Single-Atom Ni on Tungsten Oxides Drives Hydrogen Spillover for Efficient Plastic Waste Upcycling

Upcycling polyolefin waste into liquid fuels via hydrocracking demands cost-effective catalysts that integrate strong acidity with hydrogenation activity, necessitating precise atomic control of the catalytic sites. Here, we report a non-noble catalyst featuring atomically dispersed Ni on structurally engineered WO 2.72 nanowires, where heterolytic Ni–O–W sites enable heterolytic H 2 activation and hydrogen spillover. In situ infrared spectroscopy shows that active Bro̷nsted acidic W–OH groups form dynamically from terminal W═O species during hydrogen spillover, surpassing bridged W–OH-W species in WO 3 for C–C bond cleavage. The optimized 1Ni/WO 2.72 catalyst achieves complete polyethylene conversion at 240 °C with 94.3% selectivity toward gasoline- and jet-ranged liquid fuels and state-of-the-art productivity of 5.0 g liquid /g cat ·h, outperforming noble metal catalysts. Time-resolved operando infrared spectroscopy captures a stepwise hydrocracking pathway involving dehydrogenation, protonation, and C–C bond cleavage, while kinetic studies and DFT modeling confirm the critical role of these engineered sites. This work establishes a design strategy for single-atom, non-noble bifunctional catalysts through atomic-scale engineering of oxide structures and metal nuclearity, offering both mechanistic insight and practical guidance for plastic waste upcycling.