Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas
Abstract
Controlling selectivity is a key goal in the design of a heterogeneous catalyst. Herein, we present detailed characterization and activity of silica–supported cobalt catalysts modified by atomic layer deposition of ZnO. After reduction, the resulting catalysts exhibit substantial selectivity towards alcohol production during CO hydrogenation compared to catalysts containing only cobalt. The prepared catalysts have up to 46 % selectivity toward alcohols with 39 % of the alcohols corresponding to ethanol and other higher alcohols, albeit with reduced activity. In situ characterization of the catalyst by X–ray diffraction and X–ray absorption spectroscopy reveals details on the structural evolution in syngas, CO+H2, and shows that ZnO promotion of Co results in the formation of Co2C under catalytic conditions. A mechanism is proposed, supported by density functional theory calculations, which explains Co2C formation by the blocking of Co step sites by Zn species. The ZnO acts a dual promoter both by facilitating Co2C formation and by modifying the resulting Co2C. In conclusion, the Co2C formed from the ZnOpromoted Co catalysts displays improved thermal stability and selectivity compared with similar Co2C catalysts without Zn.
- Authors:
-
[2];
[2];
[1]
- Stanford Univ., Stanford, CA (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Stanford Univ., Stanford, CA (United States); Technical Univ. of Denmark Kongens, Lyngby (Denmark)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1507160
- Grant/Contract Number:
- AC02-76SF00515; DGE‐114747
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemCatChem
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1867-3880
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; higher alcohol synthesis; in situ characterization; EXAFS modelling; cobalt carbide; density functional theory
Citation Formats
Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., and Bent, Stacey F. Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas. United States: N. p., 2018.
Web. doi:10.1002/cctc.201801724.
Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., & Bent, Stacey F. Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas. United States. https://doi.org/10.1002/cctc.201801724
Singh, Joseph A., Hoffman, Adam S., Schumann, Julia, Boubnov, Alexey, Asundi, Arun S., Nathan, Sindhu S., Nørskov, Jens, Bare, Simon R., and Bent, Stacey F. Tue .
"Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas". United States. https://doi.org/10.1002/cctc.201801724. https://www.osti.gov/servlets/purl/1507160.
@article{osti_1507160,
title = {Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas},
author = {Singh, Joseph A. and Hoffman, Adam S. and Schumann, Julia and Boubnov, Alexey and Asundi, Arun S. and Nathan, Sindhu S. and Nørskov, Jens and Bare, Simon R. and Bent, Stacey F.},
abstractNote = {Controlling selectivity is a key goal in the design of a heterogeneous catalyst. Herein, we present detailed characterization and activity of silica–supported cobalt catalysts modified by atomic layer deposition of ZnO. After reduction, the resulting catalysts exhibit substantial selectivity towards alcohol production during CO hydrogenation compared to catalysts containing only cobalt. The prepared catalysts have up to 46 % selectivity toward alcohols with 39 % of the alcohols corresponding to ethanol and other higher alcohols, albeit with reduced activity. In situ characterization of the catalyst by X–ray diffraction and X–ray absorption spectroscopy reveals details on the structural evolution in syngas, CO+H2, and shows that ZnO promotion of Co results in the formation of Co2C under catalytic conditions. A mechanism is proposed, supported by density functional theory calculations, which explains Co2C formation by the blocking of Co step sites by Zn species. The ZnO acts a dual promoter both by facilitating Co2C formation and by modifying the resulting Co2C. In conclusion, the Co2C formed from the ZnOpromoted Co catalysts displays improved thermal stability and selectivity compared with similar Co2C catalysts without Zn.},
doi = {10.1002/cctc.201801724},
journal = {ChemCatChem},
number = 2,
volume = 11,
place = {United States},
year = {2018},
month = {12}
}
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Works referenced in this record:
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Metal–support interactions in cobalt-aluminum co-precipitated catalysts: XPS and CO adsorption studies
journal, October 2001
- Khassin, Alexander A.; Yurieva, Tamara M.; Kaichev, Vasiliy V.
- Journal of Molecular Catalysis A: Chemical, Vol. 175, Issue 1-2
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
Study on CaO-promoted Co/AC catalysts for synthesis of higher alcohols from syngas
journal, October 2016
- Du, Hong; Zhu, Hejun; Chen, Xingkun
- Fuel, Vol. 182
Study on a cobalt silica catalyst during reduction and Fischer–Tropsch reaction: In situ EXAFS compared to XPS and XRD
journal, March 1998
- Ernst, B.; Bensaddik, A.; Hilaire, L.
- Catalysis Today, Vol. 39, Issue 4
The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer–Tropsch reaction
journal, August 2005
- Xiong, Jianmin; Ding, Yunjie; Wang, Tao
- Catalysis Letters, Vol. 102, Issue 3-4
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
Stability of Carbon on Cobalt Surfaces in Fischer–Tropsch Reaction Conditions: A DFT Study
journal, September 2014
- Corral Valero, Manuel; Raybaud, Pascal
- The Journal of Physical Chemistry C, Vol. 118, Issue 39
ALD grown zinc oxide with controllable electrical properties
journal, June 2012
- Guziewicz, E.; Godlewski, M.; Wachnicki, L.
- Semiconductor Science and Technology, Vol. 27, Issue 7
First-Principles Study of C 2 Oxygenates Synthesis Directly from Syngas over CoCu Bimetallic Catalysts
journal, December 2014
- Xu, Xin-Chao; Su, Junjie; Tian, Pengfei
- The Journal of Physical Chemistry C, Vol. 119, Issue 1
Density Functional Theory Study of Iron and Cobalt Carbides for Fischer−Tropsch Synthesis
journal, December 2009
- Cheng, Jun; Hu, P.; Ellis, Peter
- The Journal of Physical Chemistry C, Vol. 114, Issue 2
In situ and operando structural characterisation of a Fischer–Tropsch supported cobalt catalyst
journal, August 2011
- Rochet, Amélie; Moizan, Virginie; Pichon, Christophe
- Catalysis Today, Vol. 171, Issue 1
Implementation of ultrasoft pseudopotentials in ab initio molecular dynamics
journal, March 1991
- Laasonen, Kari; Car, Roberto; Lee, Changyol
- Physical Review B, Vol. 43, Issue 8
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis
journal, May 2016
- Kuld, S.; Thorhauge, M.; Falsig, H.
- Science, Vol. 352, Issue 6288
Oxidation states of active catalytic centers in ethanol steam reforming reaction on ceria based Rh promoted Co catalysts: An XPS study
journal, February 2015
- Varga, Erika; Ferencz, Zsuzsa; Oszkó, Albert
- Journal of Molecular Catalysis A: Chemical, Vol. 397
Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010
- Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 21
Influence of carbide formation on oxygenates selectivity during Fischer-Tropsch synthesis over Ce-containing Co catalysts
journal, March 2016
- Gnanamani, Muthu Kumaran; Jacobs, Gary; Graham, Uschi M.
- Catalysis Today, Vol. 261
A study of Co/Zn/TiO2 catalysts in the Fischer–Tropsch reaction
journal, March 2002
- Madikizela, N.
- Journal of Molecular Catalysis A: Chemical, Vol. 181, Issue 1-2
CoMoS/K catalysts for higher alcohol synthesis from syngas prepared by mechano-chemical activation of molybdenite
journal, January 2014
- Simeonov, Kalin; Kim, Jae Hyung; Ferrari, Daniela
- Catalysis Science & Technology, Vol. 4, Issue 4
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
CO hydrogenation over Ni- and Co-based catalysts: Influence of alkali addition on morphological and catalytic properties
journal, March 1995
- Mirodatos, C.; Brum Pereira, E.; Gomez Cobo, A.
