Preparation method of donor-receptor type metal organic framework photocatalyst and application of donor-receptor type metal organic framework photocatalyst to photocatalytic amine oxide / thioether
By designing the body-the body-type metal organic framework light catalyst, the use of light-induced energy to transfer and activate O2 to generate ROS1O2, solving the problem of high temperature and expensive catalysts that prepare amine and sub-categorian compounds in traditional methods, and achieve efficient, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selective, selectivity, selectivity, Good photocatalytic oxidation reactions.
Patent Information
- Application Number
- CN202411363375.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-27
- Publication Date
- 2025-01-28
AI Technical Summary
Traditional methods for preparing imine and sulfoxide compounds require high temperature, expensive catalysts and complex post-treatment processes, and poor selectivity and functional group tolerance.
A designed-body-body-type metal organic frame-frame photocatalyst, which generates ROS1O2 by generating light-induced energy transfer and activation of the body-the body, to achieve high-efficiency photocatalytic oxide/sulfe ether synthesis.
Under mild conditions, high -efficiency selective photocatalytic oxide/sulfe ether synthesizes amine/sub -crickets, avoids the use of high temperature and expensive catalysts, and has high catalyst stability, and has potential commercial application value.
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Figure CN119371674A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of metal organic frameworks (MOFs) and photocatalysis, and in particular to a method for preparing a donor-acceptor type metal organic framework photocatalyst and its application in photocatalytic oxidation of amines / sulfides, which is suitable for selective photocatalytic oxidation of amines / sulfides to prepare imines / sulfoxides. Background Art
[0002] Imine compounds with C=N bonds are an important class of multi-purpose reaction intermediates, widely used in agriculture, medicine, synthetic chemistry and other fields. Traditionally, imines are usually prepared by condensation reaction of primary amines with aldehydes or ketones, but such reactions need to be carried out at high temperatures and with expensive catalysts (such as Sheppard amidation reagents) and dehydrating agents (such as molecular sieves and strong acids), and the selectivity and functional group tolerance of the reaction are poor. In addition, complex post-processing processes are required to remove by-products, dehydrating agents and catalyst residues.
[0003] As an important class of organic reaction intermediates, sulfoxide compounds play an irreplaceable role in the synthesis of biopharmaceutical molecules and natural products. Compared with the traditional process for synthesizing sulfoxide compounds, the photocatalytic selective oxidation of sulfide to synthesize sulfoxide compounds can significantly improve selectivity and avoid the production of highly toxic by-products, which meets the conditions of green catalysis and is one of the potential alternative routes.
[0004] In recent years, the synthesis of value-added chemicals by light-driven organic oxidation reactions under mild conditions has attracted great attention due to its economic and environmental advantages. Among the various reactive species (ROS) that drive photocatalytic organic oxidation transformations, singlet oxygen ( 1 O2), which has a long half-life (≈4μs) and mild oxidation ability (2.2V vs NHE), is an important candidate for achieving efficient and selective photocatalytic organic oxidation to convert ROS.
[0005] As a new type of porous crystalline material, metal organic frameworks (MOFs) can realize the co-assembly of multiple chromophore components due to their network periodic structure, and are one of the ideal platforms for simulating the energy transfer (EnT) process in natural photosynthesis. In addition, the energy transfer (EnT) system based on the MOFs platform can promote the transition of triplet excitons under light excitation, which is beneficial to improve the efficiency of artificial photosynthesis. However, most of the MOFs-based EnT systems currently developed use energy donors or energy acceptors as guest molecules, which reduces the porosity of the MOFs channels to a certain extent, limiting its application in the field of artificial photosynthesis. Summary of the invention
[0006] The main purpose of the present invention is to provide a preparation method of a donor-acceptor metal organic framework photocatalyst and its application in photocatalytic oxidation of amines / thioethers. A new donor-acceptor mixed ligand-based MOF is designed and prepared, and the effective light-induced EnT between the donor and the acceptor activates the molecular O2 to produce ROS. 1 O2, thereby efficiently photocatalytically oxidizing amine / sulfide compounds to prepare imine / sulfoxide compounds.
