Autonomous Optimization of Complex Oxides for Thermochemical Fuel Production

Abstract

Two-step thermochemical fuel production, including H2O and CO2 splitting, offers a promising route to sustainable fuel manufacturing, with performance governed by redox-active oxides that enable cyclic reduction-oxidation reactions. Maximizing thermal-to-fuel conversion efficiency demands materials that simultaneously satisfy multiple stringent thermodynamic and kinetic targets. Addressing these requirements has increasingly driven materials design toward complex, multi-cation oxides, such as mixed-cation fluorites, perovskites, and high-entropy oxides, wherein composition, defect chemistry, phase stability, and morphology should be co-optimized. This creates a challenging materials optimization problem that is poorly suited to traditional trial-and-error approaches. In this review, we argue that thermochemical fuel production provides a compelling frontier for autonomous materials design and optimization. We first examine why redox-active complex oxides are difficult to develop, owing to multidimensional phase spaces, harsh operating conditions, and competing functional targets. We then discuss how high-throughput computation, automated synthesis, characterization and testing, and machine learning can be integrated into closed-loop workflows to address these challenges. Building on broader oxide materials research, we organize recent progress into a capability roadmap for complex-oxide optimization, spanning compositionally diverse synthesis, operando characterization, robotic testing, operation-condition computation, and multi-objective optimization. Finally, we outline key experimental, computational, and data challenges for building self-improving materials development platforms for materials development in thermochemical fuel production.