The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts

Yang, Nuoya; Liu, Xinyan; Asundi, Arun S.; Nørskov, Jens K.; Bent, Stacey F.

doi:10.1007/s10562-017-2223-1

Title: The Role of Sodium in Tuning Product Distribution in Syngas Conversion by Rh Catalysts

Journal Article · Mon Oct 23 00:00:00 EDT 2017 · Catalysis Letters

DOI:https://doi.org/10.1007/s10562-017-2223-1· OSTI ID:1427466

Yang, Nuoya ^[1]; Liu, Xinyan ^[2]; Asundi, Arun S. ^[1]; Nørskov, Jens K. ^[2]; Bent, Stacey F. ^[1]

Stanford Univ., CA (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

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.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1427466

Journal Information:: Catalysis Letters, Vol. 148, Issue 1; ISSN 1011-372X

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 13 works

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References (41)

Alkali Promotion of Alumina-Supported Cobalt Fischer--Tropsch Catalysts Studied by TPR, TPD and Pulse Chemisorption. Blekkan, Edd Anders; Holmen, Anders; Vada, Sturla Acta Chemica Scandinavica, Vol. 47 https://doi.org/10.3891/acta.chem.scand.47-0275	journal	January 1993
Alkali-metal promoted rhodium-on-alumina catalysts for nitrous oxide decomposition Haber, Jerzy; Nattich, Małgorzata; Machej, Tadeusz Applied Catalysis B: Environmental, Vol. 77, Issue 3-4 https://doi.org/10.1016/j.apcatb.2007.07.028	journal	January 2008
Mechanism of syngas conversion into C ₂ -oxygenates such as ethanol catalysed on a SiO ₂ -supported Rh–Ti catalyst Ichikawa, Masaru; Fukushima, Takakazu J. Chem. Soc., Chem. Commun., Issue 6 https://doi.org/10.1039/C39850000321	journal	January 1985
Synthesis of green fuels from biogenic waste through thermochemical route – The role of heterogeneous catalyst: A review Mohanty, Pravakar; Pant, Kamal K.; Naik, Satya Narayan Renewable and Sustainable Energy Reviews, Vol. 38 https://doi.org/10.1016/j.rser.2014.05.011	journal	October 2014
An Insight into Alkali Promotion: A Density Functional Theory Study of CO Dissociation on K/Rh(111) Liu, Zhi-Pan; Hu, P. Journal of the American Chemical Society, Vol. 123, Issue 50 https://doi.org/10.1021/ja011446y	journal	December 2001
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Non-steady-state and transient effects in medium-pressure hydrogenation of carbon monoxide over rhodium catalysts Gilhooley, Kevin; Jackson, S. David; Rigby, Stuart Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 82, Issue 2 https://doi.org/10.1039/f19868200431	journal	January 1986
Size and Topological Effects of Rhodium Surfaces, Clusters and Nanoparticles on the Dissociation of CO Filot, Ivo A. W.; Shetty, Sharan G.; Hensen, Emiel J. M. The Journal of Physical Chemistry C, Vol. 115, Issue 29 https://doi.org/10.1021/jp201783f	journal	July 2011
The Mechanism of CO and CO ₂ Hydrogenation to Methanol over Cu-Based Catalysts Studt, Felix; Behrens, Malte; Kunkes, Edward L. ChemCatChem, Vol. 7, Issue 7 https://doi.org/10.1002/cctc.201500123	journal	March 2015
Infrared Spectroscopy Investigation of Fe-Promoted Rh Catalysts Supported on Titania and Ceria for CO Hydrogenation Magee, Joseph W.; Palomino, Robert M.; White, Michael G. Catalysis Letters, Vol. 146, Issue 9 https://doi.org/10.1007/s10562-016-1801-y	journal	July 2016
