A kind of porphyrin organic framework hybrid and its preparation method

An organic framework and hybrid technology, applied in the field of porphyrin organic framework hybrids and their preparation, can solve the problems of limiting the application of organic framework hybrids, difficult to achieve batch preparation and production, staying in the model experiment stage, etc. The effect of interface structure, uniform morphology, high yield

Active Publication Date: 2021-02-26
TSINGHUA UNIV
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Problems solved by technology

[0005] However, the reports on hybrids of organic frameworks and carbon materials or organic frameworks and polymers are still very limited, and currently only stay at the stage of model experiments
The obtained hybrids are high in cost, low in yield, single in structure and morphology, complex in synthesis methods, and difficult to realize batch preparation and production, which greatly limits the application of organic framework hybrids in practical systems

Method used

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  • A kind of porphyrin organic framework hybrid and its preparation method
  • A kind of porphyrin organic framework hybrid and its preparation method
  • A kind of porphyrin organic framework hybrid and its preparation method

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preparation example Construction

[0025] A kind of preparation method of porphyrin organic framework hybrid provided by the invention, it specifically comprises the following steps:

[0026] 1) Fully dissolve the five-membered heterocycle, polyaldehyde, complexing agent, acid and oxidant in an organic solvent to form a solution; wherein the ratio of the amount of five-membered heterocycle to polyaldehyde is 1:0.1-1: 10; The ratio of the five-membered heterocycle to the amount of the complexing agent is 1:0.1-1:10; the five-membered heterocycle is one or more of pyrrole, furan and thiophene; the polyaldehyde It has 3 or more carbons and has more than 2 aldehyde groups; the complexing agent is a hydrochloride, nitrate or sulfate of one of Mn, Fe, Co, Ni, Cu or Zn; Said acid is one or more mixtures of formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluoroformic acid and trifluoroacetic acid; said oxidizing agent is nitrobenzene, dinitrobenzene benzene, trini...

Embodiment 1

[0031] Weigh 1.3g of terephthalaldehyde and add it into 250mL of tetrahydrofuran, stir and fully dissolve. Add 1.4 mL of pyrrole, 0.5 mL of trifluoroacetic acid and 1.0 mL of nitrobenzene to the above solution in sequence, and form a uniform solution under stirring. Add 260mg of graphene powder, stir well to disperse it evenly and transfer it into a 500mL flask. The flask was placed in an oil bath at 150° C. under constant stirring for 24.0 hours to react at a constant temperature. After the reaction solution was cooled, the reaction solution was suction filtered to obtain a crude product. The crude product was washed with ethanol, chloroform and deionized water respectively and filtered. The washed product was dried at 60° C. for 24.0 hours to prepare a hybrid of H-coordinated N-porphyrin organic framework and graphene. The final product was a black powder with a yield of 97%.

Embodiment 2

[0033]Weigh 2.7g of terephthalaldehyde, 5.4g of cobalt chloride and 2.5g of potassium nitrate into 500mL of chloroform, stir and fully dissolve. Add 1.5mL of pyrrole, 1.7mL of thiophene and 1.0mL of hydrochloric acid in sequence to the above solution, and form a uniform solution under stirring. Add 1.5 g of carbon black, stir well to disperse evenly and transfer to a 1 L flask. The flask was placed in an oil bath at 180° C. under constant stirring for 6.0 hours at a constant temperature. After the reaction solution was cooled, the reaction solution was suction filtered to obtain a crude product. The crude product was washed three times each with ethanol and filtered. The washed product was dried at 60° C. for 24.0 hours to prepare a hybrid of Co-coordinated S-porphyrin organic framework and carbon black. The final product was a black powder with a yield of 99%.

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Abstract

The invention discloses a porphyrin organic skeleton hybrid and a preparation method thereof, belonging to the technical field of new materials and its preparation. The hybrid material is hybridized by a porphyrin organic framework and a carbon material or a porphyrin organic framework and a polymer. The porphyrin organic framework is formed by covalently connecting porphyrin and porphyrin derivative structural units; the porphyrin organic framework and carbon material or porphyrin organic framework and polymer form a hybrid through intermolecular interaction. The preparation method of the hybrid compound uses carbon material or polymer as a template, uses five-membered heterocycle and polyaldehyde as substrate, and synthesizes under the action of certain temperature, solvent, coordination agent, acid and oxidant. The invention designs a porphyrin organic framework hybrid with precise and controllable chemical structure and composition, and simultaneously exhibits the morphology and properties dependent on carbon materials or polymers. The synthesis method of the hybrid is simple, efficient, and easy to scale up, which provides the possibility for the application of porphyrin organic framework hybrids in the fields of catalysis, energy, and sensing.

Description

technical field [0001] The invention belongs to the technical field of new materials and their preparation, and in particular relates to a porphyrin organic skeleton hybrid and a preparation method thereof. Background technique [0002] The multi-scale precise control of the structure and properties of materials is considered to be the "holy grail" of material science, and it is also the core issue to fully reflect the performance of materials. Organic frameworks are molecular frameworks constructed from the bottom up through covalent bonds based on small organic molecules. They have a clear chemical structure and exhibit precise and controllable characteristics at the molecular atomic scale. Omar M.Yaghi first reported the organic framework of the borate ester system in 2005, which has a clear chemical structure, good crystallinity and regular pore structure (Adrien P.Cote et al., Science, 2005,310,1166- 1170). A large number of studies have been carried out on the molecu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G83/00
CPCC08G83/008
Inventor 张强李博权张书源
Owner TSINGHUA UNIV
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