A Novel Non‐Fullerene D‐A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction

Abstract Converting carbon dioxide (CO₂) into high‐value chemicals using solar energy remains a formidable challenge. In this study, the CSC@PM6:IDT6CN‐M:IDT8CN‐M non‐fullerene small‐molecule organic semiconductor is designed with highly efficient electron donor‐acceptor (D‐A) interface for photocatalytic reduction of CO₂. Atomic Force Microscope and Transmission Electron Microscope images confirmed the formation of an interpenetrating fibrillar network after combination of donor and acceptor. The CO yield from the CSC@PM6:IDT6CN‐M:IDT8CN‐M reached 1346 µmol g⁻¹ h⁻¹, surpassing those of numerous reported inorganic photocatalysts. The D‐A structure effectively facilitated charge separation to enable electrons transfer from the PM6 to IDT6CN‐M:IDT8CN‐M. Meanwhile, attributing to the dipole moments of the strong intermolecular interactions between IDT6CN‐M and IDT8CN‐M, the intermolecular forces are enhanced, and laminar stacking and π‐π stacking are strengthened, thereby reinforcing energy transfer between acceptor molecules and significantly enhanced charge separation. Moreover, the strong internal electric field in the D‐A interface enhanced the excited state lifetime of PM6:IDT6CN‐M:IDT8CN‐M. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that carboxylate (COOH*) is the predominant intermediate during CO₂ reduction, and possible pathways of CO₂ reduction to CO are deduced. This study presents a novel approach for designing materials with D‐A interface to achieve high photocatalytic activity.