MIL-100 (Fe) containing rich oxygen vacancies as well as one-step preparation method and application of MIL-100 (Fe)

Abstract

The invention belongs to the technical field of metal organic framework materials, and particularly relates to MIL-100 (Fe) containing rich oxygen vacancies as well as a one-step preparation method and application of the MIL-100 (Fe). The one-step preparation method of the MIL-100 (Fe) containing rich oxygen vacancies comprises the following steps: uniformly mixing ferric chloride hexahydrate, trimesic acid and vanillin in a solvent, and carrying out solvothermal reaction; and after the reaction is finished, carrying out solid-liquid separation, cleaning and drying to obtain a solid, namely the MIL-100 (Fe) containing rich oxygen vacancies. According to the one-step preparation method of the MIL-100 (Fe) containing the rich oxygen vacancies, the process is simple, the MIL-100 (Fe) containing the rich oxygen vacancies can be prepared through one-step reaction, and the preparation cost is low.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal-organic framework materials, and particularly relates to MIL-100(Fe) containing abundant oxygen vacancies, a one-step preparation method thereof, and applications thereof. Background Art

[0002] Metal-organic framework (MOF) materials have attracted much attention due to their unique permanent porosity and structural tunability. Among them, iron-based metal-organic frameworks, namely Fe-MOFs, also show great potential. In particular, MIL-100(Fe), with its uniformly distributed Fe active sites, abundant Fe-O clusters, and excellent water stability, has received extensive attention in the application as a photo-Fenton material in the field of environmental remediation. However, unfortunately, the intrinsic photo-Fenton catalytic activity of MIL-100(Fe) is not ideal, mainly due to the insufficient exposure of catalytic sites and the low electron separation efficiency. Therefore, designing and preparing photo-Fenton materials containing highly efficient active sites and rapid Fe 3+ / Fe 2+ cycle efficiency has important scientific significance and application value.

[0003] It has been reported in the literature that oxygen vacancies can be used to synergistically regulate the active sites and iron cycle efficiency of intrinsic MIL-100(Fe) to improve the photo-Fenton performance. Currently, there are two relatively common strategies for preparing MIL-100(Fe) containing oxygen vacancies: one is to use vacuum thermal activation to remove terminal coordinated water molecules and anionic ligands to generate oxygen vacancies in MIL-100(Fe). However, this method often requires two steps to complete. First, MIL-100(Fe) is prepared, and then vacuum thermal activation is carried out. The preparation process is complex, and the removed water molecules are prone to secondary coordination, resulting in low reusability; the other is to use insoluble metal precursors as metal sources to prepare defective MIL-100(Fe), but this method has a high cost (the ratio of metal source to ligand is 3.7:1). In summary, although the above methods can successfully prepare MIL-100(Fe) containing oxygen vacancies, they all face the problems of complex preparation methods and high costs.

[0004] Therefore, there is a need to provide an improved technical solution to address the above deficiencies in the prior art. Summary of the Invention

[0005] The object of the present invention is to provide MIL-100(Fe) containing abundant oxygen vacancies, a one-step preparation method thereof, and applications thereof, which helps to simplify the preparation of MIL-100(Fe) containing oxygen vacancies and reduce the preparation cost of MIL-100(Fe) containing oxygen vacancies.

[0006] To achieve the above object, the present invention provides the following technical solution: A one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies, comprising the following steps: Mix ferric chloride hexahydrate, trimesic acid and vanillin evenly in a solvent, and carry out a solvothermal reaction; After the reaction is completed, carry out solid-liquid separation, wash and dry, and the obtained solid is the MIL-100(Fe) containing abundant oxygen vacancies.

[0007] Preferably, the molar ratio of ferric chloride hexahydrate to trimesic acid is 1:1; The molar ratio of trimesic acid to vanillin is (4-8):1.

[0008] Preferably, the temperature of the solvothermal reaction is 150-160 °C, and the reaction time is 12-14 h.

[0009] Preferably, the solvent is DMF.

[0010] Preferably, after solid-liquid separation to obtain the solid, the obtained solid is washed with absolute ethanol and deionized water respectively; The drying temperature is 50-60 °C.

