Discovery of homogeneously dispersed pentacoordinated Al(V) species on the surface of amorphous silica-alumina

TL;DR

This study uncovers a high population of homogeneously dispersed Al(V) species on amorphous silica-alumina surfaces, which are accessible and potentially highly active for catalytic applications, independent of alumina phases.

Contribution

It demonstrates the direct observation and characterization of dispersed Al(V) species on silica-alumina, revealing their independence from alumina phases and their accessibility for catalysis.

Findings

Al(V) species are homogeneously dispersed on silica-alumina surfaces.

Most Al(V) species are accessible and can transform upon water adsorption.

The coordination and transformation of Al species match DFT predictions.

Abstract

The dispersion and coordination of aluminium species on the surface of silica-alumina based materials are essential for controlling their catalytic activity and selectivity. Al(IV) and Al(VI) are two common coordinations of Al species in the silica network and alumina phase, respectively. Al(V) is rare in nature and was found hitherto only in the alumina phase or interfaces containing alumina, a behavior which negatively affects the dispersion, population, and accessibility of Al(V) species on the silica-alumina surface. This constraint has limited the development of silica-alumina based catalysts, particularly because Al(V) had been confirmed to act as a highly active center for acid reactions and single-atom catalysts. Here, we report the direct observation of high population of homogenously dispersed Al(V) species in amorphous silica-alumina in the absence of any bulk alumina phase, by high resolution TEM/EDX and high magnetic-field MAS NMR. Solid-state 27Al multi-quantum MAS NMR experiments prove unambiguously that most of the Al(V) species formed independently from the alumina phase and are accessible on the surface for guest molecules. These species are mainly transferred to Al(VI) species with partial formation of Al(IV) species after adsorption of water. The NMR chemical shifts and their coordination transformation with and without water adsorption are matching that obtained in DFT calculations of the predicted clusters. The discovery presented in this study not only provides fundamental knowledge of the nature of aluminum coordination, but also paves the way for developing highly efficient catalysts.