[0007] The technical solution of the present invention is as follows:
[0008] A method for preparing a donor-acceptor type metal organic framework photocatalyst comprises the following steps and process conditions:
[0009] (1) zirconium tetrachloride (ZrCl4), 1,4-naphthalene dicarboxylic acid (H2NDC), 5,15-di(4-carboxyphenyl)porphyrin (H2DPBP) and benzoic acid (BA) were added to a 5 mL glass bottle and uniformly dispersed in N,N-dimethylformamide (DMF) by ultrasound;
[0010] (2) The solution obtained in step (1) was placed in an oven for thermal reaction, collected by centrifugation, washed three times with DMF and ethanol (C2H5OH) respectively, and then vacuum dried to obtain the UiO-66-NDC-H2DPBP photocatalyst.
[0011] In the preparation step (1), the amounts of various reaction raw materials are as follows: ZrCl4 is 30 mg, H2NDC is 26 mg, H2DPBP is 2 mg to 20 mg, BA is 600 mg, and DMF is 2 mL. Preferably, H2DPBP is 2 mg, 4 mg, 6 mg, 8 mg, 10 mg, 12 mg, 14 mg or 20 mg.
[0012] In the preparation step (2), the reaction temperature is 130°C, the reaction time is 12h, the rate of temperature reduction to room temperature is 10°C / h, and the vacuum drying activation conditions are 100°C and 12h.
[0013] The application of the donor-acceptor metal organic framework photocatalyst in the photocatalytic oxidation of amines / sulfides to prepare imine / sulfoxide compounds, using the donor-acceptor metal organic framework photocatalyst to selectively photocatalytically oxidize various amine compounds or various sulfide compounds to synthesize imine compounds or sulfoxide compounds, includes the following steps and reaction conditions:
[0014] (1) Photocatalytic oxidation of various amine compounds to prepare imine compounds: UiO-66-NDC-H2DPBP was dispersed in an acetonitrile solution containing a certain amount of substrate, stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction;
[0015] (2) Photocatalytic oxidation of various sulfide compounds to prepare sulfoxide compounds: UiO-66-NDC-H2DPBP was dispersed in a mixed solution of acetonitrile and methanol containing a certain amount of substrate, stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction.
[0016] In the application step (1), the amounts of various reaction raw materials are as follows: 0.40 mmol of amine compound, 10 mg of UiO-66-NDC-H2DPBP, 5 mL of acetonitrile, the wavelength of the xenon lamp light source is full wavelength, the power is 300 W, the natural light is outdoor natural light, the reaction temperature is controlled at 27° C. by circulating cooling water, and the reaction time is 35 min to 40 h. After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, the filtrate is subjected to gas chromatography-mass spectrometry analysis to confirm the product, and gas chromatography analysis is performed to obtain the conversion rate and selectivity of the reaction.
[0017] In the application step (1), the types of amine compounds include: benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-(trifluoromethyl)benzylamine, 4-methylbenzylamine, 4-methoxybenzylamine, 3-methoxybenzylamine, 2-methoxybenzylamine, 4-(aminomethyl)pyridine, 2-furylamine, 2-thiophenemethylamine, heptylamine, N-methylbenzylamine, N-methyl-4-methoxybenzylamine, N-methyl-4-methylbenzylamine, N-isopropylbenzylamine, dibenzylamine or 1,2,3,4-tetrahydroisoquinoline.
[0018] In the application step (2), the amounts of various reaction raw materials are as follows: 0.25 mmol of sulfide compound, 10 mg of UiO-66-NDC-H2DPBP, 5 mL of acetonitrile, 2.5 mL of methanol, the wavelength of the xenon lamp light source is full wavelength, the power is 300 W, the natural light is outdoor natural light, the reaction temperature is controlled at 27° C. by circulating cooling water, and the reaction time is 10 min to 6 h. After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, the filtrate is subjected to gas chromatography-mass spectrometry analysis to confirm the product, and gas chromatography analysis is performed to obtain the conversion rate and selectivity of the reaction.
[0019] In the applying step (2), the types of thioether compounds include: thioanisole, 4-fluorothioanisole, 4-chlorothioanisole, 4-bromothioanisole, 4-iodothioanisole, 4-methylthioanisole, 4-methoxythioanisole, 3-methoxythioanisole, 2-methoxythioanisole, 3-chlorothioanisole, 2-chlorothioanisole, phenethyl thioether, cyclopropylthiophenyl thioether, methyl (naphthalene-2-yl) sulfane, tetrahydrothiothiopyran or dibutyl sulfide.
