Atomically-precise Colloidal Nanoparticles of Cerium Dioxide

Overview

Journal Nat Commun

Specialty Biology

Date 2017 Nov 14

PMID 29129933

Citations 9

Authors

Kylie J Mitchell

Khalil A Abboud

George Christou

Affiliations

Soon will be listed here.

Abstract

Synthesis of truly monodisperse nanoparticles and their structural characterization to atomic precision are important challenges in nanoscience. Success has recently been achieved for metal nanoparticles, particularly Au, with diameters up to 3 nm, the size regime referred to as nanoclusters. In contrast, families of atomically precise metal oxide nanoparticles are currently lacking, but would have a major impact since metal oxides are of widespread importance for their magnetic, catalytic and other properties. One such material is colloidal CeO (ceria), whose applications include catalysis, new energy technologies, photochemistry, and medicine, among others. Here we report a family of atomically precise ceria nanoclusters with ultra-small dimensions up to ~1.6 nm (~100 core atoms). X-ray crystallography confirms they have the fluorite structure of bulk CeO, and identifies surface features, H binding sites, Ce locations, and O vacancies on (100) facets. Monodisperse ceria nanoclusters now permit investigation of their properties as a function of exact size, surface morphology, and Ce:Ce composition.

Citing Articles

Ligand Strategies for Regulating Atomically Precise CeO Nanoparticles: From Structure to Property.

Du P, Li S, Xu Q, He A, Yuan W, Qu X Molecules. 2025; 30(4).

PMID: 40005157 PMC: 11858138. DOI: 10.3390/molecules30040846.

Two mixed-valent cerium oxo clusters: synthesis, structure, and self-assembly.

Gao Y, Zhang Y, Han Z, Wang C, Zhang L, Qiu J Front Chem. 2024; 12:1507834.

PMID: 39686981 PMC: 11646716. DOI: 10.3389/fchem.2024.1507834.

Globular pattern formation of hierarchical ceria nanoarchitectures.

Aoyagi N, Motokawa R, Okumura M, Ueda Y, Saito T, Nishitsuji S Commun Chem. 2024; 7(1):128.

PMID: 38867063 PMC: 11549420. DOI: 10.1038/s42004-024-01199-y.

Impact of Surface Ligand Identity and Density on the Thermodynamics of H Atom Uptake at Polyoxovanadate-Alkoxide Surfaces.

Proe K, Towarnicky A, Fertig A, Lu Z, Mpourmpakis G, Matson E Inorg Chem. 2024; 63(16):7206-7217.

PMID: 38592922 PMC: 11040723. DOI: 10.1021/acs.inorgchem.3c04435.

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate.

Blanes-Diaz A, Shohel M, Rice N, Piedmonte I, McDonald M, Jorabchi K Inorg Chem. 2023; 63(21):9406-9417.

PMID: 37792316 PMC: 11134509. DOI: 10.1021/acs.inorgchem.3c02141.

References

Ju-Nam Y, Lead J . Manufactured nanoparticles: an overview of their chemistry, interactions and potential environmental implications. Sci Total Environ. 2008; 400(1-3):396-414. DOI: 10.1016/j.scitotenv.2008.06.042. View

Jin R, Zeng C, Zhou M, Chen Y . Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities. Chem Rev. 2016; 116(18):10346-413. DOI: 10.1021/acs.chemrev.5b00703. View

Mathey L, Paul M, Coperet C, Tsurugi H, Mashima K . Cerium(IV) Hexanuclear Clusters from Cerium(III) Precursors: Molecular Models for Oxidative Growth of Ceria Nanoparticles. Chemistry. 2015; 21(38):13454-61. DOI: 10.1002/chem.201501731. View

Zhang J, Kumagai H, Yamamura K, Ohara S, Takami S, Morikawa A . Extra-low-temperature oxygen storage capacity of CeO2 nanocrystals with cubic facets. Nano Lett. 2011; 11(2):361-4. DOI: 10.1021/nl102738n. View

Zherebetskyy D, Scheele M, Zhang Y, Bronstein N, Thompson C, Britt D . Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid. Science. 2014; 344(6190):1380-4. DOI: 10.1126/science.1252727. View

