Dithiocarbamate‐Linked Phthalocyanine with CdSe QDs Enhancing Charge Transfer for Selective Photocatalytic CO₂ Reduction

Abstract Photocatalytic CO₂ reduction (PCR) to chemical fuels represents a promising solution to the energy crisis and global warming. The rational design of efficient photocatalysts is key to PCR. In this study, a molecular heterogeneous photocatalyst is constructed with cobalt (II) 2,9,16,23‐tetraaminophthalocyanine (CoPc‐NH₂) covalently linked to CdSe quantum dots (QDs) via a dithiocarbamate group (─NHCS₂). This covalent bond (─NHCS₂) enables directional, efficient, and fast interfacial electron transfer, substantially improving the catalytic activity. The optimized CdSe@CoPc‐NH₂ heterojunction exhibits excellent activity for CO₂ reduction, achieving an average CO generation rate of 3, 687 µmol g⁻¹ h⁻¹ (TON_CO = 2, 360), which is 31 times higher than that of pristine CdSe QDs. Furthermore, immobilizing CoPc‐NH₂ on CdSe QDs increases the selectivity for CO from 20% to 90%. The in situ formation of molecular heterogeneous photocatalysts features a covalently bonded interface, which can offer valuable insights for designing efficient photocatalysts for solar fuel generation.