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.