Bulk and surface transformations of Ga₂O₃ nanoparticle catalysts for propane dehydrogenation induced by a H₂ treatment

Abstract

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.