The main aim of this dissertation is to study the catalytic aspects of very small transition metal clusters supported on h-BN/Rh(111). The catalytic reactions of interest were ammonia synthesis and CO oxidation on mass selected and soft landed iron and platinum clusters, respectively. A special focus was devoted to the investigation of the stability of these very small clusters on h-BN before and after the reaction. It was found that Pt7 clusters soft landed at room temperature with an energy of 1.2 eV per atom and annealed to 700 K exhibit Smoluchowski ripening. Above this temperature, these clusters undergo partial intercalation between the h-BN monolayer and the Rh(111). The intercalation initiates at 900 K and becomes more pronounced when the clusters are annealed under gas reaction conditions. A high catalytic activity was observed when the Pt catalyst remains supported on h-BN. In this case, the reaction starts at 480 K and follows Langmuir-Hinshelwood mechanism. However, the catalytic activity strongly reduces when the Pt clusters undergo partial intercalation. Nevertheless, in this case the reaction starts at only 380 K, revealing a reduction by 100 K in the Pt poisoning as a result of substrate effect and charge redistribution. In a second trail, the cluster-h-BN interaction was studied through h-BN irradiation with Pt clusters, at room temperature, within an energy window of 30-416 eV/atom. The results show that even irradiation at 30 eV/atom can lead to entire non thermal intercalation of the clusters. The energetic Pt clusters were found to be site selective as they settle only under the h-BN wires, in contrast to soft landed Pt7 clusters that were found to settle at the side edge of the h-BN depressions. After being exposed to irradiated Pt clusters, at an energy above 100 eV/atom, the h-BN layer starts to display visual cavity-type defects. These defects, induced by collision, disappeared after annealing to 600 K under gas reaction leaving behind an h-BN with no visual defects. CO temperature desorption spectroscopy (TDS) indicates that the intercalated Pt is inactive towards CO oxidation due to h-BN screening. Subsequently, we were able to produce a catalyst system made of soft-landed Pt/h-BN/intercalated Pt/Rh(111) using a combination between soft and energetic Pt deposition with which a reduction by 100 K in CO poisoning was obtained. Finally, ammonia synthesis was conducted on soft landed Fe clusters, supported on h-BN/Rh(111) and deposited at 100 K under Ultra High Vacuum (UHV). Scanning tunneling microscopy (STM) displays two imaging states of the as deposited clusters; a ring state surrounding h-BN depression which disappears above 300 K and a dot like structure. The Fe clusters are found to grow by Ostwald ripening after annealing to 600 K and above this temperature, they endure partial intercalation. It was found that, in the presence of iron, the nitrogen reaction gas experienced an exchange with the nitrogen species forming the h-BN layer. TPR (Temperature Programmed Reduction) of N$_2$ with hydrogen revealed that nitrogen reduction occurs at 620 K under high vacuum following the Haber-Bosch method. The detection of reaction intermediates NH and NH$_2$ together with desorbed atomic nitrogen, during ammonia synthesis, confirms that NH$_3$ formation involves the stepwise hydrogenation of adsorbed nitrogen.