The highly effective catalytic behavior of a metal nanocluster Ru79 on the dissociation of a N2 molecule—A quantum-chemical calculation

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

“…Typical barriers for thermal-catalytic N 2 dissociation are ranging from 60 to 115 kJ mol –1 for Ru catalysts in experiments. For instance, barriers on the terrace and stepped Ru(0001) surfaces are reported to be 1.36–1.9 eV and 0.3–0.4 eV, respectively, while a barrier of 0.79 eV was observed on a Ru(112̅1) surface by Shetty et al − Notably, Li et al proposed that the dissociation barrier of N 2 molecules could be much decreased by active sites with orbital symmetries on twinned truncated octahedral (t-TO) Ru 79 nanoparticle . This suggests that uncoordinated metal sites exhibit lower activation barriers for N 2 dissociation compared to their planar counterparts.…”

“…For instance, barriers on the terrace and stepped Ru(0001) surfaces are reported to be 1.36−1.9 eV and 0. twinned truncated octahedral (t-TO) Ru 79 nanoparticle. 26 This suggests that uncoordinated metal sites exhibit lower activation barriers for N 2 dissociation compared to their planar counterparts. These variations can also be elucidated by examining the coordination numbers (CN) of N 2 molecules in the transition state, with CN values of five observed for N 2 molecules on stepped Ru(0001) and Ru(112̅ 1) surfaces (each N atom bonded 3-fold to the cluster), 23,25 while a CN value of six is observed for N 2 molecules on the Ru 79 nanoparticle.…”

“…This suggests that uncoordinated metal sites exhibit lower activation barriers for N 2 dissociation compared to their planar counterparts. These variations can also be elucidated by examining the coordination numbers (CN) of N 2 molecules in the transition state, with CN values of five observed for N 2 molecules on stepped Ru(0001) and Ru(112̅1) surfaces (each N atom bonded 3-fold to the cluster), , while a CN value of six is observed for N 2 molecules on the Ru 79 nanoparticle . However, the proton adsorption on Ru-based catalysts is thermodynamically favorable, implying that the HER could severely limit the selectivity and formation rate of NRR. , Therefore, developing efficient Ru-based catalysts to control the proton adsorption rate and reduce the energy barrier for N 2 bond scission is crucial in achieving excellent NRR performance.…”

Structural dynamics of Ru clusters during nitrogen dissociation in ammonia synthesis

“…However, early theoretical studies on the NH 3 synthesis of Ru clusters employing DFT predetermine a stable or metastable configuration and search for the corresponding transition state of potential energy surfaces. 23–25 To a certain extent, these studies are reasonable because the lowest energy structure usually has the highest population. In comparison, the small sub-nanometer clusters often have many low-energy local minima in a narrow energy range.…”