阅读说明：本技术 高质量高柔韧mof的制备方法 (Preparation method of high-quality high-flexibility MOF ) 是由 孙云飞 孙佳惟 陈丽香 阙妙玲 姜莉 陈丰 于 2021-08-09 设计创作，主要内容包括：本发明涉及一种高质量高柔韧MOF的制备方法,包括以下步骤：将金属络合物和琥珀酸溶解于混合溶剂中,常温下充分搅拌得前驱体溶液,将前驱体溶液转移至水热反应釜中；其中,金属络合物为[Co(H-(2)O)-(6)]SO-(4),混合溶液可为乙腈和水的混合溶液；使用激光辐照反应釜内的前驱体溶液1-2小时后,自然冷却至室温,洗涤、抽滤、烘干后得到MOF。本发明还涉及制备的高质量MOF的用途。本发明通过选用过渡金属源与有机配体反应,在激光调制下制备高质量、超均匀的MOF。(The invention relates to a preparation method of high-quality high-flexibility MOF, which comprises the following steps: dissolving a metal complex and succinic acid in a mixed solvent, fully stirring at normal temperature to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle; wherein the metal complex is [ Co (H) 2 O) 6 ]SO 4 The mixed solution can be a mixed solution of acetonitrile and water; and irradiating the precursor solution in the reaction kettle by using laser for 1-2 hours, naturally cooling to room temperature, washing, filtering, and drying to obtain the MOF. The invention also relates to the use of the high quality MOFs produced. According to the invention, a transition metal source is selected to react with an organic ligand, and the high-quality and ultra-uniform MOF is prepared under the modulation of laser.)

1. A preparation method of high-quality high-flexibility MOF is characterized by comprising the following steps: the method comprises the following steps:

dissolving a metal complex and succinic acid in a mixed solvent, fully stirring at normal temperature to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle; wherein the metal complex is [ Co (H)₂O)₆]SO₄The mixed solution can be a mixed solution of acetonitrile and water;

and irradiating the precursor solution in the reaction kettle by using laser for 1-2 hours, naturally cooling to room temperature, washing, filtering, and drying to obtain the MOF.

2. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the volume ratio of the acetonitrile to the water is 4: 3.

3. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the laser is nanosecond pulse laser or femtosecond pulse laser or continuous laser.

4. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the wavelength of the laser is 500nm-15 μm, and the power is 3-12W.

5. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the hydrothermal reaction temperature in the reaction kettle is 150-250 ℃.

6. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the metal complex also includes [ Co (NH)₃)₄Br₂]VO₄、[CoCl₄]VO₂、[Co(en)₃]VO₄At least one of (1).

7. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the drying temperature is 160 ℃, and the drying time is 16 hours.

8. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the molar ratio of the metal complex to the succinic acid is 1:8 to 10: 1.

9. A method of making a high quality, high flexibility MOF according to claim 1, wherein: the pressure of the suction filtration is 5-10 MPa.

10. Use of a high quality MOF prepared by the method of claim 1 for a supercapacitor electrode material.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of preparation and application of chemical materials, in particular to a preparation method of high-quality and high-flexibility MOF.

[ background of the invention ]

Metal-organic frameworks (MOFs) are a class of materials with adjustable pore size formed by self-assembly of organic ligands with a metal centerCompared with porous materials, the MOF material has larger specific surface area, higher porosity and more various structures and functions, so the MOF material is widely applied to the fields of gas adsorption and separation, sensors, drug slow release, catalytic reaction and the like. The MOF material prepared in the prior art generally has a fixed and unchangeable structure, is poor in flexibility and difficult to react on CO₂Selective adsorption is carried out. In addition, in the existing MOF preparation process, the reaction process is difficult to control, and the quality of a final product is greatly influenced.

Accordingly, there is a need for improvements in the art that overcome the deficiencies in the prior art.

[ summary of the invention ]

Aiming at the defects in the prior art, the invention aims to provide a preparation method of a high-quality and high-flexibility MOF, which comprises the following steps:

dissolving a metal complex and succinic acid in a mixed solvent, fully stirring at normal temperature to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle; wherein the metal complex is [ Co (H)₂O)₆]SO₄The mixed solution can be a mixed solution of acetonitrile and water;

and irradiating the precursor solution in the reaction kettle by using laser for 1-2 hours, naturally cooling to room temperature, washing, filtering, and drying to obtain the MOF.

Preferably, the volume ratio of acetonitrile to water is 4: 3.

Preferably, the laser is a nanosecond pulsed laser or a femtosecond pulsed laser or a continuous laser.

Preferably, the laser has a wavelength of 500nm to 15 μm and a power of 3 to 12W.

Preferably, the hydrothermal reaction temperature in the reaction kettle is 150-250 ℃.

Preferably, the metal complex further comprises [ Co (NH)₃)₄Br₂]VO₄、[CoCl₄]VO₂、[Co(en)₃]VO₄At least one of (1).

Preferably, the drying temperature is 160 ℃, and the drying time is 16 hours.

Preferably, the molar ratio of the metal complex to the succinic acid is from 1:8 to 10: 1.

