(385e) First-Principles Design on Small Cluster Catalysts for the Electrochemical NH3 Synthesis By Ligand Engineering

The ammonia production via electrochemical nitrogen reduction is one of the most attractive and emerging chemical process in hydrogen storage applications. Especially, the development of highly efficient catalyst is essential for the electrochemical ammonia synthesis process. However, such development is still challenging issue owing to the difficulty of direct characterization of electro-catalyst property. Quantum mechanics-based first-principles density functional theory (DFT) calculation is one of flexible and powerful means which can provide the quantitative information on the electro-catalysis and in turn help to design the novel electro-catalyst composition. In this presentation, we examined the electrochemical nitrogen reduction reaction (N2RR) on the small cluster metal catalysts embedded in support using DFT calculation. We chose the single, double and triple atoms for the size of small clusters and also investigated the electrochemical N2RR catalysis for small multimetallic clusters through ligand engineering. For the support of small metal cluster catalysts, two dimensional materials such defective graphene and mexene are considered. In addition, the electronic structure was analyzed for the clear understanding of activity of small clusters toward ammonia production via electrochemical N₂ reduction. Our theoretical study provides the fundamental mechanism of NH₃ production catalysis on small clusters and gives the physical and chemical intuition for the next generation bimetallic small cluster catalysts for hydrogen storage applications.