[0011] The present invention also provides a MIL-100(Fe) containing abundant oxygen vacancies, which adopts the following technical solution: MIL-100(Fe) containing abundant oxygen vacancies, and the MIL-100(Fe) containing abundant oxygen vacancies is prepared by the method described above.

[0012] The present invention also provides an application of MIL-100(Fe) containing abundant oxygen vacancies, which adopts the following technical solution: The application of MIL-100(Fe) containing abundant oxygen vacancies as described above in the photocatalytic degradation of tetracycline hydrochloride by Fenton.

[0013] Beneficial effects:

[0014] The one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies of the present invention has a simple process, and MIL-100(Fe) containing abundant oxygen vacancies can be prepared by one-step reaction, and the preparation cost is low.

[0015] The MIL-100(Fe) containing abundant oxygen vacancies of the present invention can achieve a removal rate of up to 97% for tetracycline hydrochloride in the photocatalytic Fenton system, and the kinetic constant can reach 0.041 min -1 . Description of the drawings

[0016] The specification drawings constituting a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. Among them:

[0017] Figure 1XRD patterns of MIL-100(Fe)-O of Example 1 v and MIL-100(Fe) of Comparative Example 1;

[0018] Figure 2 EPR spectra of MIL-100(Fe)-O of Example 1 v and MIL-100(Fe) of Comparative Example 1;

[0019] Figure 3 Microscopic morphology diagrams of MIL-100(Fe)-O of Example 1 v wherein, (a) and (b) respectively show the microscopic morphologies at different positions of the same sample;

[0020] Figure 4 Transient photocurrent response curves and impedance spectra of MIL-100(Fe)-O of Example 1 v and MIL-100(Fe) of Comparative Example 1; wherein, (a) is the transient photocurrent response curve and (b) is the impedance spectrum;

[0021] Figure 5 Degradation test results diagrams of MIL-100(Fe)-O of Example 1 v and MIL-100(Fe) of Comparative Example 1 for TC-HCl and the corresponding kinetic curves; wherein, (a) is the degradation test results diagram and (b) is the kinetic curve;

[0022] Figure 6 Degradation test results diagrams of MIL-100(Fe)-O of Example 1 v and MIL-100(Fe)-O of Comparative Example 2 v -vacuum for TC-HCl and the corresponding kinetic curves; wherein, (a) is the degradation test results diagram and (b) is the kinetic curve;

[0023] Figure 7 Degradation test results diagram of MIL-100(Fe)-O of Example 2 v for TC-HCl;

[0024] Figure 8 Degradation test results diagram of MIL-100(Fe)-O of Example 3 v for TC-HCl;

[0025] Figure 9 Coordination principle diagrams of ferric chloride hexahydrate and organic ligands; wherein, (a) is the coordination diagram of trimesic acid and iron ions, (b) is the structural formula of vanillin, and (c) is the coordination diagram of vanillin and iron ions. Detailed implementation manners

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Apparently, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0027] The present invention will be described in detail below in conjunction with embodiments. It should be noted that, without conflict, the embodiments in the present invention and the features in the embodiments may be combined with each other.

[0028] Aiming at the problems of the complex preparation process and high cost of the currently available MIL-100(Fe) containing oxygen vacancies, the present invention provides a one-step preparation method for MIL-100(Fe) containing abundant oxygen vacancies.

[0029] The one-step preparation method for MIL-100(Fe) containing abundant oxygen vacancies according to the embodiments of the present invention includes the following steps: mixing ferric chloride hexahydrate, trimesic acid, and vanillin uniformly in a solvent, and performing a solvothermal reaction; after the reaction is completed, separating the solid from the liquid, washing and drying, and the obtained solid is MIL-100(Fe) containing abundant oxygen vacancies.