Preferably, the pressure of the suction filtration is 5-10 MPa.

The invention also relates to the use of a high quality MOF prepared by the method as described above for supercapacitor electrode materials.

Compared with the prior art, the invention has the beneficial effects that:

the invention relates to a preparation method of high-quality high-flexibility MOF, which comprises the following steps: dissolving a metal complex and succinic acid in a mixed solvent, fully stirring at normal temperature to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle; wherein the metal complex is [ Co (H)₂O)₆]SO₄The mixed solution can be a mixed solution of acetonitrile and water; and irradiating the precursor solution in the reaction kettle by using laser for 1-2 hours, naturally cooling to room temperature, washing, filtering, and drying to obtain the MOF. The invention also relates to the use of the high quality MOFs produced. According to the invention, a transition metal source is selected to react with an organic ligand, and the high-quality and ultra-uniform MOF is prepared under the modulation of laser.

The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention. Specific embodiments of the present invention are given in detail by the following examples.

[ detailed description ] embodiments

The present invention will be further described with reference to specific embodiments, and it should be noted that any combination of the embodiments or technical features described below can form a new embodiment without conflict. It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

A method for preparing a high quality, high flexibility MOF comprising the steps of:

mixing metalDissolving the complex and succinic acid in a mixed solvent, fully stirring at normal temperature to obtain a precursor solution, and transferring the precursor solution into a hydrothermal reaction kettle; wherein the metal complex is [ Co (H)₂O)₆]SO₄The mixed solution can be a mixed solution of acetonitrile and water;

and irradiating the precursor solution in the reaction kettle by using laser for 1-2 hours, naturally cooling to room temperature, washing, filtering, and drying to obtain the MOF. And irradiating the metal-organic compound synthesized by the metal source and the organic ligand by using laser, and preparing the high-quality and ultra-uniform MOF under laser modulation by moving the position of a light spot or the position of a sample.

According to the invention, the MOF is synthesized by taking the metal complex as a metal source and succinic acid as an organic ligand, the MOF shows certain flexibility when adsorbing polar molecules such as water, carbon dioxide and the like, and the pore channel of the material can shrink or expand. The principle is that water molecules are connected with the skeleton through hydrogen bonds, and when the water molecules act with polar molecules, strong electrostatic force is generated between the water molecules, so that the MOF can react with CO₂Selective adsorption is carried out. The MOF material can be used in the technical field of detection, such as detection of a certain substance in water; the material can also be used for preparing various membranes, separation technology and the like.

In some embodiments, the volume ratio of acetonitrile to water is 4:3 to facilitate adequate dissolution of the metal source and organic ligand in the mixed solvent.

In some embodiments, the laser is a nanosecond pulsed laser or a femtosecond pulsed laser or a continuous laser.

In some embodiments, the laser has a wavelength of 500nm to 15 μm and a power of 3 to 12W to ensure the production of high quality, ultra-uniform MOFs.

In some embodiments, the hydrothermal reaction temperature in the reaction kettle is 150 ℃ to 250 ℃ to ensure that the metal source and the organic ligand react sufficiently.

The source of the metal source is transition metal elements, and the transition elements refer to a series of metal elements in a d region in the periodic table of elements, and are also called transition metals. Generally, this region includes a total of ten elements of groups 3 to 12, but does not include the inner transition element of the f-block. One period of the transition metal element is called a transition system, and elements of periods 4, 5 and 6 belong to a first transition system, a second transition system and a third transition system respectively. Most transition metals exist in the earth crust in the form of oxides or sulfides, and only gold, silver and other simple substances can stably exist. The most typical transition metals are groups 4-10. The copper family can form complexes, but the highest valence can only reach +3 because the d10 configuration is too stable. Rare earth metals near the main group have no variable valence state and cannot form complexes. The group 12 element has only mercury in a variable valence state and zinc is essentially the main group metal. Because of the difference in properties, the elements of the two groups of copper and zinc are not regarded as transition metals, and the concept of d-block element is reduced to 3-10 groups, and the two groups of copper and zinc are called ds-block elements.

The metal source can be a metal complex, and in some embodiments, the metal complex can be a mixture of two or more metal complexes, e.g., the metal source further comprises [ Co (NH)₃)₄Br₂]VO₄、[CoCl₄]VO₂、[Co(en)₃]VO₄At least one of; the complexity and stability of the MOF structure are enhanced by selecting two or more metal complexes.

In some embodiments, the drying temperature is 160 ℃ and the drying time is 16 hours, to remove the solvent from the MOF as quickly as possible while avoiding disruption of the MOF structure as possible.

In some embodiments, the molar ratio of metal complex to succinic acid is 1:8 to 10:1 to form a MOF material having some flexibility.

In some embodiments, the pressure of suction filtration is 5-10MPa to ensure product conversion of MOF throughout the preparation process.

Use of a high quality MOF prepared as above for a supercapacitor electrode material.

Example one

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄And 2.5mmol of succinic acid dissolved in 20ml of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution into a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 91%.

Example two

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 4mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 91%.

