DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]

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 selectivitymore » 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.« 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:
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},
journal = {Journal of the American Chemical Society},
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 referenced in this record:

Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas
journal, January 2007

  • Spivey, James J.; Egbebi, Adefemi
  • Chemical Society Reviews, Vol. 36, Issue 9
  • DOI: 10.1039/b414039g

A Review of Recent Literature to Search for an Efficient Catalytic Process for the Conversion of Syngas to Ethanol
journal, March 2008

  • Subramani, Velu; Gangwal, Santosh K.
  • Energy & Fuels, Vol. 22, Issue 2
  • DOI: 10.1021/ef700411x

Synthesis of green fuels from biogenic waste through thermochemical route – The role of heterogeneous catalyst: A review
journal, October 2014

  • Mohanty, Pravakar; Pant, Kamal K.; Naik, Satya Narayan
  • Renewable and Sustainable Energy Reviews, Vol. 38
  • DOI: 10.1016/j.rser.2014.05.011

Activity and Selectivity Trends in Synthesis Gas Conversion to Higher Alcohols
journal, October 2013

  • Medford, Andrew J.; Lausche, Adam C.; Abild-Pedersen, Frank
  • Topics in Catalysis, Vol. 57, Issue 1-4
  • DOI: 10.1007/s11244-013-0169-0

Mechanism of Ethanol Synthesis from Syngas on Rh(111)
journal, September 2009

  • Choi, YongMan; Liu, Ping
  • Journal of the American Chemical Society, Vol. 131, Issue 36
  • DOI: 10.1021/ja903013x

Ab Initio Study of CO Hydrogenation to Oxygenates on Reduced Rh Terraces and Stepped Surfaces
journal, May 2010

  • Kapur, Neeti; Hyun, Jangsuk; Shan, Bin
  • The Journal of Physical Chemistry C, Vol. 114, Issue 22
  • DOI: 10.1021/jp911903u

Ethanol Synthesis from Syngas on the Stepped Rh(211) Surface: Effect of Surface Structure and Composition
journal, September 2014

  • Wang, Jiancheng; Liu, Zhixue; Zhang, Riguang
  • The Journal of Physical Chemistry C, Vol. 118, Issue 39
  • DOI: 10.1021/jp508885w

Investigation of the synthesis of oxygenates from carbon monoxide/hydrogen mixtures on supported rhodium catalysts
journal, September 1992


Fe-promotion of supported Rh catalysts for direct conversion of syngas to ethanol
journal, January 2009


Promoter action of rare earth oxides in rhodium/silica catalysts for the conversion of syngas to ethanol
journal, November 1987


Influence of iron promoter on catalytic properties of Rh-Mn-Li/SiO2 for CO hydrogenation
journal, March 2003


First-Principles-Based Microkinetics Simulations of Synthesis Gas Conversion on a Stepped Rhodium Surface
journal, August 2015

  • Filot, Ivo A. W.; Broos, Robin J. P.; van Rijn, Jeaphianne P. M.
  • ACS Catalysis, Vol. 5, Issue 9
  • DOI: 10.1021/acscatal.5b01391

Enhanced ethanol production inside carbon-nanotube reactors containing catalytic particles
journal, May 2007

  • Pan, Xiulian; Fan, Zhongli; Chen, Wei
  • Nature Materials, Vol. 6, Issue 7
  • DOI: 10.1038/nmat1916

Rh-catalyzed syngas conversion to ethanol: Studies on the promoting effect of FeOx
journal, August 2011


La, V, and Fe promotion of Rh/SiO2 for CO hydrogenation: Detailed analysis of kinetics and mechanism
journal, November 2009


Metal dispersion dependent selectivities for syngas conversion on faujasite X hosted rhodium
journal, September 1992

  • Martin, A.; Lücke, B.; Jaeger, N. J.
  • Catalysis Letters, Vol. 13, Issue 3
  • DOI: 10.1007/BF00770997

Role of promoters on Rh/SiO2 in CO hydrogenation: A comparison using DRIFTS
journal, September 2009


Synthesis of ethanol from syngas over Rh/Ce1−xZrxO2 catalysts
journal, April 2011


Role of impurities in the enhancement of C2-oxygenates activity
journal, June 1990


CO Hydrogenation to C2-oxygenates over Rh–Mn–Li/SiO2 Catalyst: Effects of Support Pretreatment with nC1–C5 Alcohols
journal, November 2007


Investigation of the reactions of acetaldehyde on promoted rhodium catalysts
journal, September 1992


The effect of Fe–Rh alloying on CO hydrogenation to C2+ oxygenates
journal, September 2015


Catalytic conversion of syngas into C2+ oxygenates over Rh/SiO2-based catalysts: The remarkable effect of hydroxyls on the SiO2
journal, February 2013


The Effect of Rh Particle Size on the Catalytic Performance of Porous Silica supported Rhodium Catalysts for CO Hydrogenation
journal, July 2005


Size and Topological Effects of Rhodium Surfaces, Clusters and Nanoparticles on the Dissociation of CO
journal, July 2011

  • Filot, Ivo A. W.; Shetty, Sharan G.; Hensen, Emiel J. M.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 29
  • DOI: 10.1021/jp201783f

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015


CO and CO2 Hydrogenation to Methanol Calculated Using the BEEF-vdW Functional
journal, December 2012


The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts
journal, March 2015


Assessing the reliability of calculated catalytic ammonia synthesis rates
journal, July 2014


