Toward Computational Design of Photocatalysts for deNOx Reaction through High-dimensional Reaction Potential Surface

• Applicant: Professor Dr. Michael Sentef, since 9/2023
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation ; Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: since 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 462776874

The removal of NOx (deNOx) is becoming increasingly critical nowadays. TiO2 was reported to be one of the suitable photocatalysts for deNOx, but the low photocatalytic efficiency is becoming a critical issue. Despite extensive experimental studies, density functional theory (DFT) calcula-tions are indispensable tools for the investigation of the catalytic mechanisms and for providing guidelines toward developing new materials. The trends in catalytic activity and selectivity can be understood based on scaling relationships and an activity volcano plot, using a few descriptors (usually the adsorption energies of key intermediates). The scaling relationships have to be obtained for both dark and illuminated conditions in photocatalytic materials. Therefore, in this project, a high-dimensional reaction potential surface will be established based on a full reaction network and using a new algorithm for selecting the optimal reaction path. Data on energetics will be obtained from calculations which correct the gap- and localization error of standard DFT, and apply a self-consistent charge correction in case of charge-assisted reactions. Based on experience with TiO2, the general scaling relations mentioned above will be calculated on different photocatalyst surfaces/active sites. The activation barriers will then be calculated, to obtain a more accurate reaction potential surface. Finally, additional descriptors will be chosen, including not only the adsorption energies, but also the stability and the synergistic effects of positive/negative charges on the surfaces, in order to accurately obtain the photocatalytic activity map to promote the design of new photocatalysts.

• DFG Programme: Research Grants
• Ehemaliger Antragsteller: Professor Dr. Thomas Frauenheim, until 9/2023