XANES-Based Quantification of Carbon Functional Group Concentrations.

X-ray absorption spectroscopy in the soft X-ray range is used in many research fields to identify the nature of functional groups in organic compounds and carbon materials. However, the concentrations of these functional groups have so far remained difficult to quantify. Using X-ray absorption near edge structure (XANES) spectra of reference materials (polymers and compounds of known molecular composition), we established a correlation between measured optical densities and functional groups concentration. This methodology relies on an alternative method for normalization to the total amount of carbon and for deconvolution of the spectra. It allows precisely quantifying the N/C atomic ratio (σ1 = 0.02 atom %) as well as the concentration of [aromatic + olefinic] groups (σ1 = 3.7 atom %), [ketone + phenol + nitrile] groups (σ1 = 2.2 atom %), [aliphatic] groups (σ1 = 11.2 atom %) and [carboxylic] groups (σ1 = 7.4 atom %). We validated this quantification by comparing with nuclear magnetic resonance data obtained on pyrolized lignin samples. We also provide an easy-to-use python program automating XANES-based quantification of carbon functional group concentrations.