An Electron Transfer Mediated Mechanism for Efficient Photoreforming of Waste Plastics Using a Ni3S4/ZnCdS Heterojunction

Abstract The oxidative degradation of plastics in conjunction with the production of clean hydrogen (H 2 ) represents a significant challenge. Herein, a Ni 3 S 4 /ZnCdS heterojunction is rationally synthesized and employed for the efficient production of H 2 and high‐selectivity value‐added chemicals from waste plastic. By integrating spectroscopic analysis techniques with density functional theory (DFT) calculations, a solely electron transfer‐mediated reaction mechanism is confirmed, wherein Ni 3 S 4 extracts electrons from ZnCdS (ZCS) to promote the spatial segregation of photogenerated electrons and holes, which not only facilitates H 2 production but also maintains the high oxidation potential of holes on the ZCS surface, favoring hole‐dominated plastic oxidation. Notably, the catalyst exhibited efficient H 2 production rates as high as 27.9 and 17.4 mmol g −1 h −1 , along with a selectivity of 94.2% and 78.3% in the liquid product toward pyruvate and acetate production from polylactic acid (PLA) and polyethylene terephthalate (PET), respectively. Additionally, carbon yields of 26.5% for pyruvate and 2.2% for acetate are measured after 9 h of photoreforming, representing the highest values reported to date. Overall, this research presents a promising approach for converting plastic waste into H 2 fuel and high‐selectivity valuable chemical products, offering a potential solution to the growing issue of “ White Pollution ”.