Frustrated Lewis Pairs Enable Efficient Polyethylene Oxidative Upcycling

ABSTRACT Catalytic oxidative upcycling of waste polyethylene (PE) into value‐added dicarboxylic acids under mild conditions is highly attractive, yet the efficient activation of molecular oxygen remains a fundamental challenge. Herein, we report a catalyst microenvironment engineering strategy that introduces frustrated Lewis pairs (FLP) characteristics into established high‐performance catalysts for unlocking their full catalytic potential, rather than relying on the development of entirely new catalytic materials. Using a Co‐based catalyst as an example, we demonstrated that the designed FLP‐CoO x catalyst, featuring abundant surface FLP sites, markedly enhances O 2 activation, enabling the efficient generation of superoxide radicals (O 2 •− ) via a single‐electron reduction pathway. As a result, an outstanding dicarboxylic acid carbon yield of up to 86.0% was achieved under mild conditions, representing a fourfold improvement over the conventional catalyst. Moreover, the catalytic system exhibited excellent performance toward the oxidative valorization of various real‐world waste plastics. This work presents FLP‐mediated catalyst microenvironment engineering as a general strategy for substantially enhancing the performance of existing catalysts, providing new opportunities for the oxidative upcycling of waste plastics.