CN111019149B - COF-5 one-dimensional rod-like crystal material and preparation method thereof - Google Patents

COF-5 one-dimensional rod-like crystal material and preparation method thereof Download PDF

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CN111019149B
CN111019149B CN201911273052.5A CN201911273052A CN111019149B CN 111019149 B CN111019149 B CN 111019149B CN 201911273052 A CN201911273052 A CN 201911273052A CN 111019149 B CN111019149 B CN 111019149B
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dimensional rod
crystal material
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CN111019149A (en
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刘曰利
王子威
陈文�
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form

Abstract

The invention provides a COF-5 one-dimensional rod-shaped crystal material and a preparation method thereof, wherein the preparation method comprises the following steps: step 1, mixing 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane according to the addition ratio of 0.1-0.3 mmol: 0.1-0.5 mmol: 10-15 mL to form a mixture in an anhydrous and oxygen-free environment; step 2, sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid; step 3, heating the dispersion liquid to a certain temperature, and reacting for a period of time; and 4, washing the reaction product, then carrying out vacuum drying, finally introducing protective gas, and carrying out heat treatment at a set temperature for a period of time to obtain the COF-5 one-dimensional rod-shaped crystal material. The method has simple preparation process, and the prepared product has good growth and regular appearance.

Description

COF-5 one-dimensional rod-like crystal material and preparation method thereof
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a COF-5 one-dimensional rod-shaped crystal material and a preparation method thereof.
Background
The covalent organic framework material is formed by combining the problems of Omar Yaghi in the earliest 2005, is a novel organic porous polymer with periodicity and crystallinity, is formed by connecting light elements such as C, H, O, N, B and the like through strong covalent bonds, and has the characteristics of low density, higher thermal stability, high chemical stability, high specific surface area and the like. COF materials, which have high gas adsorption capacity, have been used for storing gases such as hydrogen, carbon dioxide, and sulfur dioxide, and are widely used and industrialized in fuel cells, new energy vehicles, and industrial waste gas treatment. With the research of researchers on COF materials, the researchers find that the COF materials have great application potential in the fields of gas catalysis, energy storage, photoelectricity, sensing and the like, and further arouse strong research interest of people on the COF materials.
Efficient synthesis of COF materials is a major challenge that currently exists. It has been shown that since atoms in COF materials are all connected by strong covalent bonds, higher activation energy is required for the formation and extension of material constituent units, and in addition, control of reaction conditions is required for good growth of COF crystals. Therefore, in order to satisfy thermodynamic and kinetic conditions of COF synthesis, organic monomers participating in the reaction should be in a mild reaction environment with low temperature and pressure, and undergo a reversible reaction at a low reaction rate for a long time.
COF-5 is a typical two-dimensional borate COF material, and the earliest researchers carried out related researches on the material as a hydrogen storage material. In addition, borate functional groups are uniformly distributed on a COF-5 molecular layer and can possibly become active sites for gas chemical adsorption, so that the COF-5 molecular layer has certain application potential in the fields of catalysis, gas sensitivity and the like. However, the research on COF-5 is relatively less, and the specific synthetic process and mechanism are not clear. In published scientific papers relating to COF-5, the problems of irregular crystal morphology, small size and non-uniformity of the obtained COF-5 are common. If the problem can be solved, the COF-5 material with good crystal growth and relatively regular appearance can be obtained, which is possibly helpful for deeply researching the growth process and mechanism of the COF-5, provides reference for the preparation of similar COF materials, improves the working performance of the COF-5 in various applications, and expands the application field of the COF material. Particularly, the one-dimensional rod-shaped COF-5 material has a higher specific surface area compared with COF-5 materials with other shapes, can more fully utilize the molecular layers to adsorb gas molecules or other organic small molecules, has stronger adsorption capacity, and has better performance in energy storage applications such as storage of combustible gas or energy-saving and environment-friendly applications such as collection and degradation of pollutants. Therefore, it is important to study a method for producing COF-5 in order to obtain a COF-5 one-dimensional rod-like crystal having a good crystal growth.
Disclosure of Invention
The invention is carried out to solve the problems and aims to provide a COF-5 one-dimensional rod-shaped crystal material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
< preparation method >
The invention provides a preparation method of a COF-5 one-dimensional rod-shaped crystal material, which is characterized by comprising the following steps of:
step 1, adding 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-benzene diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane into a mixed solution of 1,3, 5-trimethylbenzene and 1, 4-benzene diboronic acid to form a mixture, wherein the adding ratio of the 2,3,6,7,10, 11-hexahydroxy triphenyl to the 1, 4-dioxane is 0.1-0.3 mmol: 0.1-0.5 mmol: 10-15 mL;
step 2, sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
step 3, heating the dispersion liquid to a certain temperature, and reacting for a period of time;
and 4, washing the reaction product, then carrying out vacuum drying, finally introducing protective gas, and carrying out heat treatment on the product at a set temperature for a period of time to obtain the COF-5 one-dimensional rod-shaped crystal material.
Preferably, the preparation method of the COF-5 one-dimensional rod-like crystal material provided by the invention can also have the following characteristics: in the step 3, the heating temperature is 80-100 ℃, and the reaction time is 72-120 h.