[0020] The design idea of the present invention is:
[0021] The currently designed photocatalyst activates molecular O2 to selectively produce highly reactive species 1 In order to overcome the challenges in the field of efficient artificial photosynthesis of O2, the present invention is inspired by the EnT mechanism in the natural photosynthesis system and designs a donor-acceptor MOFs photocatalyst that can produce effective EnT under light-induced conditions. The present invention adopts a one-pot strategy and successfully inserts the 5,15-di(4-carboxyphenyl)porphyrin (H2DPBP) receptor ligand as the second ligand into the 1,4-naphthalenedicarboxylic acid (H2NDC) donor ligand-based MOF UiO-66-NDC with high porosity and high stability to prepare a mixed ligand-based donor-acceptor MOF UiO-66-NDC-H2DPBP photocatalyst. The developed photocatalyst UiO-66-NDC-H2DPBP can significantly activate O2 to produce ROS due to the high efficiency of internal fluorescence resonance EnT. 1 O2, thereby achieving efficient photocatalytic oxidation of amine / sulfide compounds to prepare imine / sulfoxide compounds.
[0022] Compared with the prior art, the present invention has the following significant advantages:
[0023] (1) The emission spectrum of the donor ligand naphthalene dicarboxylic acid H2NDC selected in the present invention and the absorption spectrum of the acceptor ligand porphyrin H2DPBP have a large degree of overlap, which can produce effective fluorescence resonance EnT, thereby maximally activating molecular O2 to selectively produce 1 O2, to achieve efficient photocatalytic oxidation of amine / sulfide compounds to synthesize imine / sulfoxide compounds.
[0024] (2) The donor-acceptor type MOFs photocatalyst UiO-66-NDC-H2DPBP designed by the present invention has low-cost synthetic raw materials (the actual loading amount of porphyrin ligand is low), simple preparation process (one-pot method), and excellent stability.
[0025] (3) When UiO-66-NDC-H2DPBP is used as a photocatalyst, it can efficiently catalyze the oxidation of amine / sulfide compounds to imine / sulfoxide compounds under mild conditions such as room temperature, air as an oxidant, and xenon lamp / natural light as a light source, and has high cyclic stability. Its catalytic performance is also superior to most of the currently reported MOFs-based photocatalysts, and has certain potential commercial application value. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1: a is the molecular structure diagram of the donor ligand H2NDC and the acceptor ligand H2DPBP; b is the UV-visible absorption spectrum and fluorescence spectrum of the donor ligand H2NDC and the acceptor ligand H2DPBP, the abscissa Wavelength is the wavelength (nm), the ordinate Normalized Abs / PL Intensity is the normalized absorption / fluorescence intensity, Abs. is the absorption spectrum, and Emission is the fluorescence spectrum.
[0027] Figure 2 It is the powder X-ray diffraction pattern of UiO-66-NDC-H2DPBP, UiO-66-NDC and Simulated UiO-66 obtained by using different amounts of porphyrin H2DPBP during synthesis. The horizontal axis 2θ is the diffraction angle (degree), and the vertical axis Intensity is the relative intensity (au).
[0028] Figure 3 are scanning electron micrographs of UiO-66-NDC (a) and UiO-66-NDC-H2DPBP (b).
[0029] Figure 4 The nitrogen adsorption (ads)-desorption (des) curves of UiO-66-NDC-H2DPBP and UiO-66-NDC. In the figure, the specific surface area (BET Surface area) of UiO-66-NDC-H2DPBP is 780m 2 / g, the specific surface area of UiO-66-NDC is 806m 2 / g, the horizontal axis p / p0 is the relative pressure, and the vertical axis N2 adsorbed volume is the nitrogen adsorption volume (cm 3 g -1 STP).
[0030] Figure 5:a is the UV-visible absorption spectrum and fluorescence spectrum (λ=340nm) of UiO-66-NDC-H2DPBP and UiO-66-NDC, the horizontal axis Wavelength is the wavelength (nm), the vertical axis Normalized Abs / PL Intensity is the normalized absorption / fluorescence intensity, Abs. is the absorption spectrum, Emission is the fluorescence spectrum, and the inset shows the corresponding fluorescence lifetime. b is the fluorescence quenching curve of H2NDC in UiO-66-NDC-H2DPBP and UiO-66-NDC at 408nm (λ=340nm), the horizontal axis Time Delay is the time delay (ns), the vertical axis PL Intensity is the fluorescence intensity, and IRF is the response function (Impulse Response Function).
