Ce(III) formate-derived hierarchical cerium oxide particles with icosahedral symmetry-based architectures: Effect of third level of structural hierarchy in soot and propane oxidation

Abstract

The article investigates the role of architecture of complex hierarchically structured ceria and gadolinium doped ceria particles in soot combustion (solid-solid reaction) and propane oxidation (gas-solid reaction). Synthesis of hierarchical ceria mesostructures showing icosahedral symmetry-based architecture has been presented for the first time. Carefully choosing synthetic conditions allows to obtain particles with intended morphology of dodecahedron, rhombic hexecontahedron, great stellated dodecahedron, fractal-like branched great stellated dodecahedron and great dodecahemicosacron polyhedra. Twinning-based multiple branching of Ce(III) formate crystals by {101} twin orientation relation was proposed as a driving mechanism for the formation of macroparticles architecture that has been confirmed by the construction of macroparticle models using the identified twinning law. In the catalytic studies, the third level of the material organizational structure referring to shape of hierarchical macroparticles was chosen as a tested variable, while other architecture-related properties were controlled to be alike. In result, the shape of hierarchical particles plays a vital role in the catalytic soot oxidation, and architecture modulation allows the catalytic properties of the material to be enhanced through increasing the geometrical fit between ceria and soot particles. The best sample lowers temperature of half oxidation by 143 °C as compared to non-hierarchically organized ceria nanocrystals. The shape of hierarchical particles does not play leading role in gas-solid propane oxidation, but introduction of Gd dopant diversifies catalytic activity. The architecture of the particles may serve as a modifier of the catalytic activity through grain boundary engineering of gadolinium doped ceria.