Perovskite materials for catalytic CO₂ valorisation: Structural characteristics, synthesis and lattice substitutions for gas-phase reactions

Perovskites are emerging materials that are being extensively investigated for converting greenhouse gases (GHGs) through thermochemical processes due to their versatile properties. Given their distinct physical and chemical characteristics and their unique structure (ABO 3 , general formula), they are desirable candidates for designing state-of-the-art catalytic systems. For instance, they can be prepared with modified oxygen vacancies, enhanced redox potential, and tailored nanoparticle formulations for use in various catalytic gas-phase CO 2 conversion processes, thereby facilitating the formation of valuable, renewable raw materials such as fuels and chemicals. This comprehensive review explains the perovskite structures, including their crystallographic properties, standard synthesis methods, recent advancements in A, B, and X-site substitutions, and their effectiveness in upgrading CO 2 to produce valuable commodities via different synthetic routes in gas-phase reactions via methanation, reverse water gas shift reaction (rWGS), and dry reforming of methane (DRM). To achieve a sustainable clean energy supply, application-oriented, efficient, and advanced catalytic systems that support the necessary reaction conditions and serve as the most active and selective catalysts are reported in each synthetic gas-phase production section. This study highlights current advancements and optimised research efforts to design potential catalytic materials that meet future requirements for developing efficient decarbonised energy systems. The proposed synthesis methods are the most effective techniques for conserving time and energy. They can also yield favourable morphology and allow manipulation of nanoparticle size, both of which are essential for designing innovative catalysts. To address concerns about CO 2 emissions harming the environment, this study focuses on adaptable, sustainable gas-phase reaction methods with diverse industrial applications. The primary emphasis is on effective, robust perovskite-based catalysts that enable the efficient conversion of CO 2 into value-added chemicals and fuels, thereby supporting low-carbon energy and chemical technologies. This review delineates explicit correlations among synthesis, structure, properties, performance, and stability by relating perovskite lattice design, defect chemistry, and compositional flexibility to catalytic activity, selectivity, and durability in heterogeneous catalytic reactions. • Perovskite ABO 3 oxides provide excellent flexibility in their structure and composition. • Synthesis and defect engineering exert a significant influence on catalytic performance. • Lattice substitution allows for accurate control over activity, selectivity, and stability. • CO 2 valorisation via RWGS, DRM, and Sabatier reactions is systematically reviewed. • Suggested future pathways for structure-guided catalyst development.