A theoretical study on the role of water and its derivatives in acetic acid steam reforming on Ni(111)

Abstract Catalytic steam reforming of acetic acid can be divided into two steps, i.e. acetic acid decomposition followed by water gas shift. While theoretical studies have been devoted to these two individual reactions, the role of water and its derivatives in the reforming process, especially in CH3COOH decomposition, remains largely unknown. In this study, a thorough investigation of the effects of the solvent water and its derived O*/OH* species on some key dehydrogenation steps on Ni(111) is carried out using density functional theory. The involved dehydrogenation species include O−H bond scission species H2O*, CH3COOH*, trans-COOH* and C−H bond scission species CH3CO*, CH3C*, CH2C*. The results show that the pre-adsorbed O*, OH*, and H2O* species not only affect the adsorption stability of these species, but also influence their dehydrogenation reactivity. O* and OH* species can both enhance the O−H bond scission, and the promotional effect of O* is superior to OH*. Nevertheless, H-abstraction from C−H bond by O* and OH* are both hindered except for CH3CO* dehydrogenation in the presence of OH*. Furthermore, the solvent water notably weakens O−H bonds, yet exhibits negligible effect on the C−H bond breakage. Analogously, the solvent effect of CH3COOH* on O−H bond scission is also investigated.