Acidity and stability of Nb(V) active sites doped in SBA-15 and ZrSBA-15: A DFT study

• An expanded 5-6 type cluster was built. The proposed cluster was able to reproduce trends from larger clusters • Nb(V) species are better stabilized in ZrSBA-15 compared to SBA-15 • The synergistic effect between Zr and Nb promotes a better metal-support interaction, which leads to more stable structures Mesoporous silicas are of great interest in heterogeneous catalysis due to the structural characteristics of their pores and the adjustable catalytic properties that arise from incorporating heteroatoms. The substitution of Zr and Nb into SBA-15 introduces active sites into the material, rendering it a potential catalyst for acid catalysis reactions. However, discussions regarding the acid properties and metal-support interactions in amorphous silicas functionalized with metals are limited in computational chemistry. This study aims to determine the acid strength and charge transfer effects between Zr(IV) and Nb(V) species in mesoporous silica by proposing a representative SBA-15 cluster of type 5-6. Density Functional Theory (DFT) simulations were conducted using the B3LYP/6-31G(d,p)/def2TZVP levels. The model successfully replicated trends from larger clusters, demonstrating that the more grafted onto the silica structure (i.e. have more Si-O-M bonds), the greater the acid strength of the active site. Additionally, it was found that ZrSBA-15 structures are more stable than NbSBA-15 and possess higher acid strength, a trend supported by experimental observations. The results also suggest that Nb(V) species are more effectively stabilized in ZrSBA-15 than SBA-15, likely due to the presence of Zr(IV) centers in ZrSBA-15. This research contribute to a better understanding of how the support affects the stabilization of active phases, paving the way for the rational design of silica-based heterogeneous catalysts.