π‐Bridge Modulation in Three‐Motif Covalent Organic Framework for Efficient H <sub>2</sub> O <sub>2</sub> Photosynthesis From Water and Air
Abstract
ABSTRACT Rational integration of strong photosensitive moieties and multiple active sites into high performance photocatalysts is challenging due to uncontrollable intercrossing charge transfer. Herein, a series of imine‐bonded two‐ and three‐motif covalent organic frameworks, USTB‐65∼USTB‐68, have been studied, which feature triphenylamine unit as electron‐donor (D) together with benzothiadiazole and/or 2,4,6‐triphenyl‐1,3,5‐triazine moieties as electron‐acceptor (A). Introduction of benzene rings as π‐bridge into the D–A–A lattice of three‐motif USTB‐65 affords D–A–π–A USTB‐66, leading to more facile exciton dissociation and efficient step‐wise charge transfer among three motifs as revealed by various photophysical investigations and theoretical calculations. This, in combination with strong light absorption and multiple photocatalytic sites, results in the outstanding activity of USTB‐66 in H 2 O 2 photoproduction from water and air, achieving a production rate of 11.2 mmol g ‒1 h ‒1 , an outstanding apparent quantum yield of 27.3% at 550 nm, and a solar‐to‐chemical conversion efficiency of 2.71%. Under solar concentrator, the H 2 O 2 production rate based on USTB‐66 in a flow reactor is further increased to 33.8 mmol g ‒1 h ‒1 during 24 h irradiation.
Article Details
Authors (10)
Yucheng Jin
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Xiaoning Zhan
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Houhe Pan
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials School of Chemistry and Biological Engineering University of Science and Technology Beijing Beijing P.R. China
Hailong Wang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Yanhua Shao
School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks
Zhiying Chen
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Xiaonan Pang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Changqing Li
School of Energy and Chemical Engineering/Center for Dimension-Controllable Organic Frameworks
Jong‐Beom Baek
Department of Energy and Chemical Engineering Center For Dimension‐Controllable Organic Frameworks Ulsan National Institute of Science and Technology Ulsan South Korea
Jianzhuang Jiang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering