Enhancing Nitrogen Activation in Electrochemical Reduction: The Role of Rare Earth Oxide Surface Configurations

The pursuit of sustainable ammonia synthesis has prompted the exploration of the ambient electrochemical nitrogen reduction reaction (e-NRR) as an alternative to the energy-intensive Haber-Bosch process. This study conducted a theoretical investigation into the use of rare earth oxide materials, specifically dysprosium oxide (Dy2O3), as potential electrocatalysts for the NRR. Utilizing spin-polarized density functional theory calculations, we explored the interaction between Dy2O3 surfaces and nitrogen (N2) molecules, examining the capability of Dy2O3 to adsorb and activate N2 under ambient conditions. The results indicate that Dy2O3 surfaces exhibit diverse configurations and bonding environments, providing a variety of reactive sites that display different behaviors in N2 adsorption and activation. The distinctive electronic structure and surface chemistry of a particular Dy2O3 surface configuration were found to significantly enhance the activation of N2 by promoting charge transfer, which facilitates the NRR process. This research provides deep insights into the mechanistic pathways of N2 reduction over Dy2O3, highlighting the surface properties as pivotal in catalysis. These theoretical insights serve as a foundation for the development of novel rare-earth-based electrocatalytic materials for the efficient ambient e-NRR, potentially transforming ammonia production into a greener and more energy-efficient process.