NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional 13C Solid-State NMR and ab Initio Chemical Shift Calculations

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• 作者：Leah B. Casabianca ; Medhat A. Shaibat ; Weiwei W. Cai ; Sungjin Park ; Richard Piner ; Rodney S. Ruoff ; Yoshitaka Ishii
• 刊名：Journal of the American Chemical Society
• 出版年：2010
• 出版时间：April 28, 2010
• 年：2010
• 卷：132
• 期：16
• 页码：5672-5676
• 全文大小：252K
• 年卷期：v.132,no.16(April 28, 2010)
• ISSN：1520-5126

文摘

Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D ¹³C double-quantum/single-quantum correlation SSNMR spectrum of ¹³C-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf−Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp², 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). ¹³C chemical shift anisotropy (CSA) patterns measured by a 2D ¹³C CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems.