Selective Photoreforming of Waste Plastics into Diesel Olefins via Single Reactive Oxygen Species

The accumulation of plastic waste poses a pressing environmental challenge. Catalytic conversion stands out as an ideal approach for plastics upcycling, particularly through solar-driven plastics photoreforming. However, due to the common effects of multiple reactive oxygen species (ROS), selectively generating high-value chemicals becomes challenging. In this study, we developed a universal strategy to achieve >85 % selective production of diesel olefins (C₁₅-C₂₈) from polyolefin waste plastics via single ROS. Using tetrakis (4-carboxyphenyl) porphyrin supramolecular (TCPP) with different central metals as an example to regulate single ROS generation, results show Ni-TCPP facilitates triplet exciton production, yielding ¹O₂, while Zn-TCPP generates ⋅O₂ ^- due to its strong built-in electric field (IEF). ¹O₂ directly dechlorinates polyvinyl chloride (PVC) due to the electro-negativity of chlorine atoms and the low dissociation energy of C-Cl bonds, while ⋅O₂ ^- promotes direct dehydrogenation of polyethylene (PE) due to the electro-positivity of hydrogen atoms and the high dissociation energy of C-H bonds. This method is universally applicable to various single ROS systems. Installation experiments further affirm the application potential, achieving the highest diesel olefin production of 76.1 μmol h^-1. Such a universally adaptive approach holds promise for addressing the global plastic pollution problem.