Highly catalytically active CeO2−x-based heterojunction nanostructures with mixed micro/meso-porous architectures

Abstract

The architectural design of nanocatalysts plays a critical role in the achievement of high densities of active sites but current technologies are hindered by process complexity and limited scaleability. The present work introduces a rapid, flexible, and template-free method to synthesize three-dimensional (3D), mesoporous, CeO_2−x nanostructures comprised of extremely thin holey two-dimensional (2D) nanosheets of centimetre-scale. The process leverages the controlled conversion of stacked nanosheets of a newly developed Ce-based coordination polymer into a range of stable oxide morphologies controllably differentiated by the oxidation kinetics. The resultant polycrystalline, hybrid, 2D–3D CeO_2−x exhibits high densities of defects and surface area as high as 251 m² g⁻¹, which yield an outstanding CO conversion performance (T_90% = 148 °C) for all oxides. Modification by the creation of heterojunction nanostructures using transition metal oxides (TMOs) results in further improvements in performance (T_90% = 88 °C), which are interpreted in terms of the active sites associated with the TMOs that are identified through structural analyses and density functional theory (DFT) simulations. This unparalleled catalytic performance for CO conversion is possible through the ultra-high surface areas, defect densities, and pore volumes. This technology offers the capacity to establish efficient pathways to engineer nanostructures of advanced functionalities for catalysis.