Lee S, Song W, Cho M, Puppala H, Nguyen P, Zhu H . Antioxidant properties of cerium oxide nanocrystals as a function of nanocrystal diameter and surface coating. ACS Nano. 2013; 7(11):9693-703. DOI: 10.1021/nn4026806. View

Lawrence N, Brewer J, Wang L, Wu T, Wells-Kingsbury J, Ihrig M . Defect engineering in cubic cerium oxide nanostructures for catalytic oxidation. Nano Lett. 2011; 11(7):2666-71. DOI: 10.1021/nl200722z. View

Corma A, Atienzar P, Garcia H, Chane-Ching J . Hierarchically mesostructured doped CeO2 with potential for solar-cell use. Nat Mater. 2004; 3(6):394-7. DOI: 10.1038/nmat1129. View

Jadzinsky P, Calero G, Ackerson C, Bushnell D, Kornberg R . Structure of a thiol monolayer-protected gold nanoparticle at 1.1 A resolution. Science. 2007; 318(5849):430-3. DOI: 10.1126/science.1148624. View

10.

Wang Q, Zhao B, Li G, Zhou R . Application of rare earth modified Zr-based ceria-zirconia solid solution in three-way catalyst for automotive emission control. Environ Sci Technol. 2010; 44(10):3870-5. DOI: 10.1021/es903957e. View

11.

Baer D, Engelhard M, Johnson G, Laskin J, Lai J, Mueller K . Surface characterization of nanomaterials and nanoparticles: Important needs and challenging opportunities. J Vac Sci Technol A. 2014; 31(5):50820. PMC: 3869349. DOI: 10.1116/1.4818423. View

12.

Canevali C, Mattoni M, Morazzoni F, Scotti R, Casu M, Musinu A . Stability of luminescent trivalent cerium in silica host glasses modified by boron and phosphorus. J Am Chem Soc. 2005; 127(42):14681-91. DOI: 10.1021/ja052502o. View

13.

Nilius N, Kozlov S, Jerratsch J, Baron M, Shao X, Vines F . Formation of one-dimensional electronic states along the step edges of CeO₂(111). ACS Nano. 2011; 6(2):1126-33. DOI: 10.1021/nn2036472. View

14.

Pirmohamed T, Dowding J, Singh S, Wasserman B, Heckert E, Karakoti A . Nanoceria exhibit redox state-dependent catalase mimetic activity. Chem Commun (Camb). 2010; 46(16):2736-8. PMC: 3038687. DOI: 10.1039/b922024k. View

15.

Karakoti A, Monteiro-Riviere N, Aggarwal R, Davis J, Narayan R, Self W . Nanoceria as Antioxidant: Synthesis and Biomedical Applications. JOM (1989). 2010; 60(3):33-37. PMC: 2898180. DOI: 10.1007/s11837-008-0029-8. View

16.

Carrettin S, Concepcion P, Corma A, Lopez Nieto J, Puntes V . Nanocrystalline CeO2 increases the activity of Au for CO oxidation by two orders of magnitude. Angew Chem Int Ed Engl. 2004; 43(19):2538-40. DOI: 10.1002/anie.200353570. View

17.

Das S, Dowding J, Klump K, McGinnis J, Self W, Seal S . Cerium oxide nanoparticles: applications and prospects in nanomedicine. Nanomedicine (Lond). 2013; 8(9):1483-508. DOI: 10.2217/nnm.13.133. View

18.

Aubriet F, Gaumet J, de Jong W, Groenewold G, Gianotto A, McIlwain M . Cerium oxyhydroxide clusters: formation, structure, and reactivity. J Phys Chem A. 2009; 113(22):6239-52. DOI: 10.1021/jp9015432. View

19.

Chen J, Patil S, Seal S, McGinnis J . Rare earth nanoparticles prevent retinal degeneration induced by intracellular peroxides. Nat Nanotechnol. 2008; 1(2):142-50. DOI: 10.1038/nnano.2006.91. View

20.

Malaestean I, Ellern A, Baca S, Kogerler P . Cerium oxide nanoclusters: commensurate with concepts of polyoxometalate chemistry?. Chem Commun (Camb). 2011; 48(10):1499-501. DOI: 10.1039/c1cc14725k. View