[0031] Figure 6 This is a comparison of the oxidation rate of α-terpinene by UiO-66-NDC-H2DPBP and various MOFs photocatalysts and the analysis of the generation of ROS. In the figure, the horizontal axis H2DPBP AmountUsed is the amount of H2DPBP used (mg), and other metal organic framework photocatalysts (Other MOF Photocatalysts ah), the vertical axis Yield is the yield (%), the red part of each group is the yield of α-terpinene, and the green part of each group is the yield of ROS. α-terpinene is α-terpinene, and the reaction conditions are: Me CN, air, rt, Xe lamp, 20min, which means that acetonitrile (MeCN) is used as a solvent, the reaction is carried out in air, the reaction temperature is room temperature (rt), and a xenon lamp (Xe lamp) is used as a light source for 20 minutes. Ascaridole represents ascaridole, and 4-Isopropyl-toluene represents 4-isopropyltoluene.
[0032] Figure 7 It is the performance of UiO-66-NDC-H2DPBP photocatalytic oxidation of various amine compounds. The reaction conditions are: Air, Xe lamp / Sunlight, RT, which means that it is carried out in air, the reaction temperature is room temperature, and a xenon lamp or natural light is used as the light source.
[0033] Figure 8 It is the performance of UiO-66-NDC-H2DPBP photocatalytic oxidation of various sulfide compounds. The reaction conditions are: Air, Xe lamp / Sunlight, RT, which means that it is carried out in air, the reaction temperature is room temperature, and a xenon lamp or natural light is used as the light source.
[0034] Fig. 9This is the cyclic performance test of UiO-66-NDC-H2DPBP photocatalytic oxidation of benzylamine (a) / anisyl thioether (b). The horizontal axis Cycles is the number of cycles, the vertical axis Percentage is the percentage (%), each group of red parts is the yield (Yield), and each group of blue parts is the selectivity (Selectivity).
[0035] Fig.10 This is the cyclic stability test of UiO-66-NDC-H2DPBP photocatalytic oxidation of benzylidene amine / thioanisole. The horizontal axis 2θ is the diffraction angle (degree), and the vertical axis Intensity is the relative intensity (au). After 5 th catalysis ofThioanisole represents thioanisole, After 5 th catalysis of Benzylamine represents benzylamine, As-synthesized UiO-66-NDC-H2DPBP represents synthesized UiO-66-NDC-H2DPBP photocatalyst, and SimulatedUiO-66 represents the simulated UiO-66 structure. DETAILED DESCRIPTION
[0036] In the specific implementation process, the present invention proposes a method for preparing a donor-acceptor type metal organic framework photocatalyst, comprising the following steps and process conditions:
[0037] (1) zirconium tetrachloride (ZrCl4), 1,4-naphthalene dicarboxylic acid (H2NDC), 5,15-di(4-carboxyphenyl)porphyrin (H2DPBP) and benzoic acid (BA) were added into a 5 mL glass bottle and uniformly dispersed into N,N-dimethylformamide (DMF) by ultrasound;
[0038] (2) The solution obtained in step (1) was placed in an oven for thermal reaction, collected by centrifugation, washed three times with DMF and C2H5OH respectively, and then vacuum dried to obtain UiO-66-NDC-H2DPBP material.
[0039] The present invention adopts the application of UiO-66-NDC-H2DPBP to efficiently photocatalytically oxidize amine / sulfide compounds to synthesize imine / sulfoxide compounds, including the following steps and reaction conditions:
[0040] (1) Photocatalytic oxidation of various amine compounds to prepare imine compounds: UiO-66-NDC-H2DPBP was dispersed in an acetonitrile (CH3CN) solution containing a certain amount of substrate (various amine compounds), stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction;
[0041] (2) Photocatalytic oxidation of various sulfide compounds to prepare sulfoxide compounds: UiO-66-NDC-H2DPBP was dispersed in a mixed solution of acetonitrile (CH3CN) solution and methanol (CH3OH) containing a certain amount of substrate (various sulfide compounds), stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction.
