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Investigation of C1 + C1 Coupling Reactions in Cobalt-Catalyzed Fischer-Tropsch Synthesis by a Combined DFT and Kinetic Isotope Study

Department of Chemical Engineering, Norwegian University of Science and Technology, Sem Sælands vei 4, N-7491 Trondheim, Norway
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Catalysts 2019, 9(6), 551; https://doi.org/10.3390/catal9060551
Received: 2 June 2019 / Revised: 13 June 2019 / Accepted: 17 June 2019 / Published: 19 June 2019
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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Abstract

Understanding the chain growth mechanism is of vital importance for the development of catalysts with enhanced selectivity towards long-chain products in cobalt-catalyzed Fischer-Tropsch synthesis. Herein, we discriminate various C1 + C1 coupling reactions by theoretical calculations and kinetic isotope experiments. CHx(x=0−3), CO, HCO, COH, and HCOH are considered as the chain growth monomer respectively, and 24 possible coupling reactions are first investigated by theoretical calculations. Eight possible C1 + C1 coupling reactions are suggested to be energetically favorable because of the relative low reaction barriers. Moreover, five pathways are excluded where the C1 monomers show low thermodynamic stability. Effective chain propagation rates are calculated by deconvoluting from reaction rates of products, and an inverse kinetic isotope effect of the C1 + C1 coupling reaction is observed. The theoretical kinetic isotope effect of CO + CH2 is inverse, which is consistent with the experimental observation. Thus, the CO + CH2 pathway, owing to the relatively lower barrier, the high thermodynamic stability, and the inverse kinetic isotope effect, is suggested to be a favorable pathway. View Full-Text
Keywords: Fischer-Tropsch synthesis; chain growth; CO insertion; kinetic isotope effect; DFT Fischer-Tropsch synthesis; chain growth; CO insertion; kinetic isotope effect; DFT
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Qi, Y.; Yang, J.; Holmen, A.; Chen, D. Investigation of C1 + C1 Coupling Reactions in Cobalt-Catalyzed Fischer-Tropsch Synthesis by a Combined DFT and Kinetic Isotope Study. Catalysts 2019, 9, 551.

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