New Insights into the Structure of Nanoporous Carbons from NMR, Raman, and Pair Distribution Function Analysis
Humphreys, Elizabeth K
Griffin, John M
Chemistry of Materials
American Chemical Society
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Forse, A., Merlet, C., Allan, P., Humphreys, E. K., Griffin, J. M., Aslan, M., Zeiger, M., et al. (2015). New Insights into the Structure of Nanoporous Carbons from NMR, Raman, and Pair Distribution Function Analysis. Chemistry of Materials, 27 6848-6857. https://doi.org/10.1021/acs.chemmater.5b03216
The structural characterization of nanoporous carbons is a challenging task as they generally lack long-range order and can exhibit diverse local structures. Such characterization represents an important step toward understanding and improving the properties and functionality of porous carbons, yet few experimental techniques have been developed for this purpose. Here we demonstrate the application of nuclear magnetic resonance (NMR) spectroscopy and pair distribution function (PDF) analysis as new tools to probe the local structures of porous carbons, alongside more conventional Raman spectroscopy. Together, the PDFs and the Raman spectra allow the local chemical bonding to be probed, with the bonding becoming more ordered for carbide-derived carbons (CDCs) synthesized at higher temperatures. The ring currents induced in the NMR experiment (and thus the observed NMR chemical shifts for adsorbed species) are strongly dependent on the size of the aromatic carbon domains. We exploit this property and use computer simulations to show that the carbon domain size increases with the temperature used in the carbon synthesis. The techniques developed here are applicable to a wide range of porous carbons and offer new insights into the structures of CDCs (conventional and vacuum-annealed) and coconut shell-derived activated carbons.
A.C.F., J.M.G., C.M., P.K.A, E.K.H., and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (via the Supergen consortium, J.M.G.), and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. C.M. and P.K.A. acknowledge the School of the Physical Sciences of the University of Cambridge for funding through an Oppenheimer Research Fellowship. P.K.A. acknowledges a Junior Research Fellowship from Gonville and Caius College, Cambridge. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding. M.A., M.Z., and V.P. acknowledge funding from the German Federal Ministry for Research and Education (BMBF) in support of the nanoEES3D project (Award Number 03EK3013) as part of the strategic funding initiative energy storage framework and kindly thank Prof. Arzt (INM) for his continuing support. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Daan Frenkel for his contributions to this work and Boris Dyatkin for comments on the manuscript.
EPSRC (via Imperial College London) (EP/K002252/1)
External DOI: https://doi.org/10.1021/acs.chemmater.5b03216
This record's URL: https://www.repository.cam.ac.uk/handle/1810/254689