Molecular cage crystalline material based on phenanthroline modification as well as preparation method and photocatalytic application of molecular cage crystalline material
By preparing o-phenanthroline-modified molecular cage photocatalytic materials GXMZU115 and GXMZU116, the problems of high energy consumption and poor stability of traditional catalysts under high temperature and high pressure were solved, and efficient photocatalytic conversion of small organic molecules was achieved under normal temperature and pressure, which has the prospect of environmental protection and high efficiency in industrial applications.
Patent Information
- Application Number
- CN202511544581.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-27
- Publication Date
- 2026-02-17
AI Technical Summary
Traditional industrial oxidation processes are energy-intensive, require demanding equipment, and pose safety hazards under high temperature and pressure conditions. Furthermore, existing catalysts have poor stability, making it difficult to meet the demands of the pharmaceutical and fine chemical industries for efficient and safe oxidation processes.
We developed molecular cage photocatalytic materials {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)}2-(GXMZU115) and {[Zn(DMP)(NH3)](Ti4L6)}6-(GXMZU116) based on o-phenanthroline modification. These materials were prepared by solvothermal synthesis. Combining the active sites and π-conjugation advantages of metal-organic cages, we achieved efficient excitation of photogenerated carriers and reactive oxygen species, as well as efficient adsorption and conversion of small organic molecules.
It achieves efficient photocatalytic conversion of small organic molecules at room temperature and pressure, with yield and selectivity exceeding 99%, reducing energy consumption, simplifying the production process, reducing pollution, and providing an environmentally friendly alternative.
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Figure CN121537445A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of photocatalytic materials, and particularly relates to a molecular cage photocatalytic crystalline material {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)} 2- (named as GXMZU115) and {[Zn(DMP)(NH3)](Ti4L6)} 6- (named as GXMZU116), a preparation method thereof and photocatalytic applications. BACKGROUND
[0002] With the intensification of dependence on fossil energy with the development of industrialization, the traditional industrial oxidation process under high temperature and high pressure conditions faces problems such as high energy consumption, harsh equipment requirements and safety hazards. The development of a normal temperature and pressure light-driven catalytic system, especially the use of green catalytic technology of sunlight or ambient air, can not only break through the limitations of traditional reaction conditions, but also meet the urgent needs of the pharmaceutical and fine chemical industries for efficient and safe oxidation processes. Such technology has become an important direction for solving the dual challenges of energy and environment due to its low energy consumption, easy operation and sustainability.
[0003] Metal-organic cages (MOCs) with active sites exhibit unique photocatalytic potential due to their post-modification functionality and host-guest encapsulation mechanism: the post-modification functionality based on active sites can introduce heterometallic clusters to improve the activity of active sites; the structural confinement can optimize light absorption efficiency and suppress electron-hole recombination, solving the problem of poor stability of traditional catalysts. If the phenanthroline ligand with the dual advantages of metal chelation and π conjugation is integrated into the metal-organic cage, a cage-based supramolecular catalyst system can be obtained, which can not only strengthen the coordination of the metal center, but also expand the light response range through functionalization to improve the photocatalytic performance of the cage. This supramolecular catalyst system will open up a new path for the development of an intelligent light-driven reaction platform and has broad application prospects in the field of molecular recognition and activation. SUMMARY
[0004] To achieve the above-mentioned purpose, the present application provides two kinds of molecular cage photocatalytic crystalline materials, namely {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)} 2- (named as GXMZU115) and {[Zn(DMP)(NH3)](Ti4L6)} 6- (named as GXMZU116), which can have an X-ray powder diffraction pattern substantially as shown in Figure 4 .
[0005] Preferably, the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials can have the crystal parameters shown in Table 1 and Table 2 respectively by single crystal X-ray analysis:
[0006] Table 1
[0007]
[0008] Table 2
[0009]
[0010] The present application also provides a preparation method of the above-mentioned GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials, comprising the following steps:
[0011] The GXMZU115 molecular cage photocatalytic crystalline material is prepared by solvothermal synthesis method with Ti4L6, 3,4,7,8-tetramethyl-1,10-phenanthroline, zinc acetate, ammonia, water and 1,4-dioxane as raw materials.
