Facet Engineering of Nanoceria for Enzyme-Mimetic Catalysis

Nanomaterials with natural enzyme-mimicking characteristics have aroused extensive attention in various fields owing to their economical price, ease of large-scale production, and environmental resistance. Previous investigations have demonstrated that composition, size, shape, and surface modification play important roles in the enzymelike activity of nanomaterials; however, a fundamental understanding of the crystal facet effect, which determines surface energy or surface reactivity, has rarely been reported. Herein, fluorite cubic CeO2 nanocrystals with controllably exposed {111}, {100}, or {110} facets are fabricated as proof-of-concept candidates to study the facet effect on the peroxidase-mimetic activity. Both experiments and theoretical results show that {110}-dominated CeO2 nanorods (CeO2 NR) possess the highest peroxidase-mimetic activity due to the richest defects on their surfaces, which are beneficial to capture metal atoms to further enrich their artificial enzymatic functionality for cascade catalysis. For instance, the introduction of atomically dispersed Au on CeO2 NR surfaces not only enhances the peroxidase activity but also endows the obtained catalyst with glucose oxidase (GO(x))-mimicking activity, which realizes enzyme-free cascade reactions for glucose colorimetric detection. This work not only provides an understanding for crystal facet engineering of nanomaterials to enhance the catalytic activity but also opens up a new way for the design of biomimetic nanomaterials with multiple functions.

Automated summary

Nanomaterials with natural enzyme-mimicking characteristics have attracted great attention due to their low cost, easy large-scale production, and environmental resistance. This study investigates the effect of different crystal facets on the peroxidase-mimetic activity of fluorite cubic CeO2 nanocrystals. The results show that CeO2 nanorods dominated by the {110} facet exhibit the highest peroxidase-mimetic activity due to the abundance of surface defects, which enhance their artificial enzymatic functionality for cascade catalysis. Additionally, the introduction of atomic dispersed Au on the CeO2 nanorods enhances the peroxidase activity and enables glucose oxidase-mimicking activity for enzyme-free cascade reactions.