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Morphological dependency of antioxidant enzyme-like activities of nanoceria in energy-band structure aspect

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Abstract

Controlling the morphology of ceria nanoparticles (CeNPs) has been proven an effective approach to mimic the activities of antioxidant enzymes including catalase (CAT) and superoxide dismutase (SOD). However, the mechanism of the morphology-dependent enzyme-like activities was elusive. Energy-band structure tailoring of NPs through morphologies closely correlates with their catalytic activities. Herein, three kinds of CeNPs with octahedron, cube and rod morphologies were synthesized. Octahedron-CeO2 with exposed {111} facets, cube-shaped CeO2 with {100} facets and rod-shaped CeO2 with {110} and {111} facets were observed. Due to the lower formation energy of oxygen vacancy (VO) for {110} facets, higher VO content was detected for rod-CeO2, which directly correlated with the energy level of surface defect states (ESDS). The ESDS for rod-CeO2 (0.86 V) roughly lied in the middle point of E0 (H2O2, H+/H2O) and E0(O2, H+/H2O2) (0.83 V), which resulted in higher CAT-like activity. Likewise, the ESDS of octahedron-CeO2 (0.48 V) approximately located at the midpoint of two half-reaction potentials in SOD catalytic cycle (0.39 V) which was agreement with its enhanced SOD-like activity. Overall, regulating ESDS towards the midpoint of the half-reaction potentials becomes a feasible approach to achieve enhanced catalytic efficiency.

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Data availability

The datasets generated during the current study are not publicly available due to the rules of the institute but are available from the corresponding author on reasonable request.

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Funding

This work was supported by the National Natural Science Foundation of China (Grant No. 51971236, 51502328), the Shanghai Rising-Star Program (Grant No. 21QA1410400), the Science and Technology Commission of Shanghai Municipality (Grant No. 21S31901200), and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Grant No. 2020254).

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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Zhicheng Shi, Jieping Li and Yi Ding. The first draft of the manuscript was written by Zhicheng Shi and Kai Li, all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Kai Li or Xuebin Zheng.

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Shi, Z., Li, K., Li, J. et al. Morphological dependency of antioxidant enzyme-like activities of nanoceria in energy-band structure aspect. J Nanopart Res 25, 200 (2023). https://doi.org/10.1007/s11051-023-05848-6

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