Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study
Abstract
Although ruthenium is a common promoter for cobalt-based Fischer–Tropsch synthesis (FTS) catalysts, the origin of Ru promotion and promoter concentration effects remains controversial. To gain a fundamental understanding of the Ru promotion effects, we herein performed an in situ spectroscopic study by X-ray absorption spectroscopy (XAS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS)–Auger of working Co/TiO2 catalysts (ca. 12 wt % Co, pure anatase TiO2 phase) promoted with different amounts of Ru (0.1–1.2 wt %). At typical FTS conditions (220 °C, 20 bar, H2/CO = 2), the activity in terms of both metal-time-yield (MTY) and initial turnover frequency (TOF) was maximized for the catalysts promoted with 0.1–0.2 wt % Ru, for which most of the Ru was alloyed with Co in bimetallic nanoparticles. The analysis of Auger electrons evidenced that the lower (apparent) TOF of accessible Co0 sites in the absence of Ru and at Ru concentrations beyond 0.2 wt % is bridged to the development, under reaction conditions, of FTS-inactive cobalt carbide (CoCx) and cobalt oxide (CoOx) patches, respectively, at the outermost surface of cobalt crystallites.
- Authors:
-
[1];
[2];
[3];
[4];
[2];
[4]
- Universitat Politècnica de València−Consejo Superior de Investigaciones Científicas (UPV−CSIC), Valencia (Spain); Universidade Federal do Rio Grande do Sul (UFRGS) (Brazil)
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- CELLS-ALBA Synchrotron Radiation Facility, Barcelona (Spain)
- Universitat Politècnica de València−Consejo Superior de Investigaciones Científicas (UPV−CSIC), Valencia (Spain)
- Publication Date:
- Research Org.:
- Harvard Univ., Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1802396
- Grant/Contract Number:
- SC0012573
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Fischer−Tropsch synthesis; cobalt catalyst; ruthenium promotion; TiO2 support; in situ XAS, FTIR, and XPS−Auger spectroscopy
Citation Formats
Bertella, Francine, Lopes, Christian W., Foucher, Alexandre C., Agostini, Giovanni, Concepción, Patricia, Stach, Eric A., and Martínez, Agustín. Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study. United States: N. p., 2020.
Web. doi:10.1021/acscatal.9b05359.
Bertella, Francine, Lopes, Christian W., Foucher, Alexandre C., Agostini, Giovanni, Concepción, Patricia, Stach, Eric A., & Martínez, Agustín. Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study. United States. https://doi.org/10.1021/acscatal.9b05359
Bertella, Francine, Lopes, Christian W., Foucher, Alexandre C., Agostini, Giovanni, Concepción, Patricia, Stach, Eric A., and Martínez, Agustín. Fri .
"Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study". United States. https://doi.org/10.1021/acscatal.9b05359. https://www.osti.gov/servlets/purl/1802396.
@article{osti_1802396,
title = {Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study},
author = {Bertella, Francine and Lopes, Christian W. and Foucher, Alexandre C. and Agostini, Giovanni and Concepción, Patricia and Stach, Eric A. and Martínez, Agustín},
abstractNote = {Although ruthenium is a common promoter for cobalt-based Fischer–Tropsch synthesis (FTS) catalysts, the origin of Ru promotion and promoter concentration effects remains controversial. To gain a fundamental understanding of the Ru promotion effects, we herein performed an in situ spectroscopic study by X-ray absorption spectroscopy (XAS), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS)–Auger of working Co/TiO2 catalysts (ca. 12 wt % Co, pure anatase TiO2 phase) promoted with different amounts of Ru (0.1–1.2 wt %). At typical FTS conditions (220 °C, 20 bar, H2/CO = 2), the activity in terms of both metal-time-yield (MTY) and initial turnover frequency (TOF) was maximized for the catalysts promoted with 0.1–0.2 wt % Ru, for which most of the Ru was alloyed with Co in bimetallic nanoparticles. The analysis of Auger electrons evidenced that the lower (apparent) TOF of accessible Co0 sites in the absence of Ru and at Ru concentrations beyond 0.2 wt % is bridged to the development, under reaction conditions, of FTS-inactive cobalt carbide (CoCx) and cobalt oxide (CoOx) patches, respectively, at the outermost surface of cobalt crystallites.},
doi = {10.1021/acscatal.9b05359},
journal = {ACS Catalysis},
number = 11,
volume = 10,
place = {United States},
year = {Fri May 01 00:00:00 EDT 2020},
month = {Fri May 01 00:00:00 EDT 2020}
}
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