Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas

Singh, Joseph A.; Hoffman, Adam S.; Schumann, Julia; Boubnov, Alexey; Asundi, Arun S.; Nathan, Sindhu S.; Nørskov, Jens; Bare, Simon R.; Bent, Stacey F.

doi:10.1002/cctc.201801724

Title: Role of Co₂C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas

Journal Article · 04 December 2018 · ChemCatChem

DOI: https://doi.org/10.1002/cctc.201801724 · OSTI ID:1507160

Singh, Joseph A. ^[1];

^[2]; Schumann, Julia ^[1]; Boubnov, Alexey ^[2]; Asundi, Arun S. ^[1]; Nathan, Sindhu S. ^[1]; Nørskov, Jens ^[3];

^[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)

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.

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515; DGE‐114747

OSTI ID:: 1507160

Journal Information:: ChemCatChem, Vol. 11, Issue 2; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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References (58)

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Metal–support interactions in cobalt-aluminum co-precipitated catalysts: XPS and CO adsorption studies Khassin, Alexander A.; Yurieva, Tamara M.; Kaichev, Vasiliy V. Journal of Molecular Catalysis A: Chemical, Vol. 175, Issue 1-2 https://doi.org/10.1016/S1381-1169(01)00216-3	journal	October 2001
Status and prospects in higher alcohols synthesis from syngas Luk, Ho Ting; Mondelli, Cecilia; Ferré, Daniel Curulla Chemical Society Reviews, Vol. 46, Issue 5 https://doi.org/10.1039/C6CS00324A	journal	January 2017
Study on CaO-promoted Co/AC catalysts for synthesis of higher alcohols from syngas Du, Hong; Zhu, Hejun; Chen, Xingkun Fuel, Vol. 182 https://doi.org/10.1016/j.fuel.2016.05.089	journal	October 2016
The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer–Tropsch reaction Xiong, Jianmin; Ding, Yunjie; Wang, Tao Catalysis Letters, Vol. 102, Issue 3-4 https://doi.org/10.1007/s10562-005-5867-1	journal	August 2005
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502 https://doi.org/10.1088/0953-8984/21/39/395502	journal	September 2009
Stability of Carbon on Cobalt Surfaces in Fischer–Tropsch Reaction Conditions: A DFT Study Corral Valero, Manuel; Raybaud, Pascal The Journal of Physical Chemistry C, Vol. 118, Issue 39 https://doi.org/10.1021/jp5004177	journal	September 2014
ALD grown zinc oxide with controllable electrical properties Guziewicz, E.; Godlewski, M.; Wachnicki, L. Semiconductor Science and Technology, Vol. 27, Issue 7 https://doi.org/10.1088/0268-1242/27/7/074011	journal	June 2012
First-Principles Study of C ₂ Oxygenates Synthesis Directly from Syngas over CoCu Bimetallic Catalysts Xu, Xin-Chao; Su, Junjie; Tian, Pengfei The Journal of Physical Chemistry C, Vol. 119, Issue 1 https://doi.org/10.1021/jp5065159	journal	December 2014
Density Functional Theory Study of Iron and Cobalt Carbides for Fischer−Tropsch Synthesis Cheng, Jun; Hu, P.; Ellis, Peter The Journal of Physical Chemistry C, Vol. 114, Issue 2 https://doi.org/10.1021/jp908482q	journal	December 2009
In situ and operando structural characterisation of a Fischer–Tropsch supported cobalt catalyst Rochet, Amélie; Moizan, Virginie; Pichon, Christophe Catalysis Today, Vol. 171, Issue 1 https://doi.org/10.1016/j.cattod.2011.03.079	journal	August 2011
Implementation of ultrasoft pseudopotentials in ab initio molecular dynamics Laasonen, Kari; Car, Roberto; Lee, Changyol Physical Review B, Vol. 43, Issue 8 https://doi.org/10.1103/PhysRevB.43.6796	journal	March 1991
