CN108947813B - Process for preparing two-dimensional MOF material by one-step solvothermal method - Google Patents

Process for preparing two-dimensional MOF material by one-step solvothermal method Download PDF

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CN108947813B
CN108947813B CN201810690800.9A CN201810690800A CN108947813B CN 108947813 B CN108947813 B CN 108947813B CN 201810690800 A CN201810690800 A CN 201810690800A CN 108947813 B CN108947813 B CN 108947813B
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CN108947813A (en
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曹澥宏
刘文贤
施文慧
尹瑞连
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Zhejiang University of Technology ZJUT
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    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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Abstract

The invention relates to the technical field of organic complexes, in particular to a process for preparing a two-dimensional MOF material by a one-step solvothermal method, which comprises the following steps: dispersing three-dimensional MOF crystal powder into an organic solvent to obtain a dispersion liquid; and pouring the dispersion into a reaction kettle, reacting for 1-10 h at the temperature of 60-200 ℃, cooling, washing and drying to obtain the two-dimensional MOF material. The method has the advantages of high yield, simple steps, easily controlled conditions and universality; the prepared two-dimensional MOF material maintains the excellent characteristics of the three-dimensional MOF material, further improves the specific surface area of the material, has good uniformity, increases active sites participating in chemical reaction, and improves the application advantages in the fields of catalysis, sensing, electrochemistry and the like.

