First‐Principles Computational Screening of Dopants to Improve the Deacon Process over RuO2

Abstract

AbstractDoping of metal oxides is a promising route to further optimize their catalytic performance. To guide corresponding experimental endeavors, we performed a DFT‐based computational screening study for a wide range of metal dopant atoms in rutile RuO2. With a focus on the Deacon process, that is, the catalytic oxidation of HCl to chlorine and water, we used the rate‐controlling Cl desorption energy as a reactivity descriptor. As stability descriptors, we employed the dopant surface segregation energy and as the dopant thermodynamic stability against precipitation into the metal oxide or bulk oxide grains. In the oxygen‐rich conditions of the Deacon process, particularly the instability against oxide precipitation, represents a strong limitation. In this respect, doping with Cu appears as an optimum compromise between stability and catalytic activity enhancement.