

[0118] Catalyst cycle performance test:

[0119] The cycle performance of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6 was tested according to the operation of the present example (the cycle number was 5 times; the catalyst was filtered out after each use, and then washed and dried for the next experiment), and the test results are shown in Table 3. Figure 19

[0120] From Table 3, it can be seen that: Figure 19 After Zr-TCPP(Fe) was reused for 5 times, the yield of the product did not decrease significantly, and the yield remained above 90%.

[0121] Example 13:

[0122] Effect of reaction time on yield:

[0123] 0.5 mmol of indane, 10 mg (0.0057 mmol) of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6, 2.5 mmol of isobutyraldehyde and 2 mL of 1,2-dichloroethane were added to a sealed tube, the tube was thoroughly degassed, oxygen was introduced, and the operation was repeated 3 times, then the reaction was stirred at 25°C for 6-15 h, the filtrate was separated by filtration, and the yield of the product was determined by NMR. The results are shown in Table 2.

[0124] Table 2: Effect of reaction time on yield

[0125] ​

[0126]

[0127] It can be seen from Table 2 that the yield of the target product increases with the extension of the reaction time, but the yield no longer increases after the reaction time reaches 12 h, indicating that the optimal time for Zr-TCPP(Fe) to catalyze the reaction is 12 h.

[0128] Example 14:

[0129] Effect of reaction temperature on yield:

[0130] 0.5 mmol of indane, 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6, 2.5 mmol of isobutyraldehyde and 2 mL of 1,2-dichloroethane were added to a sealed tube. The air in the tube was completely removed and oxygen was bubbled into the tube. This operation was repeated three times. The reaction was stirred at 15°C to 45°C for 12 hours. The filtrate and residue were separated by filtration. The yield of the product was determined by NMR, as shown in Table 3.

[0131] Table 3 Effect of reaction temperature on yield

[0132]

[0133] As shown in Table 3, the yield of the target product increases with the increase of reaction temperature. However, when the reaction temperature reaches 25°C, the yield decreases with the increase of temperature, indicating that the optimal temperature for Zr-TCPP(Fe) to catalyze the reaction is 25°C.

[0134] Example 15:

[0135] Hot filtration experiment:

[0136] 0.5 mmol of indane, 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6, 2.5 mmol of isobutyraldehyde and 2 mL of 1,2-dichloroethane were added to a sealed tube. The air in the tube was completely removed and oxygen was introduced. The operation was repeated 3 times. After stirring at 25°C for 4 hours, the mother liquor was separated from the catalyst by centrifugation. The yield of the product was determined by nuclear magnetic resonance. The reaction solution was allowed to react for a period of time, and the yield of the product was determined by nuclear magnetic resonance (tested every 2 hours). The obtained hot filtration test results are as follows: Figure 20 shown.

[0137] Depend on Figure 20 It can be seen that after 4 hours of reaction, the catalyst was separated from the mother liquor and the mother liquor was allowed to continue to react. The yield of the product did not increase significantly after another 8 hours of reaction, which means that there was no Fe leakage during the reaction, indicating that the catalytic system was heterogeneous.

[0138] Example 16:

[0139] Substrate applicability test of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6:

[0140] 0.5 mmol of a benzyl-containing compound (substrate), 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Fe)) in Example 6, 2.5 mmol of isobutyraldehyde, and 2 mL of 1,2-dichloroethane were added to a sealed tube. The air in the tube was completely removed, and oxygen was introduced. The operation was repeated three times. The reaction was stirred at 25° C. for 12 h, and the filtrate and residue were separated by filtration. The yield of the product was determined by NMR, and the results are shown in Table 4.

[0141] Table 4 Substrate applicability test results of Zr-TCPP(Fe)

[0142]

[0143]

[0144] As shown in Table 4, Zr-TCPP(Fe) has good catalytic performance and can efficiently promote the conversion of different types of substrates with a high yield, up to 99%.