Description

Process for preparing two-dimensional MOF material by one-step solvothermal method
Technical Field
The invention relates to the technical field of metal organic complexes, in particular to a process for preparing a two-dimensional MOF material by a one-step solvothermal method.
Background
Metal-organic frameworks (MOFs) are materials with periodic porous network structures formed by self-assembly of Metal-organic ligands and Metal ions through Metal-ligand complexation, and have wide applications in the fields of catalysts, medical materials, energy storage and the like due to the characteristics of adjustable pore structures, large specific surface areas, stable chemical properties and the like.
The two-dimensional MOF material has larger length-diameter ratio, larger transverse size and thinner nanometer thickness than a three-dimensional material, so that the surface of the material is closer to an active site, and the material has more advantages in the fields of catalysis, sensing, electrochemistry and the like. The existing two-dimensional MOF material preparation methods mainly comprise two methods: (1) the method comprises the following steps: the three-dimensional MOF material is dispersed, and then the interaction among layers of the three-dimensional MOF material is destroyed by an ultrasonic wave or oscillation method, so that the purpose of preparing the two-dimensional MOF material is achieved; (2) a bottom-up method: the purpose of synthesizing the two-dimensional sheet material is achieved by adding a specific surfactant to control the growth of the crystal surface.
However, the above-described method for producing two-dimensional MOF materials has the following drawbacks: the two-dimensional MOF material obtained by the method (1) has extremely low yield, uneven sheet size and uneven sheet thickness, and influences the performance of the product; the method (2) has complex experimental operation and narrow application range, is mainly applied to the preparation of zinc diphenyl-1, 2-dicarboxylate (ZnBDC) and copper 1, 4-benzenedicarboxylate (CuBDC), and has high limitation.
Chinese patent literature discloses a support type ultrathin two-dimensional layered MOF membrane and a preparation method thereof, and the publication number is CN 105709610A. However, the method has high requirements on equipment, harsh process conditions, high energy consumption and high cost.
Therefore, the development of a simple and universal method for synthesizing two-dimensional MOF materials has great research significance on the development of MOF materials.
Disclosure of Invention
The invention provides a process for preparing a two-dimensional MOF material by a one-step solvothermal method, which has the advantages of simple steps, uniform product appearance and universality, and aims to solve the problems of low yield, uneven lamella, complex operation and narrow application range in the traditional two-dimensional MOF material preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the process for preparing the two-dimensional MOF material by the one-step solvothermal method comprises the following steps: dispersing three-dimensional MOF crystal powder into an organic solvent to obtain a dispersion liquid; and pouring the dispersion into a reaction kettle, reacting for 1-10 h at the temperature of 60-200 ℃, cooling, washing and drying to obtain the two-dimensional MOF material.
The invention utilizes a simple one-step hydrothermal method to prepare the two-dimensional MOF material with uniform appearance and uniform component distribution, and the reaction mechanism is as follows: the three-dimensional MOF crystals are melted and recrystallized in the solvothermal process to form a two-dimensional MOF crystal material with uniform size. The method has the advantages of simple process steps, simple and convenient operation and low requirement on experimental conditions, and the obtained two-dimensional MOF material retains the structural characteristics of the three-dimensional MOF, greatly improves the specific surface area compared with the three-dimensional MOF material, and is more beneficial to the contact between the material surface and reactants.
Preferably, the organic solvent is selected from methanol or ethanol.
Preferably, the concentration of the three-dimensional MOF crystal powder in the dispersion liquid is controlled to be 0.1-10 mg/mL. The obtained product with the concentration of the dispersion liquid controlled in the range has uniform appearance, if the concentration is too high, agglomeration is easy to cause, and the specific surface area is lower; if the concentration is too low, the yield is low.
Preferably, the concentration of the three-dimensional MOF crystal powder in the dispersion is controlled to be 0.56 mg/mL. The concentration is selected as the optimal concentration, and the prepared two-dimensional MOF material has better appearance and specific surface area performance.
Preferably, after the reaction is finished, naturally cooling the obtained product to 10-40 ℃, then centrifugally washing the product by using methanol or ethanol, repeating the washing for 1-5 times, and drying for 6-10 hours in vacuum. The reaction is carried out in a blast oven, the reaction conditions are mild, the used raw materials are non-toxic and pollution-free, the application range of the three-dimensional MOF crystal is wide, the preparation method is simple, the three-dimensional MOF crystal is suitable for large-scale production, and the yield is high.
Preferably, the reaction temperature is 120 ℃ and the reaction time is 8 h.
Preferably, the three-dimensional MOF crystal powder is one or a mixture of more of ZIF-67, MIL-53 (Fe), MIL-53 (Fe) -NH2, MIL-88 (Fe) and MIL-125 (Ti).
The three-dimensional MOF crystal powder selected by the invention is prepared by adopting a solvothermal method: and mixing metal salt or metal salt hydrate, organic ligand and solvent according to a proportion, then carrying out solvothermal reaction on the mixture to obtain MOF crystal precipitate, further carrying out centrifugal washing, and carrying out vacuum drying to obtain three-dimensional MOF crystal powder.
Therefore, the invention has the following beneficial effects:
(1) the process has the advantages of simple steps, easily controlled conditions and universality;
(2) the prepared two-dimensional MOF material maintains the excellent characteristics of the three-dimensional MOF material, further improves the specific surface area of the material, has good uniformity, increases active sites participating in chemical reaction, and improves the application advantages in the fields of catalysis, sensing, electrochemistry and the like.
Drawings
FIG. 1 is an SEM image of a MIL-53 (Fe) three-dimensional MOF material.
FIG. 2 is an SEM image of the MIL-53 (Fe) two-dimensional MOF material prepared in example 3.
FIG. 3 is an HRTEM image of MIL-53 (Fe) two-dimensional MOF material prepared in example 3.
FIG. 4 is a wide angle XRD spectrum of MIL-53 (Fe) three-dimensional MOF material.
FIG. 5 is a wide angle XRD spectrum of MIL-53 (Fe) two-dimensional MOF material prepared in example 3.
FIG. 6 is an infrared spectrum of MIL-53 (Fe) three-dimensional MOF material.
FIG. 7 is an IR spectrum of MIL-53 (Fe) two-dimensional MOF material prepared in example 3.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Preparation of three-dimensional MIL-53 (Fe) crystalline powder:
(1) weighing 54mg FeCl3•6H2Ultrasonically dispersing O in 5mL of DMF to obtain ferric chloride dispersion liquid;
(2) weighing 33.2mg of terephthalic acid (BDC) and ultrasonically dispersing in 5mL of DMF to obtain a terephthalic acid solution;
(3) and (2) uniformly mixing the terephthalic acid solution and the ferric chloride dispersion, transferring to a 20 mL reaction kettle, placing in a forced air oven to react for 8h at 120 ℃, after the reaction is finished, placing in a room to naturally cool to room temperature, centrifugally washing with methanol, repeating for 3 times, and vacuum drying for 8h at 60 ℃ to obtain the MIL-53 (Fe) three-dimensional MOF material.
Example 1
Dispersing the MIL-53 (Fe) three-dimensional MOF material into methanol to obtain a dispersion liquid with the concentration of 0.1 mg/mL; and pouring the dispersion liquid into a reaction kettle, reacting for 10 hours at the temperature of 60 ℃, naturally cooling the obtained product to 10 ℃ after the reaction is finished, centrifugally washing the product by using methanol or ethanol, repeating for 1 time, and drying in vacuum for 6 hours to obtain the MIL-53 (Fe) two-dimensional MOF material.
Example 2
Dispersing the MIL-53 (Fe) three-dimensional MOF material into ethanol to obtain a dispersion liquid with the concentration of 10 mg/mL; and pouring the dispersion liquid into a reaction kettle, reacting for 1h at the temperature of 200 ℃, naturally cooling the obtained product to 40 ℃ after the reaction is finished, centrifugally washing the product by using methanol or ethanol, repeating for 5 times, and drying in vacuum for 10h to obtain the MIL-53 (Fe) two-dimensional MOF material.
Example 3
Dispersing the MIL-53 (Fe) three-dimensional MOF material into ethanol to obtain a dispersion liquid with the concentration of 0.56 mg/mL; and pouring the dispersion liquid into a reaction kettle, reacting for 8 hours at the temperature of 120 ℃, naturally cooling the obtained product to 25 ℃ after the reaction is finished, centrifugally washing the product by using methanol or ethanol, repeating for 3 times, and drying in vacuum for 8 hours to obtain the MIL-53 (Fe) two-dimensional MOF material.
The MIL-53 (Fe) three-dimensional MOF material prepared by the invention and the MIL-53 (Fe) two-dimensional MOF material prepared in example 3 were characterized and tested:
(1) SEM analysis
SEM testing was performed on a HITACHI S-4700 scanning electron microscope using the following sample preparation: and taking a small amount of the sample to be tested, placing the sample to be tested on the surface of the support table stuck with the conductive adhesive, and then placing the sample to be tested into an SEM chamber for testing.
(2) High resolution TEM analysis
The TEM test was performed on a JEOL 2010F transmission electron microscope, using the following sample preparation method: and (3) dropwise adding about 1ml of deionized water into a sample to be detected, ultrasonically dispersing for 10min until the sample is uniformly dispersed, dropwise adding a small amount of dispersion liquid onto the surface of the copper mesh with the micro grid (containing the microporous carbon support film) by using a dropping method, and naturally drying at room temperature.
(3) Wide angle XRD analysis
The XRD test was performed on an X' Pert Pro X-ray diffractometer, and the samples to be tested were prepared as follows: and (3) removing the sample to be tested, paving the sample in the square frosted groove on the quartz plate, and compacting and flattening the sample by using a glass slide for testing.
And (3) analyzing a test result:
as shown in fig. 1, which is an SEM image of MIL-53 (Fe) three-dimensional MOF material prepared by the present invention, and as shown in fig. 2 and fig. 3, which are an SEM image and an HRTEM image of two-dimensional MIL-53 (Fe) material prepared in example 3, respectively, it can be seen by comparing fig. 1 with fig. 2 and fig. 3 that the overall morphology of the three-dimensional MOF material without solvothermal reaction is a three-dimensional regular octahedral structure with a size of about 0.5 μm; the two-dimensional MOF material prepared by one-step solvothermal reaction has a sheet structure with the overall morphology of about 1 micron in length and about 0.5 micron in width and uniform size.
FIGS. 4 and 5 are wide-angle XRD spectra of three-dimensional MOF crystal and two-dimensional MOF crystal samples, respectively, and FIG. 4 shows that the three-dimensional MOF crystal material exhibits diffraction peaks consistent with simulated MIL-101 (Fe) diffraction peaks, indicating successful synthesis of MIL-101 (Fe) three-dimensional MOF material; FIG. 5 shows that the diffraction peak positions of the MIL-53 (Fe) two-dimensional MOF material prepared by solvothermal reaction and the MIL-101 (Fe) three-dimensional MOF material are consistent, and the intensity is higher, which indicates that the prepared two-dimensional MOF material and the three-dimensional MOF material are the same metal organic coordination compound.
FIGS. 6 and 7 are the IR spectra of a sample of three-dimensional MOF material and a sample of two-dimensional MOF crystals, respectively, compared to a sample of 550/cm wavelength-1All the peaks represent Fe-O bonds, and further confirms that the prepared two-dimensional MOF material and the three-dimensional MOF material are the same metal organic coordination compound.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (6)