Preferably, the preparation method of the COF-5 one-dimensional rod-like crystal material provided by the invention can also have the following characteristics: in step 4, the temperature is set to be 200-300 ℃, and the heat treatment time is 1-3 h.
Preferably, the preparation method of the COF-5 one-dimensional rod-like crystal material provided by the invention can also have the following characteristics: in step 4, the washing reagent is any one of acetone, methanol, benzene, diethyl ether and DMF.
Preferably, the preparation method of the COF-5 one-dimensional rod-like crystal material provided by the invention can also have the following characteristics: in step 4, the protective gas is any one of nitrogen, argon and helium.
< COF-5 one-dimensional rod-shaped crystalline Material >
The invention also provides a COF-5 one-dimensional rod-shaped crystal material, which is characterized in that: was prepared by the method described in < preparation method > above.
Action and Effect of the invention
The COF-5 one-dimensional rod-shaped crystal material is prepared by a solvothermal method by controlling the addition ratio of reactants of 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane to be 0.1-0.3 mmol, 0.1-0.5 mmol, 10-15 mL and 10-15 mL; the morphology is further improved and impurities are removed by heat treating the product. The preparation method has simple process, and the COF-5 one-dimensional rod-shaped crystal product has good growth and regular appearance.
Drawings
FIG. 1 is an XRD pattern of a COF-5 one-dimensional rod-like crystalline material prepared in example one;
FIG. 2 is a FT-IR diagram of a COF-5 one-dimensional rod crystal material prepared in example two;
FIG. 3 is an SEM photograph of a COF-5 one-dimensional rod-like crystalline material prepared in example III;
FIG. 4 is an SEM photograph of a COF-5 one-dimensional rod-like crystalline material prepared in example IV.
Detailed Description
The following describes in detail specific embodiments of the COF-5 one-dimensional rod-like crystalline material according to the present invention with reference to the drawings.
< example one >
The preparation method of the COF-5 one-dimensional rod-like crystal material provided in this embodiment includes the following steps:
(1) mixing 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane in a ratio of 0.1mmol to 12.5mL in a glove box;
(2) sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
(3) heating the dispersion to 85 ℃, and reacting for 72 hours;
(4) washing the reaction product with acetone, vacuum drying the product, introducing argon protective gas, and performing heat treatment on the product at 200 ℃ for 1 hour to obtain the COF-5 one-dimensional rod-shaped crystal material.
< example two >
The preparation method of the COF-5 one-dimensional rod-like crystalline material provided in this embodiment two includes the following steps:
(1) mixing 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane in a ratio of 0.2mmol to 0.3mmol to 12mL to 13mL in a glove box;
(2) sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
(3) heating the dispersion to 100 ℃ and reacting for 84 hours;
(4) washing the reaction product with acetone, drying the product in vacuum, introducing argon protective gas, and performing heat treatment on the product at 220 ℃ for 1 hour to obtain the COF-5 one-dimensional rod-shaped crystal material.
< example three >
The preparation method of the COF-5 one-dimensional rod-like crystalline material provided in the third embodiment includes the following steps:
(1) mixing 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane in a ratio of 0.3mmol to 0.5mmol to 10mL to 15mL in a glove box;
(2) sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
(3) heating the dispersion to 80 ℃ and reacting for 96 hours;
(4) washing the reaction product with acetone, vacuum drying the product, introducing argon protective gas, and performing heat treatment on the product at 250 ℃ for 2 hours to obtain the COF-5 one-dimensional rod-shaped crystal material.
< example four >
The fourth embodiment provides a method for preparing a COF-5 one-dimensional rod-like crystalline material, which comprises the following steps:
(1) mixing 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-phenyl diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane in a ratio of 0.3mmol to 15mL to 10mL in a glove box;
(2) sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
(3) heating the dispersion to 95 ℃ and reacting for 120 hours;
(4) washing the reaction product with acetone, vacuum drying the product, introducing argon protective gas, and performing heat treatment on the product at 300 ℃ for 2 hours to obtain the COF-5 one-dimensional rod-shaped crystal material.
Further, characterization and performance tests were performed on the COF-5 one-dimensional rod-like crystalline material prepared in the above example:
as shown in fig. 1, in the XRD spectrum, the matching degree of the position and relative intensity of each diffraction peak obtained by actual test (experimental value) and theoretical calculation (simulated value) is high; as shown in FIG. 2, each infrared absorption peak in the FT-IR spectrum corresponds one-to-one to the characteristic absorption peak of the functional group contained in the COF-5 crystal material. These map data all indicate that the product synthesized by the present invention is a COF-5 crystalline material.
As shown in fig. 3 and 4, the COF-5 crystal materials obtained in different embodiments of the present invention have one-dimensional rod-like morphology and larger crystal size, and the COF-5 one-dimensional rod-like crystal obtained at the reaction temperature of 80 ℃ has a larger and more uniform crystal size than the COF-5 one-dimensional rod-like crystal obtained at the reaction temperature of 95 ℃, so that the size of the synthesized COF-5 one-dimensional rod-like crystal can be controlled to some extent by changing the reaction temperature.
In addition, in the above embodiments: step 2, the ultrasonic treatment frequency is 70Hz, and the ultrasonic time is 5-10 min; the oscillation treatment adopts a vortex mixing instrument, and the oscillation time is about 1 min; step 4, drying under vacuum at 60-90 ℃ for 24-36 h; and, step 2 and step 3 are both performed under sealed conditions.
The above embodiments are merely illustrative of the technical solutions of the present invention. The COF-5 one-dimensional rod-like crystalline material and the method for preparing the same according to the present invention are not limited to the description in the above examples, but are subject to the scope defined in the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.

Claims (4)

  1. A preparation method of a COF-5 one-dimensional rod-shaped crystal material is characterized by comprising the following steps:
    step 1, adding 2,3,6,7,10, 11-hexahydroxy triphenyl, 1, 4-benzene diboronic acid, 1,3, 5-trimethylbenzene and 1, 4-dioxane into a mixed solution of 1,3, 5-trimethylbenzene and 1, 4-benzene diboronic acid to form a mixture, wherein the adding ratio of the 2,3,6,7,10, 11-hexahydroxy triphenyl to the 1, 4-dioxane is 0.1-0.3 mmol: 0.1-0.5 mmol: 10-15 mL;
    step 2, sealing the mixture, ultrasonically dispersing and oscillating to obtain uniform dispersion liquid;
    step 3, heating the dispersion liquid to 80-100 ℃, and reacting for 72-120 h;
    and 4, washing the reaction product, then carrying out vacuum drying, finally introducing protective gas, and carrying out heat treatment on the product at the temperature of 200-300 ℃ for 1-3 h to obtain the COF-5 one-dimensional rod-shaped crystal material.
  2. 2. The method for preparing a COF-5 one-dimensional rod-like crystalline material according to claim 1, wherein:
    wherein, in the step 4, the washing reagent is any one of acetone, methanol, benzene, diethyl ether and DMF.
  3. 3. The method for preparing a COF-5 one-dimensional rod-like crystalline material according to claim 1, wherein:
    in step 4, the protective gas is any one of nitrogen, argon and helium.
  4. COF-5 one-dimensional rod-like crystalline material characterized by:
    the COF-5 one-dimensional rod-like crystalline material according to any one of claims 1 to 3.
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CN113856753B (en) * 2021-09-24 2023-11-17 武汉理工大学 COF-5/CoAl-LDH heterojunction composite photocatalyst and preparation method and application thereof
CN113856755B (en) * 2021-09-30 2024-02-02 武汉理工大学 CsPbBr 3-x I x Quantum dot@COF-5 composite photocatalytic material and preparation method and application thereof
CN116966759B (en) * 2023-08-08 2024-01-30 山东中盛药化设备有限公司 Preparation method and application of organic framework mixed membrane for VOCs recovery

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US8692020B2 (en) * 2008-11-17 2014-04-08 Insilicotech Co., Ltd Organic framework
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CN106629820B (en) * 2016-09-09 2019-05-24 武汉理工大学 Cu2ZnSnS4The controllable method for preparing of nanocrystalline material
CN106475137A (en) * 2016-10-11 2017-03-08 天津大学 Catalyst COF 5 for carbon dioxide photo-reduction and preparation method thereof
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CN106882797A (en) * 2017-01-15 2017-06-23 复旦大学 A kind of grapheme material of covalent organic frame modification and its synthetic method and application
CN108503828B (en) * 2018-05-23 2019-06-28 青岛科技大学 A kind of controllable method for preparing of covalent organic porous polymer material different-shape
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