Self-Sacrificing Photocatalyst Enables Polymer Synthesis and In Situ Decolorization

A long-standing challenge for homogeneous catalysis lies in the contamination of residual catalyst, necessitating complex and costly postprocessing. Inspired by self-sacrificing behavior in nature, we developed a programmed, self-decomposing catalytic system that enables light-driven polymer synthesis and in situ decolorization. As a proof of concept, we designed a green aluminum porphyrin-backbone polymeric catalyst (P-Cat) for the photothermal telomerization of epoxides and CO2, enabling the synthesis of ultralow-molecular-weight (Mn < 1000 g·mol–1) and multifunctional CO2-based polyols under low catalyst loadings (<0.025 mol %). Furthermore, upon switching to an air atmosphere, P-Cat undergoes rapid photodegradation caused by the in situ generated superoxide radical (O2•–), without affecting the quality of the products. This work presents a nature-inspired strategy for designing advanced catalytic systems with self-eliminating functionality, providing new insights into polymer synthesis.