Heterolytic H2 Activation over Platinum Supported on Oxygen‑Vacancy‑Rich CeO2 (Pt/CeO2–Vo) for Efficient Reductive Amination of Levulinic Acid to Pyrrolidones under Ambient Conditions

Reductive amination of biomass-derived levulinic acid (LA) to N -substituted-5-methyl-2-pyrrolidone (BMP), versatile nitrogen-containing chemicals, under ambient conditions is highly desirable but challenging due to inefficient H 2 activation. To address this limitation, a platinum (Pt)-based catalyst supported on oxygen-vacancy-rich CeO 2 (Pt/CeO 2 -V o ) was developed, comprising uniformly dispersed Pt/PtO 2 heterostructures with adjacent Pt–O–Ce interfacial sites. At these Pt–O–Ce interfaces, electron-deficient Pt and electron-rich O atoms, modulated by neighboring oxygen vacancies, facilitate in situ hydrogen spillover from Pt nanoparticles, generating highly reactive H δ ⁺ –O···Pt–H δ – pairs that enable the efficient hydrogenation of the condensation intermediates formed between LA and amine substrates. Therefore, Pt/CeO 2 -V o achieved a high BMP yield of 95.2% with a productivity of 476.0 mol/(mol·h) within 1 h under ambient conditions. Even at a high LA concentration of 11.4% ( w ), the yield remained above 90%, demonstrating the catalyst’s efficiency under ambient conditions. It also showed excellent recyclability over six consecutive cycles and maintained stable performance for over 80 h in a fixed-bed flow reactor. This work underscores the critical importance of interfacial engineering in optimizing Pt-based catalysts and provides a robust and sustainable strategy for biomass upgrading under mild conditions.