A Sensible Mechanism of Alkali Promotion in Fischer−Tropsch Synthesis: Adsorbate Mobilities Uner, D. O. Industrial & Engineering Chemistry Research, Vol. 37, Issue 6 https://doi.org/10.1021/ie970696d	journal	June 1998
The effect of alkali and alkaline earth elements on cobalt based Fischer–Tropsch catalysts Lillebø, Andreas Helland; Patanou, Eleni; Yang, Jia Catalysis Today, Vol. 215 https://doi.org/10.1016/j.cattod.2013.03.030	journal	October 2013
Selectivity of Rh catalysts in the syngas reactions. On the role of supports and promoters Bastein, A. G. T. M.; van Der Boogert, W. J.; van Der Lee, G. Applied Catalysis, Vol. 29, Issue 2 https://doi.org/10.1016/S0166-9834(00)82896-1	journal	January 1987
A Review of Recent Literature to Search for an Efficient Catalytic Process for the Conversion of Syngas to Ethanol Subramani, Velu; Gangwal, Santosh K. Energy & Fuels, Vol. 22, Issue 2 https://doi.org/10.1021/ef700411x	journal	March 2008
Investigation of the synthesis of oxygenates from carbon monoxide/hydrogen mixtures on supported rhodium catalysts Burch, R.; Petch, M. I. Applied Catalysis A: General, Vol. 88, Issue 1 https://doi.org/10.1016/0926-860X(92)80195-I	journal	September 1992
Identification of step-edge sites on Rh nanoparticles for facile CO dissociation Ligthart, D. A. J. Michel; Filot, Ivo A. W.; Almutairi, Abdulkarim A. H. Catalysis Communications, Vol. 77 https://doi.org/10.1016/j.catcom.2016.01.006	journal	March 2016
Effect of Li Promoter on titania-supported Rh catalyst for ethanol formation from CO hydrogenation Egbebi, Adefemi; Schwartz, Viviane; Overbury, Steven H. Catalysis Today, Vol. 149, Issue 1-2 https://doi.org/10.1016/j.cattod.2009.07.104	journal	January 2010
Infrared Spectroscopic Studies of CO Adsorption on Rhodium Supported by SiO2, Al2O3, and TiO2 Trautmann, S.; Baerns, M. Journal of Catalysis, Vol. 150, Issue 2 https://doi.org/10.1006/jcat.1994.1352	journal	December 1994
Infrared spectra of chemisorbed CO on Rh Yates, J. T.; Duncan, T. M.; Worley, S. D. The Journal of Chemical Physics, Vol. 70, Issue 3 https://doi.org/10.1063/1.437603	journal	February 1979
Impact of Na Promoter on Structural Properties and Catalytic Performance of CoNi/Al2O3 Nanocatalysts for the CO Hydrogenation Process: Fischer–Tropsch Technology Nikparsa, Paria; Mirzaei, Ali Akbar; Rauch, Reinhard Catalysis Letters, Vol. 146, Issue 1 https://doi.org/10.1007/s10562-015-1620-6	journal	September 2015
A Comparative Study of CO and CO2Hydrogenation over Rh/SiO2 Fisher, Ian A.; Bell, Alexis T. Journal of Catalysis, Vol. 162, Issue 1 https://doi.org/10.1006/jcat.1996.0259	journal	August 1996
CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends Medford, Andrew J.; Shi, Chuan; Hoffmann, Max J. Catalysis Letters, Vol. 145, Issue 3 https://doi.org/10.1007/s10562-015-1495-6	journal	February 2015
CO2 hydrogenation to ethanol over promoted Rh/SiO2 catalysts Kusama, Hitoshi; Okabe, Kiyomi; Sayama, Kazuhiro Catalysis Today, Vol. 28, Issue 3 https://doi.org/10.1016/0920-5861(95)00246-4	journal	May 1996
Effect of Alkali Metal Impurities on Co–Re Catalysts for Fischer–Tropsch Synthesis from Biomass-Derived Syngas Balonek, Christine M.; Lillebø, Andreas H.; Rane, Shreyas Catalysis Letters, Vol. 138, Issue 1-2 https://doi.org/10.1007/s10562-010-0366-4	journal	May 2010
Oxygenates from syngas over highly dispersed cobalt catalysts Matsuzaki, Takehiko; Hanaoka, Taka-aki; Takeuchi, Kazuhiko Catalysis Today, Vol. 36, Issue 3 https://doi.org/10.1016/S0920-5861(96)00224-6	journal	June 1997