[0042] The present invention is further described in conjunction with specific embodiments and drawings. It should be understood that these embodiments are only used to illustrate the present invention rather than to limit the scope of the present invention.
[0043] Example 1
[0044] In this embodiment, a novel donor-acceptor type mixed ligand-based MOFs photocatalyst is prepared by the following steps:
[0045] (1) ZrCl4 (30 mg, 0.129 mmol), H2NDC (26 mg, 0.120 mmol), H2DPBP (2 mg, 0.0036 mmol; 4 mg, 0.0073 mmol; 6 mg, 0.0109 mmol; 8 mg, 0.0145 mmol; 10 mg, 0.0182 mmol; 12 mg, 0.0218 mmol; 14 mg, 0.0255 mmol; 20 mg, 0.0364 mmol) and BA (600 mg, 4.918 mmol) were added to a 5 mL glass bottle and uniformly dispersed in DMF (2 mL) by ultrasound;
[0046] (2) The solution obtained in step (1) was placed in an oven for thermal reaction (130°C, 12h), centrifuged, washed three times with DMF and C2H5OH respectively, and then vacuum dried (100°C, 12h) to obtain UiO-66-NDC-H2DPBP material. In terms of weight percentage, the H2DPBP content in the obtained photocatalysts was 1.0%, 2.7%, 3.2%, 3.5%, 3.7%, 3.9%, 4.0%, and 4.1%, respectively.
[0047] from Figure 1 It can be seen that the fluorescence emission spectrum of the selected donor ligand H2NDC has a large overlap with the UV-visible absorption spectrum of the acceptor ligand H2DPBP. Figure 2 Powder X-ray diffraction shows that different amounts of acceptor porphyrin H2DPBP can be used to successfully prepare donor-acceptor MOF UiO-66-NDC-H2DPBP, which is the same as the UiO-66-NDC crystal form and has a similar morphology ( Figure 3 ) and specific surface area ( Figure 4 ).from Figure 5It can be seen that effective photoinduced fluorescence resonance EnT can occur in UiO-66-NDC-H2DPBP.
[0048] Example 2
[0049] In this embodiment, the prepared UiO-66-NDC-H2DPBP photocatalytically oxidizes α-terpinene, including the following steps and reaction conditions:
[0050] (1) UiO-66-NDC-H2DPBP (10 mg) was dispersed in a CH3CN (5 mL) solution containing a certain amount of α-terpinene (0.40 mmol), stirred evenly, and then placed under a xenon lamp (300 W, full wavelength) at room temperature (27°C) in an open system for reaction for 15 min.
[0051] (2) After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, the filtrate is analyzed by gas chromatography-mass spectrometry (GC-MS) to confirm the product, and gas chromatography (GC) analysis is performed to obtain the conversion rate and selectivity of the reaction.
[0052] from Figure 6 It can be seen that UiO-66-NDC-H2DPBP synthesized using 6 mg H2DPBP has the strongest 1 O2 production capacity (can provide the highest 1 O2-regulated oxidation products), and its catalytic performance is better than that of the MOFs photocatalysts selected in other examples.
[0053] Example 3
[0054] In this example, the prepared UiO-66-NDC-H2DPBP has a selective photocatalytic oxidation effect on amine compounds:
[0055] (1) UiO-66-NDC-H2DPBP (10 mg) was dispersed in a solution containing a certain amount of substrate (substrate is Figure 7 The various amine compounds shown are added to a CH3CN solution (0.40 mmol), stirred evenly, and then placed under irradiation with a xenon lamp (300 W, full wavelength) or natural light (August 2024, Changsha, Hunan), room temperature (27°C), and an open system for reaction, and the reaction time is 35 min to 40 h.
[0056] (2) After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, and the filtrate is analyzed by GC-MS to confirm the product, and GC analysis is performed to obtain the conversion rate and selectivity of the reaction.
[0057] (3) When photocatalytically oxidizing various amine compounds to prepare imine compounds, the types of amine compounds include: benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-(trifluoromethyl)benzylamine, 4-methylbenzylamine, 4-methoxybenzylamine, 3-methoxybenzylamine, 2-methoxybenzylamine, 4-(aminomethyl)pyridine, 2-furylmethylamine, 2-thiophenemethylamine, heptylamine, N-methylbenzylamine, N-methyl-4-methoxybenzylamine, N-methyl-4-methylbenzylamine, N-isopropylbenzylamine, dibenzylamine, and 1,2,3,4-tetrahydroisoquinoline.
