阅读说明：本技术 用于高效光催化分解水产氧的新型组合物及其应用 (Novel composition for efficient photocatalytic water decomposition to produce oxygen and application thereof ) 是由 黄飞 邢晔彤 胡志诚 曹镛 于 2019-10-12 设计创作，主要内容包括：本发明涉及用于高效光催化分解水产氧的新型组合物及其应用。本发明所述的光催化分解水的组合物包括苝酰亚胺类共轭小分子/聚合物光催化材料及金属纳米助催化剂。所述的共轭小分子/聚合物光催化材料具有良好的水溶性及和合适的能级,并且与金属纳米助催化剂能够较好结合在一起,发挥较好的催化性能。本发明所述材料及其组合物能够高效催化水分解产氧。与现有技术相比,本发明提供的材料及组合物能够极大地提高产氧效率。(The invention relates to a novel composition for efficient photocatalytic water decomposition to produce oxygen and application thereof. The composition for decomposing water by photocatalysis comprises perylene bisimide conjugated micromolecules/polymer photocatalysis materials and metal nano cocatalyst. The conjugated micromolecule/polymer photocatalytic material has good water solubility and proper energy level, and can be well combined with a metal nano cocatalyst to play a good catalytic performance. The material and the composition thereof can efficiently catalyze the decomposition of water to generate oxygen. Compared with the prior art, the material and the composition provided by the invention can greatly improve the oxygen production efficiency.)

1. The novel composition for efficiently decomposing water by photocatalysis to generate oxygen is characterized by comprising a perylene bisimide photocatalysis material and a metal nano cocatalyst; the perylene imide photocatalytic material comprises more than one of perylene imide conjugated micromolecule photocatalytic materials and perylene imide conjugated polymer photocatalytic materials; the perylene bisimide conjugated micromolecule photocatalytic material and the perylene bisimide conjugated polymer photocatalytic material have the following structures:

wherein n is a positive integer less than 100 ten thousand; m is more than 1; r₁、R₂Is a neutral amine group or a quaternary ammonium salt group, and the anion in the quaternary ammonium salt is fluorine, chlorine, bromine, iodine or trifluoromethanesulfonate, tetrafluoroborate ion; r₃、R₄、R₅、R₆Is an alkyl chain, wherein the tail end of at least one alkyl chain is a neutral amine group or a quaternary ammonium salt group, and the anion in the quaternary ammonium salt is halogen ion or iodate, nitrate, trifluoromethanesulfonate, tetrafluoroborate and tetramisole borate ion; the halide ions comprise fluoride, chloride, bromide or iodide ions; a is a conjugated unit structure; x₁～X₈Is hydrogen, fluorine, chlorine, bromine or iodine atom.

2. The novel composition for efficient photocatalytic water splitting for oxygen production as claimed in claim 1, wherein said R is₃、R₄、R₅、R₆Is a straight chain, branched chain or cyclic alkyl chain with 1-40 carbon atoms, wherein one or more carbon atoms are replaced by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups, methyl groups, ethyl groups, methoxyl groups and nitro groups, and hydrogen atoms are replaced by fluorine atoms or the functional groups; r₃、R₄、R₅、R₆The same or different.

3. The novel composition for efficient photocatalytic water splitting for oxygen generation according to claim 1, wherein a is a conjugated unit structure having one or more of the following structures:

4. the novel composition for efficient photocatalytic water splitting for oxygen generation as claimed in claim 1, wherein the metal nanocatalyst is cobalt, nickel metal and one or more of their oxide, sulfide, phosphide nanoparticles with a size of 10nm to 500 nm.

5. The novel composition for efficient photocatalytic water decomposition and oxygen generation according to claim 1, wherein the mass ratio of the metal nano-cocatalyst to the perylene imide photocatalytic material is (0.01-0.05): 1.

6. the use of the novel composition of claim 1 as a catalyst for the efficient photocatalytic decomposition of water to produce oxygen.

Technical Field

The invention relates to the field of photocatalysis, in particular to a composition based on perylene bisimide conjugated micromolecules/polymers as well as metal and metal oxides, sulfides and phosphide and a preparation method thereof, and application of the composition in organic photocatalysis oxygen production.

Background

At present, the world energy demand depends on fossil fuels such as petroleum, coal, natural gas and the like which are rapidly exhausted to a great extent, so that the problem of energy shortage is more and more serious, and a series of adverse effects such as environmental pollution, greenhouse effect and the like are brought. Under such circumstances, it has become necessary to develop new clean sustainable energy sources. The photocatalysis process of decomposing water into oxygen and hydrogen by utilizing solar illumination can continuously produce and store chemical fuel and carry out green energy circulation, thereby having received wide attention. In the water decomposition process, the oxygen generation reaction is a thermodynamic energy absorption reaction, huge activation energy is needed, the reaction kinetics is slow, 4 electrons and 4 protons need to be transferred simultaneously, and therefore the reaction is considered to be more challenging. Therefore, the research of the active oxygen-generating photocatalyst plays an important role in the research of water photolysis.

