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Cited by 230Catalysts for Methane ReformingCatalytic Processes in Materials ScienceCatalysis and Oxidation Reactions

Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C2+ Oxygenate Production

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Yang, Nuoya, Medford, Andrew J., Liu, Xinyan, Studt, Felix, Bligaard, Thomas, Bent, Stacey F., Nørskov, Jens K.·2016·Journal of the American Chemical Society
DOI 10.1021/jacs.5b12087
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Abstract

Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.

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Authors
Yang, N., Medford, A. J., Liu, X., Studt, F., Bligaard, T., Bent, S. F., & Nørskov, J. K.
Affiliations
  • Stanford University (US)
  • SLAC National Accelerator Laboratory (US)
Corresponding author
Nørskov, Jens K.
ORCID
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2016-03-09
Volume
138
Issue
11
Pages
3705-3714
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.5b12087
OpenAlex
W2266904741
Cited by
230
References
59
Citations by year
2026: 11 · 2025: 19 · 2024: 27 · 2023: 21 · 2022: 22 · 2021: 32 · 2020: 27 · 2019: 26 · 2018: 18 · 2017: 21 · 2016: 6
FWCI
7.91
Type
journal article
Language
en
Open access
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders
  • Basic Energy Sciences
  • U.S. Department of Defense
Topics
  • Physical Sciences › Chemical Engineering › Catalysis › Catalysts for Methane Reforming
  • Physical Sciences › Materials Science › Materials Chemistry › Catalytic Processes in Materials Science
  • Physical Sciences › Chemical Engineering › Catalysis › Catalysis and Oxidation Reactions
Keywords
rhodium catalysts, syngas conversion, C2 oxygenates, ethanol production, acetaldehyde, methane, Rh(111) surface, structure sensitivity, microkinetic model, iron impurities, Rh/SiO2 catalyst, coal liquefaction

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