Photocatalytic Cracking of non‐Biodegradable Plastics to Chemicals and Fuels

Abstract Plastic pollution is worsening the living conditions on Earth, primarily due to the toxicity and stability of non‐biodegradable plastics (NBPs). Photocatalytic cracking of NBPs is emerging as a promising way to cleave inert C−C bonds and abstract the carbon atoms from these wastes into valuable chemicals and fuels. However, controlling these processes is a huge challenge, ascribed to the complicated reactions of various NBPs. Herein, we summarize recent advances in the CO 2 and carbon‐radical‐mediated photocatalytic cracking of NBPs, with an emphasis on the pivotal intermediates. The CO 2 ‐mediated cracking proceeded with indiscriminate C−H/C−C bond cleavage of NBPs and tandem photoreduction of CO 2 , while carbon‐radical‐mediated cracking was realized by the prior activation of C−H bonds for selective C−C bond cleavage of NBPs. Catalytic generation and conversion of different intermediates greatly depend on the kinds of active species and the structure of photocatalysts under irradiation. Meanwhile, the fate of a specific intermediate is compared with small molecule activation to reveal the key problems in the cracking of NBPs. Finally, the challenges and potential directions are discussed to improve the overall efficiency in the photocatalytic cracking of NBPs.