Nature of Five-Coordinated Al in γ-Al₂O₃ Revealed by Ultra-High-Field Solid-State NMR

Five-coordinated Als (Al(V)) on the surface of aluminas play important roles when they are used as catalysts or catalyst supports. However, the comprehensive characterization and understanding of the intrinsic structural properties of the Al(V) remain a challenge, due to the very small amount in commonly used aluminas. Herein, the surface structures of γ-Al₂O₃ and Al(V)-rich Al₂O₃ nanosheets (Al₂O₃-NS) have been investigated and compared in detail by multinuclear high-field solid-state NMR. Thanks to the high resolution and sensitivity of ultra-high-field (up to 35.2 T) NMR, the arrangements of surface Als were clearly demonstrated, which are substantially different from the bulk phase in γ-Al₂O₃ due to the structure reconstruction. It reveals for the first time that most of the commonly observed Al(V)s tend to exist as aggregated states on the surface of γ-Al₂O₃, like those in amorphous Al₂O₃-NS liable to structure reconstruction. Our new insights into surface Al(V) species may help in understanding the structure-function relationship of alumina.