A method for synthesizing copper coordination polymers with different dimensions

Abstract

The application belongs to the technical field of nanometer material preparation, and discloses a regulation method for synthesizing copper coordination polymers with different dimensions. The method is to obtain copper coordination polymers with different dimensional morphologies under room temperature conditions by controlling the reaction sequence of copper ion solution, uniform benzenetricarboxylic acid and 4,4-dipyridine and the molar ratio of uniform benzenetricarboxylic acid and 4,4-dipyridine. The synthesis process is simple, the cost is low, the dimension of the morphology is adjustable, large-scale industrial production is possible, and good economic benefits and environmental benefits are achieved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nanomaterial preparation, and particularly relates to a regulation method for synthesizing copper coordination polymers with different dimensions. BACKGROUND

[0002] The copper coordination polymer is a framework structure formed by coordination of copper ions and organic ligands, has high porosity and large specific surface, and is an ideal adsorption and catalytic material. The nanometer coordination polymer with different dimensional morphologies has different structural characteristics, for example, the 1D material has a high aspect ratio and a directional electron motion direction, and the 2D material has a larger specific surface area and exposes more unsaturated coordination atoms. Therefore, the copper coordination polymer with different dimensional morphologies is suitable for different application fields, and development and preparation of the copper coordination polymer with adjustable dimensions in morphology is one of key steps for commercialization of the copper coordination polymer.

[0003] The commonly used morphology regulation method is to realize the morphology regulation through a surfactant or a hard template method. The surfactant does not participate in the coordination structure of the copper coordination polymer, is usually adsorbed on the surface of the copper coordination polymer, is not easy to remove, and is easy to cause blockage of the surface and exposure of active sites. The hard template method needs to remove the template through acid-alkali etching and high-temperature calcination, and is easy to damage the structure of the copper coordination polymer itself and reduce the adsorption and catalytic capacity of the copper coordination polymer. The steps of using the surfactant or the hard template method are complicated, the production cost is relatively high, and the industrialization popularization of the copper coordination polymer with different dimensional morphologies is limited. Therefore, it is of great significance to develop a simple, surfactant / template-free method for preparing the copper coordination polymer with adjustable dimensions in morphology, and the method is one of current research hotspots. SUMMARY

[0004] The application provides a method for simply and quickly realizing the copper coordination polymer with adjustable dimensions in morphology without using a surfactant and a template.

[0005] To achieve the above object, the application adopts the following technical scheme:

[0006] A regulation method for synthesizing copper coordination polymers with different dimensions comprises the following steps:

[0007] (1) under the condition of not using a surfactant, a hard template and a mixed solvent, copper metal salt (CuH6N2O9), organic ligand (C9H6O6) and 4,4-bipyridine (C 10 H8N2) are respectively dissolved into N,N-dimethylformamide (DMF) to form solutions A, B and C;

[0008] (2) After complete dissolution, solution B is added to solution A, and after a certain time of reaction, solution C is added to the above mixed reaction solution, and the stirring reaction is continued;

[0009] (3) The copper coordination polymer is obtained by centrifugal separation, and is washed and dried.

[0010] Further, the amount of CuH6N2O9 in solution A in step (1) is 0.10-0.3 mmol / mL.

[0011] Further, the total molar amount of C9H6O6 in solution B and C 10 H8N2 in solution C in step (1) is 2.4-2.0 times the molar amount of CuH6N2O9 in solution A.

[0012] Further, the molar ratio of C9H6O6 in solution B to C 10 H8N2 in solution C in step (1) is 0.05-15.

[0013] Further, the volume of DMF in solutions A, B and C in step (1) is equal.

[0014] Further, the reaction time of solution B added to solution A in step (2) is 30 min.

[0015] Further, the reaction time of solution C added to the mixed reaction solution in step (2) is 30-60 min.

[0016] Further, the stirring speed of the solution in step (2) is 300-1000 rpm.

[0017] Further, the washing agent in step (3) is DMF and methanol, and each is washed 3 times.

[0018] The significant advantages of the present application are:

[0019] (1) Using easily available raw materials, a copper coordination polymer with adjustable morphology and dimensions is synthesized in one step under the conditions of no surfactant, template and mixed solvent and at room temperature.

[0020] (2) By changing the ratio of the two ligands, 1D, 2D and 3D copper coordination polymers can be obtained, and further use of the structural advantages of their morphology and structure can make them show the best performance in different adsorption and catalysis fields.