[0030] In the one-step preparation method for MIL-100(Fe) containing abundant oxygen vacancies of the present invention, ferric chloride hexahydrate and trimesic acid are used as a metal ion source and an organic ligand respectively to participate in the preparation of the metal-organic framework material. Vanillin is used as a monodentate ligand. During the hydrothermal self-assembly process, part of the trimesic acid (polydentate ligand) is replaced by the monodentate ligand, thereby realizing the loss of oxygen atoms in the system and further generating oxygen vacancies (in the present invention, the coordinatively unsaturated metal sites generated by the oxygen vacancies exhibit Lewis acidity and can act as a Lewis base for H 2 O 2 to produce specific adsorption); meanwhile, the aldehyde group in vanillin has reducibility and can reduce Fe 3 + to produce mixed-valence Fe 3+ / Fe 2+ . The present invention can prepare MIL-100(Fe) containing abundant oxygen vacancies through a one-step reaction. The preparation process is simple, and the photo-Fenton catalytic activity of the prepared MIL-100(Fe) containing abundant oxygen vacancies is significantly improved.

[0031] Specifically, as Figure 9 shown: during the self-assembly of ferric chloride hexahydrate and trimesic acid, the coordination of trimesic acid and ferric chloride hexahydrate is as shown in (a) (in the case where the organic ligand only contains trimesic acid, the two uncoordinated carboxyl groups of trimesic acid in (a) will coordinate with other iron ions); but when vanillin (structural formula as shown in (b)) is added, the aldehyde group will undergo an oxidation-reduction reaction to produce Fe2+ Meanwhile, it is oxidized to a carboxyl group itself, and the coordination mode of MIL-100(Fe) changes (the coordination mode after adding vanillin is shown in (c)). Compared with the case of only adding trimesic acid as a ligand (trimesic acid has 3 carboxyl groups for coordination), there are fewer ligand sites, thus generating Fe 2+ Meanwhile, oxygen vacancies are also generated.

[0032] In a preferred embodiment of the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, the molar ratio of ferric chloride hexahydrate to trimesic acid is 1:1; the molar ratio of trimesic acid to vanillin is (4 - 8):1 (for example, 4:1, 5:1, 6:1, 7:1 or 8:1). In the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, the molar ratio of the metal source to the ligand is significantly smaller (in the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, the molar ratio of the metal source to the ligand is 1:1.125 - 1:1.25; compared with the prior art when using an insoluble metal as the metal source to prepare defective MIL-100(Fe), the ratio of the metal source to the ligand is 3.7:1, significantly reducing the molar ratio of the metal source to the ligand), which helps to reduce costs.

[0033] In a preferred embodiment of the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, the temperature of the solvothermal reaction is 150 - 160 °C (for example, 150 °C, 152 °C, 154 °C, 156 °C, 158 °C or 160 °C), and the reaction time is 12 - 14 h (for example, 12 h, 12.5 h, 13 h, 13.5 h or 14 h).

[0034] In a preferred embodiment of the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, the solvent is DMF. Among them, using DMF as the solvent can enable the ionic salt (ferric chloride hexahydrate) and the organic ligand to fully react and self-assemble.

[0035] In a preferred embodiment of the one-step preparation method of MIL-100(Fe) with rich oxygen vacancies of the present invention, after solid-liquid separation to obtain a solid, the obtained solid is washed with absolute ethanol and deionized water respectively; the drying temperature is 50 - 60 °C (for example, 50 °C, 52 °C, 54 °C, 56 °C, 58 °C or 60 °C).

[0036] The present invention also proposes a MIL-100(Fe) with rich oxygen vacancies, and the MIL-100(Fe) with rich oxygen vacancies in the embodiments of the present invention is prepared by the method described above.

[0037] The present invention also provides an application of the above-mentioned MIL-100(Fe) with rich oxygen vacancies, and an application of the above-mentioned MIL-100(Fe) with rich oxygen vacancies in the photocatalytic degradation of tetracycline hydrochloride by Fenton reaction.

[0038] The following specific examples are used to illustrate in detail the MIL-100(Fe) with rich oxygen vacancies, its one-step preparation method and application of the present invention.

[0039] Sources of the main raw materials used in the following examples: ferric chloride hexahydrate was purchased from Tianjin Guangfu Reagent Co., Ltd.; trimesic acid was purchased from Aladdin Reagent Co., Ltd.; vanillin was purchased from Aladdin Reagent Co., Ltd.; DMF was purchased from Tianjin Zhiyuan Chemical Reagent Co., Ltd.