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis Kuld, S.; Thorhauge, M.; Falsig, H. Science, Vol. 352, Issue 6288 https://doi.org/10.1126/science.aaf0718	journal	May 2016
Oxidation states of active catalytic centers in ethanol steam reforming reaction on ceria based Rh promoted Co catalysts: An XPS study Varga, Erika; Ferencz, Zsuzsa; Oszkó, Albert Journal of Molecular Catalysis A: Chemical, Vol. 397 https://doi.org/10.1016/j.molcata.2014.11.010	journal	February 2015
Parameter-free calculations of X-ray spectra with FEFF9 Rehr, John J.; Kas, Joshua J.; Vila, Fernando D. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/b926434e	journal	January 2010
Influence of carbide formation on oxygenates selectivity during Fischer-Tropsch synthesis over Ce-containing Co catalysts Gnanamani, Muthu Kumaran; Jacobs, Gary; Graham, Uschi M. Catalysis Today, Vol. 261 https://doi.org/10.1016/j.cattod.2015.08.047	journal	March 2016
A study of Co/Zn/TiO2 catalysts in the Fischer–Tropsch reaction Madikizela, N. Journal of Molecular Catalysis A: Chemical, Vol. 181, Issue 1-2 https://doi.org/10.1016/S1381-1169(01)00357-0	journal	March 2002
CoMoS/K catalysts for higher alcohol synthesis from syngas prepared by mechano-chemical activation of molybdenite Simeonov, Kalin; Kim, Jae Hyung; Ferrari, Daniela Catalysis Science & Technology, Vol. 4, Issue 4 https://doi.org/10.1039/c3cy00865g	journal	January 2014
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
CO hydrogenation over Ni- and Co-based catalysts: Influence of alkali addition on morphological and catalytic properties Mirodatos, C.; Brum Pereira, E.; Gomez Cobo, A. Topics in Catalysis, Vol. 2, Issue 1-4 https://doi.org/10.1007/BF01491966	journal	March 1995
Mechanistic Insight into the Synthesis of Higher Alcohols from Syngas: The Role of K Promotion on MoS ₂ Catalysts Santos, Vera P.; van der Linden, Bart; Chojecki, Adam ACS Catalysis, Vol. 3, Issue 7 https://doi.org/10.1021/cs4003518	journal	June 2013
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
In situXRD investigation of the evolution of alumina-supported cobaltcatalysts under realistic conditions of Fischer-Tropsch synthesis Karaca, Héline; Hong, Jingping; Fongarland, Pascal Chem. Commun., Vol. 46, Issue 5 https://doi.org/10.1039/B920110F	journal	January 2010
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P. Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730 https://doi.org/10.1016/j.apsusc.2010.10.051	journal	January 2011
High Alcohols Synthesis via Fischer–Tropsch Reaction at Cobalt Metal/Carbide Interface Pei, Yan-Peng; Liu, Jin-Xun; Zhao, Yong-Hui ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00791	journal	May 2015
In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst Navarro, Violeta; van Spronsen, Matthijs A.; Frenken, Joost W. M. Nature Chemistry, Vol. 8, Issue 10 https://doi.org/10.1038/nchem.2613	journal	September 2016
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 Hoffman, Adam S.; Singh, Joseph A.; Bent, Stacey F. Journal of Synchrotron Radiation, Vol. 25, Issue 6 https://doi.org/10.1107/S1600577518013942	journal	October 2018
In situ monitoring during the transition of cobalt carbide to metal state and its application as Fischer–Tropsch catalyst in slurry phase Kwak, Geunjae; Woo, Min Hee; Kang, Seok Chang Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.06.029	journal	November 2013
