Affiliation:
1. Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education Northeast Normal University Changchun 130024 China
2. School of Chemistry and Environmental Engineering Jilin Provincial Science and Technology Innovation Center of Optical Materials and Chemistry Jilin Provincial International Joint Research Center of Photo functional Materials and Chemistry Changchun University of Science and Technology Changchun 130022 China
3. Jiangsu Key Laboratory for Carbon‐based Functional Materials and Devices Institute of Functional Nano and Soft Materials (FUNSOM) Soochow University Suzhou 215123 China
Abstract
AbstractAggregation‐induced emission (AIE) materials are considered promising photocatalyst candidates due to their robust light‐harvesting and efficient photoexcitation, if their photoexcited carriers can be separated effectively. Herein, by skillfully selecting multi‐alkynyl ligands instead of phenylacetylene to construct multi‐channel charge separation, copper‐phenylacetylide (CP‐1) with AIE properties is successfully transformed into efficient photocatalysts CP‐2P (copper‐1,4‐diethynylbenzene) and CP‐2M (copper‐1,3‐diethylnylbenzene). In these structures, the multi‐alkynyl ligands connects the copper‐ladder into multi‐dimensional metal‐organic frameworks with greatly reduced bandgap, enhances charge transfer and separation, and facilitated oxygen adsorption and activation. As a representative, CP‐2P has the best photocatalytic activity and stability for photocatalytic aerobic oxidation, such as thioanisole oxidation (conv. > 99%, methyl phenyl sulfoxide sel. ≧ 94%), benzyl alcohol oxidation (conv. > 99%, benzaldehyde sel. > 99%) and benzylamine oxidation (conv. > 99%, N‐benzylidene benzylamine sel. > 99%), which can be used for large‐scale sunlight‐driven organic photosynthesis. This work confirms the feasibility of controlled conversion of the conventional copper‐alkynyl from AIE material to efficient photocatalyst using charge separation strategy, which provides an important guidance for the rational design of new high‐efficiency photocatalyst.
Funder
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities
Subject
Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials