Preparation method of organic-inorganic hybrid material containing transition metal complex

Abstract

The invention discloses a preparation method of an organic-inorganic hybrid material containing a transition metal complex, which comprises the following steps: S1, synthesizing organosiloxane: adding 4 '-(4-pyridyl)-2, 2': 6 ', 2' '-terpyridyl and 3-bromopropyltrimethoxysilane into acetonitrile for dissolving, carrying out reflux reaction in a nitrogen atmosphere, and concentrating after the reaction is finished to obtain organosiloxane; s2, dissolving organosiloxane in chloroform, slowly dropwise adding into a methanol solution containing transition metal salt, stirring for 10-30 minutes after dropwise adding is finished, standing for volatilization, cleaning and drying to obtain organosiloxane coupled with transition metal. According to the preparation method of the organic-inorganic hybrid material containing the transition metal complex provided by the invention, the transition metal is coupled to the terpyridyl structure compound and further grafted to the mesoporous carbon material, so that various properties of the mesoporous carbon material are more stable, and the application scene of the mesoporous carbon material is enriched.

Description

Technical Field

[0001] The invention relates to the technical field of nanomaterials, and in particular to a method for preparing an organic-inorganic hybrid material containing a transition metal complex. Background Art

[0002] Terpyridine and its derivatives have attracted wide attention as ligands because their three pyridine rings have strong chelation, can provide abundant lone electron pairs, and are easy to coordinate with various transition metals. In addition, terpyridine-based complexes have been widely explored and have various potential applications, such as antibacterial, catalytic, photoluminescent, and antitumor drugs. Cobalt, as a transition metal element in the ninth group of the periodic table, has many advantages: its complexes have effective activity in the fields of antibacterial, anticancer, and chemical catalysis; cobalt is an important trace element for the growth and development of organisms, and is also a basic element involved in many physiological processes in cells; in addition, cobalt has the advantages of low price and easy availability compared with platinum and ruthenium in the same group. Terpyridine Co(II) complexes have excellent antibacterial properties. In mammals, iron affects the normal function of heme cleavage enzymes, mitochondrial enzymes, and enzymes involved in DNA synthesis. Studies have shown that iron chelates also have important applications in anticancer. Among metal ions, zinc ion (Zn2+) is the second most abundant essential trace element in organisms and plays a very important role in various physiological and pathological processes.

[0003] In order to improve the application scope of transition metal complexes, the present invention provides a method for preparing an organic-inorganic hybrid material containing a transition metal complex, by coupling the transition metal to a terpyridine structure compound and further grafting it to a mesoporous carbon material, so that its various properties are more stable. Summary of the invention

[0004] In view of the above technical problems, the present invention provides a method for preparing an organic-inorganic hybrid material containing a transition metal complex.

[0005] Technical solution: A method for preparing an organic-inorganic hybrid material containing a transition metal complex comprises the following steps: S1: Synthetic organosiloxane: 4'-(4-pyridyl)-2,2':6',2''-terpyridine and 3-bromopropyltrimethoxysilane are added to acetonitrile and dissolved, and refluxed under a nitrogen atmosphere for reaction. After the reaction is completed, the mixture is concentrated to obtain an organosiloxane; S2: dissolving the organosiloxane in chloroform, slowly dropping it into the methanol solution containing the transition metal salt, stirring for 10-30 minutes after the dropping, standing to evaporate, washing and drying to obtain the organosiloxane coupled with the transition metal; S3: dissolving the organosiloxane coupled with transition metal in chloroform, adding the toluene suspension containing the mesoporous carbon material, stirring at 100°C for 1-2h under nitrogen protection, filtering, extracting with chloroform for 20-30h, and vacuum drying to obtain the hybrid material. Furthermore, the molar ratio of 4'-(4-pyridyl)-2,2':6',2''-terpyridine to 3-bromopropyltrimethoxysilane in S1 is 1:1.

[0006] Furthermore, the molar ratio of the organosiloxane to the transition metal salt in S2 is 1:5-1:7.

[0007] Furthermore, the transition metal salt in S2 is cobalt chloride, ferric bromide or zinc chloride.

