The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts
Abstract
Alkali metal oxides commonly exist as impurities or promoters in syngas conversion catalysts and can significantly influence the activity and selectivity towards higher oxygenate products. In this study, we investigate the effects of sodium oxide on silica-supported Rh catalysts by experimentally introducing different amounts of sodium and monitoring the change in reactivity and CO adsorption behavior. The experimental results combined with density functional theory (DFT) calculations show that sodium selectively blocks step/defect sites on Rh surfaces, leading to reduced activity but higher C2 oxygenate selectivity. DFT calculations also suggest that sodium present on Rh terrace sites can facilitate CO dissociation, potentially increasing C2 oxygenate production. The overall activity and selectivity toward various products can be changed significantly based on the degree of site blocking by the added sodium.
- Authors:
-
- Stanford Univ., CA (United States)
- Stanford Univ., 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:
- 1427466
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Catalysis Letters
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 1; Journal ID: ISSN 1011-372X
- Publisher:
- Springer
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yang, Nuoya, Liu, Xinyan, Asundi, Arun S., Nørskov, Jens K., and Bent, Stacey F. The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts. United States: N. p., 2017.
Web. doi:10.1007/s10562-017-2223-1.
Yang, Nuoya, Liu, Xinyan, Asundi, Arun S., Nørskov, Jens K., & Bent, Stacey F. The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts. United States. https://doi.org/10.1007/s10562-017-2223-1
Yang, Nuoya, Liu, Xinyan, Asundi, Arun S., Nørskov, Jens K., and Bent, Stacey F. Mon .
"The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts". United States. https://doi.org/10.1007/s10562-017-2223-1. https://www.osti.gov/servlets/purl/1427466.
@article{osti_1427466,
title = {The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts},
author = {Yang, Nuoya and Liu, Xinyan and Asundi, Arun S. and Nørskov, Jens K. and Bent, Stacey F.},
abstractNote = {Alkali metal oxides commonly exist as impurities or promoters in syngas conversion catalysts and can significantly influence the activity and selectivity towards higher oxygenate products. In this study, we investigate the effects of sodium oxide on silica-supported Rh catalysts by experimentally introducing different amounts of sodium and monitoring the change in reactivity and CO adsorption behavior. The experimental results combined with density functional theory (DFT) calculations show that sodium selectively blocks step/defect sites on Rh surfaces, leading to reduced activity but higher C2 oxygenate selectivity. DFT calculations also suggest that sodium present on Rh terrace sites can facilitate CO dissociation, potentially increasing C2 oxygenate production. The overall activity and selectivity toward various products can be changed significantly based on the degree of site blocking by the added sodium.},
doi = {10.1007/s10562-017-2223-1},
journal = {Catalysis Letters},
number = 1,
volume = 148,
place = {United States},
year = {Mon Oct 23 00:00:00 EDT 2017},
month = {Mon Oct 23 00:00:00 EDT 2017}
}
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Works referenced in this record:
Alkali Promotion of Alumina-Supported Cobalt Fischer--Tropsch Catalysts Studied by TPR, TPD and Pulse Chemisorption.
journal, January 1993
- Blekkan, Edd Anders; Holmen, Anders; Vada, Sturla
- Acta Chemica Scandinavica, Vol. 47
Alkali-metal promoted rhodium-on-alumina catalysts for nitrous oxide decomposition
journal, January 2008
- Haber, Jerzy; Nattich, Małgorzata; Machej, Tadeusz
- Applied Catalysis B: Environmental, Vol. 77, Issue 3-4
Mechanism of syngas conversion into C 2 -oxygenates such as ethanol catalysed on a SiO 2 -supported Rh–Ti catalyst
journal, January 1985
- Ichikawa, Masaru; Fukushima, Takakazu
- J. Chem. Soc., Chem. Commun., Issue 6
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
An Insight into Alkali Promotion: A Density Functional Theory Study of CO Dissociation on K/Rh(111)
journal, December 2001
- Liu, Zhi-Pan; Hu, P.
- Journal of the American Chemical Society, Vol. 123, Issue 50
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
Non-steady-state and transient effects in medium-pressure hydrogenation of carbon monoxide over rhodium catalysts
journal, January 1986
- Gilhooley, Kevin; Jackson, S. David; Rigby, Stuart
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, Issue 2
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
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts
journal, March 2015
- Studt, Felix; Behrens, Malte; Kunkes, Edward L.
- ChemCatChem, Vol. 7, Issue 7
Infrared Spectroscopy Investigation of Fe-Promoted Rh Catalysts Supported on Titania and Ceria for CO Hydrogenation
journal, July 2016
- Magee, Joseph W.; Palomino, Robert M.; White, Michael G.
- Catalysis Letters, Vol. 146, Issue 9
A Sensible Mechanism of Alkali Promotion in Fischer−Tropsch Synthesis: Adsorbate Mobilities
journal, June 1998
- Uner, D. O.
- Industrial & Engineering Chemistry Research, Vol. 37, Issue 6
The effect of alkali and alkaline earth elements on cobalt based Fischer–Tropsch catalysts
journal, October 2013
- Lillebø, Andreas Helland; Patanou, Eleni; Yang, Jia
- Catalysis Today, Vol. 215
Selectivity of Rh catalysts in the syngas reactions. On the role of supports and promoters
journal, January 1987
- Bastein, A. G. T. M.; van Der Boogert, W. J.; van Der Lee, G.
- Applied Catalysis, Vol. 29, Issue 2
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
Investigation of the synthesis of oxygenates from carbon monoxide/hydrogen mixtures on supported rhodium catalysts
journal, September 1992
- Burch, R.; Petch, M. I.
- Applied Catalysis A: General, Vol. 88, Issue 1
Identification of step-edge sites on Rh nanoparticles for facile CO dissociation
journal, March 2016
- Ligthart, D. A. J. Michel; Filot, Ivo A. W.; Almutairi, Abdulkarim A. H.
- Catalysis Communications, Vol. 77
Effect of Li Promoter on titania-supported Rh catalyst for ethanol formation from CO hydrogenation
journal, January 2010
- Egbebi, Adefemi; Schwartz, Viviane; Overbury, Steven H.
- Catalysis Today, Vol. 149, Issue 1-2
Infrared Spectroscopic Studies of CO Adsorption on Rhodium Supported by SiO2, Al2O3, and TiO2
journal, December 1994
- Trautmann, S.; Baerns, M.
- Journal of Catalysis, Vol. 150, Issue 2
Infrared spectra of chemisorbed CO on Rh
journal, February 1979
- Yates, J. T.; Duncan, T. M.; Worley, S. D.
- The Journal of Chemical Physics, Vol. 70, Issue 3
Impact of Na Promoter on Structural Properties and Catalytic Performance of CoNi/Al2O3 Nanocatalysts for the CO Hydrogenation Process: Fischer–Tropsch Technology
journal, September 2015
- Nikparsa, Paria; Mirzaei, Ali Akbar; Rauch, Reinhard
- Catalysis Letters, Vol. 146, Issue 1
A Comparative Study of CO and CO2Hydrogenation over Rh/SiO2
journal, August 1996
- Fisher, Ian A.; Bell, Alexis T.
- Journal of Catalysis, Vol. 162, Issue 1
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends
journal, February 2015
- Medford, Andrew J.; Shi, Chuan; Hoffmann, Max J.
- Catalysis Letters, Vol. 145, Issue 3
CO2 hydrogenation to ethanol over promoted Rh/SiO2 catalysts
journal, May 1996
- Kusama, Hitoshi; Okabe, Kiyomi; Sayama, Kazuhiro
- Catalysis Today, Vol. 28, Issue 3
Effect of Alkali Metal Impurities on Co–Re Catalysts for Fischer–Tropsch Synthesis from Biomass-Derived Syngas
journal, May 2010
- Balonek, Christine M.; Lillebø, Andreas H.; Rane, Shreyas
- Catalysis Letters, Vol. 138, Issue 1-2
Oxygenates from syngas over highly dispersed cobalt catalysts
journal, June 1997
- Matsuzaki, Takehiko; Hanaoka, Taka-aki; Takeuchi, Kazuhiko
- Catalysis Today, Vol. 36, Issue 3
Cobalt carbide nanoprisms for direct production of lower olefins from syngas
journal, October 2016
- Zhong, Liangshu; Yu, Fei; An, Yunlei
- Nature, Vol. 538, Issue 7623
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012
- Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas
- Physical Review B, Vol. 85, Issue 23
Dissociation of CO on Rh surfaces
journal, July 1990
- de Koster, A.; van Santen, R. A.
- Surface Science, Vol. 233, Issue 3
Progress and perspectives in converting biogas to transportation fuels
journal, December 2014
- Yang, Liangcheng; Ge, Xumeng; Wan, Caixia
- Renewable and Sustainable Energy Reviews, Vol. 40
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
Role of impurities in the enhancement of C2-oxygenates activity
journal, June 1990
- Nonneman, L. E. Y.; Bastein, A. G. T. M.; Ponec, V.
- Applied Catalysis, Vol. 62, Issue 1
Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C 2+ Oxygenate Production
journal, March 2016
- Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan
- Journal of the American Chemical Society, Vol. 138, Issue 11
Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas
journal, January 2007
- Spivey, James J.; Egbebi, Adefemi
- Chemical Society Reviews, Vol. 36, Issue 9
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
The effect of alkali promotion on CO hydrogenation over Rh/TiO2
journal, October 1985
- Chuang, S.
- Journal of Catalysis, Vol. 95, Issue 2
Advances in the Rational Design of Rhodium Nanoparticle Catalysts: Control via Manipulation of the Nanoparticle Core and Stabilizer
journal, April 2012
- Yuan, Yuan; Yan, Ning; Dyson, Paul J.
- ACS Catalysis, Vol. 2, Issue 6
On the mechanism of ethanol synthesis on rhodium
journal, May 1992
- Bwoker, M.
- Catalysis Today, Vol. 15, Issue 1
A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas
journal, September 2009
- Fang, Kegong; Li, Debao; Lin, Minggui
- Catalysis Today, Vol. 147, Issue 2, p. 133-138
Ethylene hydroformylation and carbon monoxide hydrogenation over modified and unmodified silica supported rhodium catalysts
journal, May 2000
- Hanaoka, T.; Arakawa, H.; Matsuzaki, T.
- Catalysis Today, Vol. 58, Issue 4
A Method for Evaluating and Correlating Thermodynamic Da ta
journal, April 1954
- Shomate, C. Howard
- The Journal of Physical Chemistry, Vol. 58, Issue 4
Mechanism of C2+ oxygenate synthesis on Rh catalysts
journal, March 2005
- Chuang, Steven S. C.; Stevens, Robert W.; Khatri, Rajesh
- Topics in Catalysis, Vol. 32, Issue 3-4, p. 225-232