Toward an atomic-scale understanding of the nitrogen oxidation reaction over Pd-based electrodes: Combining density functional theory and descriptor-based analyses (TP 11)

• Applicant: Professor Dr. Kai Steffen Exner
• Subject Area: Theoretical Chemistry: Molecules, Materials, Surfaces ; Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: since 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 413163866

In this project, we theoretically investigate the electrocatalytic formation of nitrate from dinitrogen. Studying this electrocatalytic process is motivated by the fact that nitrate is industrially manufactured by a combination of steam reforming, the Haber-Bosch process, and the Ostwald process, which is an energetically unfavorable scenario with a severe carbon dioxide footprint. Yet, electrochemistry reveals the exciting opportunity to offer an alternate option of how to produce nitrate, namely by the direct oxidation of dinitrogen under anodic polarization conditions. Using a high-throughput screening framework based on electronic structure calculations in the density functional theory (DFT) approximation, we focus on Pd-based electrode materials to comprehend nitrogen oxidation on the atomic scale. Particular attention is given to the selectivity problem with respect to the competing oxygen evolution reaction under experimental reaction conditions. We apply a binding-energy approach in conjunction with in-house approaches to comprehend selectivity, aiming to derive strategies of how to steer electrolysis toward the formation of high-value nitrogen-based chemicals rather than gaseous oxygen. We closely interact with various other subprojects within the Research Unit UNODE to address the oxidation of dinitrogen by electrolysis in a conjoint fashion, thereby transferring knowledge back and forth between theory and experiments.

• DFG Programme: Research Units
• Subproject of: FOR 2982: UNODE - Unusual Anode Reactions