文献类型：期刊文献

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

作者：Wang, Meng[1];Wu, Xin-Ping[2,3];Zheng, Sujuan[1];Zhao, Li[1];Li, Lei[1];Shen, Li[1];Gao, Yuxian[4];Xue, Nianhua[1];Guo, Xuefeng[1];Huang, Weixin[4];Gan, Zhehong[5];Blanc, Frederic[6,7,8];Yu, Zhiwu[9];Ke, Xiaokang[1];Ding, Weiping[1];Gong, Xue-Qing[2,3];Grey, Clare P.[6,10];Peng, Luming[1]

机构：[1]Nanjing Univ, Sch Chem & Chem Engn, Key Lab Mesoscop Chem, Minist Educ, Nanjing 210093, Jiangsu, Peoples R China;[2]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[4]Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Anhui, Peoples R China;[5]Natl High Magnet Field Lab, Tallahassee, FL 32310 USA;[6]Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England;[7]Univ Liverpool, Dept Chem, Liverpool L69 7ZD, Merseyside, England;[8]Univ Liverpool, Stephenson Inst Renewable Energy, Liverpool L69 7ZD, Merseyside, England;[9]Chinese Acad Sci, High Magnet Field Lab, Hefei 230031, Anhui, Peoples R China;[10]SUNY Stony Brook, Dept Chem, Stony Brook, NY 11974 USA

年份：2015

卷号：1

期号：1

外文期刊名：SCIENCE ADVANCES

收录：;EI(收录号：20180804816338);WOS:【SCI-EXPANDED(收录号:WOS:000216590300007)】；

基金：This work was supported by the National Basic Research Program of China (2013CB934800 and 2011CB808505), the National Natural Science Foundation of China (NSFC) (20903056, 21222302, 21322307, and 21073083), NSFC-Royal Society Joint Program (21111130201), Program for New Century Excellent Talents in University (NCET-10-0483), the Fundamental Research Funds for the Central Universities (1124020512), and National Science Fund for Talent Training in Basic Science (J1103310). The ECUST group also thanks the Shanghai Rising-Star Program (12QH1400700) and National Super Computing Centre in Jinan for computing time. F.B. thanks the EU Marie Curie actions for an International Incoming fellowship 2011-2013 (grant no. 275212), Clare Hall, University of Cambridge, UK, for a Research fellowship and the University of Liverpool, UK, for funding. C.P.G. thanks the European Research Council for an Advanced Fellowship. This work was also supported by a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

语种：英文

外文关键词：Cerium oxide - Density functional theory - Nuclear magnetic resonance spectroscopy - Environmental management - Nanomagnetics - Nanostructures - Oxygen vacancies - Electronic properties

摘要：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 O-17 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 O-17 chemical shifts being observed for the lower coordinated surface sites. (H2O)-O-17 can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. O-17 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.