Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study

Bertella, Francine; Lopes, Christian W.; Foucher, Alexandre C.; Agostini, Giovanni; Concepción, Patricia; Stach, Eric A.; Martínez, Agustín

doi:10.1021/acscatal.9b05359

Insights into the Promotion with Ru of Co/TiO ₂ Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study

Journal Article · Fri May 01 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b05359· OSTI ID:1802396

Bertella, Francine ^[1]; ^[2]; ^[3]; ^[4]; ^[5]; ^[3]; ^[5]

Universitat Politècnica de València−Consejo Superior de Investigaciones Científicas (UPV−CSIC), Valencia (Spain); Universidade Federal do Rio Grande do Sul (UFRGS) (Brazil); OSTI
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)

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 (CoC_x) and cobalt oxide (CoO_x) patches, respectively, at the outermost surface of cobalt crystallites.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0012573

OSTI ID:: 1802396

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 11 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fischer−Tropsch synthesis
TiO2 support
cobalt catalyst
in situ XAS, FTIR, and XPS−Auger spectroscopy
ruthenium promotion

Insights into the Promotion with Ru of Co/TiO 2 Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study

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Insights into the Promotion with Ru of Co/TiO ₂ Fischer–Tropsch Catalysts: An In Situ Spectroscopic Study