Rationally Designed Cyclooctatetrathiophene‐Based Porous Aromatic Frameworks (COTh‐PAFs) for Efficient Photocatalytic Hydrogen Peroxide Production

Abstract Constructing stable and efficient photocatalysts for H 2 O 2 production is of great importance and is challenging. In this study, the synthesis of three photoactive cyclooctatetrathiophene (COTh)‐based porous aromatic frameworks (COTh‐PAFs) in an alternating donor‐acceptor (D−A) fashion is presented. In combination with a triazine‐derived electron acceptor, PAF‐363 exhibits high efficiency for the photosynthesis of H 2 O 2 with production rates of 11733 μmol g −1 h −1 (with sacrificial agent) and 3930 μmol g −1 h −1 (without sacrificial agent) from water and oxygen under visible light irradiation. Experimental results and theoretical calculations reveal that the charge transfer positions and the O 2 adsorption sites in PAF‐363 are both concentrated on COTh fragments, which facilitate the H 2 O 2 production through the oxygen reduction reaction (ORR) pathway. This work highlights that the rational design of COTh‐PAFs with consideration of D−A direction, charge transfer positions, and O 2 adsorption sites provides a feasible access to efficient H 2 O 2 production photocatalysts.