Understanding the Mechanism of CO Hydrogenation to Oxygenates over Ternary Catalysts: An Integrated Approach Using In Situ and Operando Experimental Techniques
EMSL Project ID
49398
Abstract
The submitted proposal will enable highly focused scientific research using unique facilities and expertise at EMSL. This research is largely complementary to ongoing work on oxygenates formation via CO hydrogenation at WSU, which is based on a grant recently awarded by the National Science Foundation (NSF). As PI in both the EMSL proposal and the NSF granted research, Professor Kruse provides a wealth of experience in both the application and science of heterogeneous catalysis to ensuring sustainable energy and materials solutions for the future. In fact, syngas (CO/H2) which can be generated from renewable resources such as biogas, is currently at the crossroads of many advanced chemical conversion routes. One example is hydroformylation which according to our recent research has the potential of turning from an energy-demanding large-scale process of homogeneous catalysis into a 'one step - one pot' low-cost process of heterogeneous catalysis. Another example is the formation of short-chain alcohols which in the case of syngas-out-of-biomass could be turned entirely green. The submitted EMSL proposal will help lay the essential scientific basis by providing a detailed picture of the catalytically active surface phases of novel ternary base metal-metal oxides and the mechanistic details of the reaction therefore enabling the targeted design of relevant catalyst formulations with the potential of an industrial implementation. The research we describe here is foundational to our integrated research approach in that it suggests using unique EMSL facilities to 1) demonstrate the relevant atomic-scale compositions and dynamic processes at the surface of ternary metal - metal oxide catalysts using APT and ETEM; 2) utilize APT for unique in-situ characterization, atom-by-atom, prior and after catalytic CO hydrogenation and ETEM for in-situ and, respectively, operando-type reaction dynamic studies. The results of APT and ETEM experimental studies at EMSL will be combined with transient kinetic techniques, environmental XPS and DFT calculations at WSU to reach the goal of a predictive catalyst design enabling a large-scale industrial implementation. We advance the working hypothesis that the selective production of oxygenates versus hydrocarbons using the FT technology involves a subtle balance of metal-metal oxide in pristine catalyst formulations. Titania- and niobia- derived metal oxide clusters on the surface of Co-Cu bimetallic catalysts will then promote the formation of the relevant metal-metal oxide local interface structures which develop, in the presence of adsorbing CO and hydrogen, the primary surface complexes such as surface hydroxyl or formate, necessary for a repetitive CO insertion mechanism to take place so as to induce hydrocarbon growth and oxygenate production.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2016-10-01
End Date
2018-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Athariboroujeny M., A. Raub, V. Iablokov, S. Chenakin, L. Kovarik, and N.H. Kruse. 2019. "Competing Mechanisms in CO Hydrogenation over Co-MnOx Catalysts." ACS Catalysis 9, no. 6:5603-5612. PNNL-SA-145155. doi:10.1021/acscatal.9b00967
Collinge G B,Kruse N H,McEwen JS 2017. "Role of Carbon Monoxide in Catalyst Reconstruction for CO Hydrogenation: First-Principles Study of the Composition, Structure, and Stability of Cu/Co(101?2) as a Function of CO Pressure" The Journal of Physical Chemistry C 121(4):2181–2191. 10.1021/acs.jpcc.6b09527
Collinge G.B., N. Kruse, and J. McEwen. 2018. "Dissolution of CoCu Catalyst Step Defects by Co Subcarbonyl Formation." Journal of Catalysis 368. doi:10.1016/j.jcat.2018.08.011
Collinge G.B., Y. Xiang, R. Barbosa, J. McEwen, and N.H. Kruse. 2016. "CO-Induced Inversion of the Layer Sequence of a Model CoCu Catalyst." Surface Science 648. doi:10.1016/j.susc.2015.10.014
lablokou V.S., S.A. Alekseev, S. Gryn, I. Bezverkhyy, V. Zaitsev, L. Kovarik, and V. de Bocarme, et al. 2020. "Superior Fischer-Tropsch Performance of Uniform Cobalt Nanoparticles Deposited into Mesoporous SiC." Journal of Catalysis 383. PNNL-SA-150647. doi:10.1016/j.jcat.2020.01.028
Therrien A.J., A.J. Hensley, M.D. Marcinkowski, R. Zhang, F.R. Lucci, B. Coughlin, and A.C. Schilling, et al. 2018. "An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation." Nature Catalysis. PNNL-SA-135489. doi:10.1038/s41929-018-0028-2
Therrien A.J., A.J. Hensley, R. Zhang, A. Pronschinske, M.D. Marcinkowski, J. McEwen, and E.H. Sykes. 2017. "Characterizing the Geometric and Electronic Structure of Defects in the “29” Copper." Journal of Chemical Physics. doi:10.1063/1.4996729
Therrien A.J., K.J. Groden, A.J. Hensley, A.C. Schilling, R.T. Hannagan, M.D. Marcinkowski, and A. Pronschinske, et al. 2018. "Water Activation by Single Pt Atoms Supported on a Cu2O Thin Film." Journal of Catalysis 364. doi:10.1016/j.jcat.2018.04.024
Voss J., Y. Xiang, G.B. Collinge, D.E. Perea, L. Kovarik, J. McEwen, and N. Kruse. 2018. "Characterization of CoCu- and CoMn-based catalysts for the Fischer Tropsch reaction toward chain-lengthened oxygenates." Topics in Catalysis 61, no. 9-11:1016-1023. PNNL-SA-129636. doi:10.1007/s11244-018-0938-x
Xiang Y ,Kruse N H 2016. "Cobalt–Copper Based Catalysts for Higher Terminal Alcohols Synthesis via Fischer–Tropsch Reaction" Journal of Energy Chemistry 25(6):895–906. 10.1016/j.jechem.2016.09.014
Xiang Y ,Kruse N H 2016. "Tuning the catalytic CO hydrogenation to straight- and long-chaim aldehydes/alcohols and olefins/paraffins" Nature Communications 7():13058. 10.1038/ncomms13058
Xiang Y., L. Kovarik, and N. Kruse. 2019. "Rate and selectivity hysteresis during the carbon monoxide hydrogenation over promoted Co/MnOx catalysts." Nature Communications 10. PNNL-SA-146618. doi:10.1038/s41467-019-11836-z
Zhang R., and J. McEwen. 2018. "Local Environment Sensitivity of the Cu K-Edge XANES Features in Cu-SSZ-13: Analysis from First-Principles." Journal of Physical Chemistry Letters 9, no. 11:3035–3042. doi:10.1021/acs.jpclett.8b00675