1. The process for preparing the two-dimensional MOF material by the one-step solvothermal method is characterized by comprising the following steps of: dispersing three-dimensional MOF crystal powder into an organic solvent to obtain a dispersion liquid; pouring the dispersion into a reaction kettle, reacting for 1-10 h at the temperature of 60-200 ℃, cooling, washing and drying to obtain a two-dimensional MOF material; the three-dimensional MOF crystal powder is MIL-53 (Fe).
2. The process for the one-step solvothermal preparation of a two-dimensional MOF material according to claim 1, wherein the organic solvent is selected from methanol or ethanol.
3. The process for preparing the two-dimensional MOF material by the one-step solvothermal method according to claim 1, wherein the concentration of the three-dimensional MOF crystal powder in the dispersion liquid is controlled to be 0.1-10 mg/mL.
4. A process for the preparation of two-dimensional MOF material according to claim 3, wherein the concentration of the three-dimensional MOF crystal powder in the dispersion is controlled at 0.56 mg/mL.
5. The process for preparing the two-dimensional MOF material by the one-step solvothermal method according to claim 1, wherein after the reaction is finished, the obtained product is naturally cooled to 10-40 ℃, centrifugally washed by methanol or ethanol, repeated for 1-5 times, and vacuum-dried for 6-10 hours.
6. The process for preparing two-dimensional MOF materials by the one-step solvothermal method according to claim 1, wherein the reaction temperature is 120 ℃ and the reaction time is 8 h.
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CN110589897B (en) * 2019-09-05 2022-04-22 北京工业大学 Method for preparing carbon-loaded Fe-Ti-O negative electrode material by taking metal organic framework as precursor
CN111111668A (en) * 2019-12-18 2020-05-08 济南大学 MOF-based derivative composite photocatalyst and preparation method thereof
CN111921561B (en) * 2020-08-18 2023-06-23 浙江工业大学 Hierarchical hollow structure NH 2 Preparation method of MIL-125 (Ti) desulfurization catalyst
CN113957454B (en) * 2021-10-27 2023-05-23 中国华能集团清洁能源技术研究院有限公司 Double-layer electrode for water electrolysis hydrogen production and preparation method and application thereof

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CN102329333A (en) * 2011-06-24 2012-01-25 东南大学 Preparation method of aluminum-based organic microporous coordination polymer
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