EXAMPLE III

A method for preparing a high quality, high flexibility MOF comprising the steps of:

take 2mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 0.2mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 91%.

Comparative example 1

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 5mmol succinic acid in 20ml mixed solvent of acetonitrile/water (V/V is 4/3), stirring thoroughly at 25 deg.C to obtain precursor solution, transferring the precursor solution into hydrothermal reaction kettle at 200 deg.C;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 81%.

Comparative example No. two

A method for preparing a high quality, high flexibility MOF comprising the steps of:

take 6mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 0.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 80%.

Comparative example No. three

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 3/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 78%.

Comparative example No. four

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 5/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 80%.

Comparative example five

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄、0.5mmol[Co(NH₃)₄Br₂]VO₄Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 88%.

Comparative example six

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 100 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 82%.

Comparative example seven

A method for preparing a high quality, high flexibility MOF comprising the steps of:

taking 0.5mmol FeSO₄Dissolving 1,3, 5-benzene tricarboxylic acid 2.5mmol in mixed solvent of acetonitrile/water (V/V-4/3), stirring at 25 deg.C to obtain precursor solution, and transferring the precursor solution to hydrothermal reaction kettle at 200 deg.C;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 88%.

Comparative example eight

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (H) ]₂O)₆]SO₄And 2.5mmol of succinic acid are dissolved in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), the mixture is fully stirred at 25 ℃ to obtain precursor solution, the precursor solution is transferred to a hydrothermal reaction kettle at 200 ℃ to react for 1 hour, then the mixture is naturally cooled to room temperature, and the mixture is alternately and repeatedly washed by methanol and deionized water, filtered and dried to obtain the MOF.

The MOF product yield was 75%.

Comparative example No. nine

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ Co (NH) was taken₃)₄Br₂]VO₄Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 90%.

Comparative example ten

A method for preparing a high quality, high flexibility MOF comprising the steps of:

0.5mmol of [ CoCl ] was taken₄]VO₂Dissolving 2.5mmol of succinic acid in 20ml of mixed solvent of acetonitrile/water (V/V is 4/3), fully stirring at 25 ℃ to obtain a precursor solution, and transferring the precursor solution to a hydrothermal reaction kettle at 200 ℃;

and irradiating the precursor solution in the reaction kettle for 1 hour by using nanosecond pulse laser with the wavelength of 500nm and the power of 5w, naturally cooling to room temperature, alternately and repeatedly washing by using methanol and deionized water, performing suction filtration, and drying to obtain the MOF.

The MOF product yield was 92%.

And (3) testing mechanical properties:

films formed from a control group of MOF materials (from a product of Mobil scientific name Co-gate, code CLY21A 12) and films formed from MOF materials prepared in examples one to three and comparative examples one to ten were provided, and each film sample was cut into fourteen groups of 7 films each having a length of 100mm, a width of 10mm and a thickness of 10mm for mechanical property testing. And characterizing the mechanical properties of the fourteen groups by using a universal testing machine, referring to GB/T1040.3-2006, fixing the fourteen groups on the testing machine, wherein the initial distance is 100mm, the stretching speed is 50mm/min, 7 parallels are measured in each group, and the results are averaged and are shown in table 1.

	Tensile Strength (MPa)	Elongation at Break (%)
			Control group	15.6±4.9	28.3±0.7
Example one	45.4±5.1	5.9±0.5
			Example two	44.8±4.7	6.5±0.2
EXAMPLE III	45.1±4.5	6.1±0.2
			Comparative example 1	37.5±5.8	7.9±0.3
Comparative example No. two	37.1±5.1	8.5±0.9
			Comparative example No. three	40.7±5.3	6.8±0.3
Comparative example No. four	41.2±4.9	6.2±0.4
			Comparative example five	48.3±6.8	5.1±0.5
Comparative example six	40.5±5.5	7.1±0.4
			Comparative example seven	16.2±5.4	26.8±0.4
Comparative example eight	38.5±4.8	7.5±0.6
			Comparative example No. nine	46.5±4.1	5.1±0.4
Comparative example ten	45.0±3.2	6.0±0.2

As shown in the table, the MOF prepared by the raw materials with the mass parts has better flexibility as can be seen from the examples I to III and the comparative example I and the comparative example II; as can be seen from the examples one to three, the comparative example three and the comparative example four, the volume ratio of the mixed solvent also affects the flexibility of the final product; as can be seen from examples one to three and comparative example five, when multiple metal sources are used, the flexibility of the final MOF is improved; as can be seen from the first to third examples and the sixth comparative example, when the temperature of the reaction kettle is adjusted to be 100 ℃, the quality of the final product is influenced, and the flexibility of the product is further influenced; as can be seen from the examples I to III and the comparative example VII, the MOF synthesized by the metal source and the organic ligand selected by the invention has excellent flexibility; as can be seen from the first to third examples and the eighth comparative example, when no laser modulation is used in the whole synthesis reaction, the quality of the final product is affected, and the flexibility of the product is further affected; as can be seen from examples one to three and comparative examples nine and ten, the metal source of the present invention is preferably a transition metal.

The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.