An integrated approach to Deacon chemistry on RuO2-based catalysts
authors Teschner, D; Farra, R; Yao, LD; Schlogl, R; Soerijanto, H; Schomacker, R; Schmidt, T; Szentmiklosi, L; Amrute, AP; Mondelli, C; Perez-Ramirez, J; Novell-Leruth, G; Lopez, N
nationality International
journal JOURNAL OF CATALYSIS
author keywords HCl oxidation; RuO2/SnO2; HRTEM; PGAA; TAP; DFT; Kinetics; Deacon reaction
keywords HCL OXIDATION; ACTIVATION-ANALYSIS; MECHANISM; RUO2(110); HYDROGEN; RUO2
abstract Rationally designed RuO2-based Deacon catalysts can contribute to massive energy saving compared to the current electrolysis process in chemically recycling HCl to produce molecular chlorine. Here, we report on our integrated approach between state-of-the-art experiments and calculations. The aim is to understand industrial Deacon catalyst in its realistic surface state and to derive mechanistic insights into this sustainable reaction. We show that the practically relevant RuO2/SnO2 consists of two major RuO2 morphologies, namely 2-4 nm-sized particles and 1-3-ML-thick epitaxial RuO2 films attached to the SnO2 support particles. A large fraction of the small nanoparticles expose {1 1 0) and {1 0 1} facets, whereas the film grows with the same orientations, due to the preferential surface orientation of the rutile-type support. Steady-state Deacon kinetics indicate a medium-to-strong positive effect of the partial pressures of reactants and deep inhibition by both water and chlorine products. Temporal Analysis of Products and in situ Prompt Gamma Activation Analysis strongly suggest a Langmuir-Hinshelwood mechanism and that adsorbed Cl poisons the surface. Under relevant operation conditions, the reactivity is proportional to the coverage of a specific atomic oxygen species. On the extensively chlorinated surface that can be described as surface oxy-chloride, oxygen activation is the rate-determining step. DFT-based micro-kinetic modeling reproduced all experimental observations and additionally suggested that the reaction is structure sensitive. Out of the investigated models, the 2 ML RuO2 film-covered SnO2 gives rise to significantly higher reactivity than the (1 0 1) surface, whereas the 1 ML film seems to be inactive. (C) 2011 Elsevier Inc. All rights reserved.
publisher ACADEMIC PRESS INC ELSEVIER SCIENCE
issn 0021-9517
year published 2012
volume 285
issue 1
beginning page 273
ending page 284
digital object identifier (doi) 10.1016/j.jcat.2011.09.039
web of science category Chemistry, Physical; Engineering, Chemical
subject category Chemistry; Engineering
unique article identifier WOS:000300074300030
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journal impact factor 6.759
5 year journal impact factor 7.502
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