Modulating the Catalytic Selectivity for Urea Production in CO2 and N2 Reduction Reaction through Cu19@Ru60 Core/Shell Nanoparticle: A DFT Study

In this work, we have investigated density functional theory calculations concerning urea production on a twinned truncated octahedral (t-TO) Cu19@Ru60 core/shell nanoparticle (CSNP). Compared to Ru79, it is found that CO2 undergoes preferential reduction to CO in a thermodynamically favorable manner within the Cu19@Ru60 CSNP. This process not only suppresses the generation of NNH intermediates but also significantly affects NH3 production through the unique core/shell structure of the Cu19@Ru60 CSNP. Notably, the valley-like active site of the twinned truncated octahedral structure of Cu19@Ru60 CSNP can induce a significant transfer of charge from the d orbital of Ru atoms to the 2 pi* orbital of the adsorbed N2 molecule, implying that dissociating the N equivalent to N bond of the N2 molecule requires overcoming a minimal reaction barrier (0.28 eV). The energetics of the examined molecular species and the reaction mechanism show that the Cu19@Ru60 CSNP promotes the C-N coupling of a specific intermediate with the appropriate activation energy and exhibits high stability in urea production from the reduction of CO2 and N2 reduction. Finally, it is hoped that our findings will bridge the gaps between critical issues and knowledge, thus paving the way for developments in C-N bond formation.