Mechanism of the Water–Gas Shift Reaction Catalyzed by Efficient Ruthenium‐Based Catalysts: A Computational and Experimental Study |
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Authors: | Robert Stepi ,Christian R. Wick,Vinzent Strobel,Daniel Berger,Nata a Vu
emilovi ‐Alagi ,Marco Haumann,Peter Wasserscheid,Ana‐Sun
ana Smith,David M. Smith |
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Affiliation: | Robert Stepić,Christian R. Wick,Vinzent Strobel,Daniel Berger,Nataša Vučemilović‐Alagić,Marco Haumann,Peter Wasserscheid,Ana‐Sunčana Smith,David M. Smith |
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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)3Cl3]? 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 D2O 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. |
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Keywords: | Ab-initio-Rechnungen Reaktionsmechanismen Ruthenium Trä gerkatalysatoren Wassergas-Shift-Reaktion |
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