[0040] Example 1

[0041] The one-step preparation method of the MIL-100(Fe) with rich oxygen vacancies in this example includes the following steps:

[0042] a. Measure 20 mL of DMF into a beaker and start stirring;

[0043] b. Weigh ferric chloride hexahydrate, trimesic acid and vanillin into 20 mL of DMF respectively (the final concentrations of ferric chloride hexahydrate and trimesic acid are both 1 mM, and the molar ratio of trimesic acid to vanillin is 6:1), and stir vigorously for 30 min to obtain a homogeneous mixed solution;

[0044] c. Transfer the above mixed solution to a 50 mL polytetrafluoroethylene reaction kettle and carry out a solvothermal reaction (150 °C, keep the temperature for 12 h);

[0045] d. After the reaction is completed, centrifuge the cooled reaction solution, and add anhydrous ethanol and deionized water to the obtained solid respectively and centrifuge and wash three times;

[0046] e. Place the washed powder in an oven at 60 °C and dry overnight, and grind it to obtain a bright orange powder, which is the MIL-100(Fe) with rich oxygen vacancies in this example (abbreviated as MIL-100(Fe)-O v )

[0047] Example 2

[0048] The one-step preparation method of the MIL-100(Fe) with rich oxygen vacancies in this example includes the following steps:

[0049] a. Measure 20 mL of DMF into a beaker and start stirring;

[0050] b. Weigh ferric chloride hexahydrate, trimesic acid, and vanillin separately into 20 mL of DMF (the final concentrations of ferric chloride hexahydrate and trimesic acid are 1 mM respectively, and the molar ratio of trimesic acid to vanillin is 8:1), and stir vigorously for 30 min to obtain a homogeneous mixed solution;

[0051] c. Transfer the above mixed solution to a 50 mL polytetrafluoroethylene reaction kettle and carry out a solvothermal reaction (150 °C, keep the temperature for 12 h);

[0052] d. After the reaction is completed, centrifuge the cooled reaction solution, and add anhydrous ethanol and deionized water to the obtained solid respectively and centrifuge and wash three times;

[0053] e. Place the washed powder in an oven at 60 °C and dry overnight, and grind to obtain a bright orange powder, which is the MIL-100(Fe) containing rich oxygen vacancies in this example (abbreviated as MIL-100(Fe)-O v ).

[0054] Example 3

[0055] The one-step preparation method of MIL-100(Fe) containing rich oxygen vacancies in this example includes the following steps:

[0056] a. Measure 20 mL of DMF into a beaker and start stirring;

[0057] b. Weigh ferric chloride hexahydrate, trimesic acid, and vanillin separately into 20 mL of DMF (the final concentrations of ferric chloride hexahydrate and trimesic acid are 1 mM respectively, and the molar ratio of trimesic acid to vanillin is 4:1), and stir vigorously for 30 min to obtain a homogeneous mixed solution;

[0058] c. Transfer the above mixed solution to a 50 mL polytetrafluoroethylene reaction kettle and carry out a solvothermal reaction (150 °C, keep the temperature for 12 h);

[0059] d. After the reaction is completed, centrifuge the cooled reaction solution, and add anhydrous ethanol and deionized water to the obtained solid respectively and centrifuge and wash three times;

[0060] e. Place the washed powder in an oven at 60 °C and dry overnight, and grind to obtain a bright orange powder, which is the MIL-100(Fe) containing rich oxygen vacancies in this example (abbreviated as MIL-100(Fe)-O v ).

[0061] Comparative Example 1

[0062] The preparation method of MIL-100(Fe) in this comparative example includes the following steps:

[0063] a. Measure 20 mL of DMF in a beaker and start stirring;

[0064] b. Weigh ferric chloride hexahydrate and trimesic acid separately into 20 mL of DMF (the final concentrations of ferric chloride hexahydrate and trimesic acid are 1 mM respectively), stir vigorously for 30 min to obtain a homogeneous mixed solution;

[0065] c. Transfer the above mixed solution to a 50 mL polytetrafluoroethylene reaction kettle and carry out a solvothermal reaction (150 °C, keep the temperature for 12 h);

[0066] d. After the reaction is completed, centrifuge the cooled reaction solution, and add anhydrous ethanol and deionized water to the obtained solid respectively and centrifuge and wash three times;

[0067] e. Place the washed powder in an oven at 60 °C and dry overnight, and grind to obtain MIL-100(Fe) of this comparative example.

