A class of aza-condensed and conjugated ladder polymers and their preparation methods and applications in catalytic water splitting under visible light

A polymer and visible light technology, applied in the direction of organic compound/hydride/coordination complex catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of increased cost, complicated operation, unfavorable photocatalytic industrial applications, etc. question

Active Publication Date: 2021-07-06
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

"Journal of the American Chemical Society" (Journal of the American Chemical Society, 2015, Vol. 137, page 15338) reported that a ladder polymer BBL (polyphenanthroline ladder polymer) was used as a photoanode for photoelectric water splitting, The BBL photoanode shows good photoelectrochemical stability after 3 hours of water oxidation reaction, and there is no obvious degradation phenomenon. Although the material meets the conditions of oxidizing water to produce oxygen in thermodynamics, its oxidation product is actually hydrogen peroxide. Based on the BBL material, the composite layered titanium dioxide acts as an electron channel and supports a nickel-cobalt catalyst to decompose water to generate oxygen. The yield is very low, 20nmol / h
This method is complex in operation, low in performance, and due to the need for external voltage, the introduction of metals and other operations greatly increases the cost, which is not conducive to the application of photocatalytic industry

Method used

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  • A class of aza-condensed and conjugated ladder polymers and their preparation methods and applications in catalytic water splitting under visible light
  • A class of aza-condensed and conjugated ladder polymers and their preparation methods and applications in catalytic water splitting under visible light
  • A class of aza-condensed and conjugated ladder polymers and their preparation methods and applications in catalytic water splitting under visible light

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0075] Add 100 grams of polyphosphoric acid (PAA) to a 150 ml two-neck flask equipped with a nitrogen inlet and outlet, control the nitrogen flow rate to be 30 ml / min to blow air into the polyphosphoric acid, and heat the polyphosphoric acid at 120 ° C 24 hours to completely deoxidize polyphosphoric acid. Then the temperature of the system was lowered to 50°C, and 568 mg of 1,2,4,5-benzenetetramine tetrahydrochloride was quickly added to the deoxygenated polyphosphoric acid in a nitrogen atmosphere, while the system was heated to 120°C for 12 hours To remove all the hydrogen chloride in 1,2,4,5-benzenetetramine tetrahydrochloride. Then, 282 mg of 2,5-dihydroxy-1,4-benzoquinone was added to the mixture at 110°C, and the mixture was slowly heated (with a heating rate of 4°C / min) to 180°C and kept for 12 hours. After cooling the obtained viscous solution to room temperature, transfer it to a 500 ml beaker, and add 400 ml of water to the beaker, stir vigorously so that polyphosph...

Embodiment 2

[0078] Add 1 g of 1,2,4,5-benzenetetramine tetrahydrochloride and 500 mg of piperazine-2,3,5,6-tetraketone into a 200-ml round-bottomed flask under an inert atmosphere, and then place the round-bottomed The flask was placed in an ice bath (temperature controlled at 0°C). 80 milliliters of N-methylpyrrolidone (NMP) was deoxidized, then mixed with 0.5 milliliters of sulfuric acid, and the mixed solution was slowly added dropwise to the above-mentioned round bottom flask. Then the reaction device was raised to room temperature, and after stirring for 2 hours, an oil bath was used instead of an ice-water bath and the entire reaction device was heated to 180°C. After continuous reaction for 8 hours, the heating was stopped and the device was cooled to room temperature. Add water to quench the reaction in the round-bottomed flask, and the suspension after the reaction uses polytetrafluoroethylene (PTFE, 0.22 micron) organic filter membrane to carry out suction filtration to obtain t...

Embodiment 3

[0081] Add 1 g of 1,2,4,5-benzenetetramine tetrahydrochloride and 922 mg of pyrene-4,5,9,10-tetraketone into a 200-ml round-bottomed flask under an inert atmosphere, and then place the round-bottomed flask Place in an ice bath (temperature controlled at 0°C). 80 milliliters of N-methylpyrrolidone (NMP) was deoxidized, then mixed with 0.5 milliliters of sulfuric acid, and the mixed solution was slowly added dropwise to the above-mentioned round bottom flask. Then the reaction device was raised to room temperature, and after stirring for 2 hours, an oil bath was used instead of an ice-water bath and the entire reaction device was heated to 180°C. After continuous reaction for 8 hours, the heating was stopped and the device was cooled to room temperature. Add water to the round-bottomed flask to quench the reaction, and the suspension after the reaction is suction-filtered with a polytetrafluoroethylene (PTFE, 0.22 micron) organic filter membrane to obtain a black solid product, ...

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Abstract

The invention provides a class of aza-condensed and conjugated ladder polymers, which are obtained by polymerization of 1,2,4,5-benzenetetramine tetrahydrochloride and 2,5-dihydroxy-1,4-benzoquinone ; or obtained by polymerization of 1,2,4,5-benzenetetramine tetrahydrochloride and piperazine-2,3,5,6-tetraketone; or by 1,2,4,5-benzenetetramine Tetrahydrochloride and pyrene-4,5,9,10-tetraketone are obtained by polymerization reaction. In the above-mentioned conjugated ladder polymers, the fused ring structure restricts the free torsional movement between the aromatic units along the skeleton, which can provide stable and effective conjugation and facilitate the transport of carriers. The conjugated ladder polymer has good absorption in the range of visible light, and its energy band structure meets the requirements of photolysis of water for oxygen production under visible light irradiation, and has excellent oxygen production performance. The present invention uses the ladder polymer for visible light decomposition for the first time Water produces oxygen, which greatly broadens the application of ladder polymers in the field of photocatalysis.

Description

technical field [0001] The invention relates to the technical field of photolysis of water to produce oxygen, in particular to a class of aza-condensed and conjugated ladder polymers, a preparation method thereof and an application of catalytic water splitting under visible light. Background technique [0002] At present, nearly 80% of the world's energy consumption comes from fossil energy. However, with the increasing energy demand, limited fossil energy reserves and increasingly severe environmental situation, people urgently need to develop a new type of environmentally friendly alternative energy. Solar energy, an inexhaustible energy source, has attracted widespread attention. Among them, the use of semiconductor catalysts to photocatalytically split water is an effective method that can directly convert solar energy into chemical energy, and is a new energy source with great development potential. technology. [0003] The photocatalytic total water splitting reaction...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D487/22B01J31/06C01B13/02C08G73/06
CPCB01J31/06B01J35/004C01B13/0207C07D487/22C08G73/0694
Inventor 徐航勋麻晓宇王磊张颖
Owner UNIV OF SCI & TECH OF CHINA
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