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Abstract
The rational design and fabrication of highly-active and cost-efficient catalytic materials constitutes the main research pillar in catalysis field. In this context, the fine-tuning of size and shape at the nanometer scale can exert an intense impact not only on the inherent reactivity of catalyst’s counterparts but also on their interfacial interactions; it can also opening up new horizons for the development of highly active and robust materials. The present critical review, focusing mainly on our recent advances on the topic, aims to highlight the pivotal role of shape engineering in catalysis, exemplified by noble metal-free, CeO2-based transition metal catalysts (TMs/CeO2). The underlying mechanism of facet-dependent reactivity is initially discussed. The main implications of ceria nanoparticles’ shape engineering (rods, cubes, and polyhedra) in catalysis are next discussed, on the ground of some of the most pertinent heterogeneous reactions, such as CO2 hydrogenation, CO oxidation, and N2O decomposition. It is clearly revealed that shape functionalization can remarkably affect the intrinsic features and in turn the reactivity of ceria nanoparticles. More importantly, by combining ceria nanoparticles (CeO2 NPs) of specific architecture with various transition metals (e.g., Cu, Fe, Co, and Ni) remarkably active multifunctional composites can be obtained due mainly to the synergistic metalceria interactions. From the practical point of view, novel catalyst formulations with similar or even superior reactivity to that of noble metals can be obtained by co-adjusting the shape and composition of mixed oxides, such as Cu/ceria nanorods for CO oxidation and Ni/ceria nanorods for CO2 hydrogenation. The conclusions derived could provide the design principles of earth-abundant metal oxide catalysts for various real-life environmental and energy applications.
Highlights
Catalysis has gained ongoing attention from academic and industrial community, since it is massively involved in numerous energy and environmental processes, including, among others, the manufacture of value-added fuels and chemicals, hydrocarbons processing, fuel cell applications, photocatalytic degradation, abatement of hazardous substances, etc
These results clearly showed that the rod-shaped ceria nanoparticles species, which is of paramount importance in several reaction processes obeying a possess the highest population of weakly bound labile oxygen species
The effect of ceria nanoparticles geometry on the catalytic behavior of transition metals (TMs)/CeO2 oxides is demonstrated on the grounds of indicative oxidation/reduction reactions, such as CO oxidation, nitrous oxide (N2 O)
Summary
Catalysis has gained ongoing attention from academic and industrial community, since it is massively involved in numerous energy and environmental processes, including, among others, the manufacture of value-added fuels and chemicals, hydrocarbons processing, fuel cell applications, photocatalytic degradation, abatement of hazardous substances, etc. The combination of reducible oxides (e.g., CeO2 ) with TMs (e.g., Fe, Co, Ni, and Cu) could offer novel catalyst formulations with exceptional properties, arising mainly from the multifaceted electronic and geometric interactions amongst the different counterparts [14,16,25,27,41,49,50,51,52,53,54,59,60] In this respect, it was recently appraised on account of both experimental and theoretical studies that various interconnected phenomena could be at work at metal-support interface, which in turn exert a profound influence on the catalytic activity, including the following [14,25,27,41,59,60,61]: i. Energy formation anionic vacancies; energy formation of anionicofvacancies; redox features redox features work function; work function; redox characteristics redox characteristics redox properties; structuralstructural defects; defects; redox properties; electronicelectronic environment environment
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