Propane Dehydrogenation on Ga₂O₃-Based Catalysts: Contrasting Performance with Coordination Environment and Acidity of Surface Sites

Abstract

α-Ga2O3, β-Ga2O3, and γ-Ga2O3 as well as the silica-supported catalysts γ-Ga2O3/SiO2, β-Ga2O3/SiO2, and Ga(NO3)3-derived Ga/SiO2 were prepared, characterized, and evaluated for propane dehydrogenation (PDH) at 550 °C. The coordination environment and acidity of surface sites in stand-alone and SiO2-supported Ga2O3 catalysts were studied using FTIR, 15N dynamic nuclear polarization surface-enhanced NMR spectroscopy (15N DNP SENS), and DFT modeling of the adsorbed pyridine probe molecule. The spectroscopic data suggest that the Lewis acidic surface Ga sites in γ-Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of γ-Ga2O3 via thermal treatment at 750 °C) are similar, except that β-Ga2O3 contains a larger relative fraction of weak Ga3+ Lewis acid sites. In contrast, α-Ga2O3 features mostly strong Lewis acid sites. This difference in surface sites parallels their difference in catalytic activities: i.e., weak Lewis acid surface sites are more abundant in β-Ga2O3 relative to α-Ga2O3 and γ-Ga2O3 and the increased relative abundance of weak Lewis acidity correlates with a higher initial catalytic activity in PDH, 0.41 > 0.28 > 0.14 mmol C3H6 m–2 (Ga2O3) h–1 at 550 °C, for respectively β-, α-, and γ-Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of γ-Ga2O3 or β-Ga2O3 on a silica support introduces strong as well as abundant weak Brønsted acidity to the catalysts, lowering the PDH selectivity. The γ-Ga2O3/SiO2 catalyst was slightly more active than β-Ga2O3/SiO2 in PDH (Ga normalized activity) with initial propene formation rates of 11 and 9 mol C3H6 mol Ga–1 h–1 (sel = 76 and 73%, respectively). However, these catalysts deactivated by ca. 55% within 100 min time on stream (TOS) due to coking. In contrast, Ga/SiO2, with mostly tetracoordinated surface Ga sites and abundant, strong Brønsted acid sites, gave a lower activity and selectivity in PDH (3.5 mol C3H6 mol Ga–1 h–1 and 49%, respectively) but showed no deactivation with TOS. DFT calculations using a fully dehydroxylated oxygen-deficient model β-Ga2O3 surface show that tetra- and pentacoordinated Ga Lewis acid sites bind pyridine more strongly than tricoordinated Ga sites and a higher relative fraction of strong Lewis acid sites correlates with increased coking. Overall, our results indicate that weakly Lewis acidic, tricoordinated Ga3+ sites are likely driving the superior PDH activity of β-Ga2O3.