Structure, Location, and Spatial Proximities of Hydroxyls on γ‑Alumina Crystallites by High-Resolution Solid-State NMR and DFT Modeling: Why Edges Hold the Key

• Published in: ACS catalysis 2023-05, Vol.13 (10), p.6536-6548
• Main Authors: Batista, Ana T. F., Pigeon, Thomas, Meyet, Jordan, Wisser, Dorothea, Rivallan, Mickael, Gajan, David, Catita, Leonor, Diehl, Fabrice, Gay, Anne-Sophie, Chizallet, Céline, Lesage, Anne, Raybaud, Pascal
• Format: Article
• Language: English
• Subjects: Catalysis; Chemical Sciences
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.3c00495

The atomic-scale characterization of surface active sites on γ-alumina still represents a great challenge for numerous catalytic applications. Here, we combine advanced density functional theory (DFT) calculations with one- and two-dimensional proton solid-state NMR experiments to identify the exact location and the spatial proximity of hydroxyl groups on γ-alumina crystallites. Our approach relies on revisited models for the (100), (111), basal (110)b, and lateral (110)l facets of γ-alumina, as well as for the edges at their intersections. Notably, we show that the ≃0 ppm AlTd-μ1-OH protons are predominantly located on edges, where these are free from the H-bond network. The proximities among the AlTd-μ1-OH as well as with μ2-OH groups are revealed by 1H–1H dipolar correlation experiments and analyzed in the light of the DFT calculations, which identify their location on the basal (110)b facet and on the (110)b/(100) and (110)b/(110)l edges. Using chlorine atoms to probe the presence of hydroxyls, we show that the chlorination occurs selectively by exchanging μ1-OH located on edges and on lateral (110)l facets. By contrast, the basal (110)b and lateral (111) facets are not probed by Cl. This exchange explains the disappearance of the ≃0 ppm peak and of the correlations involving AlTd-μ1-OH species. Moreover, after chlorination, a deshielding of the AlTd is observed on high-resolution 27Al NMR spectra. More subtle effects are visible on the proton correlation spectra, which are attributed to the disruption of the H-bond network in the course of chlorination.