The photocatalytic material should have a broad absorption spectrum over a broad spectral range to absorb more sunlight, provide a sufficiently deep HOMO level to provide a sufficient driving force for oxygen production, and have good photostability to sustain long-term applications. In addition, each component in the system should bind well together to promote charge transfer and photocatalytic oxygen generation. However, there is a great challenge to achieve all of the above conditions, and designing a good photocatalytic material and adjusting its interaction with other components is a key issue.

The method aims at solving the problems of the existing oxygen production catalyst, and the added metal and nanoparticles of oxides, sulfides and phosphides of the metal can effectively promote the transmission of holes to water, thereby reducing the carrier recombination and improving the photocatalytic hydrogen production efficiency.

Disclosure of Invention

The invention aims to design and synthesize perylene imide conjugated micromolecules/polymers and compositions of metal and metal oxides, sulfides and phosphides for efficient photocatalytic oxygen generation.

The technical scheme of the invention is as follows.

The novel composition for efficiently decomposing water by photocatalysis to generate oxygen comprises a perylene bisimide photocatalysis material and a metal nano cocatalyst; the perylene imide photocatalytic material comprises more than one of perylene imide conjugated micromolecule photocatalytic materials and perylene imide conjugated polymer photocatalytic materials; the perylene bisimide conjugated micromolecule photocatalytic material and the perylene bisimide conjugated polymer photocatalytic material have the following structures:

wherein n is a positive integer less than 100 ten thousand; m is more than 1; r₁、R₂Is a neutral amine group or a quaternary ammonium salt group, and the anion in the quaternary ammonium salt is fluorine, chlorine, bromine, iodine or trifluoromethanesulfonate, tetrafluoroborate ion; r₃、R₄、R₅、R₆Is an alkyl chain, wherein the tail end of at least one alkyl chain is a neutral amine group or a quaternary ammonium salt group, and the anion in the quaternary ammonium salt is halogen ion or iodate, nitrate, trifluoromethanesulfonate, tetrafluoroborate and tetramisole borate ion; the halide ions comprise fluoride, chloride, bromide or iodide ions; a is a conjugated unit structure; x₁～X₈Is hydrogen, fluorine, chlorine, bromine or iodine atom.

Further, said R₃、R₄、R₅、R₆Is a straight chain, branched chain or cyclic alkyl chain with 1-40 carbon atoms, wherein one or more carbon atoms are replaced by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups, methyl groups, ethyl groups, methoxyl groups and nitro groups, and hydrogen atoms are replaced by fluorine atoms or the functional groups; r₃、R₄、R₅、R₆The same or different.

Further, A is a conjugated unit structure and has one or more than one of the following structures:

furthermore, the metal nano-cocatalyst is more than one of cobalt and nickel metal with the size of 10 nm-500 nm and oxide, sulfide and phosphide nano-particles thereof.

Further, the mass ratio of the metal nano cocatalyst to the perylene imide photocatalytic material is (0.01-0.05): 1.

an application of the novel composition as a catalyst for decomposing water into oxygen by high-efficiency photocatalysis.

Compared with the prior art, the invention has the following advantages:

(1) the invention designs the perylene bisimide conjugated micromolecule/polymer photocatalytic material, and the interaction between the polymer and metal, oxides and sulfides thereof can be greatly improved by adjusting the side chain of the perylene bisimide conjugated micromolecule/polymer photocatalytic material, so that the charge separation and the electron transmission are promoted, and the photocatalytic oxygen production efficiency can be greatly improved;

(2) the perylene bisimide conjugated micromolecules/polymers are designed, have deeper highest occupied molecular orbitals, can generate larger photocatalytic oxygen generation driving force, and improve the oxygen generation efficiency;

(3) the invention designs perylene bisimide conjugated micromolecules/polymers, and the cationic groups on the side chains of the perylene bisimide conjugated micromolecules/polymers can enhance the dispersibility of the photocatalyst in water, so that the perylene bisimide conjugated micromolecules/polymers are favorable for improving the charge separation efficiency and the oxygen generation efficiency.

Drawings

FIG. 1 shows a UV-visible-NIR absorption spectrum of a perylene bisimide conjugated small molecule/polymer;

FIG. 2 represents a graph of the photocatalytic oxygen generation efficiency of the perylene bisimide conjugated small molecule/polymer and metal nanoparticle composition.

Detailed Description

The invention is further illustrated by the following specific examples, which are intended to facilitate a better understanding of the context of the invention, including in particular the synthesis, characterization and device fabrication, but which are not intended to limit the scope of the invention in any way.