Fischer–Tropsch synthesis: An XAS/XRPD combined in situ study from catalyst activation to deactivation Tsakoumis, Nikolaos E.; Voronov, Alexey; Rønning, Magnus Journal of Catalysis, Vol. 291 https://doi.org/10.1016/j.jcat.2012.04.018	journal	July 2012
Long-Chain Terminal Alcohols through Catalytic CO Hydrogenation Xiang, Yizhi; Chitry, Véronique; Liddicoat, Peter Journal of the American Chemical Society, Vol. 135, Issue 19 https://doi.org/10.1021/ja402512r	journal	May 2013
Variation Trends of CO Hydrogenation Performance of (Al)–O–(Zn) Supported Cobalt Nanocomposites: Effects of Gradual Doping with Zn–O Lewis Base Xing, Yu; Liu, Zhenxin; Xue, Yingying Catalysis Letters, Vol. 146, Issue 3 https://doi.org/10.1007/s10562-016-1692-y	journal	January 2016
Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates Yang, Nuoya; Yoo, Jong Suk; Schumann, Julia ACS Catalysis, Vol. 7, Issue 9 https://doi.org/10.1021/acscatal.7b01851	journal	August 2017
The preparation and study of sol–gel synthesized Co/Zn/TiO2 Fischer–Tropsch catalysts Madikizela-Mnqanqeni, Nobuntu N.; Coville, Neil J. Applied Catalysis A: General, Vol. 317, Issue 2 https://doi.org/10.1016/j.apcata.2006.10.026	journal	February 2007
Atomic layer deposition—Sequential self-limiting surface reactions for advanced catalyst “bottom-up” synthesis Lu, Junling; Elam, Jeffrey W.; Stair, Peter C. Surface Science Reports, Vol. 71, Issue 2 https://doi.org/10.1016/j.surfrep.2016.03.003	journal	June 2016
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
An Atomistic View of the Incipient Growth of Zinc Oxide Nanolayers Chu, Manh Hung; Tian, Liang; Chaker, Ahmad Crystal Growth & Design, Vol. 16, Issue 9 https://doi.org/10.1021/acs.cgd.6b00844	journal	August 2016
Fischer–Tropsch Synthesis: Characterization and Reaction Testing of Cobalt Carbide Mohandas, Janet Chakkamadathil; Gnanamani, Muthu Kumaran; Jacobs, Gary ACS Catalysis, Vol. 1, Issue 11 https://doi.org/10.1021/cs200236q	journal	October 2011
Catalyst Design with Atomic Layer Deposition O’Neill, Brandon J.; Jackson, David H. K.; Lee, Jechan ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/cs501862h	journal	February 2015
Selectivity of Synthesis Gas Conversion to C ₂₊ Oxygenates on fcc(111) Transition-Metal Surfaces Schumann, Julia; Medford, Andrew J.; Yoo, Jong Suk ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.8b00201	journal	March 2018
Conformal ZnO coatings on high surface area silica gel using atomic layer deposition Libera, J. A.; Elam, J. W.; Pellin, M. J. Thin Solid Films, Vol. 516, Issue 18 https://doi.org/10.1016/j.tsf.2007.11.044	journal	July 2008
In situ magnetometer study on the formation and stability of cobalt carbide in Fischer–Tropsch synthesis Claeys, M.; Dry, M. E.; van Steen, E. Journal of Catalysis, Vol. 318 https://doi.org/10.1016/j.jcat.2014.08.002	journal	October 2014
Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition Singh, Joseph A.; Yang, Nuoya; Bent, Stacey F. Annual Review of Chemical and Biomolecular Engineering, Vol. 8, Issue 1 https://doi.org/10.1146/annurev-chembioeng-060816-101547	journal	June 2017
In Situ XRD Study of the Influence of Thermal Treatment on the Characteristics and the Catalytic Properties of Cobalt-Based Fischer–Tropsch Catalysts Enache, Dan I.; Rebours, Bernadette; Roy-Auberger, Magalie Journal of Catalysis, Vol. 205, Issue 2 https://doi.org/10.1006/jcat.2001.3462	journal	January 2002
