Cooperative and bifunctional materials (BFMs) that integrate adsorbents and catalysts offer a promising strategy for the reactive capture of CO₂ to produce valuable fuels and chemicals.1-3 This work details the development of structured, cooperative “bifunctional” materials (BFMs) consisting of (i) a high-temperature adsorbent and (ii) a heterogeneous catalyst, which enable single-bed CO₂ capture and utilization in oxidative ethane dehydrogenation (ODHE) and oxidative propane dehydrogenation (ODHP) processes. We developed and processed structured BFMs via 3D printing, combining CaO and CaO-CaZrO₃ as adsorbents with Ga-Ca-Cr₂O₃ metal oxides and Cr₂O₃/ZSM-5 as catalysts for the reactive capture of CO₂ and its subsequent conversion to light olefins (C₃H₆ and C₂H₄) via the oxidative dehydrogenation of C₃H₈ and C₂H₆ (CO₂-ODH). Three different Ga₁₋ₓCaₓ ratios were used to modify the catalyst surface characteristics and enhance C₂H₄ selectivity. In these formulations, Ga ions stabilize the oxygen lattice of the BFM, while Ca ions interact strongly with Cr to form CaCrO₄, thereby altering the oxygen species and enhancing the material’s basic properties. Under adsorption–reaction conditions at 600–650°C, the optimal BFM achieved excellent C₂H₄ and C₃H₆ selectivities of 95% and 52%, respectively, attributed to a balanced redox process and improved basicity, which facilitate efficient C₃H₈ and C₂H₆ conversion and rapid desorption of C₃H₆ and C₂H₄ without excessive oxidation.