- Topics in Catalysis, Vol. 2, Issue 1-4
Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS 2 Catalysts
journal, June 2013
- Santos, Vera P.; van der Linden, Bart; Chojecki, Adam
- ACS Catalysis, Vol. 3, Issue 7
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
In situXRD investigation of the evolution of alumina-supported cobaltcatalysts under realistic conditions of Fischer-Tropsch synthesis
journal, January 2010
- Karaca, Héline; Hong, Jingping; Fongarland, Pascal
- Chem. Commun., Vol. 46, Issue 5
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni
journal, January 2011
- Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P.
- Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730
High Alcohols Synthesis via Fischer–Tropsch Reaction at Cobalt Metal/Carbide Interface
journal, May 2015
- Pei, Yan-Peng; Liu, Jin-Xun; Zhao, Yong-Hui
- ACS Catalysis, Vol. 5, Issue 6
In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst
journal, September 2016
- Navarro, Violeta; van Spronsen, Matthijs A.; Frenken, Joost W. M.
- Nature Chemistry, Vol. 8, Issue 10
In situ observation of phase changes of a silica-supported cobalt catalyst for the Fischer–Tropsch process by the development of a synchrotron-compatible in situ/operando powder X-ray diffraction cell
journal, October 2018
- Hoffman, Adam S.; Singh, Joseph A.; Bent, Stacey F.
- Journal of Synchrotron Radiation, Vol. 25, Issue 6
In situ monitoring during the transition of cobalt carbide to metal state and its application as Fischer–Tropsch catalyst in slurry phase
journal, November 2013
- Kwak, Geunjae; Woo, Min Hee; Kang, Seok Chang
- Journal of Catalysis, Vol. 307
Fischer–Tropsch synthesis: An XAS/XRPD combined in situ study from catalyst activation to deactivation
journal, July 2012
- Tsakoumis, Nikolaos E.; Voronov, Alexey; Rønning, Magnus
- Journal of Catalysis, Vol. 291
Long-Chain Terminal Alcohols through Catalytic CO Hydrogenation
journal, May 2013
- Xiang, Yizhi; Chitry, Véronique; Liddicoat, Peter
- Journal of the American Chemical Society, Vol. 135, Issue 19
Variation Trends of CO Hydrogenation Performance of (Al)–O–(Zn) Supported Cobalt Nanocomposites: Effects of Gradual Doping with Zn–O Lewis Base
journal, January 2016
- Xing, Yu; Liu, Zhenxin; Xue, Yingying
- Catalysis Letters, Vol. 146, Issue 3
Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates
journal, August 2017
- Yang, Nuoya; Yoo, Jong Suk; Schumann, Julia
- ACS Catalysis, Vol. 7, Issue 9
The preparation and study of sol–gel synthesized Co/Zn/TiO2 Fischer–Tropsch catalysts
journal, February 2007
- Madikizela-Mnqanqeni, Nobuntu N.; Coville, Neil J.
- Applied Catalysis A: General, Vol. 317, Issue 2
Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis
journal, June 2016
- Lu, Junling; Elam, Jeffrey W.; Stair, Peter C.
- Surface Science Reports, Vol. 71, Issue 2
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
An Atomistic View of the Incipient Growth of Zinc Oxide Nanolayers
journal, August 2016
- Chu, Manh Hung; Tian, Liang; Chaker, Ahmad
- Crystal Growth & Design, Vol. 16, Issue 9
Fischer–Tropsch Synthesis: Characterization and Reaction Testing of Cobalt Carbide
journal, October 2011
- Mohandas, Janet Chakkamadathil; Gnanamani, Muthu Kumaran; Jacobs, Gary
- ACS Catalysis, Vol. 1, Issue 11
Catalyst Design with Atomic Layer Deposition
journal, February 2015
- O’Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan
- ACS Catalysis, Vol. 5, Issue 3
Selectivity of Synthesis Gas Conversion to C 2+ Oxygenates on fcc(111) Transition-Metal Surfaces
journal, March 2018
- Schumann, Julia; Medford, Andrew J.; Yoo, Jong Suk
- ACS Catalysis, Vol. 8, Issue 4
Conformal ZnO coatings on high surface area silica gel using atomic layer deposition
journal, July 2008
- Libera, J. A.; Elam, J. W.; Pellin, M. J.
