The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates
Abstract
A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO2 catalysts for the synthesis of ethanol and other C2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburization as evidenced by the formation of small amounts of Fe3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeOx also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed tomore »
- Authors:
-
- Stony Brook Univ., Stony Brook, NY (United States)
- Univ. of Catalonia, Barcelona (Spain)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab., Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1228866
- Alternate Identifier(s):
- OSTI ID: 1252810
- Report Number(s):
- BNL-108607-2015-JA
Journal ID: ISSN 0021-9517; R&D Project: CO009; KC0302010
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Catalysis
- Additional Journal Information:
- Journal Volume: 329; Journal Issue: C; Journal ID: ISSN 0021-9517
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ethanol synthesis; bimetallic catalysts; CO hydrogenation
Citation Formats
Palomino, Robert, Magee, Joseph W., Llorca, Jordi, Senanayake, Sanjaya D., and White, Michael G. The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates. United States: N. p., 2015.
Web. doi:10.1016/j.jcat.2015.04.033.
Palomino, Robert, Magee, Joseph W., Llorca, Jordi, Senanayake, Sanjaya D., & White, Michael G. The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates. United States. https://doi.org/10.1016/j.jcat.2015.04.033
Palomino, Robert, Magee, Joseph W., Llorca, Jordi, Senanayake, Sanjaya D., and White, Michael G. Wed .
"The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates". United States. https://doi.org/10.1016/j.jcat.2015.04.033. https://www.osti.gov/servlets/purl/1228866.
@article{osti_1228866,
title = {The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates},
author = {Palomino, Robert and Magee, Joseph W. and Llorca, Jordi and Senanayake, Sanjaya D. and White, Michael G.},
abstractNote = {A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO2 catalysts for the synthesis of ethanol and other C2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburization as evidenced by the formation of small amounts of Fe3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeOx also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites.},
doi = {10.1016/j.jcat.2015.04.033},
journal = {Journal of Catalysis},
number = C,
volume = 329,
place = {United States},
year = {Wed May 20 00:00:00 EDT 2015},
month = {Wed May 20 00:00:00 EDT 2015}
}
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