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Porphyrin conjugated polymer bridged by pincerlike complex, synthetic method and application

A technology of conjugated polymer and synthesis method, which is applied in the direction of electrolysis components, electrolysis process, electrodes, etc., to achieve the effect of good hydrogen evolution performance

Active Publication Date: 2021-05-28
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, there are no research reports or patent publications at home and abroad on the preparation method of porphyrin conjugated polymers containing transition metal clamp complexes as bridging units and single-atom active sites and their electrocatalytic hydrogen evolution applications.

Method used

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  • Porphyrin conjugated polymer bridged by pincerlike complex, synthetic method and application
  • Porphyrin conjugated polymer bridged by pincerlike complex, synthetic method and application
  • Porphyrin conjugated polymer bridged by pincerlike complex, synthetic method and application

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Experimental program
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Effect test

Embodiment 1

[0048] M was synthesized using the above synthetic route for conjugated polymers 1 Por-M 2 N 3 CP, M 1 =H 2 , M 2 = Ru, the product is labeled H 2 Por-RuN 3 CP.

[0049] Proceed as follows:

[0050] Add H to the sealed tube 2 Por (17.4mg) and RuN 3 (28.6mg), then put into a 1:1 volume ratio of o-dichlorobenzene-n-butanol mixed solvent (1.0mL), ultrasonic for 20 minutes, then add 6M acetic acid (0.1mL), after three freeze-pump-thaw cycles Afterwards, the tube was flame-sealed and reacted at 120° C. for 72 hours. The product was filtered, washed with methanol and dichloromethane, and extracted by Soxhlet for 24 hours, and finally vacuum-dried to obtain the conjugated polymer (H 2 Por-RuN 3 CP).

Embodiment 2

[0052] M was synthesized using the above synthetic route for conjugated polymers 1 Por-M 2 N 3 CP; M 1 = Cu, no M 2 When , the product is labeled as CuPor-N 3 CP.

[0053] Proceed as follows:

[0054] In a sealed tube add CuPor (18.9mg) and N 3 (16.4mg), then put it into a 1:1 volume ratio of o-dichlorobenzene-n-butanol mixed solvent (1.0mL), sonicate for 20 minutes, then add 6M acetic acid (0.1mL), and freeze-pump-thaw three times Afterwards, the tube was flame-sealed and reacted at 120° C. for 72 hours. The product was filtered, washed with methanol and dichloromethane, and extracted by Soxhlet for 24 hours, and finally dried in vacuum to obtain a conjugated polymer (CuPor-N 3 CP).

Embodiment 3

[0056] M was synthesized using the above synthetic route for conjugated polymers 1 Por-M 2 N 3 CPs; M 1 =H 2 , without M 2 , the product is labeled as H 2 Por-N 3 CP.

[0057] Proceed as follows:

[0058] Add H to the sealed tube 2 Por (17.4mg) and N 3 (16.4mg), then put it into a 1:1 volume ratio of o-dichlorobenzene-n-butanol mixed solvent (1.0mL), sonicate for 20 minutes, then add 6M acetic acid (0.1mL), and freeze-pump-thaw three times Afterwards, the tube was flame-sealed and reacted at 120° C. for 72 hours. The product was filtered, washed with methanol and dichloromethane, and extracted by Soxhlet for 24 hours, and finally vacuum-dried to obtain the conjugated polymer (H 2 Por-N 3 CP).

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Abstract

The invention discloses a pincerlike complex bridged porphyrin conjugated polymer as well as a synthesis method and application thereof. According to the invention, 5,10,15,20-tetra(4-formylphenyl)porphyrin or a corresponding copper complex (namely CuPor) thereof and a pincer-like ligand 2,6-bis(5-amino-1H-benzimidazolyl)pyridine or a corresponding ruthenium pincer-like complex (namely RuN3) thereof are polymerized into a conjugated polymer by adopting a Schiff alkali condensation reaction; wherein, a ruthenium / copper bimetallic center and a conjugated structure of CuPor-RuN3CP improve the intrinsic conductivity and water molecule adsorption of the polymer and accelerate electron transfer between copper and ruthenium metal centers, so that the electro-catalytic hydrogen evolution performance of the polymer is improved. The conjugated polymer has a good application prospect as a universal hydrogen evolution electrocatalyst in a full pH value range.

Description

technical field [0001] The invention belongs to the technical field of organic polymer-based electrocatalytic materials and their electrocatalytic hydrogen evolution applications, and specifically relates to a porphyrin conjugated polymer bridged by clamp complexes, a synthesis method and applications thereof. Background technique [0002] Compared with fossil energy, hydrogen energy is considered an environmentally friendly fuel, with the advantages of non-pollution, renewable and high combustion value, and is considered an ideal substitute for fossil fuels. Hydrogen production from water splitting is a sustainable method to produce hydrogen energy, and electrocatalytic hydrogen evolution reaction (HER) has attracted widespread interest as an economical and environmentally friendly new energy technology. The method mainly uses a certain voltage applied to the electrodes in different electrolytes, the anode undergoes an oxygen evolution reaction, and the cathode undergoes a ...

Claims

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Application Information

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IPC IPC(8): C08G12/08C25B1/04C25B11/075
CPCC08G12/08C25B1/04Y02E60/36
Inventor 彭天右李仁杰王婷霞郭璐璐
Owner WUHAN UNIV
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