In this study, novel perovskite-type oxygen transport membranes were designed and synthesised by a scalable reverse co-precipitation. The substitution of Cu2+ and Zn2+ for partial Fe3+ in La0.7Ca0.3Co0.3Fe0.7O3–δ led to the generation of additional oxygen vacancies, an expansion in crystal volume for enhanced oxygen ion transport, and the formation of holes fostering higher concentrations of electronic conducting carriers, thereby improving oxygen permeability. The membrane’s resilience to pure CO2 exposure, maintaining structure for over 1600 hours, underscores its durability. First-principles calculations reveal Cu/Zn substitution effects on oxygen vacancy formation and transport, accelerating short-range oxygen ion migration. This facilitates faster oxygen permeability, crucial for membrane design. Experimental and computational synergy provides insights into ionic and electronic conductivity, establishing equilibrium for permeability and CO2 tolerance. The newly developed membranes exhibit high potential for applications in separating oxygen from highly concentrated CO2 atmospheres and for plasma-based CO2 conversion and unitization. (Guoxing Chen, Wenmei Liu, Marc Widenmeyer, Xiao Yu, Zhijun Zhao, Songhak Yoon, Ruijuan Yan, Wenjie Xie, Armin Feldhoff,Gert Homm, Emanuel Ionescu, Maria Fyta, Anke Weidenkaff, Front. Chem. Sci. Eng. 2024, 18(6): 62)
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