X-ray Raman scattering for bulk chemical and structural insight into green carbon

Luke J.R. Higgins; Christoph J. Sahle; Mahalingam Balasubramanian; Bhoopesh Mishra

doi:10.1039/d0cp00417k

X-ray Raman scattering for bulk chemical and structural insight into green carbon

Luke J.R. Higgins
, Christoph J. Sahle
, Mahalingam Balasubramanian
, Bhoopesh Mishra

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

X-ray Raman scattering (XRS) spectroscopy is an emerging inelastic scattering technique which uses hard X-rays to study the X-ray absorption edges of low-Z elements (e.g. C, N, O) in bulk. This study applies XRS spectroscopy to pyrolysis and hydrothermal carbons. These materials are thermochemically-produced carbon from renewable resources and represent a route for the sustainable production of carbon materials for many applications. Results confirm local structural differences between biomass-derived (Oak, Quercus Ilex) pyrolysis and hydrothermal carbon. In comparison with NEXAFS, XRS spectroscopy has been shown to be more resilient to experimental artefacts such as self-absorption. Density functional theory XRS calculations of potential structural sub-units confirm that hydrothermal carbon is a highly disordered carbon material formed principally of furan units linked by the α carbon atoms. Comparison of two pyrolysis temperatures (450 °C and 650 °C) shows the development of an increasingly condensed carbon structure. Based on our results, we have proposed a semi-quantitative route to pyrolysis condensation.

Original language	English
Pages (from-to)	18435-18446
Number of pages	12
Journal	Physical Chemistry Chemical Physics
Volume	22
Issue number	33
DOIs	https://doi.org/10.1039/d0cp00417k
State	Published - Sep 7 2020
Externally published	Yes

Funding

This work was supported by the Engineering and Physical Sciences Research Council [EP/L014912/1] as part of the UK Centre for Doctoral Training in Bioenergy at Leeds University. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. NEXAFS spectra were collected at beam-line I08 of the Diamond Light Source as part of proposal numbers SP19228-1 and MG23583-1. The authors are thankful for the technical support of the beamline scientists at I08: T. Araki, M. Kazemian and B. Kaulich. Assistance in wet chemical analyses by Mr Simon Lloyd and Dr Adrian Cunliffe is gratefully acknowledged. B. M. and L. J. R. H. thank Prof. Andrew B. Ross for helpful discussions.

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title = "X-ray Raman scattering for bulk chemical and structural insight into green carbon",

abstract = "X-ray Raman scattering (XRS) spectroscopy is an emerging inelastic scattering technique which uses hard X-rays to study the X-ray absorption edges of low-Z elements (e.g. C, N, O) in bulk. This study applies XRS spectroscopy to pyrolysis and hydrothermal carbons. These materials are thermochemically-produced carbon from renewable resources and represent a route for the sustainable production of carbon materials for many applications. Results confirm local structural differences between biomass-derived (Oak, Quercus Ilex) pyrolysis and hydrothermal carbon. In comparison with NEXAFS, XRS spectroscopy has been shown to be more resilient to experimental artefacts such as self-absorption. Density functional theory XRS calculations of potential structural sub-units confirm that hydrothermal carbon is a highly disordered carbon material formed principally of furan units linked by the α carbon atoms. Comparison of two pyrolysis temperatures (450 °C and 650 °C) shows the development of an increasingly condensed carbon structure. Based on our results, we have proposed a semi-quantitative route to pyrolysis condensation.",

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AU - Higgins, Luke J.R.

AU - Sahle, Christoph J.

AU - Balasubramanian, Mahalingam

AU - Mishra, Bhoopesh

N1 - Publisher Copyright: © the Owner Societies.

PY - 2020/9/7

Y1 - 2020/9/7

N2 - X-ray Raman scattering (XRS) spectroscopy is an emerging inelastic scattering technique which uses hard X-rays to study the X-ray absorption edges of low-Z elements (e.g. C, N, O) in bulk. This study applies XRS spectroscopy to pyrolysis and hydrothermal carbons. These materials are thermochemically-produced carbon from renewable resources and represent a route for the sustainable production of carbon materials for many applications. Results confirm local structural differences between biomass-derived (Oak, Quercus Ilex) pyrolysis and hydrothermal carbon. In comparison with NEXAFS, XRS spectroscopy has been shown to be more resilient to experimental artefacts such as self-absorption. Density functional theory XRS calculations of potential structural sub-units confirm that hydrothermal carbon is a highly disordered carbon material formed principally of furan units linked by the α carbon atoms. Comparison of two pyrolysis temperatures (450 °C and 650 °C) shows the development of an increasingly condensed carbon structure. Based on our results, we have proposed a semi-quantitative route to pyrolysis condensation.

AB - X-ray Raman scattering (XRS) spectroscopy is an emerging inelastic scattering technique which uses hard X-rays to study the X-ray absorption edges of low-Z elements (e.g. C, N, O) in bulk. This study applies XRS spectroscopy to pyrolysis and hydrothermal carbons. These materials are thermochemically-produced carbon from renewable resources and represent a route for the sustainable production of carbon materials for many applications. Results confirm local structural differences between biomass-derived (Oak, Quercus Ilex) pyrolysis and hydrothermal carbon. In comparison with NEXAFS, XRS spectroscopy has been shown to be more resilient to experimental artefacts such as self-absorption. Density functional theory XRS calculations of potential structural sub-units confirm that hydrothermal carbon is a highly disordered carbon material formed principally of furan units linked by the α carbon atoms. Comparison of two pyrolysis temperatures (450 °C and 650 °C) shows the development of an increasingly condensed carbon structure. Based on our results, we have proposed a semi-quantitative route to pyrolysis condensation.

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X-ray Raman scattering for bulk chemical and structural insight into green carbon

Abstract

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