Cobalt carbide nanoprisms for direct production of lower olefins from syngas Zhong, Liangshu; Yu, Fei; An, Yunlei Nature, Vol. 538, Issue 7623 https://doi.org/10.1038/nature19786	journal	October 2016
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235149	journal	June 2012
Dissociation of CO on Rh surfaces de Koster, A.; van Santen, R. A. Surface Science, Vol. 233, Issue 3 https://doi.org/10.1016/0039-6028(90)90650-W	journal	July 1990
Progress and perspectives in converting biogas to transportation fuels Yang, Liangcheng; Ge, Xumeng; Wan, Caixia Renewable and Sustainable Energy Reviews, Vol. 40 https://doi.org/10.1016/j.rser.2014.08.008	journal	December 2014
EXAFS and FT-IR Characterization of Mn and Li Promoted Titania-Supported Rh Catalysts for CO Hydrogenation Schwartz, Viviane; Campos, Andrew; Egbebi, Adefemi ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs200281g	journal	August 2011
Role of impurities in the enhancement of C2-oxygenates activity Nonneman, L. E. Y.; Bastein, A. G. T. M.; Ponec, V. Applied Catalysis, Vol. 62, Issue 1 https://doi.org/10.1016/S0166-9834(00)82230-7	journal	June 1990
Intrinsic Selectivity and Structure Sensitivity of Rhodium Catalysts for C ₂₊ Oxygenate Production Yang, Nuoya; Medford, Andrew J.; Liu, Xinyan Journal of the American Chemical Society, Vol. 138, Issue 11 https://doi.org/10.1021/jacs.5b12087	journal	March 2016
Heterogeneous catalytic synthesis of ethanol from biomass-derived syngas Spivey, James J.; Egbebi, Adefemi Chemical Society Reviews, Vol. 36, Issue 9 https://doi.org/10.1039/b414039g	journal	January 2007
An object-oriented scripting interface to a legacy electronic structure code Bahn, S. R.; Jacobsen, K. W. Computing in Science & Engineering, Vol. 4, Issue 3 https://doi.org/10.1109/5992.998641	journal	January 2002
The effect of alkali promotion on CO hydrogenation over Rh/TiO2 Chuang, S. Journal of Catalysis, Vol. 95, Issue 2 https://doi.org/10.1016/0021-9517(85)90121-6	journal	October 1985
Advances in the Rational Design of Rhodium Nanoparticle Catalysts: Control via Manipulation of the Nanoparticle Core and Stabilizer Yuan, Yuan; Yan, Ning; Dyson, Paul J. ACS Catalysis, Vol. 2, Issue 6 https://doi.org/10.1021/cs300142u	journal	April 2012
On the mechanism of ethanol synthesis on rhodium Bwoker, M. Catalysis Today, Vol. 15, Issue 1 https://doi.org/10.1016/0920-5861(92)80123-5	journal	May 1992
A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas Fang, Kegong; Li, Debao; Lin, Minggui Catalysis Today, Vol. 147, Issue 2, p. 133-138 https://doi.org/10.1016/j.cattod.2009.01.038	journal	September 2009
Ethylene hydroformylation and carbon monoxide hydrogenation over modified and unmodified silica supported rhodium catalysts Hanaoka, T.; Arakawa, H.; Matsuzaki, T. Catalysis Today, Vol. 58, Issue 4 https://doi.org/10.1016/S0920-5861(00)00261-3	journal	May 2000
A Method for Evaluating and Correlating Thermodynamic Da ta Shomate, C. Howard The Journal of Physical Chemistry, Vol. 58, Issue 4 https://doi.org/10.1021/j150514a018	journal	April 1954
Mechanism of C₂₊ oxygenate synthesis on Rh catalysts Chuang, Steven S. C.; Stevens, Robert W.; Khatri, Rajesh Topics in Catalysis, Vol. 32, Issue 3-4, p. 225-232 https://doi.org/10.1007/s11244-005-2897-2	journal	March 2005

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