Entropy-Driven Modulation of Lattice Oxygen Stabilization and Oxygen Activation for Durable and Efficient Volatile Organic Oxidation

Achieving sustained activity without deactivation in metal oxide catalysts poses a critical challenge in volatile organic compounds abatement. Here, we introduce an entropy-increasing strategy to circumvent the inherent activity–stability trade-off by progressively incorporating thermodynamically diverse elements Zr, Mg, Co, Ni, and Mn into a CeO2 fluorite lattice to construct low-, medium-, and high-entropy oxides (LEO, MEO, and HEO). The optimized HEO affords 90% cyclohexane conversion at a markedly low 274 °C, alongside outstanding stability during both a 48 h accelerated aging test and a 100 h stability evaluation. Comprehensive analysis of fresh, used, and aged catalysts indicates that increasing configurational entropy modulates the strength of metal–oxygen bonds, precisely balancing lattice robustness and oxygen mobility, thereby sustaining a robust redox cycle. In-depth characterization under both O2-rich and O2-free conditions, combined with DFT calculations of the crystal orbital Hamiltonian population, further reveals that thermally sensitive Mn promote electron transfer for rapid oxygen activation, while thermally inert Zr strengthens metal–oxygen lattice anchoring of active elements. This synergistic enhancement enables HEO to generate the lowest ring-opening intermediates among 19 identified byproducts compared to MEO counterparts, effectively driving the deep oxidation of key intermediate benzene. This work provides a novel strategy for developing advanced non-noble metal catalysts.