[0058] from Figure 7 From the performance of UiO-66-NDC-H2DPBP in photocatalytic oxidation of amine compounds, UiO-66-NDC-H2DPBP can achieve efficient photocatalytic oxidation of amine compounds to prepare imine compounds. Fig. 9 a and Fig.10 From the above data, it can be seen that UiO-66-NDC-H2DPBP has high cyclic stability in the photocatalytic oxidation of amine compounds to prepare imine compounds.
[0059] Example 4
[0060] In this embodiment, the prepared UiO-66-NDC-H2DPBP has a selective photocatalytic oxidation effect on sulfide compounds:
[0061] (1) UiO-66-NDC-H2DPBP (10 mg) was dispersed in a solution containing a certain amount of substrate (substrate is Figure 8 The various sulfide compounds shown were added to a mixed solution of CH3CN (5 mL) and CH3OH (2.5 mL) (0.25 mmol), stirred evenly, and then placed under irradiation with a xenon lamp (300 W, full wavelength) or natural light (August 2024, Changsha, Hunan), room temperature (27°C), and an open system for reaction, and the reaction time was 10 min to 6 h.
[0062] (2) After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, and the filtrate is analyzed by GC-MS to confirm the product, and GC analysis is performed to obtain the conversion rate and selectivity of the reaction.
[0063] (3) When photocatalytically oxidizing various sulfide compounds to prepare sulfoxide compounds, the types of sulfide compounds include: anisole, 4-fluoroanisole, 4-chloroanisole, 4-bromoanisole, 4-iodoanisole, 4-methylanisole, 4-methoxyanisole, 3-methoxyanisole, 2-methoxyanisole, 3-chloroanisole, 2-chloroanisole, phenethyl sulfide, cyclopropylphenyl sulfide, methyl (naphthalene-2-yl) sulfane, tetrahydrothiothiopyran, and dibutyl sulfide.
[0064] from Figure 8From the performance of UiO-66-NDC-H2DPBP in photocatalytic oxidation of sulfide compounds, UiO-66-NDC-H2DPBP can achieve efficient photocatalytic oxidation of sulfide compounds to prepare sulfoxide. Fig. 9 b and Fig.10 From the above, it can be seen that UiO-66-NDC-H2DPBP has high cyclic stability in the photocatalytic oxidation of sulfide compounds to prepare sulfoxide compounds.
[0065] The implementation results show that the present invention utilizes the efficient fluorescence resonance energy transfer between the H2NDC donor ligand and the H2DPBP porphyrin receptor ligand in UiO-66-NDC-H2DPBP to promote the singlet oxygen ( 1 O2) is produced to achieve efficient photocatalytic oxidation of amine / sulfide compounds to synthesize imine / sulfoxide compounds. Compared with the currently reported MOFs photocatalysts, the UiO-66-NDC-H2DPBP photocatalyst obtained by the present invention is simple to prepare, has high stability, and is low in cost. When photocatalytic oxidation of amine / sulfide compounds to synthesize imine / sulfoxide compounds has the advantages of mild reaction conditions (room temperature, air, xenon lamp light source / natural light), high catalytic activity, high selectivity, excellent cycle performance, and good substrate compatibility, and has certain potential market application prospects.
[0066] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims
1. A method for preparing a donor-acceptor metal organic framework photocatalyst, characterized in that: The process includes the following steps and process conditions: (1) zirconium tetrachloride (ZrCl4), 1,4-naphthalene dicarboxylic acid (H2NDC), 5,15-di(4-carboxyphenyl)porphyrin (H2DPBP) and benzoic acid (BA) were added to a 5 mL glass bottle and uniformly dispersed in N,N-dimethylformamide (DMF) by ultrasound; (2) The solution obtained in step (1) was placed in an oven for thermal reaction, collected by centrifugation, washed three times with DMF and ethanol (C2H5OH) respectively, and then vacuum dried to obtain the UiO-66-NDC-H2DPBP photocatalyst.
