Theoretical evaluation of M/H-magadiite and Al modified M/H-[Al]-magadiites single-atom catalysts (M = Ag, Au, Pd, and Pt)

This work intends to simulate the interaction of metal single-atom(s) supported on surfaces of H-magadiite (H₄Si₁₄O₃₀) and Al substituted H-[Al]-magadiites (H₅AlSi₁₃O₃₀), hereafter called M/H-magadiite and M/H-[Al]-magadiite (M = Ag, Au, Pt, Pd), using DFT calculations (PBE and PBE-D3 functionals). Three distinct positions were defined in all surfaces to optimize each simulated model: “hydroxyl”, “edge” and “cavity”. The Au/H-magadiite and Ag/H-magadiite models were more stable at the “hydroxyl” sites. Meanwhile, in the aluminated surfaces, the presence of an extra hydrogen atom (here called H_extra, located in the “edge” region) was responsible for a more stable situation of these metal atoms. On the other hand, the Pd and Pt single-atoms present in H-magadiite and H-[Al]-magadiites showed greater interaction with all the sites, compared to the Au- and Ag- models. Based on the binding energies and other electronic calculations, the aluminol site at H-[Al]-magadiites has the best capacity to support metal species. For example, the Pt/H-[Al]-magadiite showed the lowest binding energy (-2.64 eV for PBE and -2.93 eV for PBE-D3), the strongest charge interaction and the smallest Pt – H_extra distance (1.55 Å). The migration barriers (PBE) in Ag/H-magadiite, Au/H-magadiite, and Pd/H-magadiite were lower than 21.50 kJ·mol⁻¹, suggesting the high possibility of metal sintering. For all the cases, the PBE-D3 overestimated the barriers. Contrarily, the Pt/H-magadiite structures stabilized in the “cavity” region, inside the silicon rings of the silicate, and presented a migration barrier greater than 200 kJ·mol⁻¹. These calculations offered the first indications of the behavior of single-atoms, which will serve as the basis for a broader description, in future works, of the migration of metal species in the Al-models simulated here, as well as for modeling single-atom catalysts that can be used in stable conditions.