Distinguishing faceted oxide nanocrystals with 17O solid-state NMR spectroscopy

Yuhong Li; Xin-Ping Wu; Ningxin Jiang; Ming Lin; Li Shen; Haicheng Sun; Yongzheng Wang; Meng Wang; Xiaokang Ke; Zhiwu Yu; Fei Gao; Lin Dong; Xuefeng Guo; Wenhua Hou; Weiping Ding; Xue-Qing Gong; Clare P Grey; Luming Peng

doi:10.1038/s41467-017-00603-7

Distinguishing faceted oxide nanocrystals with ¹⁷O solid-state NMR spectroscopy

Nat Commun. 2017 Sep 18;8(1):581. doi: 10.1038/s41467-017-00603-7.

Authors

Yuhong Li^{1

2}, Xin-Ping Wu³, Ningxin Jiang¹, Ming Lin⁴, Li Shen¹, Haicheng Sun¹, Yongzheng Wang¹, Meng Wang¹, Xiaokang Ke¹, Zhiwu Yu⁵, Fei Gao^{1

6}, Lin Dong^{1

6}, Xuefeng Guo¹, Wenhua Hou¹, Weiping Ding¹, Xue-Qing Gong⁷, Clare P Grey^{8

9}, Luming Peng¹⁰

Affiliations

¹ Key Laboratory of Mesoscopic Chemistry of Ministry of Education and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
² Jiangsu Laboratory of Advanced Functional Materials, School of Chemistry and Material Engineering, Changshu Institute of Technology, Changshu, 215500, China.
³ Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China.
⁴ Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, #08-03, Innovis, Singapore, 138634, Republic of Singapore.
⁵ High Magnetic Field Laboratory of the Chinese Academy of Sciences, Hefei, 230031, China.
⁶ Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing, 210093, China.
⁷ Key Laboratory for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, China. xgong@ecust.edu.cn.
⁸ Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
⁹ Department of Chemistry, Stony Brook University, Stony Brook, NY, 11974-3400, USA.
¹⁰ Key Laboratory of Mesoscopic Chemistry of Ministry of Education and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China. luming@nju.edu.cn.

Abstract

Facet engineering of oxide nanocrystals represents a powerful method for generating diverse properties for practical and innovative applications. Therefore, it is crucial to determine the nature of the exposed facets of oxides in order to develop the facet/morphology-property relationships and rationally design nanostructures with desired properties. Despite the extensive applications of electron microscopy for visualizing the facet structure of nanocrystals, the volumes sampled by such techniques are very small and may not be representative of the whole sample. Here, we develop a convenient ¹⁷O nuclear magnetic resonance (NMR) strategy to distinguish oxide nanocrystals exposing different facets. In combination with density functional theory calculations, we show that the oxygen ions on the exposed (001) and (101) facets of anatase titania nanocrystals have distinct ¹⁷O NMR shifts, which are sensitive to surface reconstruction and the nature of the steps on the surface. The results presented here open up methods for characterizing faceted nanocrystalline oxides and related materials.The exposed facets of oxide nanocrystals are key to their properties. Here, the authors use ¹⁷O solid-state NMR spectroscopy to discriminate between oxygen species on different facets of anatase titania nanocrystals, providing compelling evidence for the value of NMR spectroscopy in characterizing faceted oxides.

Publication types

Research Support, Non-U.S. Gov't