Surface Structure Dependent Activation of Hydrogen over Metal Oxides during Syngas Conversion

Abstract

Despite the extensive studies on the adsorption and activation of hydrogen over metal oxides, it remains a challenge to investigate the structure-dependent activation of hydrogen and its selectivity mechanism in hydrogenation reactions. Herein we take spinel and solid solution MnGaOx with a similar bulk chemical composition and study the hydrogen activation mechanism and reactivity in syngas conversion. The results show that MnGaOx-Solid Solution (MnGaOx-SS) is a typical Mn-doped hexagonal close-packed (HCP) Ga2O3 with a Ga-rich surface. Upon exposure to hydrogen, Ga-H and O-H species are simultaneously generated. Ga-H species are highly active but unselective in CO activation, forming CHxO, and ethylene hydrogenation, forming ethane. In contrast, MnGaOx-Spinel is a face-centered-cubic (FCC) spinel phase featuring a Mn-rich surface, thus effectively suppressing the formation of Ga-H species. Interestingly, only part of the O-H species are active for CO activation while the O-H species are inert for olefin hydrogenation over MnGaOx-Spinel. Therefore, MnGaOx-Spinel exhibits a higher activity and higher light-olefin selectivity than MnGaOx-SS in combination with SAPO-18 during syngas conversion. These fundamental understandings are essential to guide the design and further optimization of metal oxide catalysts for selectivity control in hydrogenations.