Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts
Abstract
The evolution in local structure and electronic properties of cobalt was investigated during in situ sulfurization. Using a combination of 1s X-ray absorption (XAS) and 1s3p resonant inelastic X-ray scattering (RIXS), the valence, coordination and symmetry of cobalt ions were tracked in two cobalt-promoted molybdenum oxide precursors of the hydrodesulfurization catalyst system, namely Co–Mo/Al2O3 and Co–Ni–Mo/Al2O3. Extended X-ray absorption fine structure shows that the Co—O bonds were replaced with Co—S bonds as a function of reaction temperature. The cobalt K pre-edge intensity shows that the symmetry of cobalt was modified from Co3+ Oh and Co2+ Oh to a Co2+ ion where the inversion symmetry is broken, in agreement with a square-pyramidal site. The 1s3p RIXS data revealed the presence of an intermediate cobalt oxy-sulfide species. This species was not detected from XAS and was determined from the increased information obtained from the 1s3p RIXS data. The cobalt XAS and RIXS data show that nickel has a significant influence on the formation of the cobalt oxy-sulfide intermediate species prior to achieving the fully sulfided state at T > 400°C.
- Authors:
-
[2];
[3];
[2];
[2]
- Utrecht Univ., Utrecht (The Netherlands); Max Planck Institute for Chemical Energy Conversion, Mulheim (Germany)
- Utrecht Univ., Utrecht (The Netherlands)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Utrecht Univ., Utrecht (The Netherlands); European Synchrotron Radiation Facility (ESRF), Grenoble (France)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1528874
- Grant/Contract Number:
- AC02-76SF00515; NANO-11507
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Synchrotron Radiation (Online)
- Additional Journal Information:
- Journal Name: Journal of Synchrotron Radiation (Online); Journal Volume: 26; Journal Issue: 3; Journal ID: ISSN 1600-5775
- Publisher:
- International Union of Crystallography
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; heterogeneous catalysis; hydrodesulfurization (HDS) catalyst systems; CoMoS structure; hydrotreating catalysts; X-ray absorption spectroscopy; resonant inelastic X-ray scattering (RIXS)
Citation Formats
al Samarai, Mustafa, van Oversteeg, Christa H. M., Delgado-Jaime, Mario Ulises, Weng, Tsu -Chien, Sokaras, Dimosthenis, Liu, Boyang, van der Linden, Marte, van der Eerden, Ad M. J., Vogt, Eelco T. C., Weckhuysen, Bert M., and de Groot, Frank M. F. Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts. United States: N. p., 2019.
Web. doi:10.1107/s1600577519002546.
al Samarai, Mustafa, van Oversteeg, Christa H. M., Delgado-Jaime, Mario Ulises, Weng, Tsu -Chien, Sokaras, Dimosthenis, Liu, Boyang, van der Linden, Marte, van der Eerden, Ad M. J., Vogt, Eelco T. C., Weckhuysen, Bert M., & de Groot, Frank M. F. Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts. United States. https://doi.org/10.1107/s1600577519002546
al Samarai, Mustafa, van Oversteeg, Christa H. M., Delgado-Jaime, Mario Ulises, Weng, Tsu -Chien, Sokaras, Dimosthenis, Liu, Boyang, van der Linden, Marte, van der Eerden, Ad M. J., Vogt, Eelco T. C., Weckhuysen, Bert M., and de Groot, Frank M. F. Fri .
"Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts". United States. https://doi.org/10.1107/s1600577519002546. https://www.osti.gov/servlets/purl/1528874.
@article{osti_1528874,
title = {Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts},
author = {al Samarai, Mustafa and van Oversteeg, Christa H. M. and Delgado-Jaime, Mario Ulises and Weng, Tsu -Chien and Sokaras, Dimosthenis and Liu, Boyang and van der Linden, Marte and van der Eerden, Ad M. J. and Vogt, Eelco T. C. and Weckhuysen, Bert M. and de Groot, Frank M. F.},
abstractNote = {The evolution in local structure and electronic properties of cobalt was investigated during in situ sulfurization. Using a combination of 1s X-ray absorption (XAS) and 1s3p resonant inelastic X-ray scattering (RIXS), the valence, coordination and symmetry of cobalt ions were tracked in two cobalt-promoted molybdenum oxide precursors of the hydrodesulfurization catalyst system, namely Co–Mo/Al2O3 and Co–Ni–Mo/Al2O3. Extended X-ray absorption fine structure shows that the Co—O bonds were replaced with Co—S bonds as a function of reaction temperature. The cobalt K pre-edge intensity shows that the symmetry of cobalt was modified from Co3+ Oh and Co2+ Oh to a Co2+ ion where the inversion symmetry is broken, in agreement with a square-pyramidal site. The 1s3p RIXS data revealed the presence of an intermediate cobalt oxy-sulfide species. This species was not detected from XAS and was determined from the increased information obtained from the 1s3p RIXS data. The cobalt XAS and RIXS data show that nickel has a significant influence on the formation of the cobalt oxy-sulfide intermediate species prior to achieving the fully sulfided state at T > 400°C.},
doi = {10.1107/s1600577519002546},
journal = {Journal of Synchrotron Radiation (Online)},
number = 3,
volume = 26,
place = {United States},
year = {Fri Apr 26 00:00:00 EDT 2019},
month = {Fri Apr 26 00:00:00 EDT 2019}
}
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