Three γ/β-Ga₂O₃ nanoparticle catalysts that differ in the relative ratio of γ-Ga₂O₃ to β-Ga₂O₃ were prepared to evaluate the effect of H₂ treatment (500 °C, 2 h) on the coordination environment of bulk and surface Ga sites, Lewis acidity and catalytic activity in propane dehydrogenation (PDH). Independent of the H₂ treatment, the initial PDH activity of the γ/β-Ga₂O₃ catalysts increases with the fraction of the β-Ga₂O₃ phase. This is explained by the presence of weak Lewis acid sites (LAS) in β-Ga₂O₃ while such sites are absent in γ-Ga₂O₃. Treatment with H₂ increases the catalytic activity of all three γ/β-Ga₂O₃ catalysts but for different reasons. For catalysts with higher fractions of β-Ga₂O₃, H₂ treatment increases further the relative abundance of weak LAS, likely by generating coordinatively unsaturated Ga sites (such as tricoordinated Ga sites nearby oxygen vacancies). In contrast, H₂ treatment of a catalyst containing a predominant fraction of γ-Ga₂O₃ phase induces disorder in the sub-surface structure of the nanoparticle, that is, it forms gallium and oxygen vacancies in the bulk and favors migration of gallium, and likely also of oxygen, to the surface. This induces a surface reconstruction that notably increases the fraction of strong LAS (and proportionally decreases the fraction of medium LAS), while creating no weak LAS in γ-Ga₂O₃-H₂. Therefore, the increase in the catalytic activity of H₂-treated γ-Ga₂O₃ is explained by the higher density of surface Ga sites in γ-Ga₂O₃-H₂ relative to calcined γ-Ga₂O₃. H₂-treated catalysts that contain a higher relative amount of weak LAS also feature a higher relative abundance of gallium hydride species associated with a low frequency FTIR band at ca. 1931–1939 cm⁻¹, that is, weak LAS likely give weakly-bound hydrides in β-Ga₂O₃. Our results highlight that weak LAS in unsupported Ga₂O₃ catalysts are more active in PDH than mild or strong LAS.

α-Ga2O3, β-Ga2O3, and I -Ga2O3 as well as the silica-supported catalysts I -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 I -Ga2O3 and β-Ga2O3 (the latter obtained from colloidal nanocrystals of I -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 I -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 I -Ga2O3 with initial propene selectivities of 86, 83, and 88%. Dispersion of I -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 I -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- A nd 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.

Although the local geometry of Mo in Mo/HZSM-5 has been characterized before, we present a systematic way to manipulate the configuration of Mo and link it to its catalytic properties. The location and geometry of cationic Mo-complexes, the precursor of the active metal site for methane dehydroaromatization, are altered by directing the way they anchor to the framework of the zeolite. The feature used to direct the anchoring of Mo is the location of Al in the zeolite framework. According to DFT calculations, the local geometry of Mo should change, while UV-vis and pyridine FTIR spectroscopy indicated differences in the dispersion of Mo. Both aspects, however, did not influence the catalytic behavior of Mo/HZSM-5, indicating that as long as enough isolated Mo species are present inside the pores of the zeolite, the catalytic behavior is unaffected. This paves the way to better understand how the Mo oxo precursor transforms into the active phase under the reaction conditions.