Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from Density Functional Theory (DFT) Studies

Abstract

Amorphous silica (SiO2) is commonly used as a support in heterogeneous catalysis. However, because of the structural disorder and temperature-induced change of surface morphology, the structures of silica-supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica-supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory (DFT) calculations to understand the effect of siloxane ring strain on structure and activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal–silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and a correlation between the metal–silanol interaction energy and the ring strain energy has been observed. In addition to ring strain, the strength of the metal–silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal–silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the extended X-ray absorption fine structure (EXAFS) data of monomeric Zn(II) and Ga(III) ions grafted on silica. The molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.