[0008] Furthermore, the added mass of the mesoporous carbon in S3 is 0.5-2 times that of the organosiloxane coupled with the transition metal.

[0009] Furthermore, the mesoporous carbon material in S3 is prepared by the following method: a certain amount of citric acid, sucrose and aluminum nitrate are weighed and dissolved in water, a certain amount of phosphoric acid with a concentration of 85wt% is added thereto under continuous stirring, the pH value of the solution is adjusted to 5.0 with 10wt% dilute ammonia water at room temperature, and stirring is continued for 3 hours, and then it is dried in a water bath at 80°C to obtain a dark brown solid complex; the solid is treated in an air atmosphere at 300°C for 10 minutes, and then calcined in an argon atmosphere for 6 hours to obtain a black solid, the black solid is heated and stirred in a 4M nitric acid solution for 5 hours, filtered, washed and dried to obtain the mesoporous carbon material.

[0010] Preferably, the molar ratio of citric acid, sucrose, aluminum nitrate, phosphoric acid and water is 0.5:1:1:1:1.

[0011] Beneficial effects: The present invention provides a method for preparing an organic-inorganic hybrid material containing a transition metal complex. By coupling the transition metal to a terpyridine structure compound and further grafting it to a mesoporous carbon material, the various properties of the material are made more stable and its application scenarios are enriched. For example, the antibacterial property is further enhanced after the cobalt ion is coupled to the terpyridine structure compound. The rich pores of the mesoporous carbon material have adsorption properties. The surface area of ​​the material is increased after grafting, and the bactericidal effect is further improved. DETAILED DESCRIPTION

[0012] The present invention is described in detail below.

[0013] Embodiment 1: Preparation of mesoporous carbon material: Weigh a certain amount of citric acid, sucrose and aluminum nitrate and dissolve them in water, add a certain amount of 85wt% phosphoric acid thereto under continuous stirring, the molar ratio of citric acid, sucrose, aluminum nitrate, phosphoric acid and water is 0.5:1:1:1:1, adjust the pH value of the solution to 5.0 with 10wt% dilute ammonia water at room temperature, continue stirring for 3 hours, and then dry in a water bath at 80°C to obtain a dark brown solid complex; treat the solid in an air atmosphere at 300°C for 10 minutes, and then calcine in an argon atmosphere for 6 hours to obtain a black solid, heat and stir the black solid in a 4M nitric acid solution for 5 hours, filter, wash and dry to obtain the mesoporous carbon material.

[0014] Embodiment 2: A method for preparing an organic-inorganic hybrid material containing a transition metal complex comprises the following steps: S1: Synthetic organosiloxane: 4'-(4-pyridyl)-2,2':6',2''-terpyridine (5 g, 16.11 mmol) and 3-bromopropyltrimethoxysilane (4.6 g, 16.11 mmol) were added to acetonitrile (250 mL) and dissolved, and refluxed under a nitrogen atmosphere. After the reaction, the mixture was concentrated to obtain an organosiloxane; S2: Dissolve the organosiloxane (1 g, 1.67 mmol) in chloroform (10 mL), slowly dropwise add it into a methanol (10 mL) solution containing cobalt chloride (1.1 g, 8.47 mmol), stir for 10-30 min after the addition is completed, let it stand for evaporation, wash with water and dry to obtain the organosiloxane coupled with the transition metal (1.2 g); S3: Dissolve the transition metal-coupled organosiloxane (1.2 g) in chloroform (15 mL), add a toluene (10 mL) suspension containing 1 g of mesoporous carbon material, stir at 100 °C for 1-2 h under nitrogen protection, filter, extract with chloroform for 24 h, and vacuum dry to obtain the hybrid material.

