Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy

Holden, William M.; Seidler, Gerald T.; Cheah, Singfoong

doi:10.1021/acs.jpca.8b02816

Title: Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy

Journal Article · 21 May 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.8b02816 · OSTI ID:1454908

Holden, William M. ^[1]; Seidler, Gerald T. ^[1]; Cheah, Singfoong ^[2]

Univ. of Washington, Seattle, WA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1454908

Report Number(s):: NREL/JA-5100-71758

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 122, Issue 23; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 20 works

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