Thin film characterization of zinc tin oxide deposited by thermal atomic layer deposition Mullings, Marja N.; Hägglund, Carl; Tanskanen, Jukka T. Thin Solid Films, Vol. 556 https://doi.org/10.1016/j.tsf.2014.01.068	journal	April 2014
Understanding the Active Sites of CO Hydrogenation on Pt–Co Catalysts Prepared Using Atomic Layer Deposition Singh, Joseph A.; Yang, Nuoya; Liu, Xinyan The Journal of Physical Chemistry C, Vol. 122, Issue 4 https://doi.org/10.1021/acs.jpcc.7b10541	journal	January 2018
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
Active Centers of Catalysts for Higher Alcohol Synthesis from Syngas: A Review Ao, Min; Pham, Gia Hung; Sunarso, Jaka ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b01391	journal	June 2018
Selective synthesis of alcohols from syngas and hydroformylation of ethylene over supported cluster-derived cobalt catalysts Llorca, J.; Barbier, A.; Martin, G. A. Catalysis Letters, Vol. 42, Issue 1-2 https://doi.org/10.1007/BF00814471	journal	January 1996
Single-site zinc on silica catalysts for propylene hydrogenation and propane dehydrogenation: Synthesis and reactivity evaluation using an integrated atomic layer deposition-catalysis instrument Camacho-Bunquin, Jeffrey; Aich, Payoli; Ferrandon, Magali Journal of Catalysis, Vol. 345 https://doi.org/10.1016/j.jcat.2016.10.017	journal	January 2017
Role of the Cu–Co alloy and cobalt carbide in higher alcohol synthesis Volkova, G. G.; Yurieva, T. M.; Plyasova, L. M. Journal of Molecular Catalysis A: Chemical, Vol. 158, Issue 1 https://doi.org/10.1016/S1381-1169(00)00110-2	journal	September 2000
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
In Situ X-ray Absorption Fine Structure Studies on the Effect of pH on Pt Electronic Density during Aqueous Phase Reforming of Glycerol Karim, Ayman M.; Howard, Christopher; Roberts, Benjamin ACS Catalysis, Vol. 2, Issue 11 https://doi.org/10.1021/cs3005049	journal	September 2012
XPS and X-ray diffraction studies of aluminum-doped zinc oxide transparent conducting films Islam, Md Nurul; Ghosh, T. B.; Chopra, K. L. Thin Solid Films, Vol. 280, Issue 1-2 https://doi.org/10.1016/0040-6090(95)08239-5	journal	July 1996
Combined XRD and XANES studies of a Re-promoted Co/γ-Al2O3 catalyst at Fischer–Tropsch synthesis conditions Rønning, Magnus; Tsakoumis, Nikolaos E.; Voronov, Alexey Catalysis Today, Vol. 155, Issue 3-4 https://doi.org/10.1016/j.cattod.2009.10.010	journal	October 2010
Microstructure of Supported Cobalt Fischer-Tropsch Catalysts Ducreux, O.; Rebours, B.; Lynch, J. Oil & Gas Science and Technology - Revue de l'IFP, Vol. 64, Issue 1 https://doi.org/10.2516/ogst:2008039	journal	October 2008
Ga-promoted CO insertion and C–C coupling on Co catalysts for the synthesis of ethanol and higher alcohols from syngas An, Zhe; Ning, Xun; He, Jing Journal of Catalysis, Vol. 356 https://doi.org/10.1016/j.jcat.2017.09.020	journal	December 2017
Heterogeneous Catalytic Synthesis of Ethanol from Biomass-Derived Syngas Spivey, James J.; Egbebi, Adefemi ChemInform, Vol. 38, Issue 50 https://doi.org/10.1002/chin.200750248	journal	December 2007

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Title: Role of Co2C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas

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Title: Role of Co₂C in ZnO-promoted Co Catalysts for Alcohol Synthesis from Syngas