[0145] Example 17:

[0146] Substrate applicability test of the zirconium-based metal-organic framework material (Zr-TCPP(Mn)) in Example 7:

[0147] 0.5 mmol of a benzyl-containing compound (substrate), 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Mn)) in Example 7, 2.5 mmol of isobutyraldehyde, and 2 mL of 1,2-dichloroethane were added to a sealed tube. The air in the tube was completely removed, and oxygen was introduced. The operation was repeated three times. The reaction was stirred at 25°C for 12 hours, and the filtrate and residue were separated by filtration. The yield of the product was determined by NMR, and the results are shown in Table 5.

[0148] Table 5 Substrate applicability test results of Zr-TCPP(Mn)

[0149]

[0150]

[0151] Depend on Figure 5 It can be seen that Zr-TCPP(Mn) has good catalytic performance and can efficiently promote the conversion of different types of substrates with a high yield, up to 86%.

[0152] Example 18:

[0153] Substrate applicability test of the zirconium-based metal-organic framework material (Zr-TCPP(Co)) in Example 8:

[0154] 0.5 mmol of the benzyl-containing compound (substrate), 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Co)) in Example 8, 2.5 mmol of isobutyraldehyde and 2 mL of 1,2-dichloroethane were added into a sealed tube, the tube was thoroughly degassed and filled with oxygen, and the operation was repeated for 3 times, and then the reaction was stirred at 25℃ for 12 h. The filtrate was separated by filtration, and the yield of the product was determined by NMR. The results are shown in Table 6.

[0155] Table 6: Results of substrate applicability test of Zr-TCPP(Co)

[0156]

[0157]

[0158] It can be seen from Table 6 that the Zr-TCPP(Co) can effectively promote the conversion of different types of substrates.

[0159] Example 19:

[0160] Substrate applicability test of the zirconium-based metal-organic framework material (Zr-TCPP(Cu)) in Example 10:

[0161] 0.5 mmol of the benzyl-containing compound (substrate), 10 mg of the zirconium-based metal-organic framework material (Zr-TCPP(Cu)) in Example 10, 2.5 mmol of isobutyraldehyde and 2 mL of 1,2-dichloroethane were added into a sealed tube, the tube was thoroughly degassed and filled with oxygen, and the operation was repeated for 3 times, and then the reaction was stirred at 25℃ for 12 h. The filtrate was separated by filtration, and the yield of the product was determined by NMR. The results are shown in Table 7.

[0162] Table 7: Results of substrate applicability test of Zr-TCPP(Cu)

[0163]

[0164]

[0165] It can be seen from Table 7 that the Zr-TCPP(Cu) can effectively promote the conversion of different types of substrates.

[0166] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application shall be equivalent replacement methods, and shall be included in the protection scope of the present application.

Claims

1. A method for selective oxidation of indane, characterized in that: The following steps are involved: Indane, zirconium-based metal-organic framework material and isobutyraldehyde are dispersed in an organic solvent and then placed in an oxygen atmosphere for reaction; the zirconium-based metal-organic framework material is prepared by a preparation method comprising the following steps: 1) dispersing zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin and a regulator in an organic solvent for reaction to obtain a two-dimensional zirconium-based metal-porphyrin framework; 2) dispersing the two-dimensional zirconium-based metal-porphyrin framework and a transition metal salt in an organic solvent for reaction to obtain a zirconium-based metal-organic framework material; in step 1) the zirconium salt, 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin and a regulator are dispersed in an organic solvent for reaction to obtain a two-dimensional zirconium-based metal-porphyrin framework; The molar ratio of 20-tetrakis(4-carboxyphenyl)porphyrin to the regulator is 1:(0.25-0.50):(36-1176); the regulator in step 1) is a mixture of water and at least one of formic acid, glacial acetic acid, lauric acid, oleic acid, and benzoic acid; the reaction in step 1) is carried out at a temperature of 90°C to 130°C and a reaction time of 12h to 36h; the transition metal salt in step 2) is at least one of a ferrous salt and a manganese salt; the reaction in step 2) is carried out at a temperature of 50°C to 150°C and a reaction time of 12h to 36h.

2. The selective oxidation method of indane according to claim 1, wherein: Step 2) The molar ratio of the two-dimensional zirconium-based metal-porphyrin framework to the transition metal salt is 1:(1-14).

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