[0012] According to the present application, {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)} 2 L in the molecular cage crystalline material (GXM ZU115, GXMZU = Guangxi University for Nationalities) is pamoic acid, and the CAS of L is 130-85-8; the Ti4L6 is a red crystalline material; TMP is 3,4,7,8-tetramethyl-1,10-phenanthroline, and the CAS of TMP is 1660-93-1.
[0013] According to the present application, the concentration of the ammonia can be 20-34%, preferably 25-29%, for example 25% or 29%.
[0014] According to the present application, the molar ratio of the Ti4L6 to the TMP can be (2:1)-(4:1), preferably (3:1).
[0015] According to the present application, the molar ratio of the Ti4L6 to the ammonia can be (0.5:1)-(5:1), preferably (2:1).
[0016] According to the present application, the solvothermal synthesis is a heating reaction in a solvent. The volume ratio of the solvent water to 1,4-dioxane can be (0.5:1)-(4:1), preferably (2:2)-(2:3).
[0017] According to the present application, the temperature of the solvothermal reaction can be 70-90℃; preferably 75-85℃, for example 80℃.
[0018] The reaction time can be 6-120 hours; further preferably 12-48 hours, such as 24 hours. For example, the reaction can be carried out at 80℃ for 24 hours, or at 80℃ for 12 hours, or at 90℃ for 24 hours.
[0019] According to the present application, the reaction can be carried out in a glass bottle or a polytetrafluoroethylene pressure container.
[0020] Preferably, the reaction further comprises a step of purifying the product after the reaction, which comprises washing and separating the product after the reaction. Further preferably, the product after the reaction is washed with an alcohol solvent; and preferably, the GXMZU115 molecular cage photocatalytic crystalline material is obtained by air-drying at room temperature.
[0021] Preferably, the yield of the GXMZU115 molecular cage photocatalytic crystalline material can be more than 90%.
[0022] The GXMZU116 molecular cage photocatalytic crystalline material is prepared by solvothermal synthesis using Ti4L6, 2,9-dimethyl-1,10-phenanthroline, zinc nitrate, ammonia, water and acetonitrile as raw materials.
[0023] According to the present application, {[Zn(DMP)(NH3)](Ti4L6)} 6- L in the molecular cage crystalline material (GXMZU116) is pamoic acid, and the CAS of L is 130-85-8; the Ti4L6 is a red crystalline material; DMP is 2,9
[0024] dimethyl-1,10-phenanthroline, and the CAS of DMP is 34302-69-7.
[0025] According to the present application, the concentration of the ammonia water can be 20-34%, preferably 25-29%, such as 25% or 29%.
[0026] According to the present application, the molar ratio of Ti4L6 to DMP can be (2:1)-(4:1), preferably (3:1).
[0027] According to the present application, the molar ratio of Ti4L6 to ammonia water can be (0.5:1)-(5:1), preferably (2:1).
[0028] According to the present application, the solvothermal synthesis is a heating reaction in a solvent. The volume ratio of water to acetonitrile can be (0.5:1)-(4:1), preferably (1:1)-(2:3).
[0029] According to the present application, the temperature of the solvothermal reaction can be 70-90℃; preferably 75-85℃, such as 80℃.
[0030] The reaction time can be 6-120 hours; further preferably 6-48 hours, such as 24 hours. For example, the reaction can be carried out at 80°C for 24 hours, or at 80°C for 6 hours, or at 100°C for 24 hours.
[0031] According to the present application, the reaction can be carried out in a glass bottle or a polytetrafluoroethylene pressure container.
[0032] Preferably, the reaction further comprises a step of purifying the product after the reaction, which comprises washing and separating the product after the reaction. Further preferably, the product after the reaction is washed with an alcohol solvent; and preferably, the GXMZU116 molecular cage photocatalytic crystalline material is obtained by air-drying at room temperature.
