Transition metal oxide manipulating <scp>ZrO₂</scp>‐based non‐precious metal catalysts for enhanced <scp>CO₂</scp>‐mediated oxidative dehydrogenation of propane

Abstract BACKGROUND Developing highly stable and cost‐effective catalysts for CO 2 ‐mediated oxidative dehydrogenation of propane (CO 2 ‐ODP) is critical to advancing sustainable propylene production. While ZrO 2 ‐based supports offer promising thermal stability and tunable acid–base properties, integrating transition metal oxides (TMO x ) as active sites to optimize CO 2 activation and propane conversion remains underexplored. RESULTS Here, we systematically design a series of non‐precious metal TMO x /ZrO 2 catalysts (TM = Cr, Fe, Co, Ni, Cu, Zn) via a coprecipitation–gel method to uncover structure–activity relationships. Among them, CrO x /ZrO 2 emerges as the optimal candidate, achieving notable C 3 H 8 /CO 2 conversions of 46.24%/38.27% and 86.49%/27.03% C 3 H 6 selectivity/yield at 600 °C. Characterization reveals that the coexistence of Cr 3+ /Cr 4+ species (XPS) and mixed‐phase Cr 2 O 3 /CrO 2 (XRD/Raman) creates abundant oxygen vacancies and enhances CO 2 adsorption (TPD), while HRTEM/EDX confirms uniform CrO x dispersion on ZrO 2 . Further optimizing the Cr/Zr ratio to 1:1 maximizes active site exposure while preventing excessive aggregation, thereby balancing redox activity and structural stability. CONCLUSIONS This work elucidates how tailored TMO x /ZrO 2 interfaces leverage synergistic electronic and geometric effects to drive CO 2 ‐ODP efficiency, offering a blueprint for designing high‐performance non‐precious metal catalysts for alkane valorization. © 2025 Society of Chemical Industry (SCI).