Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics

Abstract

Promoting the photocatalytic proton-coupled electron transfer (PCET) kinetics in the two-electron oxygen reduction reaction (2e⁻ ORR) is crucial for the photocatalytic hydrogen peroxide (H₂O₂) production. Herein, four kinds of covalent organic frameworks (COFs) were successfully prepared via a sub-stoichiometric strategy through a one-step solvothermal method. Among them, B_1.5T₁-COF with polar aldehyde groups displays a high photocatalytic H₂O₂ generation rate of 1081.8 µmol·g⁻¹·h⁻¹, which is 3 times higher than that of B₁T_1.5-COF and 2 times higher than that of B₁T₁-COF. Through the corresponding experiments and density functional theory (DFT) calculation, the photocatalytic mechanism is revealed that B_1.5T₁-COF with free aldehyde groups can raise the PCET kinetics for 2e⁻ ORR with the aid of a stable transfer channel for e⁻ and a favorable hydrogen donation for H⁺. This work might provide some insights for design and preparation of COFs with functional groups through a sub-stoichiometric strategy to modulate their photocatalytic activities.

Keywords

Photocatalytic H₂O₂ production / Sub-stoichiometric / Covalent organic framework

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RIGHTS & PERMISSIONS

Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH