Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts

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.

doi:10.1107/s1600577519002546

Title: Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al₂O₃ hydrodesulfurization catalysts

Journal Article · Fri Apr 26 00:00:00 EDT 2019 · Journal of Synchrotron Radiation (Online)

DOI:https://doi.org/10.1107/s1600577519002546· OSTI ID:1528874

al Samarai, Mustafa ^[1];

^[2]; Delgado-Jaime, Mario Ulises ^[2]; Weng, Tsu -Chien ^[3];

^[3]; Liu, Boyang ^[2]; van der Linden, Marte ^[4]; van der Eerden, Ad M. J. ^[2];

^[2]; Weckhuysen, Bert M. ^[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)

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⁺ O_h and Co²⁺ O_h 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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515; NANO-11507

OSTI ID:: 1528874

Journal Information:: Journal of Synchrotron Radiation (Online), Vol. 26, Issue 3; ISSN 1600-5775

Publisher:: International Union of CrystallographyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

References (38)

Structure and Function of the Catalyst and the Promoter in Co—Mo Hydrodesulfurization Catalysts Prins, R.; De Beer, V. H. J.; Somorjai, G. A. Catalysis Reviews, Vol. 31, Issue 1-2 https://doi.org/10.1080/01614948909351347	journal	February 1989
Structure of the molybdenum sulfide phase in carbon-supported molybdenum and cobalt-molybdenum sulfide catalysts as studied by EXAFS Bouwens, S. M. A. M.; Prins, R.; De Beer, V. H. J. The Journal of Physical Chemistry, Vol. 94, Issue 9 https://doi.org/10.1021/j100372a065	journal	May 1990
Temperature-programmed sulfiding of MoO3/Al2O3 catalysts Arnoldy, P. Journal of Catalysis, Vol. 92, Issue 1 https://doi.org/10.1016/0021-9517(85)90235-0	journal	March 1985
1s3p Resonant Inelastic X-ray Scattering of Cobalt Oxides and Sulfides Al Samarai, Mustafa; Delgado-Jaime, Mario Ulises; Ishii, Hirofumi The Journal of Physical Chemistry C, Vol. 120, Issue 42 https://doi.org/10.1021/acs.jpcc.6b06444	journal	October 2016
Support effects on hydrotreating catalysts Breysse, M.; Portefaix, J. L.; Vrinat, M. Catalysis Today, Vol. 10, Issue 4 https://doi.org/10.1016/0920-5861(91)80035-8	journal	November 1991
Preparation Techniques for Hydrotreating Catalysts and Their Influence on the Location of the Metal Oxides and Performance Keely, W. M.; Jerus, P.; Dienes, E. K. Catalysis Reviews, Vol. 26, Issue 3-4 https://doi.org/10.1080/01614948408064723	journal	August 1984
Modeling the adsorption of sulfur containing molecules and their hydrodesulfurization intermediates on the Co-promoted MoS2 catalyst by DFT Šarić, Manuel; Rossmeisl, Jan; Moses, Poul Georg Journal of Catalysis, Vol. 358 https://doi.org/10.1016/j.jcat.2017.12.001	journal	February 2018
In situ hard X-ray quick RIXS to probe dynamic changes in the electronic structure of functional materials Szlachetko, J.; Sá, J.; Safonova, O. V. Journal of Electron Spectroscopy and Related Phenomena, Vol. 188 https://doi.org/10.1016/j.elspec.2012.11.002	journal	June 2013
Structural Chemistry of Co-Mo-Alumnina Catalysts Ratnasamy, P.; Sivasanker, S. Catalysis Reviews, Vol. 22, Issue 3 https://doi.org/10.1080/03602458008067539	journal	January 1980
The Mechanism of HDS Catalysis Startsev, Anatolii N. Catalysis Reviews, Vol. 37, Issue 3 https://doi.org/10.1080/01614949508006446	journal	August 1995
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information Glatzel, Pieter; Bergmann, Uwe Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.04.011	journal	January 2005
Molecular simulation on hydrodesulfurization of thiophenic compounds over MoS2 using ZINDO Ma, Xiaoliang; Schobert, Harold H. Journal of Molecular Catalysis A: Chemical, Vol. 160, Issue 2 https://doi.org/10.1016/S1381-1169(00)00278-8	journal	October 2000
Modeling the active sites of Co-promoted MoS ₂ particles by DFT Šarić, Manuel; Rossmeisl, Jan; Moses, Poul Georg Physical Chemistry Chemical Physics, Vol. 19, Issue 3 https://doi.org/10.1039/C6CP06881B	journal	January 2017
Probing topological electronic effects in catalysis: thiophene adsorption on NiMoS and CoMoS clusters Borges Jr., Itamar; Silva, Alexander M. Journal of the Brazilian Chemical Society, Vol. 23, Issue 10 https://doi.org/10.1590/S0103-50532012005000044	journal	January 2012
On the Structural Differences Between Alumina-Supported Comos Type I and Alumina-, Silica-, and Carbon-Supported Comos Type II Phases Studied by XAFS, MES, and XPS Bouwens, S. M. A. M.; Vanzon, F. B. M.; Vandijk, M. P. Journal of Catalysis, Vol. 146, Issue 2 https://doi.org/10.1006/jcat.1994.1076	journal	April 1994
Towards Understanding the Catalytic Reforming of Biomass in Supercritical Water Rabe, Stefan; Nachtegaal, Maarten; Ulrich, Thomas Angewandte Chemie International Edition, Vol. 49, Issue 36 https://doi.org/10.1002/anie.201001160	journal	July 2010
A volcano-type relationship between the adsorption energy of thiophene on promoted MoS2 cluster-model catalysts and the experimental HDS activity: ab initio density functional study Orita, Hideo; Uchida, Kunio; Itoh, Naotsugu Applied Catalysis A: General, Vol. 258, Issue 1 https://doi.org/10.1016/j.apcata.2003.08.016	journal	February 2004
Temperature Programmed Sulfiding of CoO/MoO3/γ-Al2O3 Catalysts Scheffer, B.; De Jonge, J. C. M.; Arnoldy, P. Bulletin des Sociétés Chimiques Belges, Vol. 93, Issue 8-9 https://doi.org/10.1002/bscb.19840930817	journal	January 1984
The effect of phosphate and glycol on the sulfidation mechanism of CoMo/Al2O3 hydrotreating catalysts: an in situ QEXAFS study Nicosia, D.; Prins, R. Journal of Catalysis, Vol. 231, Issue 2 https://doi.org/10.1016/j.jcat.2005.01.018	journal	April 2005
Computational studies of (mixed) sulfide hydrotreating catalysts Paul, Jean-François; Cristol, Sylvain; Payen, Edmond Catalysis Today, Vol. 130, Issue 1 https://doi.org/10.1016/j.cattod.2007.07.020	journal	January 2008
Hard X-ray photon-in photon-out spectroscopy Glatzel, Pieter; Sikora, Marcin; Smolentsev, Grigory Catalysis Today, Vol. 145, Issue 3-4 https://doi.org/10.1016/j.cattod.2008.10.049	journal	July 2009
Resonant inelastic x-ray scattering spectra for electrons in solids Kotani, Akio; Shin, Shik Reviews of Modern Physics, Vol. 73, Issue 1 https://doi.org/10.1103/RevModPhys.73.203	journal	February 2001
EXAFS determination of the structure of cobalt in carbon-supported cobalt and cobalt-molybdenum sulfide hydrodesulfurization catalysts Bouwens, S. M. A. M.; Van Veen, J. A. R.; Koningsberger, D. C. The Journal of Physical Chemistry, Vol. 95, Issue 1 https://doi.org/10.1021/j100154a028	journal	January 1991
Active sites and support effects in hydrodesulfurization catalysts Topsøe, Henrik; Clausen, Bjerne S. Applied Catalysis, Vol. 25, Issue 1-2 https://doi.org/10.1016/S0166-9834(00)81246-4	journal	August 1986
X-ray absorption spectroscopy under reaction conditions: suitability of different reaction cells for combined catalyst characterization and time-resolved studies Grunwaldt, J. -D.; Caravati, M.; Hannemann, S. Physical Chemistry Chemical Physics, Vol. 6, Issue 11 https://doi.org/10.1039/b403071k	journal	January 2004
Similarity of Co-Species in Co and Co-Mo Sulfide Catalysts Supported on Carbon and Alumina. A Mössbauer Emission Spectroscopic Study Crajé, M. W. J.; De Beer, V. H. J.; van Der Kraan, A. M. Bulletin des Sociétés Chimiques Belges, Vol. 100, Issue 11-12 https://doi.org/10.1002/bscb.19911001121	journal	January 1991
Comparative atomic-scale analysis of promotional effects by late 3d-transition metals in MoS2 hydrotreating catalysts Kibsgaard, Jakob; Tuxen, Anders; Knudsen, Kim G. Journal of Catalysis, Vol. 272, Issue 2 https://doi.org/10.1016/j.jcat.2010.03.018	journal	June 2010
Importance of Co-Mo-S Type Structures in Hydrodesulfurization Tops⊘e, Henrik; Clausen, Bjerne S. Catalysis Reviews, Vol. 26, Issue 3-4 https://doi.org/10.1080/01614948408064719	journal	August 1984
Co-K and Mo-K edges Quick-XAS study of the sulphidation properties of Mo/Al2O3 and CoMo/Al2O3 catalysts Rochet, Amélie; Baubet, Bertrand; Moizan, Virginie Comptes Rendus Chimie, Vol. 19, Issue 10 https://doi.org/10.1016/j.crci.2016.01.009	journal	October 2016
Resonant Inelastic X-Ray Scattering in ${Nd}_{2} {CuO}_{4}$ Hill, J. P.; Kao, C. -C.; Caliebe, W. A. L. Physical Review Letters, Vol. 80, Issue 22 https://doi.org/10.1103/PhysRevLett.80.4967	journal	June 1998
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource Sokaras, D.; Weng, T. -C.; Nordlund, D. Review of Scientific Instruments, Vol. 84, Issue 5 https://doi.org/10.1063/1.4803669	journal	May 2013
Development and exploration of a new methodology for the fitting and analysis of XAS data Delgado-Jaime, Mario Ulises; Kennepohl, Pierre Journal of Synchrotron Radiation, Vol. 17, Issue 1 https://doi.org/10.1107/S090904950904655X	journal	December 2009
Recent basic research in hydrodesulfurization catalysis Topsoee, Henrik; Clausen, Bjerne S.; Topsoee, Nan Yu Industrial & Engineering Chemistry Fundamentals, Vol. 25, Issue 1 https://doi.org/10.1021/i100021a004	journal	February 1986
Life cycle of hydroprocessing catalysts and total catalyst management Eijsbouts, S.; Battiston, A.; Vanleerdam, G. Catalysis Today, Vol. 130, Issue 2-4 https://doi.org/10.1016/j.cattod.2007.10.112	journal	January 2008
On the so-called “Co-Mo-S” phase observed in carbon-supported cobalt sulfide catalysts: Temperature dependence of the in-situ Mössbauer emission spectrum Crajé, M. W. J.; de Beer, V. H. J.; van der Kraan*, A. M. Applied Catalysis, Vol. 70, Issue 1 https://doi.org/10.1016/S0166-9834(00)84147-0	journal	January 1991
High-resolution large-acceptance analyzer for x-ray fluorescence and Raman spectroscopy Bergmann, Uwe; Cramer, Stephen P. SPIE's International Symposium on Optical Science, Engineering, and Instrumentation, SPIE Proceedings https://doi.org/10.1117/12.332507	conference	December 1998
Blueprint XAS : a Matlab -based toolbox for the fitting and analysis of XAS spectra Delgado-Jaime, Mario Ulises; Mewis, Craig Philip; Kennepohl, Pierre Journal of Synchrotron Radiation, Vol. 17, Issue 1 https://doi.org/10.1107/S0909049509046561	journal	December 2009
Similarity of Co-Species in Co and CoMo-sulfide catalysts supported on carbon and alumina. A Mössbauer emission spectroscopic study Crajé, M. W. J.; de Beer, V. H. J.; van der Kraan, A. M. Hyperfine Interactions, Vol. 69, Issue 1-4 https://doi.org/10.1007/bf02401946	journal	April 1992

Similar Records

X-ray photoelectron spectroscopy study of various CoMo/Al/sub 2/O/sub 3/ hydrodesulfurization catalysts

Journal Article · Thu Apr 20 00:00:00 EST 1978 · J. Phys. Chem.; (United States) · OSTI ID:1528874

Declerck-Grimee, R I; Canesson, P; Friedman, R M; +1 more

Activation of unsupported Co-Mo catalysts in thiophene hydrodesulfurization

Journal Article · Sat Apr 01 00:00:00 EST 1989 · Journal of Catalysis; (USA) · OSTI ID:1528874

Koranyi, T I; Manninger, I; Paal, Z; +2 more

Surface structure and catalytic activity of MoO/sub 3//Al/sub 2/O/sub 3/ catalysts in the hydrodesulfurization of thiophene studied by x-ray photoelectron spectroscopy

Journal Article · Thu Jul 10 00:00:00 EDT 1980 · J. Phys. Chem.; (United States) · OSTI ID:1528874

Okamoto, Y; Tomioka, H; Katoh, Y; +2 more

Related Subjects

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)

Title: Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al2O3 hydrodesulfurization catalysts

Citation Formats

References (38)

Similar Records

Related Subjects

Title: Nature of cobalt species during the in situ sulfurization of Co(Ni)Mo/Al₂O₃ hydrodesulfurization catalysts