Unraveling the Role of the Rh–ZrO₂ Interface in the Water–Gas-Shift Reaction via a First-Principles Microkinetic Study

Abstract

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Escaping Scaling Relationships for Water Dissociation at Interfacial Sites of Zirconia-Supported Rh and Pt Clusters

“…Our research group has previously found the activation of water over pure zirconia to be spontaneous and mildly exothermic. 6 Therefore, the water activation might occur over zirconia first, followed by hydrogen diffusion to the metal frame. The presence of hydrogen at the metal site is desired for further reaction with CO in the WGS process because, as previously observed, CO strongly prefers metal sites.…”

“…Cu, 3 Au, 3 Pt, 2 and Rh 2 ). Varying kinetic barriers are reported for ideal metal surfaces, ranging from as low as 0.67 4 to 0.96 1 eV on Ni(111), ∼ 0.8 eV over Pt(111) 1,5 and Rh(111), 2,6 and even as high as ∼ 2 eV over Au(111). 1,7 Numerous studies strongly advocate the vital role of support, and the metalsupport interface, for the overall catalytic activity.…”

“…1,7 Numerous studies strongly advocate the vital role of support, and the metalsupport interface, for the overall catalytic activity. 6,[8][9][10][11][12] Therefore, both the metal and the support should be considered when investigating such systems computationally. The choice of the supported metal catalyst model is non-trivial; typical models employ either supported finite clusters or nanorods, and different metal-support combinations have been investigated (e.g.…”

“…The choice of the supported metal catalyst model is non-trivial; typical models employ either supported finite clusters or nanorods, and different metal-support combinations have been investigated (e.g. Au/MgO, 7 Cu/ZrO 2 , 13 Rh/ZrO 2 , 6 Ni/Al 2 O 3 , 9 Pt/CeO 2 10 ). In contrast to clean metal surfaces, on the metal-support interfaces such as Ni/Al 2 O 3 , 9 Rh/ZrO 2 , 6 Cu/ZrO 2 , 13 and Au/TiO 2 14 the barriers are reported to be much lower than those on the corresponding pure metals.…”

Catalytic Reaction Mechanism of NO–CO on the ZrO2 (110) and (111) Surfaces

“…As zirconium dioxide (ZrO 2 ) has high thermal stability, excellent redox properties and an acid-basic site on its surface, it is a good catalyst and support material for various reactions, such as CO 2 methanation [3,4], water-gas shift [5,6], NH 3 selective catalytic reduction [7,8], and hydrodeoxygenation [9,10]. Especially, the transition metal oxide dispersed onto the surface of ZrO 2 exhibits powerful activity for NO reduction.…”