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Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions

Meng Lu, Shuai‐Bing Zhang, Mingyi Yang, Yufei Liu, Jia‐Peng Liao, Pei Huang, Mi Zhang, Shun‐Li Li, Zhong‐Min Su, Ya‐Qian Lan

2023Angewandte Chemie20 citationsDOI

Abstract

Abstract In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy) 3 2+ /Fe(bpy) 3 2+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series of dual photosensitizer‐based three‐dimensional metal‐covalent organic frameworks (3D MCOFs), which behaved strong visible light‐absorbing ability, efficient electron transfer and suitable band gap for highly efficient photocatalytic hydrogen (H 2 ) evolution. Rubpy‐ZnPor COF achieved the highest H 2 yield (30 338 μmol g −1 h −1 ) with apparent quantum efficiency (AQE) of 9.68 %@420 nm, which showed one of the best performances among all reported COF based photocatalysts. Furthermore, the in situ produced H 2 was successfully tandem used in the alkyne hydrogenation with ≈99.9 % conversion efficiency. Theoretical calculations reveal that both the two photosensitizer units in MCOFs can be photoexcited and thus contribute optimal photocatalytic activity. This work develops a general strategy and shows the great potential of using multiple photosensitive materials in the field of photocatalysis.

Topics & Concepts

PhotosensitizerPhotocatalysisCovalent bondPhotochemistryPorphyrinChemistryQuantum yieldRutheniumCovalent organic frameworkPyridineMetalCatalysisCombinatorial chemistryOrganic chemistryFluorescenceQuantum mechanicsPhysicsCovalent Organic Framework ApplicationsAdvanced Photocatalysis TechniquesMetal-Organic Frameworks: Synthesis and Applications