[0021] (3) The equipment and materials required by the preparation method of the present application are cheap, the operation and process conditions are simple, and the present application has the advantages of low cost, safety and high efficiency, and can be mass-produced; the present application is an eco-friendly material, and has good popularization and application value. Attached Figure Description

[0022] Figure 1 The morphology of the 1D copper coordination polymer sample synthesized in Example 1 is shown.

[0023] Figure 2 The morphology of the 2D copper coordination polymer sample synthesized in Example 2 is shown.

[0024] Figure 3 This shows the morphology of the 3D copper coordination polymer sample synthesized in Example 3;

[0025] Figure 4 The morphology of the 3D copper coordination polymer sample synthesized in Example 4 is shown.

[0026] Figure 5 The morphology of the sample synthesized in Comparative Example 1 is shown.

[0027] Figure 6 The morphology is shown in Comparative Example 2. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined as long as they do not conflict with each other.

[0029] Example 1

[0030] Preparation of 1D copper coordination polymer 1:

[0031] (1) Add 0.3624 g of CuH6N2O9 to 10 mL of DMF to form solution A, add 0.422 g of C9H6O6 to 10 mL of DMF to form solution B, and add 0.192 g of C 10 H8N2 was added to 10 mL of DMF to form solution C. Solutions A, B and C were stirred at 500 rpm at room temperature for 30 min.

[0032] (2) After stirring, pour solution B directly into solution A and stir at 500 rpm at room temperature for 30 min; then pour solution C directly into the above mixed reaction solution and stir at 500 rpm at room temperature for 60 min.

[0033] (3) The precipitate was obtained by centrifugation, and washed three times each with DMF and methanol. After centrifugation and washing, it was placed in a vacuum drying oven at 100°C. o Dry at C for 8 hours.

[0034] Example 2

[0035] Preparation of 1D copper coordination polymer 2:

[0036] (1) 0.3624 g of CuH6N2O9was added into 10 mL DMF to form solution A, 0.504 g of C9H6O6was added into 10 mL DMF to form solution B, 0.092 g of C 10 H8N2was added into 10 mL DMF to form solution C, and solutions A, B and C were stirred at a speed of 500 rpm at room temperature for 30 min;

[0037] (2) After stirring was completed, solution B was directly poured into solution A, which was stirred at a speed of 500 rpm at room temperature for 30 min; then solution C was directly poured into the above mixed reaction liquid, which was continuously stirred at a speed of 500 rpm at room temperature for 60 min.

[0038] (3) The precipitate was separated by centrifugation, washed with DMF and methanol for 3 times respectively, and placed in a vacuum drying box at 100 o C for 8 h.

[0039] Example 3

[0040] Preparation of 2D copper coordination polymer:

[0041] (1) 0.3624 g of CuH6N2O9was added into 10 mL DMF to form solution A, 0.063 g of C9H6O6was added into 10 mL DMF to form solution B, 0.5184 g of C 10 H8N2was added into 10 mL DMF to form solution C, and solutions A, B and C were stirred at a speed of 500 rpm at room temperature for 30 min;

[0042] (2) After stirring was completed, solution B was directly poured into solution A, which was stirred at a speed of 500 rpm at room temperature for 30 min; then solution C was directly poured into the above mixed reaction liquid, which was continuously stirred at a speed of 500 rpm at room temperature for 60 min.

[0043] (3) The precipitate was separated by centrifugation, washed with DMF and methanol for 3 times respectively, and placed in a vacuum drying box at 100 o C for 8 h.

[0044] Example 4

[0045] Preparation of 3D copper coordination polymer:

[0046] (1) 0.3624 g of CuH6N2O9 was added to 10 mL of DMF to form solution A, 0.5697 g of C9H6O6 was added to 10 mL of DMF to form solution B, and 0.0576 g of C 10 H8N2 was added to 10 mL of DMF to form solution C, and solutions A, B and C were stirred at room temperature at a speed of 500 rpm for 30 min;

[0047] (2) After stirring was completed, solution B was directly poured into solution A, and stirring was continued at room temperature at a speed of 500 rpm for 30 min; then solution C was directly poured into the above-mentioned mixed reaction liquid, and stirring was continued at room temperature at a speed of 500 rpm for 60 min.

[0048] (3) The precipitate was separated by centrifugation, washed with DMF and methanol for 3 times respectively, and then placed in a vacuum drying box at 100 o C for 8 h.

