Catalytic activity of Co-Ag nanoalloys to dissociate molecular hydrogen. New insights on the chemical environment

Adsorption of molecular hydrogen on the surface of catalytic metal nanoparticles and its dissociation in atomic hydrogen are processes of interest in many chemical technologies. As in other chemical reactions, alloying can improve the efficiency of the catalysts. By focusing on Co6, Co5Ag, Co3Ag3 and CoAg5, we explore the effect of changing the relative concentration of the two components in small ComAgn clusters, a peculiar nanoalloy because Co and Ag do not form bulk solid alloys. Molecular hydrogen adsorbs preferentially on the Co atoms, and the binding is mainly due to the electrical polarization of the charges of adsorbate and host. The preference for Co sites and the trend in the strength of the H-2-cluster binding are explained by the combination of two effects characterizing the host environment. One of these is geometric, arising from the degree of exposure of the host atom: the lower the atomic coordination of the host atom, the stronger its bonding with H-2. The second effect, newly identified, reveals the importance of the chemical nature of the host atom environment: host Co atoms having both Co and Ag neighbors maintain their capacity to bind hydrogen more intact than those with only Co neighbors. The alloy nanoclusters catalyze the dissociation of adsorbed H-2 by building up quite small activation barriers. After dissociation, the H atoms occupy bridge positions between Co atoms (between Co and Ag in CoAg5). H-2 adsorption and dissociation may trigger structural transformations of the cluster. The work shows that the adsorption and dissociation properties of H2 can be tuned by varying the relative composition of the two atomic species in the nanoalloy. (c) 2022 The Authors. Published by Elsevier Ltd

Automated summary

This study investigates the effect of changing the relative concentration of two components in small Co-mAg-n nanoalloys on the adsorption and dissociation of molecular hydrogen. The results show that alloying can improve the efficiency of catalysts, and the adsorption and dissociation properties can be tuned by varying the relative composition of the two atomic species in the nanoalloy.