Enhanced Metathesis Activity and Stability of Methyltrioxorhenium on a Mostly Amorphous Alumina: Role of the Local Grafting Environment

Inorganic oxides play a crucial role in the activation of atomically dispersed metal oxides for catalytic olefin transformations, but the inefficient activation processes remain poorly understood. Activation of methyltrioxorhenium (MTO) for propene metathesis via its deposition on the surface of gamma-Al2O3 typically results in <5% active sites, and these sites deactivate rapidly. Simple substitution of the support by a less crystalline (largely amorphous) alumina (alpha-Al2O3) results in ca. 4X more activity and at least 10X more productivity. On both types of alumina, metathesis is initiated only at specific sites, whose availability limits the catalytic activity. While the two aluminas have similar total numbers of Lewis acid sites, the less crystalline support activates twice as many grafted MTO sites. Interestingly, alpha-Al2O3 has nearly double the number of strong Lewis acid sites. However, the number of active sites is ca. 10X lower than the total number of strong Lewis acid sites, and metathesis proceeds even when most are occupied by pyridine. DQSQ and D-HMQC H-1 and Al-27 solid-state NMR reveal that many Lewis acid sites are co-located with surface hydroxyl groups, which prevent activation and/or cause rapid deactivation. Undercoordinated Al sites on dominant (110) facets, which retain hydroxyl groups under catalyst preparation conditions, are therefore unlikely to lead to stable active sites. In contrast, the minor (100) facets of gamma-Al2O3, which are completely dehydroxylated, contain strongly Lewis-acidic five-coordinate Al sites that are necessarily remote from surface hydroxyl groups. Such sites, which are relatively more abundant on less well-crystallized aluminas, are inferred to be responsible for generating stable metathesis sites.