skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production]

Abstract

Synthesis gas (CO + H 2) 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 C 2+ 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 H 2 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/SiO 2 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 catalyticmore » activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, 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.« less

Authors:
 [1];  [2];  [2];  [2];  [2];  [1];  [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1351912
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 11; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; syngas conversion; higher oxygenate synthesis; Rhodium catalyst

Citation Formats

Yang, Nuoya, Medford, Andrew J., Liu, Xinyan, Studt, Felix, Bligaard, Thomas, Bent, Stacey F., and Nørskov, Jens K. Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production]. United States: N. p., 2016. Web. doi:10.1021/jacs.5b12087.
Yang, Nuoya, Medford, Andrew J., Liu, Xinyan, Studt, Felix, Bligaard, Thomas, Bent, Stacey F., & Nørskov, Jens K. Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production]. United States. https://doi.org/10.1021/jacs.5b12087
Yang, Nuoya, Medford, Andrew J., Liu, Xinyan, Studt, Felix, Bligaard, Thomas, Bent, Stacey F., and Nørskov, Jens K. Sun . "Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production]". United States. https://doi.org/10.1021/jacs.5b12087. https://www.osti.gov/servlets/purl/1351912.
@article{osti_1351912,
title = {Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C2+ oxygenate production]},
author = {Yang, Nuoya and Medford, Andrew J. and Liu, Xinyan and Studt, Felix and Bligaard, Thomas and Bent, Stacey F. and Nørskov, Jens K.},
abstractNote = {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. As a result, 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.},
doi = {10.1021/jacs.5b12087},
url = {https://www.osti.gov/biblio/1351912}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 11,
volume = 138,
place = {United States},
year = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Nanoparticles of Rh confined and tailored by LaFeO 3 –La 2 O 3 on SiO 2 for direct ethanol synthesis from syngas
journal, January 2019


Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
journal, February 2019


Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
journal, February 2019


Nanoparticles of Rh confined and tailored by LaFeO 3 –La 2 O 3 on SiO 2 for direct ethanol synthesis from syngas
journal, January 2019


Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts
journal, May 2019


Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts
journal, June 2019


Role of Co 2 C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas
journal, December 2018


Selective CO 2 Conversion into Fuels on Nanochannels
journal, July 2019


To address surface reaction network complexity using scaling relations machine learning and DFT calculations
journal, March 2017


Understanding trends in electrochemical carbon dioxide reduction rates
journal, May 2017


pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper
journal, January 2019


Status and prospects in higher alcohols synthesis from syngas
journal, January 2017


Bimetallic Ni–Co catalysts supported on Mn–Al oxide for selective catalytic CO hydrogenation to higher alcohols
journal, January 2018


Synergetic catalysis of bimetallic copper–cobalt nanosheets for direct synthesis of ethanol and higher alcohols from syngas
journal, January 2018


How to control selectivity in alkane oxidation?
journal, January 2019


Hydroxyl-mediated ethanol selectivity of CO 2 hydrogenation
journal, January 2019


The Fischer–Tropsch reaction in the aqueous phase over rhodium catalysts: a promising route to selective synthesis and separation of oxygenates and hydrocarbons
journal, January 2020


Insight into the branched alcohol formation mechanism on K–ZnCr catalysts from syngas
journal, January 2019


Perspective: On the active site model in computational catalyst screening
journal, January 2017


Assessment of mean-field microkinetic models for CO methanation on stepped metal surfaces using accelerated kinetic Monte Carlo
journal, October 2017