Enabling High Spectral Resolution of Liquid Mixtures in Porous Media by Antidiagonal Projections of Two-Dimensional H NMR COSY Spectra.

J Phys Chem Lett

Department of Chemical Engineering and Biotechnology , University of Cambridge, Philippa Fawcett Drive, West Cambridge Site , Cambridge CB3 0AS , U.K.

Published: October 2019

The noninvasive, in situ chemical identification of liquid mixtures confined in porous materials is experimentally challenging. NMR is chemically resolved and applicable to optically opaque systems but suffers from a significant loss in spectral resolution in the presence of the magnetic field inhomogeneities typical of porous media. In this work, we introduce a method of analysis of conventional two-dimensional (2D) H NMR correlation spectroscopy (COSY) spectra based on the extraction of 1D antidiagonal projections, which are free from line-broadening effects and can therefore be used for chemical species identification. Here, we show the application of the technique to the measurement of linear -alkanes where the cross-to-diagonal peak ratios are shown to follow a power-law curve as a function of the chain length. This calibration enables quantifying mixtures of linear hydrocarbons confined in any porous material independently of temperature or -molecular dynamics. Thus, this is a promising tool for quantitative chemical reaction monitoring studies in heterogeneous systems under operando experimental conditions.

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http://dx.doi.org/10.1021/acs.jpclett.9b02334DOI Listing

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