Modifying the Surface Structure of Perovskite-Based Catalysts by Nanoparticle Exsolution

In heterogeneous catalysis, surfaces decorated with uniformly dispersed, catalytically-active (nano)particles are a key requirement for excellent performance. Beside standard catalyst preparation routines-with limitations in controlling catalyst surface structure (i.e., particle size distribution or dispersion)-we present here a novel time efficient route to precisely tailor catalyst surface morphology and composition of perovskites. Perovskite-type oxides of nominal composition ABO(3) with transition metal cations on the B-site can exsolve the B-site transition metal upon controlled reduction. In this exsolution process, the transition metal emerges from the oxide lattice and migrates to the surface where it forms catalytically active nanoparticles. Doping the B-site with reducible and catalytically highly active elements, offers the opportunity of tailoring properties of exsolution catalysts. Here, we present the synthesis of two novel perovskite catalysts Nd0.6Ca0.4FeO3-delta and Nd0.6Ca0.4Fe0.9Co0.1O3-delta with characterisation by (in situ) XRD, SEM/TEM and XPS, supported by theory (DFT+U). Fe nanoparticle formation was observed for Nd0.6Ca0.4FeO3-delta. In comparison, B site cobalt doping leads, already at lower reduction temperatures, to formation of finely dispersed Co nanoparticles on the surface. These novel perovskite-type catalysts are highly promising for applications in chemical energy conversion. First measurements revealed that exsolved Co nanoparticles significantly improve the catalytic activity for CO2 activation via reverse water gas shift reaction.