Realizing Photocatalytic Overall Water Splitting by Modulating the Thickness‐Induced Reaction Energy Barrier of Fluorenone‐Based Covalent Organic Frameworks

Abstract Direct photocatalytic hydrogen and oxygen evolution from water splitting is an attractive approach for producing chemical fuels. In this work, a novel fluorenone‐based covalent organic framework (COF‐SCAU‐2) is successfully exfoliated into ultrathin three‐layer nanosheets (UCOF‐SCAU‐2) for photocatalytic overall water splitting (OWS) under visible light. The ultrathin structures of UCOF‐SCAU‐2 greatly enhance carrier separation, utilization efficiency, and the exposure of active surface sites. Surprisingly, UCOF‐SCAU‐2 exhibits efficient photocatalytic OWS performance, with hydrogen and oxygen evolution rates reaching 0.046 and 0.021 mmol h⁻¹ g⁻¹, respectively, under visible‐light irradiation, whereas bulk COF‐SCAU‐2 shows no activity for photocatalytic OWS. Charge‐carrier kinetic analysis and DFT calculations confirm that reducing the thickness of the COF nanosheets increases the number of accessible active sites, reduces the distance for charge migration, prolongs the lifetimes of photogenerated carriers, and decreases the Gibbs free energy of the rate‐limiting step compared to nonexfoliated COFs. This work offers new insights into the effect of the layer thickness of COFs on photocatalytic OWS.