Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy

Meng Wang, Xin Ping Wu, Sujuan Zheng, Li Zhao, Lei Li, Li Shen, Yuxian Gao, Nianhua Xue, Xuefeng Guo, Weixin Huang, Zhehong Gan, Frédéric Blanc, Zhiwu Yu, Xiaokang Ke, Weiping Ding, Xue Qing Gong, Clare P. Grey, Luming Peng

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

Nanostructured oxides find multiple uses in a diverse range of applications including catalysis, energy storage, and environmental management, their higher surface areas, and, in some cases, electronic properties resulting in different physical properties from their bulk counterparts. Developing structure-property relations for these materials requires a determination of surface and subsurface structure. Although microscopy plays a critical role owing to the fact that the volumes sampled by such techniques may not be representative of the whole sample, complementary characterization methods are urgently required. We develop a simple nuclear magnetic resonance (NMR) strategy to detect the first few layers of a nanomaterial, demonstrating the approach with technologically relevant ceria nanoparticles. We show that the 17O resonances arising from the first to third surface layer oxygen ions, hydroxyl sites, and oxygen species near vacancies can be distinguished from the oxygen ions in the bulk, with higher-frequency 17O chemical shifts being observed for the lower coordinated surface sites. H2 17O can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. 17O NMR spectra of thermally treated nanosized ceria clearly show how different oxygen species interconvert at elevated temperature. Density functional theory calculations confirm the assignments and reveal a strong dependence of chemical shift on the nature of the surface. These results open up new strategies for characterizing nanostructured oxides and their applications.

Original languageEnglish (US)
Article numbere1400133
JournalScience Advances
Volume1
Issue number1
DOIs
StatePublished - Feb 1 2015

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Oxides
Nuclear magnetic resonance spectroscopy
Nanostructures
Oxygen
Cerium compounds
Chemical shift
Nuclear magnetic resonance
Storage management
Environmental management
Nanostructured materials
Electronic properties
Energy storage
Catalysis
Vacancies
Density functional theory
Microscopic examination
Physical properties
Ions
Nanoparticles
Temperature

Cite this

Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy. / Wang, Meng; Wu, Xin Ping; Zheng, Sujuan; Zhao, Li; Li, Lei; Shen, Li; Gao, Yuxian; Xue, Nianhua; Guo, Xuefeng; Huang, Weixin; Gan, Zhehong; Blanc, Frédéric; Yu, Zhiwu; Ke, Xiaokang; Ding, Weiping; Gong, Xue Qing; Grey, Clare P.; Peng, Luming.

In: Science Advances, Vol. 1, No. 1, e1400133, 01.02.2015.

Research output: Contribution to journalArticle

Wang, M, Wu, XP, Zheng, S, Zhao, L, Li, L, Shen, L, Gao, Y, Xue, N, Guo, X, Huang, W, Gan, Z, Blanc, F, Yu, Z, Ke, X, Ding, W, Gong, XQ, Grey, CP & Peng, L 2015, 'Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy', Science Advances, vol. 1, no. 1, e1400133. https://doi.org/10.1126/sciadv.1400133
Wang, Meng ; Wu, Xin Ping ; Zheng, Sujuan ; Zhao, Li ; Li, Lei ; Shen, Li ; Gao, Yuxian ; Xue, Nianhua ; Guo, Xuefeng ; Huang, Weixin ; Gan, Zhehong ; Blanc, Frédéric ; Yu, Zhiwu ; Ke, Xiaokang ; Ding, Weiping ; Gong, Xue Qing ; Grey, Clare P. ; Peng, Luming. / Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy. In: Science Advances. 2015 ; Vol. 1, No. 1.
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