Stabilizing Oxidative Dehydrogenation Active Sites at High Temperature with Steam: ZnFe2O4‑Catalyzed Oxidative Dehydrogenation of 1‑Butene to 1,3-Butadiene

Dehydrogenation reactions are central for the production of functional molecules. Steam plays a pivotal role in ZnFe2O4-catalyzed 1-butene oxidative dehydrogenation (ODH). However, the essential effect of steam on this reaction is still unclear. Herein, we describe the structure–performance relationships of ZnFe2O4 in the presence/absence of steam by combined density functional theory and experimental studies. The catalytic performances of ZnFe2O4 under different reaction conditions were investigated. The ZnFe2O4(110) surface properties under reaction conditions and molecular reaction pathways were modeled. Free-energy profiles were calculated. We found that an oxygen-excess ZnFe2O4(110)–O termination, with an extra O atom bridging two Fe cations, is preferred under oxygen-rich conditions. However, both experimental and theoretical approaches indicate that this surface bicoordinated O is not stable at relatively high temperatures in the absence of steam, resulting in the reduction of surface Fe3+ cations to Fe2+ which are inactive in the 1-butene ODH reaction. It was found that steam interacts strongly with the ZnFe2O4(110)–O surface. Steam stabilizes the catalyst surface Fe3+ ions by converting bicoordinated O to more thermally stable hydroxyl groups. Surface hydroxyls are active sites for C–H bond cleavage in the 1-butene ODH reaction in the presence of steam. We propose that the role of steam elucidated here represents a general mode of steam influence in ODH reactions over oxide surfaces.