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.
Similar content being viewed by others
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.
References
Wei M, Lee J, Xia F, Lin PH, Hu X, Li FY, Ling DS (2021) Chemical design of nanozymes for biomedical applications. Acta Biomater 126:15–30
Celardo I, Pedersen JZ, Traversa E, Ghibelli L (2011) Pharmacological potential of cerium oxide nanoparticles. Nanoscale 3:1411–1420
Xu C, Qu XG (2014) Cerium oxide nanoparticle: a remarkably versatile rare earth nanomaterial for biological applications. Npg Asia Materials 6:e90
Xiao G, Li HT, Zhao YL, Wei HL, Li JY, Su HJ (2022) Nanoceria-Based Artificial Nanozymes: Review of Materials and Applications. Acs Applied Nano Materials 5:14147–14170
Tan ZC, Wang Y, Zhang J, Zhang Z, Wong SSM, Zhang SQ, Sun HY, Yung KKL, Peng YK (2022) Shape Regulation of CeO2 Nanozymes Boosts Reaction Specificity and Activity. Eur J Inorg Chem 2022:e202200202
Li X, Qi ML, Sun XL, Weir MD, Tay FR, Oates TW, Dong B, Zhou YM, Wang L, Xu HHK (2019) Surface treatments on titanium implants via nanostructured ceria for antibacterial and anti-inflammatory capabilities. Acta Biomater 94:627–643
Fu YF, Kolanthai E, Neal CJ, Kumar U, Zgheib C, Liechty KW, Seal S (2022) Engineered Faceted Cerium Oxide Nanoparticles for Therapeutic miRNA Delivery. Nanomaterials-Basel 12:4389
Naganuma T (2017) Shape design of cerium oxide nanoparticles for enhancement of enzyme mimetic activity in therapeutic applications. Nano Res 10:199–217
Yang YS, Mao Z, Huang WJ, Liu LH, Li JL, Li JL, Wu QZ (2016) Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets. Sci Rep-Uk 6:35344
Na-Phattalung S, Smith MF, Kim K, Du MH, Wei SH, Zhang SB, Limpijumnong S (2006) First-principles study of native defects in anatase TiO2. Phys Rev B 73:125205
Ma YY, Gao W, Zhang ZY, Zhang S, Tian ZM, Liu YX, Ho JC, Qu YQ (2018) Regulating the surface of nanoceria and its applications in heterogeneous catalysis. Surf Sci Rep 73:1–36
Vernekar AA, Das T, Mugesh G (2016) Vacancy-Engineered Nanoceria: Enzyme Mimetic Hotspots for the Degradation of Nerve Agents. Angew Chem Int Edit 55:1412–1416
Ma BF, Han JY, Zhang K, Jiang QK, Sui ZG, Zhang ZX, Zhao BF, Liang Z, Zhang LH, Zhang YK (2022) Targeted killing of tumor cells based on isoelectric point suitable nanoceria-rod with high oxygen vacancies. J Mater Chem B 10:1410–1417
Paier J, Penschke C, Sauer J (2013) Oxygen Defects and Surface Chemistry of Ceria: Quantum Chemical Studies Compared to Experiment. Chem Rev 113:3949–3985
Wang ZZ, Shen XM, Gao XF, Zhao YL (2019) Simultaneous enzyme mimicking and chemical reduction mechanisms for nanoceria as a bio-antioxidant: a catalytic model bridging computations and experiments for nanozymes. Nanoscale 11:13289–13299
Bixenmann L, He JY, Liang MM, Tremel W (2018) Functional Superoxide Dismutase Mimics Become Diverse: From Simple Compounds on Prebiotic Earth to Nanozymes. Progress Biochem Biophys 45:148–169
Sheng YW, Abreu IA, Cabelli DE, Maroney MJ, Miller AF, Teixeira M, Valentine JS (2014) Superoxide Dismutases and Superoxide Reductases. Chem Rev 114:3854–3918
Shao DD, Li K, Hu T, Wang SJ, Xu HW, Zhang SB, Liu SW, Xie YT, Zheng XB (2021) Titania nanotube array supported nanoceria with redox cycling stability ameliorates oxidative stress-inhibited osteogenesis. Chem Eng J 415:128913
Bi H, Zhang L-X, Xing Y, Zhang P, Chen J-J, Yin J, Bie L-J (2021) Morphology-controlled synthesis of CeO2 nanocrystals and their facet-dependent gas sensing properties. Sens Actuators, B Chem 330:129374