[0033] Preferably, the yield of the GXMZU116 molecular cage photocatalytic crystalline material can be more than 90%.
[0034] The present application also provides the use of the above-mentioned GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials, which can be used for photocatalytic conversion of small organic molecules.
[0035] The present application also provides a method for photocatalytic oxidation of benzylamine and benzyl sulfide and derivatives thereof, which comprises: adding GXMZU115 or GXMZU116 molecular cage photocatalytic crystalline material into an acetonitrile solution of benzylamine and benzyl sulfide and derivatives thereof; and then irradiating under air condition with a 300W xenon lamp, to obtain (E)-N-benzylidene-1-phenylmethylamine and benzyl sulfoxide and derivative products, respectively.
[0036] According to the present application, the preparation method of the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials has the definition described above.
[0037] Advantages
[0038] The inventors have found that Ti4L6 has abundant active coordination sites, and further assembling with 2,9-dimethyl-1,10-phenanthroline and zinc metal can prepare GXMZU116 molecular cage photocatalytic crystalline material. Through experimental structure analysis, it is found that, compared with the GXMZU115 co-crystal structure, the zinc-based 2,9-dimethyl-1,10-phenanthroline cation and the antenna reactor catalytic structure formed by assembling Ti4L6 in the GXMZU116 molecular cage photocatalytic crystalline material can realize efficient excitation and full utilization of photo-generated carriers and active oxygen species, and through the interaction of host-guest chemistry, it has high adsorption of organic small molecules in a solution containing a high content of benzylamine and other organic small molecules, so as to achieve the purpose of efficient photocatalytic conversion of organic small molecules.
[0039] The inventors successfully designed and synthesized GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials. Meanwhile, the synthesis process has simple requirements, low requirements on purity of raw materials, easy availability and low price of raw materials, and is convenient for large-scale production. In addition, the post-treatment is simple and easy to operate, and only needs to be separated through simple alcohol washing and dried at room temperature to obtain a pure-phase crystalline product. The synthesis process has less pollution, and the molecular cage crystalline material has stable structure, is in a heterogeneous catalytic reaction system and is easy to separate without pollution, and meets the green and environmental protection requirements.
[0040] By using the application, the GXMZU116 molecular cage photocatalytic crystalline material is used as a photocatalyst, and organic small molecules in a solution system can be efficiently converted into high-value products, with a conversion rate of more than 99% and a selectivity of more than 95%. Therefore, from the industrial production and environmental protection points of view, the application develops an environmentally friendly photocatalytic organic small molecule conversion process by using environment-friendly chemicals, and provides a feasible method for replacing high-temperature and high-pressure environments and using toxic heavy metal inorganic catalysts to realize organic small molecule conversion, and has an industrial application prospect. BRIEF DESCRIPTION OF DRAWINGS
[0041] Figure 1 A crystal synthesis schematic diagram of GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials prepared in Example 1 is shown in the figure.
[0042] Figure 2 A crystal structure diagram of GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials prepared in Example 1 is shown in the figure.
[0043] Figure 3 A scanning electron microscope picture of GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials prepared in Example 1 is shown in the figure.
[0044] Figure 4 An X-ray diffraction pattern of GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials prepared in Example 1 and corresponding simulation data is shown in the figure.
[0045] Figure 5 A schematic diagram of photocatalytic oxidation of benzylamine by GXMZU116 molecular cage photocatalytic crystalline material prepared in Example 1 and a control experiment chart are shown in the figure.
[0046] Figure 6 A schematic diagram of photocatalytic oxidation of benzyl sulfide by GXMZU116 molecular cage photocatalytic crystalline material prepared in Example 2 and a control experiment chart are shown in the figure.