[0068] Comparative Example 2

[0069] Vacuum calcine the MIL-100(Fe) of Comparative Example 1 (the calcination temperature is 250 °C, the vacuum degree is -0.085 MPa, and the calcination time is 12 h) to obtain MIL-100(Fe)-O of this comparative example v - Vacuum.

[0070] Experimental Example

[0071] 1. XRD test: Use an X-ray diffractometer (XRD; SmartLab, Rigaku, Cu-Kα ray, ) to characterize the crystal structure of the catalyst.

[0072] Figure 1 The XRD spectra of MIL-100(Fe) of Comparative Example 1 and MIL-100(Fe)-O of Example 1 are shown; it can be seen that MIL-100(Fe) exhibits its characteristic diffraction peaks, which is consistent with the literature reports; the sharp and strong diffraction peaks indicate good crystallinity of MIL-100(Fe). MIL-100(Fe)-O v exhibits diffraction peaks similar to those of MIL-100(Fe), which indicates that the original crystal structure is well maintained during the introduction of the missing ligand of vanillin. v 2. EPR test: Use an electron paramagnetic resonance spectrometer (EPR; Bruker A300) to analyze the defect states of the samples.

[0073] The EPR spectra of MIL-100(Fe) and MIL-100(Fe)-O of Example 1 are shown;

[0074] Figure 2 The EPR spectra of MIL-100(Fe) and MIL-100(Fe)-O of Example 1 are shown;v EPR spectra; it can be seen that MIL-100(Fe) and MIL-100(Fe)-O v both exhibit unique resonance signal peaks at g = 2.003, which are related to oxygen vacancies. The signal peak of MIL-100(Fe) is weak, which may be related to intrinsic defects. MIL-100(Fe)-O v shows a significantly enhanced resonance signal peak, indicating that vanillin, as a monodentate ligand, successfully replaces part of the trimesic acid during the hydrothermal self-assembly process, thus generating abundant oxygen vacancies in the system.

[0075] 3. SEM test: The morphology of the catalyst was characterized by field emission scanning electron microscopy (FESEM; JSM-6700F, JEOL).

[0076] Figure 3 Among them, (a) and (b) present the high-magnification SEM images of MIL-100(Fe)-O in Example 1 v ; it can be seen that MIL-100(Fe)-O v has an irregular nanoparticle morphology, and the particle size is approximately between 20 nm and 50 nm. This observation result is consistent with the morphology of MIL-100(Fe) reported in previous literature. This indicates that the introduction of the vanillin-deficient ligand has no significant effect on the surface morphological characteristics of MIL-100(Fe).

[0077] 4. Transient photocurrent response curve and impedance spectrum test: The photoelectrochemical performance test was carried out on an electrochemical workstation (CHI660E; CH Instruments, China). The transient photocurrent (TPC) and alternating current impedance (EIS) were measured using a standard three-electrode system.

[0078] Figure 4 Among them, (a) and (b) respectively show the transient photocurrent response curves and impedance spectra of MIL-100(Fe) and MIL-100(Fe)-O in Example 1 v ; as shown in the figure, MIL-100(Fe)-O v shows a higher photocurrent density compared to MIL-100(Fe) (the photocurrent density of MIL-100(Fe)-O in Example 1 v can reach 2.5 times that of MIL-100(Fe)), and at the same time, its arc radius is smaller.

