Density functional theory and thermodynamics analysis of MAl12 Keggin substitution reactions: Insights into ion incorporation and experimental confirmation

Abstract

Polyaluminum cations, such as the MAl₁₂ Keggin, undergo atomic substitutions at the heteroatom site (M), where nanoclusters with M = Al³⁺, Ga³⁺, and Ge⁴⁺ have been experimentally studied. The identity of the heteroatom M has been shown to influence the structural and electronic properties of the nanocluster and the kinetics of ligand exchange reactions. To date, only three ε-analogs have been identified, and there is a need for a predictive model to guide experiment to the discovery of new MAl₁₂ species. Here, we present a density functional theory (DFT) and thermodynamics approach to predicting favorable heteroatom substitution reactions, alongside structural analyses on hypothetical ε-MAl₁₂ nanocluster models. We delineate trends in energetics and geometry based on heteroatom cation properties, finding that Al³⁺-O bond lengths are related to heteroatom cation size, charge, and speciation. Our analyses also enable us to identify potentially isolable new ε-MAl₁₂ species, such as FeAl₁₂ ⁷⁺. Based upon these results, we evaluated the Al³⁺/Zn²⁺/Cr³⁺ system and determined that substitution of Cr³⁺ is unfavorable in the heteroatom site but is preferred for Zn²⁺, in agreement with the experimental structures. Complimentary experimental studies resulted in the isolation of Cr³⁺-substituted δ-Keggin species where Cr³⁺ substitution occurs only in the octahedral positions. The isolated structures Na[AlO₄Al_9.6Cr_2.4(OH)₂₄(H₂O)₁₂](2,6-NDS)₄(H₂O)₂₂ (δ-Cr_nAl_13-n-1) and Na[AlO₄Al_9.5Cr_2.5(OH)₂₄(H₂O)₁₂](2,7-NDS)₄(H₂O)_18.5 (δ-Cr_nAl_13-n-2) are the first pieces of evidence of mixed Al³⁺/Cr³⁺ Keggin-type nanoclusters that prefer substitution at the octahedral sites. The δ-Cr_nAl_13-n-2 structure also exhibits a unique placement of the bound Na⁺ cation, which may indicate that Cr³⁺ substitution can alter the surface reactivity of Keggin-type species.