- Thin Solid Films, Vol. 516, Issue 18
In situ magnetometer study on the formation and stability of cobalt carbide in Fischer–Tropsch synthesis
journal, October 2014
- Claeys, M.; Dry, M. E.; van Steen, E.
- Journal of Catalysis, Vol. 318
Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition
journal, June 2017
- Singh, Joseph A.; Yang, Nuoya; Bent, Stacey F.
- Annual Review of Chemical and Biomolecular Engineering, Vol. 8, Issue 1
In Situ XRD Study of the Influence of Thermal Treatment on the Characteristics and the Catalytic Properties of Cobalt-Based Fischer–Tropsch Catalysts
journal, January 2002
- Enache, Dan I.; Rebours, Bernadette; Roy-Auberger, Magalie
- Journal of Catalysis, Vol. 205, Issue 2
Thin film characterization of zinc tin oxide deposited by thermal atomic layer deposition
journal, April 2014
- Mullings, Marja N.; Hägglund, Carl; Tanskanen, Jukka T.
- Thin Solid Films, Vol. 556
Understanding the Active Sites of CO Hydrogenation on Pt–Co Catalysts Prepared Using Atomic Layer Deposition
journal, January 2018
- Singh, Joseph A.; Yang, Nuoya; Liu, Xinyan
- The Journal of Physical Chemistry C, Vol. 122, Issue 4
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
Active Centers of Catalysts for Higher Alcohol Synthesis from Syngas: A Review
journal, June 2018
- Ao, Min; Pham, Gia Hung; Sunarso, Jaka
- ACS Catalysis, Vol. 8, Issue 8
Selective synthesis of alcohols from syngas and hydroformylation of ethylene over supported cluster-derived cobalt catalysts
journal, January 1996
- Llorca, J.; Barbier, A.; Martin, G. A.
- Catalysis Letters, Vol. 42, Issue 1-2
Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument
journal, January 2017
- Camacho-Bunquin, Jeffrey; Aich, Payoli; Ferrandon, Magali
- Journal of Catalysis, Vol. 345
Role of the Cu–Co alloy and cobalt carbide in higher alcohol synthesis
journal, September 2000
- Volkova, G. G.; Yurieva, T. M.; Plyasova, L. M.
- Journal of Molecular Catalysis A: Chemical, Vol. 158, 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
In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol
journal, September 2012
- Karim, Ayman M.; Howard, Christopher; Roberts, Benjamin
- ACS Catalysis, Vol. 2, Issue 11
XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films
journal, July 1996
- Islam, Md Nurul; Ghosh, T. B.; Chopra, K. L.
- Thin Solid Films, Vol. 280, Issue 1-2
Combined XRD and XANES studies of a Re-promoted Co/γ-Al2O3 catalyst at Fischer–Tropsch synthesis conditions
journal, October 2010
- Rønning, Magnus; Tsakoumis, Nikolaos E.; Voronov, Alexey
- Catalysis Today, Vol. 155, Issue 3-4
Microstructure of Supported Cobalt Fischer-Tropsch Catalysts
journal, October 2008
- Ducreux, O.; Rebours, B.; Lynch, J.
- Oil & Gas Science and Technology - Revue de l'IFP, Vol. 64, Issue 1
Ga-promoted CO insertion and C–C coupling on Co catalysts for the synthesis of ethanol and higher alcohols from syngas
journal, December 2017
- An, Zhe; Ning, Xun; He, Jing
- Journal of Catalysis, Vol. 356
Heterogeneous Catalytic Synthesis of Ethanol from Biomass-Derived Syngas
journal, December 2007
- Spivey, James J.; Egbebi, Adefemi
- ChemInform, Vol. 38, Issue 50
Works referencing / citing this record:
Elucidating the K‐Edge X‐Ray Absorption Near‐Edge Structure of Cobalt Carbide
journal, June 2019
- Moya‐Cancino, José G.; Honkanen, Ari‐Pekka; van der Eerden, Ad M. J.
- ChemCatChem, Vol. 11, Issue 13