Adsorbate effects on metal nanoparticles, from synthesis of bimetallic systems and 3d assemblies of nanoparticles to the impact on catalysis

Adsorbate effects on metal nanoparticles, from synthesis of bimetallic systems and 3d assemblies of nanoparticles to the impact on catalysis

In our research, intertwining theoretical and experimental work, we have focused on the modification of metallic surfaces by the addition of a second metal, a coordinating ligand, or a combination of both, to understand the effect of these adsorbates in the outcome of the catalytic reactions; additionally, we have explored the reactivity of single-atom materials as catalysts. In this sense we have developed a family of hybrid materials, allowing obtaining from ultra-small Ru NP to ordered materials in a precise manner.^[2] Also, the control of the electronic properties of the ligands present on the surface allows to understand and modulate the activity and selectivity of ruthenium NP used as catalysts in several hydrogenation reactions.^{[3, 4]} Finally, ruthenium nanoparticles can be finely tuned by adding a second non precious metal. These bimetallic nanoparticles have been successfully used as catalysts in the selective 5-hydroxymethylfurfural hydrogenation, which is a promising intermediate for the synthesis of a wide variety of chemicals and alternative fuels based on bio-refinery.^[5]

References

[1] Pérez-Ramírez, J.; López, N. Strategies to break linear scaling relationships. Nature Catalysis 2019, 2 , 971-976.

[2] Min, Y.; Nasrallah, H.; Poinsot, D.; Lecante, P.; Tison, Y.; Martinez, H.; Roblin, P.; Falqui, A.; Poteau, R.; del Rosal, I.; et al. 3D Ruthenium nanoparticle covalent assemblies from polymantane ligands for confined catalysis. Chem. Mater. 2020, 32, 2365-2378.

[3] Bruna, L.; Cardona-Farreny, M.; Colliere, V.; Philippot, K.; Axet, M. R. In situ ruthenium catalyst modification for the conversion of furfural to 1,2-pentanediol. Nanomaterials 2022, 12, 328.

[4] Axet, M. R.; Conejero, S.; Gerber, I. C. Ligand effects on the selective hydrogenation of nitrobenzene to cyclohexylamine using ruthenium nanoparticles as catalysts. ACS Appl. Nano Mater. 2018, 1, 5885-5894.

[5] Cardona-Farreny, M.; Lecante, P.; Esvan, J.; Dinoi, C.; Del Rosal, I.; Poteau, R.; Philippot, K.; Axet, M. R. Bimetallic RuNi nanoparticles as catalysts for upgrading biomass: metal dilution and solvent effects on selectivity shifts. Green Chem. 2021, 23, 8480-8500.