[0047] Figure 7The catalytic performance chart and X-ray diffraction pattern of the GXMZU116 molecular cage photocatalytic crystalline material prepared in Example 1 before and after 5 catalytic cycles are shown in the following table:
[0048] Figure 8 The reaction mechanism chart of the GXMZU116 molecular cage photocatalytic crystalline material prepared in Example 1 and Example 2 for photocatalyzing the reaction of benzylamine and benzyl sulfide is shown in the following table. DETAILED DESCRIPTION
[0049] In order to make the purpose, technical scheme and advantages of the present application more clear, the present application is further described in detail below in combination with the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the protection scope of the present application.
[0050] Unless otherwise specified, the reagents used in the present application are commercially available.
[0051] The gas chromatography analysis of the present application uses a 7820A gas chromatograph of Agilent, USA.
[0052] The flame ionization detector (FID) analyzes the oxidation products and quantitatively analyzes them by external standard method.
[0053] Example 1: photocatalytic oxidation of benzylamine
[0054] GXMZU115 or GXMZU116 molecular cage photocatalytic crystalline material (5 mg), benzylamine (10 μL, 0.10 mmol), and acetonitrile (4 mL) were measured and placed in a 20 mL glass tube, and then ultrasonically mixed uniformly at room temperature. After that, the mixture was placed in a 300 W xenon lamp for constant temperature reaction for 12 h. Then, the liquid phase was separated, and the liquid phase material was analyzed by gas chromatography to determine the types and yield of the oxidation reaction products.
[0055] It was tested that the yield of (E)-N-phenylmethylene-1-phenylmethylamine was 99% and the selectivity was 100% when the GXMZU116 molecular cage photocatalytic crystalline material in Example 1 catalyzed benzylamine.
[0056] The gas chromatography spectrum and nuclear magnetic resonance data of the catalytic product (E)-N-phenylmethylene-1-phenylmethylamine in Example 1 are shown in the following table: Figure 1 .
[0057] Example 2: photocatalytic oxidation of benzyl sulfide
[0058] GXMZU115 or GXMZU116 molecular cage photocatalytic crystalline material (5 mg), benzyl sulfide (14 μL, 0.10 mmol), acetonitrile (4 mL) were measured in a 20 mL glass tube, ultrasonic mixing uniformly at room temperature, then open and placed in the 300 W xenon lamp under light constant temperature reaction 6 h, removed, separated out the liquid phase, then the liquid phase material was analyzed by gas chromatography, to determine the oxidation reaction product type and yield.
[0059] Tested, the yield of GXMZU116 molecular cage photocatalytic crystalline material catalyzing benzyl sulfide to benzyl sulfoxide in Example 1 was 99%, and the selectivity was 100%.
[0060] The gas chromatogram of the catalytic product benzyl sulfoxide in Example 2 and the nuclear magnetic resonance data are specifically shown in Figure 2 .
[0061] It is confirmed by gas chromatography and nuclear magnetic resonance spectrum analysis that the use of the present application can realize efficient and high-selectivity catalysis of small organic molecules, and can convert low-value small organic molecules into high-value products (such as pharmaceutical intermediates) at low cost. From the perspective of industrial production, the present application realizes efficient and high-selectivity conversion of small organic molecules by using light energy, which reduces the cost of industrial production and the use of non-renewable energy. From the perspective of environmental protection, an environmentally friendly and stable photocatalyst is developed, which provides a feasible method for replacing the use of inorganic catalysts containing toxic heavy metals.
[0062] Those skilled in the art will readily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims
1. {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)} 2- (Masterpiece GXMZU115) and {[Zn(DMP)(NH3)](Ti4L6)} 6- (GXMZU116), two types of molecular cage photocatalytic crystalline materials. Its characteristic is that... The GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials can have X-ray powder diffraction patterns that are essentially as shown in Figure 4.
