Topics in Catalysis

, Volume 61, Issue 9–11, pp 1016–1023 | Cite as

Characterization of CoCu- and CoMn-Based Catalysts for the Fischer–Tropsch Reaction Toward Chain-Lengthened Oxygenates

  • Jenny M. Voss
  • Yizhi Xiang
  • Greg Collinge
  • Daniel E. Perea
  • Libor Kovarik
  • Jean-Sabin McEwen
  • Norbert KruseEmail author
Original Paper


The need for a sustainable energy supply in the face of depleting oil reserves has reignited the importance of Fischer–Tropsch (FT) synthesis technology. Presently, the FT process is practiced at the industrial scale to predominately produce synthetic diesel-type fuels and lubricants. More recently, the possibility of hydrogenating CO toward oxygenates, and not just hydrocarbons, has been explored. We have developed a series of CoCuMn and CoMnK catalysts prepared via the oxalate co-precipitation route that are capable of forming oxygenates with desirable selectivity. Upon H2-assisted thermal decomposition of the resultant mixed metal Co1Cu1Mn1 oxalates, catalysts naturally exhibited a cobalt core–copper shell configuration with Mn5O8 dispersed throughout the catalyst nanoparticle as determined via Atom Probe Tomography (APT). We suggest structural changes are induced by the CO and H2 reactants to form the catalytically active phase under real-time reaction conditions as demonstrated by corroborative Density Functional Theory calculations and experimental evidence. APT studies also show that a Co4Mn1K0.1 catalyst post reaction contained a cobalt carbide phase as determined from a Co/C ratio of 2/1. Manganese and potassium were found only in the outermost part of the particle. Both catalysts were found to contain the presence of a Mn5O8 oxidic phase before and post reaction which we attribute to the high activity toward oxygenates of these two catalysts.


Fischer–Tropsch Oxygenates Co-based catalysts Atom Probe Tomography Density Functional Theory 



J.-S.M. and N.K. were supported by the National foundation under contract no. CBET-1438227. G.C. was supported by the National Science Foundation Graduate Student Fellowship Program under contract number 1347973. J.V. was also supported by the National Science Foundation Graduate Student Fellowship Program. G.C. and J.V, Seattle Chapter ARCS Fellows, gratefully acknowledge financial support from the Achievement Rewards for College Scientists foundation. J.V. acknowledges the support of the U.S. Department of Energy, Office of Science Graduate Student Research program administered by the Oak Ridge Institute for Science and Education (ORISE) which is managed by ORAU under contract number DE-SC0014664. A portion of the research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL. PNNL is a multiprogram national laboratory operated for the U.S. DOE by Battelle. We finally thank Simon Ringer (University of Sydney) and his group for providing one of us (N.K.) with the possibility of performing APT measurements on CoCuMn catalysts.


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Jenny M. Voss
    • 1
  • Yizhi Xiang
    • 1
    • 4
  • Greg Collinge
    • 1
  • Daniel E. Perea
    • 3
  • Libor Kovarik
    • 3
  • Jean-Sabin McEwen
    • 1
    • 2
    • 5
    • 6
  • Norbert Kruse
    • 1
    • 2
    Email author
  1. 1.Voiland School of Chemical Engineering and BioengineeringWashington State UniversityPullmanUSA
  2. 2.Institute for Integrated CatalysisPacific Northwest National LaboratoryRichlandUSA
  3. 3.Environmental Molecular Sciences Laboratory, Pacific Northwest National LaboratoryRichlandUSA
  4. 4.Dave C. Swalm School of Chemical EngineeringMississippi State UniversityMississippi StateUSA
  5. 5.Department of ChemistryWashington State UniversityPullmanUSA
  6. 6.Department of PhysicsWashington State UniversityPullmanUSA

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