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Irregular ternary conjugated polymer photocatalytic material as well as preparation method and application thereof

A technology of regular ternary copolymerization structure and conjugated polymer, which is applied in the field of non-regular ternary conjugated polymer photocatalytic materials and its preparation, can solve the problems of low utilization rate of visible light, high recombination rate of photogenerated electrons and holes, etc. Achieve the effect of improving photocatalytic performance, enhancing π-π interaction force and prolonging service life

Pending Publication Date: 2022-07-22
TAIYUAN UNIV OF TECH +1
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  • Description
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Problems solved by technology

However, the existing polymers still have problems such as low utilization rate of visible light and high recombination rate of photogenerated electrons and holes (J. Mater. Chem. A 2019, 7, 8938-8951; Appl. Catal. B 2019, 257, 117935 )

Method used

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  • Irregular ternary conjugated polymer photocatalytic material as well as preparation method and application thereof
  • Irregular ternary conjugated polymer photocatalytic material as well as preparation method and application thereof
  • Irregular ternary conjugated polymer photocatalytic material as well as preparation method and application thereof

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preparation example Construction

[0027] The present invention also discloses a preparation method of the above-mentioned non-regular ternary conjugated polymer photocatalytic material, and obtains a non-regular ternary conjugated polymer photocatalytic material through the following reaction polymerization, which specifically includes the following steps:

[0028] Under the nitrogen atmosphere, A, B monomers and π bridging units are synthesized by random copolymerization under the action of catalysts according to different molar ratios. A non-regular ternary conjugated polymer photocatalytic material is synthesized. The sum of the three units is 1, and the ratio can be chosen arbitrarily, that is, x+y=1 and x>0, y>0. According to the different combinations of the selected monomers A, B and bridging units, it is generally a Stille cross-coupling reaction of halogenated aromatic hydrocarbons with organotin compounds or organoboronate esters. The choice of monomers only affects the reaction temperature and the c...

Embodiment 1

[0033] Synthesis of a non-regular ternary conjugated polymer photocatalytic material DIn (n=1, 2, 3):

[0034]

[0035] As shown above, when the synthetic DIn (n=1, 2, 3) has different values ​​of n, the ratios of x and y are:

[0036] DI1 x:y=1:3

[0037] DI2 x:y=2:2

[0038] DI3 x:y=3:1

[0039] The synthesis steps are as follows:

[0040] (1) Synthesis of DI1

[0041] In a two-necked flask, 6,6'-dibromo-1,1'-bis(2-hexyldecyl)isoindigo (287.40 mg, 0.331 mmol), 3,6-bis(5-bromo-2-thienyl) )-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (100 mg, 0.110 mmol), (3,3'-dione Fluoro-[2,2'-bithiophene]-5,5'-diyl)bis(trimethylstannane) (232.79 mg, 0.441 mmol), tris(dibenzylideneacetone)dipalladium (40.38 mg, 0.044 mmol) mixed. Under nitrogen atmosphere, 25 mL of anhydrous chlorobenzene was added to the flask, and the reaction mixture was heated to reflux at 130° C. for 48 h. After cooling to room temperature, the mixture was poured into methanol. The precipitate...

Embodiment 2

[0047] The optical and electrochemical properties of DI1 in the non-regular terpolymer material synthesized in Example 1 were tested and compared with g-C 3 N 4 The prepared type I heterojunction is used in the field of photocatalytic hydrogen production.

[0048] Synthesis steps:

[0049] First, the prepared g-C 3 N 4 It was ultrasonically dispersed with DI1 in 20 mL of chloroform solution at mass ratios of 0 wt %, 0.5 wt %, 1 wt %, 2 wt %, 3 wt %, and 4 wt % for 1 h, and then stirred vigorously at room temperature overnight. The mixed solution was evaporated to dryness on a rotary evaporator. Finally, the product was collected by filtration drying the mixed sample.

[0050] The results show that: in g-C 3 N 4 In the / DI1 heterojunction, when the mass ratio of DI1 is 2wt%, the photocatalytic hydrogen evolution rate can reach 16000 μmol g -1 h -1 . It is shown that the non-regular ternary conjugated polymer photocatalytic material DI1 matches the carbon nitride energ...

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Abstract

The invention belongs to the technical field of polymer materials for multifunctional photoelectric application. At present, existing polymers still have the problems of low visible light utilization rate, high recombination rate of photo-induced electrons and holes and the like. The invention provides an irregular ternary conjugated polymer photocatalytic material as well as a preparation method and application thereof, different pi bridging units are introduced into a basic framework of a polymer material in an irregular copolymerization manner by changing the types of monomers forming the polymer photocatalytic material and regulating and controlling the molar ratio of monomer feeding, and the irregular ternary conjugated polymer photocatalytic material is obtained. The energy levels of the highest occupied orbital and the lowest occupied orbital are regulated, the pi-pi interaction force between molecular chains is enhanced, the light absorption is widened and enhanced, and the charge transfer capability is improved, so that the photocatalytic performance is improved. The material has good thermal stability and matched energy level, the synthesis steps of the material are simple, and the material can be widely applied to the fields of photocatalysis, perovskite solar cells, organic field effect transistors, organic electroluminescent devices and organic photovoltaic solar cells.

Description

technical field [0001] The invention belongs to the technical field of polymer materials for multifunctional optoelectronic applications, in particular to a non-regular ternary conjugated polymer photocatalytic material and a preparation method and application thereof. Background technique [0002] Energy is an indispensable material basis for human beings. With the rapid development of economy and technology, the environmental pollution and energy crisis caused by non-renewable fossil fuels have attracted global attention, and there is an urgent need for alternative green and clean energy. Using solar energy to catalyze hydrogen evolution is a simple and effective method. Hydrogen energy has high energy density, is non-polluting, and can be stored. It is expected to replace traditional fossil energy (J.Colloid Interface Sci. 2019, 533, 636-648). [0003] The activity of photocatalytic hydrogen evolution depends on the selection of semiconductor photocatalyst materials. Orga...

Claims

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Application Information

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IPC IPC(8): C08G61/12B01J31/06B01J35/00C01B3/04
CPCC08G61/126C08G61/124B01J31/06C01B3/042C01B2203/0277C01B2203/1041C08G2261/122C08G2261/1412C08G2261/146C08G2261/3223C08G2261/414C08G2261/91C08G2261/92B01J35/39
Inventor 李战峰焦正旭刘宝友岳刚王锦涛田跃田碧凝
Owner TAIYUAN UNIV OF TECH
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