2. The GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to claim 1, characterized in that, Single-crystal X-ray diffraction revealed the following crystal parameters for the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials:
3. The method for preparing the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to claim 1 or 2, characterized in that, The preparation method includes the following steps: GXMZU115 molecular cage photocatalytic crystalline material was prepared by solvothermal synthesis using Ti4L6, 3,4,7,8-tetramethyl-1,10-phenanthroline, zinc acetate, ammonia, water, and 1,4-dioxane as raw materials. GXMZU116 molecular cage photocatalytic crystalline material was prepared by solvothermal synthesis using Ti4L6, 2,9-dimethyl-1,10-phenanthroline, zinc nitrate, ammonia, water, and acetonitrile as raw materials.
4. The preparation method of the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to claim 3, characterized in that, {[Zn(DMP)(NH3)](Ti4L6)} 6- (GXMZU116) In the molecular cage crystalline compound, L is pamoic acid, CAS: 130-85-8; the Ti4L6 is a red crystalline compound; DMP is 2,9-dimethyl-1,10-phenanthroline, CAS: 34302-69-7. {[Zn(TMP)3][Zn(TMP)(NH3)3][Zn(NH3)4](Ti4L6)} 2- (Masterpiece GXMZU115) In the molecular cage crystalline form, L is pamoic acid, and the CAS of L is 130-85-8; the Ti4L6 is a red crystalline form; TMP is 3,4,7,8-tetramethyl-1,10-phenanthroline, and the CAS of TMP is 1660-93-1. Preferably, the concentration of the ammonia water can be 20-34%, more preferably 25-29%, for example 25% or 29%.
5. The method for preparing GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to claim 3 or 4, characterized in that, The molar ratio of Ti4L6 to TMP can be (2:1) to (4:1), preferably (3:1). Preferably, the molar ratio of Ti4L6 to ammonia can be (0.5:1) to (5:1), and more preferably (2:1). Preferably, the solvothermal synthesis is carried out by heating the reaction in a solvent. The volume ratio of the solvent water to 1,4-dioxane can be (0.5:1) to (4:1), preferably (2:2) to (2:3). The molar ratio of Ti4L6 to DMP can be (2:1) to (4:1), preferably (2.5:1) to (3.5:1). Preferably, the molar ratio of Ti4L6 to ammonia water can be (0.5:1) to (5:1), and more preferably (1:1) to (2:1). Preferably, the solvothermal synthesis is carried out by heating the reaction in a solvent. The volume ratio of the solvent water to acetonitrile can be (0.5:1) to (4:1), preferably (1:1) to (2:3).
6. The method for preparing GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to any one of claims 3-5, characterized in that, The solvothermal synthesis involves a heated reaction in a solvent; the solvent is GXMZU115: water and 1,4-dioxane; GXMZU116: water and acetonitrile. Preferably, the temperature of the solvothermal reaction can be 70–90°C; more preferably 75–90°C, such as 80°C.
7. The method for preparing GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to any one of claims 3-6, characterized in that, The reaction time can be 6 to 120 hours; more preferably 6 to 48 hours, such as 24 hours. Preferably, the reaction can be carried out in a glass bottle or a polytetrafluoroethylene pressure vessel.
8. The method for preparing GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to any one of claims 3-7, characterized in that, The reaction also includes a step of purifying the product after the reaction, which includes: washing and separating the product after the reaction; preferably using an alcohol solvent to wash the product after the reaction; and preferably air-drying at room temperature to obtain GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials.
9. The use of the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials according to claim 1 or 2, characterized in that, The GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials can be used for photocatalytic conversion of small organic molecules.
10. A method for photocatalytic oxidation of benzylamine with anisole and its derivatives, the photocatalytic oxidation method comprising: GXMZU115 or GXMZU116 molecular cage photocatalytic crystalline materials were added to an acetonitrile solution containing benzylamine and benzyl sulfide and their derivatives; then, the mixture was irradiated with a 300W xenon lamp under air conditions to obtain (E)-N-benzylmethylene-1-phenylmethylamine and benzyl sulfoxide and their derivatives, respectively. Preferably, the preparation method of the GXMZU115 and GXMZU116 molecular cage photocatalytic crystalline materials has the definition described in any one of claims 3-8.