Shao D, Li K, You M, Liu S, Hu T, Huang L, Xie Y, Zheng X (2020) Macrophage polarization by plasma sprayed ceria coatings on titanium-based implants: Cerium valence state matters. Appl Surf Sci 504:144070
Zhao EW, Xin Y, Hagelin-Weaver HE, Bowers CR (2016) Semihydrogenation of Propyne over Cerium Oxide Nanorods, Nanocubes, and Nano-Octahedra: Facet-Dependent Parahydrogen-Induced Polarization. ChemCatChem 8:2197–2201
Manto MJ, Xie P, Wang C (2017) Catalytic Dephosphorylation Using Ceria Nanocrystals. ACS Catal 7:1931–1938
Jiang D, Wang W, Zhang L, Zheng Y, Wang Z (2015) Insights into the Surface-Defect Dependence of Photoreactivity over CeO2 Nanocrystals with Well-Defined Crystal Facets. ACS Catal 5:4851–4858
Li K, Xie Y, You M, Huang L, Zheng X (2016) Plasma sprayed cerium oxide coating inhibits H2O2-induced oxidative stress and supports cell viability. J Mater Sci Mater Med 27:100
Saifi MA, Seal S, Godugu C (2021) Nanoceria, the versatile nanoparticles: Promising biomedical applications. J Control Release 338:164–189
Li J, Li K, Shao D, Ding Y, Huang L, Zheng X (2023) The synergistic antioxidant effect of polydopamine coating with amino-functionalized graphene quantum dots on osteoblast protection against oxidative stress. Appl Surf Sci 613:155950
Gogoi A, Navgire M, Sarma KC, Gogoi P (2017) Fe 3 O 4 -CeO 2 metal oxide nanocomposite as a Fenton-like heterogeneous catalyst for degradation of catechol. Chem Eng J 311:153–162
Li T, Yin J, Sun D, Zhang M, Pang H, Xu L, Zhang Y, Yang J, Tang Y, Xue J (2022) Manipulation of Mott-Schottky Ni/CeO(2) Heterojunctions into N-Doped Carbon Nanofibers for High-Efficiency Electrochemical Water Splitting. Small 18:e2106592
Huang Y-C, Wu S-H, Hsiao C-H, Lee A-T, Huang MH (2020) Mild Synthesis of Size-Tunable CeO2 Octahedra for Band Gap Variation. Chem Mater 32:2631–2638
Ma H, Liu Z, Koshy P, Sorrell CC, Hart JN (2022) Density Functional Theory Investigation of the Biocatalytic Mechanisms of pH-Driven Biomimetic Behavior in CeO(2). ACS Appl Mater Interfaces 14:11937–11949
Wang Z, Wu J, Zheng JJ, Shen X, Yan L, Wei H, Gao X, Zhao Y (2021) Accelerated discovery of superoxide-dismutase nanozymes via high-throughput computational screening. Nat Commun 12:6866
Shen XM, Wang ZZ, Gao XJ, Gao XF (2023) Reaction mechanisms and kinetics of nanozymes: insights from theory and computation. Adv Mater 2211151
Pirmohamed T, Dowding JM, Singh S, Wasserman B, Heckert E, Karakoti AS, King JES, Seal S, Self WT (2010) Nanoceria exhibit redox state-dependent catalase mimetic activity. Chem Commun 46:2736–2738
Li YY, He X, Yin JJ, Ma YH, Zhang P, Li JY, Ding YY, Zhang J, Zhao YL, Chai ZF, Zhang ZY (2015) Acquired Superoxide-Scavenging Ability of Ceria Nanoparticles. Angew Chem Int Edit 54:1832–1835
Celardo I, De Nicola M, Mandoli C, Pedersen JZ, Traversa E, Ghibelli L (2011) Ce3+ Ions Determine Redox-Dependent Anti-apoptotic Effect of Cerium Oxide Nanoparticles. ACS Nano 5:4537–4549
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).
Author information
Authors and Affiliations
Contributions
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.
Corresponding authors
Ethics declarations
Competing interests
The authors declare they have no financial interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
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
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-023-05848-6