[0049] Figure 1 Example 1 was 1.6, and the molar ratio of C 10 H8N2 in Example 1 was 4.0, and all were 1D copper coordination polymers. As can be seen from the figure, they were nanowires with a length greater than 1 µm. Figure 2 Example 1 was 1.6, and the molar ratio of C 10 H8N2 in Example 1 was 4.0, and all were 1D copper coordination polymers. As can be seen from the figure, they were nanowires with a length greater than 1 µm. Figure 3 Example 1 was 0.09, and the molar ratio of C 10 H8N2 in Example 1 was 0.09, and all were 2D copper coordination polymers. As can be seen from the figure, they were nanosheets with a length and width greater than 1 µm. Figure 4 Example 1 was 7.35, and the molar ratio of C 10 H8N2 in Example 1 was 7.35, and all were 3D copper coordination polymers. They were 3D book-like morphologies self-assembled from 2D nanosheets.

[0050] Comparative Example 1

[0051] (1) 0.3624 g of CuH6N2O9 was added to 20 mL of DMF to form solution A, 0.422 g of C9H6O6 was added to 20 mL of DMF to form solution B, and 0.192 g of C 10 H8N2 was added to 20 mL of DMF to form solution C, and solutions A, B and C were stirred at room temperature at a speed of 500 rpm for 30 min;

[0052] (2) After stirring, solution C is directly poured into solution A, and the reaction is stirred at room temperature at a rotation speed of 500 rpm for 60 min; then solution B is directly poured into the above mixed reaction solution, and the reaction is continuously stirred at room temperature at a rotation speed of 500 rpm for 30 min.

[0053] (3) The precipitate is obtained by centrifugal separation, washed with DMF and methanol for 3 times respectively, and then placed in a vacuum drying box for 100 o C drying for 8 h.

[0054] Comparative Example 2

[0055] (1) 0.3624 g of CuH6N2O9 is added into 20 mL of DMF to form solution A, 0.5697 g of C9H6O6 is added into 20 mL of DMF to form solution B, and 0.0576 g of C 10 H8N2 is added into 20 mL of DMF to form solution C, and solution A, B and C are stirred at room temperature at a rotation speed of 500 rpm for 30 min;

[0056] (2) After stirring, solution C is directly poured into solution A, and the reaction is stirred at room temperature at a rotation speed of 500 rpm for 60 min; then solution B is directly poured into the above mixed reaction solution, and the reaction is continuously stirred at room temperature at a rotation speed of 500 rpm for 30 min.

[0057] (3) The precipitate is obtained by centrifugal separation, washed with DMF and methanol for 3 times respectively, and then placed in a vacuum drying box for 100 o C drying for 8 h.

[0058] Figure 4 The molar ratio of C9H6O6 to C 10 H8N2 is 1.6, and the ligand addition sequence is opposite to that of Example 1, and the morphology is nanoparticles and nanowires. Figure 5 The molar ratio of C9H6O6 to C 10 H8N2 is 7.35, and the ligand addition sequence is opposite to that of Example 4, and the morphology is nanoparticles with different particle sizes. The different morphologies caused by the addition sequence are due to the differences in the nucleation speed and complexing ability of C9H6O6 and C 10 H8N2 to form complexes with Cu. 10 H8N2 is first added, and it is easy to form nanoparticles.

[0059] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. A method for the synthesis of copper coordination polymers of different dimensionality, characterized in that: The method comprises the following steps: (1) dissolving copper metal salt, organic ligand trimesic acid and 4,4-bipyridine into N,N-dimethylformamide to form solutions A, B and C respectively; (2) first, solution B is added into solution A, after a certain time of reaction, solution C is added into the mixed reaction liquid after reaction, and the reaction is continued; The copper coordination polymer is obtained after centrifugal separation, washing and drying; the molar ratio of C9H6O6 in solution B to C in solution C in step (2) is 0.05-15. 10 H8N2 is 0.05-15. The reaction time of solution B added into solution A in step (2) is 30 min; The reaction time of solution C added into the mixed reaction liquid in step (2) is 30-60 min; Different dimensions of the morphology include one-dimensional nanowires, two-dimensional nanosheets and three-dimensional book-like.

2. The method for the synthesis of different dimensional copper coordination polymers according to claim 1, characterized in that: The copper metal salt in step (1) is CuH6N2O9.

3. The method for the synthesis of different dimensional copper coordination polymers according to claim 1, wherein: In step (2), the ratio of the sum of the total molar amounts of C9H6O6 in solution B and CuH6N2O9 in solution A to the molar amount of C in solution C is 2.4-2.

0. 10 The ratio of the sum of the total molar amounts of H8N2 to the molar amount of CuH6N2O9 in solution A is 2.4-2.

0.

4. The method of claim 1, wherein the method is characterized by: The volumes of N,N-dimethylformamide in solutions A, B and C in step (1) are equal.

5. The method of claim 1, wherein the method is characterized by: The stirring speed in step (2) is 300-1000 rpm.

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