2. The preparation method according to claim 1, characterized in that: In step (1), the amounts of various reaction raw materials are as follows: ZrCl4 is 30 mg, H2NDC is 26 mg, H2DPBP is 2 mg to 20 mg, BA is 600 mg, and DMF is 2 mL.
3. The preparation method according to claim 2, characterized in that: The preferred H2DPBP is 2 mg, 4 mg, 6 mg, 8 mg, 10 mg, 12 mg, 14 mg or 20 mg.
4. The preparation method according to claim 1, characterized in that: In step (2), the reaction temperature is 130°C, the reaction time is 12h, the rate of temperature reduction to room temperature is 10°C / h, and the vacuum drying activation conditions are 100°C and 12h.
5. Use of the donor-acceptor metal organic framework photocatalyst according to any one of claims 1 to 4 in the photocatalytic oxidation of amines / sulfides to prepare imine / sulfoxide compounds.
6. The use according to claim 5, characterized in that: The method uses a donor-acceptor metal organic framework photocatalyst to selectively photocatalytically oxidize various amine compounds or various sulfide compounds to synthesize imine compounds or sulfoxide compounds, including the following steps and reaction conditions: (1) Photocatalytic oxidation of various amine compounds to prepare imine compounds: UiO-66-NDC-H2DPBP was dispersed in an acetonitrile solution containing a certain amount of substrate, stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction; (2) Photocatalytic oxidation of various sulfide compounds to prepare sulfoxide compounds: UiO-66-NDC-H2DPBP was dispersed in a mixed solution of acetonitrile and methanol containing a certain amount of substrate, stirred evenly, and then placed under xenon lamp / natural light, room temperature, and an open system for reaction.
7. The use according to claim 6, characterized in that: In step (1), the amounts of various reaction raw materials are as follows: 0.40 mmol of amine compound, 10 mg of UiO-66-NDC-H2DPBP, 5 mL of acetonitrile, full wavelength of xenon lamp light source, 300 W of power, outdoor natural light, reaction temperature controlled at 27° C. by circulating cooling water, reaction time of 35 min to 40 h; after the reaction, the catalyst solid and liquid are separated by centrifugation, the filtrate is subjected to gas chromatography-mass spectrometry analysis to confirm the product, and gas chromatography analysis is performed to obtain the conversion rate and selectivity of the reaction.
8. The use according to claim 6 or 7, characterized in that: In step (1), the types of amine compounds include: benzylamine, 4-fluorobenzylamine, 4-chlorobenzylamine, 4-(trifluoromethyl)benzylamine, 4-methylbenzylamine, 4-methoxybenzylamine, 3-methoxybenzylamine, 2-methoxybenzylamine, 4-(aminomethyl)pyridine, 2-furylmethylamine, 2-thiophenemethylamine, heptylamine, N-methylbenzylamine, N-methyl-4-methoxybenzylamine, N-methyl-4-methylbenzylamine, N-isopropylbenzylamine, dibenzylamine or 1,2,3,4-tetrahydroisoquinoline.
9. The use according to claim 6, characterized in that: In step (2), the amounts of various reaction raw materials are as follows: 0.25 mmol of sulfide compound, 10 mg of UiO-66-NDC-H2DPBP, 5 mL of acetonitrile, 2.5 mL of methanol, the wavelength of the xenon lamp light source is full wavelength, the power is 300 W, the natural light is outdoor natural light, the reaction temperature is controlled at 27° C. by circulating cooling water, and the reaction time is 10 min to 6 h. After the reaction is completed, the catalyst solid and liquid are separated by centrifugation, the filtrate is subjected to gas chromatography-mass spectrometry analysis to confirm the product, and gas chromatography analysis is performed to obtain the conversion rate and selectivity of the reaction.
10. The use according to claim 6 or 9, characterized in that: In step (2), the types of thioether compounds include: thioanisole, 4-fluorothioanisole, 4-chlorothioanisole, 4-bromothioanisole, 4-iodothioanisole, 4-methylthioanisole, 4-methoxythioanisole, 3-methoxythioanisole, 2-methoxythioanisole, 3-chlorothioanisole, 2-chlorothioanisole, phenethyl thioether, cyclopropyl phenyl thioether, methyl (naphthalene-2-yl) sulfane, tetrahydrothiothiopyran or dibutyl sulfide.