CO 2 Hydrogenation Over Nanoceria-Supported Transition Metal Catalysts: Role of Ceria Morphology (Nanorods Versus Nanocubes) and Active Phase Nature (Co Versus Cu)

Nanomaterials (Basel). 2019 Dec 6;9(12):1739. doi: 10.3390/nano9121739.

Abstract

In this work we report on the combined impact of active phase nature (M: Co or Cu) and ceria nanoparticles support morphology (nanorods (NR) or nanocubes (NC)) on the physicochemical characteristics and CO2 hydrogenation performance of M/CeO2 composites at atmospheric pressure. It was found that CO2 conversion followed the order: Co/CeO2 > Cu/CeO2 > CeO2, independently of the support morphology. Co/CeO2 catalysts demonstrated the highest CO2 conversion (92% at 450 °C), accompanied by 93% CH4 selectivity. On the other hand, Cu/CeO2 samples were very selective for CO production, exhibiting 52% CO2 conversion and 95% CO selectivity at 380 °C. The results obtained in a wide range of H2:CO2 ratios (1-9) and temperatures (200-500 °C) are reaching in both cases the corresponding thermodynamic equilibrium conversions, revealing the superiority of Co- and Cu-based samples in methanation and reverse water-gas shift (rWGS) reactions, respectively. Moreover, samples supported on ceria nanocubes exhibited higher specific activity (µmol CO2·m-2·s-1) compared to samples of rod-like shape, disclosing the significant role of support morphology, besides that of metal nature (Co or Cu). Results are interpreted on the basis of different textural and redox properties of as-prepared samples in conjunction to the different impact of metal entity (Co or Cu) on CO2 hydrogenation process.

Keywords: CO2 hydrogenation; cobalt; copper; methanation (Sabatier) reaction; nanoceria; reverse water-gas shift reaction.