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Higher-accuracy van der Waals density functional
journal, August 2010


Thermochemistry and micro-kinetic analysis of methanol synthesis on ZnO (0001)
journal, January 2014


Modeling van der Waals Interactions in Zeolites with Periodic DFT: Physisorption of n-Alkanes in ZSM-22
journal, July 2012


An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

  • Bahn, S. R.; Jacobsen, K. W.
  • Computing in Science & Engineering, Vol. 4, Issue 3
  • DOI: 10.1109/5992.998641

Global Optimization of Adsorbate–Surface Structures While Preserving Molecular Identity
journal, October 2013


Density-functional tight-binding for beginners
journal, November 2009


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Methanol-to-hydrocarbons conversion: The alkene methylation pathway
journal, May 2014


A Method for Evaluating and Correlating Thermodynamic Da ta
journal, April 1954

  • Shomate, C. Howard
  • The Journal of Physical Chemistry, Vol. 58, Issue 4
  • DOI: 10.1021/j150514a018

CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends
journal, February 2015


On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces
journal, November 2013


Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999


Understanding the structure of high coverage CO adlayers
journal, August 1990

  • T�shaus, M.; Berndt, W.; Conrad, H.
  • Applied Physics A Solids and Surfaces, Vol. 51, Issue 2
  • DOI: 10.1007/BF00324270

Kinetic effects of impurities on the growth of single crystals from solutions
journal, May 1999


Steam Reforming and Graphite Formation on Ni Catalysts
journal, July 2002

  • Bengaard, H. S.; Nørskov, J. K.; Sehested, J.
  • Journal of Catalysis, Vol. 209, Issue 2
  • DOI: 10.1006/jcat.2002.3579

The role of Mn and Li promoters in supported rhodium catalysts in the formation of acetic acid and acetaldehyde
journal, August 1997


EXAFS and FT-IR Characterization of Mn and Li Promoted Titania-Supported Rh Catalysts for CO Hydrogenation
journal, August 2011

  • Schwartz, Viviane; Campos, Andrew; Egbebi, Adefemi
  • ACS Catalysis, Vol. 1, Issue 10
  • DOI: 10.1021/cs200281g

Investigation by ethylene addition of alkali promotion of CO hydrogenation on Rh/TiO2
journal, April 1985


Conversion of biomass-derived syngas to alcohols and C2 oxygenates using supported Rh catalysts in a microchannel reactor
journal, January 2007


Works referencing / citing this record:

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

  • Li, Xuan; Teschner, Detre; Streibel, Verena
  • Chemical Science, Vol. 10, Issue 8
  • DOI: 10.1039/c8sc04641g

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

  • Ulissi, Zachary W.; Medford, Andrew J.; Bligaard, Thomas
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14621

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

  • Peregudova, Aleksandra S.; Barrios, Alan J.; Ordomsky, Vitaly V.
  • Chemical Communications, Vol. 56, Issue 2
  • DOI: 10.1039/c9cc09026f

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

  • Huang, Xing; Teschner, Detre; Dimitrakopoulou, Maria
  • Angewandte Chemie, Vol. 131, Issue 26
  • DOI: 10.1002/ange.201902750

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

  • Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla
  • Chemical Society Reviews, Vol. 46, Issue 5
  • DOI: 10.1039/c6cs00324a

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

  • Liu, Xinyan; Xiao, Jianping; Peng, Hongjie
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15438

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

  • Sun, Kai; Gao, Xiaofeng; Bai, Yunxing
  • Catalysis Science & Technology, Vol. 8, Issue 15
  • DOI: 10.1039/c8cy01074a

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

  • Zhong, Huixian; Wang, Jiaming; An, Kang
  • Catalysis Science & Technology, Vol. 9, Issue 13
  • DOI: 10.1039/c9cy00416e

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

  • Andersen, Mie; Plaisance, Craig P.; Reuter, Karsten
  • The Journal of Chemical Physics, Vol. 147, Issue 15
  • DOI: 10.1063/1.4989511

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

  • Singh, Joseph A.; Hoffman, Adam S.; Schumann, Julia
  • ChemCatChem, Vol. 11, Issue 2
  • DOI: 10.1002/cctc.201801724

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


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

  • Zhao, Lu; Mu, Xiaoliang; Liu, Tianshuo
  • Catalysis Science & Technology, Vol. 8, Issue 8
  • DOI: 10.1039/c7cy02555f

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


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

  • Sharapa, Dmitry I.; Doronkin, Dmitry E.; Studt, Felix
  • Advanced Materials, Vol. 31, Issue 26
  • DOI: 10.1002/adma.201807381

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

  • Reuter, Karsten; Plaisance, Craig P.; Oberhofer, Harald
  • The Journal of Chemical Physics, Vol. 146, Issue 4
  • DOI: 10.1063/1.4974931

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

  • Huang, Xing; Teschner, Detre; Dimitrakopoulou, Maria
  • Angewandte Chemie International Edition, Vol. 58, Issue 26
  • DOI: 10.1002/anie.201902750

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

  • Wu, Yingquan; Gong, Nana; Zhang, Min
  • Catalysis Science & Technology, Vol. 9, Issue 10
  • DOI: 10.1039/c9cy00542k

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

  • Yang, Chengsheng; Mu, Rentao; Wang, Guishuo
  • Chemical Science, Vol. 10, Issue 11
  • DOI: 10.1039/c8sc05608k

Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
text, January 2019