Mechanism of the Water–Gas Shift Reaction Catalyzed by Efficient Ruthenium-Based Catalysts: A Computational and Experimental Study

Stepic R, Wick C, Strobel V, Berger D, Vucemilovic-Alagic N, Haumann M, Wasserscheid P, Smith AS, Smith DM (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Book Volume: 58

Pages Range: 741-745

Journal Issue: 3

DOI: 10.1002/anie.201811627

Abstract

Supported ionic liquid phase (SILP) catalysis enables a highly efficient, Ru-based, homogeneously catalyzed water-gas shift reaction (WGSR) between 100 °C and 150 °C. The active Ru-complexes have been found to exist in imidazolium chloride melts under operating conditions in a dynamic equilibrium, which is dominated by the [Ru(CO) 3 Cl 3 ] ⁻ complex. Herein we present state-of-the-art theoretical calculations to elucidate the reaction mechanism in more detail. We show that the mechanism includes the intermediate formation and degradation of hydrogen chloride, which effectively reduces the high barrier for the formation of the requisite dihydrogen complex. The hypothesis that the rate-limiting step involves water is supported by using D 2 O in continuous catalytic WGSR experiments. The resulting mechanism constitutes a highly competitive alternative to earlier reported generic routes involving nucleophilic addition of hydroxide in the gas phase and in solution.

Authors with CRIS profile

Involved external institutions

Forschungszentrum Jülich / Research Centre Jülich (FZJ) Germany (DE) Rudjer Boskovic Institute (RBI) / Institut Ruđer Bošković (IRB) Croatia (HR)

How to cite

APA:

Stepic, R., Wick, C., Strobel, V., Berger, D., Vucemilovic-Alagic, N., Haumann, M.,... Smith, D.M. (2019). Mechanism of the Water–Gas Shift Reaction Catalyzed by Efficient Ruthenium-Based Catalysts: A Computational and Experimental Study. Angewandte Chemie International Edition, 58(3), 741-745. https://doi.org/10.1002/anie.201811627

MLA:

Stepic, Robert, et al. "Mechanism of the Water–Gas Shift Reaction Catalyzed by Efficient Ruthenium-Based Catalysts: A Computational and Experimental Study." Angewandte Chemie International Edition 58.3 (2019): 741-745.

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