Use of A-Site Metal Exsolution from a Hydrated Perovskite Titanate for Combined Steam and CO₂ Reforming of Methane

Metal segregation from a perovskite oxide (ABO₃) usually referring to "redox metal exsolution" has recently been used for in situ preparation of a well-designed catalyst where metal nanoparticles are homogeneously and strongly embedded on perovskite scaffolds upon reduction. The exsolution concept of B-site transition metal ions has grown, but several issues such as segregation of A-site alkaline-earth metal ions (altering electronic structures of the perovskite surface, causing deformation of perovskite structures, or creating undesirable products via side reactions) and carbon formations on metal nanoparticles should be addressed for stable catalysts in greenhouse gas (CO₂ or CH₄) conversion. Here, we suggest a new approach to designing metal-perovskite composite catalysts via A-site metal segregation from a hydrated perovskite titanate. In situ formation of A-site-deficient hydrated CaTiO₃ accompanied with Ni exsolution solids leads to ∼78 and 65% of CH₄ and CO₂ conversion, respectively, suppressing carbon formations and alkaline-earth metal segregations in combined steam and carbon dioxide reforming of methane at 700 °C. It would help to design active and stable metal-perovskite catalysts for energy and environmental applications.