Photocatalyst Design for Plastic Upcycling: From Polymer Deconstruction to Selective Valorization

ABSTRACT Plastic waste poses a severe threat to our environment, yet represents an abundant and largely underutilized reservoir of chemically processed carbon and embedded energy. Photocatalytic conversion offers a promising route to valorize plastic waste into fuels and value‐added chemicals. However, practical plastic photovalorization remains severely limited by sluggish polymer deconstruction and poor product selectivity. These challenges are further complicated by diverse polymer structures and crystallinity, which dictate distinct conversion strategies and impose varied requirements on photocatalysts. In this review, we map photocatalytic plastic upcycling across major plastic categories to establish the relationships between polymer properties, conversion routes, and the corresponding photocatalyst requirements. On this basis, we focus on photocatalyst design from polymer deconstruction to selective product formation, highlighting material design strategies for improving polymer accessibility and deconstruction, regulating selective intermediate conversion, and coordinating coupled redox reactions. We further detail the selective formation of value‐added oxygenates, hydrocarbons, aromatics, and C─N products, with particular emphasis on how active‐site engineering of photocatalysts directs the corresponding reaction pathways. Finally, key material and system challenges in plastic photovalorization, including real‐world plastic feedstock complexity, low carbon efficiency, process viability, and scale‐up, are highlighted. Future perspectives are discussed to guide the development of practical plastic photovalorization systems.