Mechanism of the Water–Gas Shift Reaction Catalyzed by Efficient Ruthenium‐Based Catalysts: A Computational and Experimental Study. Issue 3 (12th December 2018)

• Record Type: Journal Article
• Authors: Stepić, Robert; Wick, Christian R.; Strobel, Vinzent; Berger, Daniel; Vučemilović‐Alagić, Nataša; Haumann, Marco; Wasserscheid, Peter; Smith, Ana‐Sunčana; Smith, David M.
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 3(2019)
• Page Start: 741
• Page End: 745
• Publication Date: 2018-12-12
• Subjects: ab initio calculations -- reaction mechanisms -- supported catalysts -- ruthenium -- water–gas shift reaction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201811627
• Languages: English
• ISSNs: 1433-7851

Abstract

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 Cl3 ] − 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 D2 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. Abstract : Shift work : Using high‐level quantum chemical techniques, leads to a new mechanism for the low temperature water–gas shift reaction (WGSR) using ruthenium‐based supported ionic liquid phase (SILP) catalysts. A mechanism involving anionic, chloride‐rich ruthenium carbonyl complexes is supported by the kinetic isotope effect of the reaction.