[0079] The above analysis shows that constructing oxygen vacancies is beneficial to the separation and transfer of photo-generated carriers in the system and improves the photo-generated carrier behavior of MIL-100(Fe). Thus, there are more photo-generated electrons for accelerating the Fe 3+ / Fe 2+ cycle and H2 O 2 Activation of

[0080] 5. To evaluate the photo-Fenton activity of the prepared materials, we used the removal efficiency of TC-HCl as an indicator: The photo-Fenton performance of the catalyst was evaluated by removing TC-HCl (tetracycline hydrochloride). The degradation experiment was carried out in a reactor with a condensing circulating water device. Before illumination, a certain amount of catalyst was added to a glass reactor containing 100 mL of TC-HCl solution (50 mg / L) (pH = 4), and the mixed solution was stirred in the dark for 30 min to reach the adsorption-desorption equilibrium. Then, a certain amount of H 2 O 2 (100 mM) was added, and the reaction was initiated by irradiating from the top with a 300 W xenon lamp equipped with an ultraviolet cut-off filter. During the reaction, 3 mL of samples were extracted at regular intervals and filtered through a 0.45 μm filter membrane. The remaining concentration of the reactant was calculated by analyzing the absorbance at 357 nm with an ultraviolet-visible spectrophotometer.

[0081] Due to the high stability of TC-HCl, it did not degrade under the condition of only visible light irradiation. However, in the photo-Fenton system, TC-HCl began to be effectively degraded. Specifically, as Figure 5 shown, in the Vis / MIL-100(Fe)-O v / H 2 O 2 system of Example 1, the removal efficiency of TC-HCl was as high as 97%, and the kinetic constant reached 0.041 min -1 ; while in the Vis / MIL-100(Fe) / H 2 O 2 system of Comparative Example 1, the removal efficiency of TC-HCl was only up to 73.7%, and the kinetic constant was 0.015 min -1 . As Figure 6 shown, in the Vis / MIL-100(Fe)-O v -vacuum / H 2 O 2 system of Comparative Example 2, the removal efficiency of TC-HCl was 85.5%, and the kinetic constant was 0.023 min -1 . This strongly proves that the MIL-100(Fe) containing rich oxygen vacancies prepared by the present invention (i.e., MIL-100(Fe)-O v ) has significantly better photo-Fenton catalytic activity than MIL-100(Fe) of Comparative Example 1 and MIL-100(Fe)-O v -vacuum of Comparative Example 2, and can significantly improve the removal ability of the material for pollutants.

[0082] Vis / MIL-100(Fe)-O of Example 2 and Example 3 v / H 2 O 2 In the system, the test results of the removal rate of TC-HCl are respectively as Figures 7-8 shown. In the Vis / MIL-100(Fe)-O v / H 2 O 2 system of Example 2, the removal efficiency of TC-HCl is 89.6%; in the Vis / MIL-100(Fe)-O v / H 2 O 2 system of Example 3, the removal efficiency of TC-HCl is 89%. The photo-Fenton catalytic activity of MIL-100(Fe)-O of Example 2-3 is also significantly greater than that of MIL-100(Fe) of Comparative Example 1 and MIL-100(Fe)-O v -vacuum of Comparative Example 2. v -vacuum.

[0083] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies, characterized in that: The method comprises the following steps: uniformly mixing ferric chloride hexahydrate, trimesic acid and vanillin in a solvent, and performing a solvothermal reaction; After the reaction is completed, the solid and liquid are separated, washed and dried, and the obtained solid is the MIL-100 (Fe) containing abundant oxygen vacancies.

2. The one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies according to claim 1, characterized in that: The molar ratio of the ferric chloride hexahydrate to trimesic acid is 1:1; The molar ratio of trimesic acid to vanillin is (4-8):

1.

3. The one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies according to claim 1, characterized in that: The temperature of the solvent thermal reaction is 150-160°C and the reaction time is 12-14h.

4. The one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies according to claim 1, characterized in that: The solvent is DMF.

5. The one-step preparation method of MIL-100(Fe) containing abundant oxygen vacancies according to claim 1, characterized in that: After solid-liquid separation to obtain solid, the obtained solid is washed with anhydrous ethanol and deionized water respectively; The drying temperature is 50-60°C.

6. MIL-100(Fe) rich in oxygen vacancies, characterized in that: The MIL-100(Fe) rich in oxygen vacancies is prepared by the method according to any one of claims 1 to 5.

7. Use of MIL-100(Fe) rich in oxygen vacancies as claimed in claim 6 in photo-Fenton catalytic degradation of tetracycline hydrochloride.

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