Synergistic effect of hydroxyl modification and transition metal doping on Cu–Ce interface for chemical looping preferential oxidation

A “hydroxyl-transition metal synergistic” strategy was developed to enhance Cu-Ce oxygen carriers for chemical looping preferential oxidation (CL-PROX). Among synthesized MCuCe (M = Mn, Fe, Co) samples, MnCuCe exhibited superior performance. Mn doping strengthened strong interfacial interactions via oxygen vacancy-mediated charge compensation, yielding the highest surface Cu + (77.44%), Ce 3+ (20.94%), and oxygen vacancies (35.30%). Consequently, MnCuCe achieved >99% CO conversion at 180 °C with <3% H 2 consumption, showing no deactivation after 30 cycles. In situ FTIR verified that Cu + serves as the pivotal active site within a Mars-van Krevelen (MvK) mechanism. DFT calculations confirmed that the synergistic construction of stable M−Cu + −O v −Ce 3+ sites results in the most negative CO adsorption energy (−3.00 eV). This study provides a novel paradigm for designing high-performance CL-PROX oxygen carriers.