Sustainable routes to adipic acid from biomass-derived C6 polyols typically rely on a two-step deoxydehydration (DODH)–hydrogenation sequence, of which the DODH step remains the primary barrier to industrial adoption. Here, we report a tunable rhenium catalyst supported on ceria–zirconia mixed oxides (Re/CexZr1-xO2) engineered through precise control of metal-support interactions. Thermal diffusion of Zr4+ into CeO2 nanorods induces lattice contraction and elevates the Ce3+ fraction, substantially enhancing the reducibility of surface rhenium species and accelerating the rate-determining step in Re-catalyzed DODH. Remarkably, up to 70 at% Zr can be incorporated without structural degradation, providing an unprecedented combination of oxygen mobility and rhenium redox synergy. The optimized Re/Ce0.3Zr0.7O2 catalyst delivers trans, trans-muconate in 94% yield from galactarate using n-butanol, which functions simultaneously as solvent and green reductant.