[0015] Embodiment 3: A method for preparing an organic-inorganic hybrid material containing a transition metal complex comprises the following steps: S1: the same as step S1 in embodiment 2; S2: Dissolve the organosiloxane (1 g, 1.67 mmol) in chloroform (10 mL), slowly dropwise add it into a methanol (10 mL) solution containing iron bromide (2.5 g, 8.47 mmol), stir for 10-30 min after the addition is completed, let it stand for evaporation, wash with water and dry to obtain the organosiloxane coupled with the transition metal (1.4 g); S3: Dissolve the transition metal-coupled organosiloxane (1.4 g) in chloroform (20 mL), add a toluene (10 mL) suspension containing 1 g of mesoporous carbon material, stir at 100 °C for 1-2 h under nitrogen protection, filter, extract with chloroform for 24 h, and vacuum dry to obtain the hybrid material.

[0016] Embodiment 4: A method for preparing an organic-inorganic hybrid material containing a transition metal complex comprises the following steps: S1: the same as step S1 in embodiment 2; S2: Dissolve the organosiloxane (1 g, 1.67 mmol) in chloroform (10 mL), slowly dropwise add it into a methanol (10 mL) solution containing zinc chloride (1.15 g, 8.47 mmol), stir for 10-30 min after the addition is completed, let it stand for evaporation, wash with water and dry to obtain the organosiloxane coupled with transition metal (1.3 g); S3: Dissolve the transition metal-coupled organosiloxane (1.3 g) in chloroform (20 mL), add a toluene (10 mL) suspension containing 1 g of mesoporous carbon material, stir at 100 °C for 1-2 h under nitrogen protection, filter, extract with chloroform for 24 h, and vacuum dry to obtain the hybrid material.

[0017] Although the present invention has been disclosed as above in terms of preferred embodiments, they are not intended to limit the present invention. Anyone skilled in the art can make various changes or modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection defined by the claims of this application.

Claims

1. A method for preparing an organic-inorganic hybrid material containing a transition metal complex, characterized in that: The following steps are involved: S1: Synthetic organosiloxane: 4'-(4-pyridyl)-2,2':6',2''-terpyridine and 3-bromopropyltrimethoxysilane are added to acetonitrile and dissolved, and refluxed under a nitrogen atmosphere for reaction. After the reaction is completed, the mixture is concentrated to obtain an organosiloxane; S2: dissolving the organosiloxane in chloroform, slowly dropping it into the methanol solution containing the transition metal salt, stirring for 10-30 minutes after the dropping, standing to evaporate, washing and drying to obtain the organosiloxane coupled with the transition metal; S3: dissolving the organosiloxane coupled with transition metal in chloroform, adding the toluene suspension containing the mesoporous carbon material, stirring at 100°C for 1-2h under nitrogen protection, filtering, extracting with chloroform for 20-30h, and vacuum drying to obtain the hybrid material.

2. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 1, characterized in that: The molar ratio of 4'-(4-pyridyl)-2,2':6',2''-terpyridine to 3-bromopropyltrimethoxysilane in S1 is 1:

1.

3. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 1 or 2, characterized in that: The molar ratio of the organosiloxane to the transition metal salt in S2 is 1:5-1:

7.

4. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 3, characterized in that: The transition metal salt in S2 is cobalt chloride, iron tribromide or zinc chloride.

5. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 1 or 4, characterized in that: The added mass of the mesoporous carbon in S3 is 0.5-2 times that of the organosiloxane coupled with the transition metal.

6. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 5, characterized in that: The mesoporous carbon material in S3 is prepared by the following method: a certain amount of citric acid, sucrose and aluminum nitrate are weighed and dissolved in water, a certain amount of phosphoric acid with a concentration of 85wt% is added thereto under continuous stirring, the pH value of the solution is adjusted to 5.0 with 10wt% dilute ammonia water at room temperature, stirring is continued for 3 hours, and then it is dried in a water bath at 80°C to obtain a dark brown solid complex; the solid is treated in an air atmosphere at 300°C for 10 minutes, and then calcined in an argon atmosphere for 6 hours to obtain a black solid, the black solid is heated and stirred in a 4M nitric acid solution for 5 hours, filtered, washed and dried to obtain the mesoporous carbon material.

7. The method for preparing an organic-inorganic hybrid material containing a transition metal complex according to claim 6, characterized in that: The molar ratio of the citric acid, sucrose, aluminum nitrate, phosphoric acid and water is 0.5:1:1:1:1.

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