PNNL

Abstract

A series of Ag–ZrO2/SiO2 catalysts with different metal–support interfaces were synthesized in an effort to elucidate the roles of specific interfaces in controlling the ethanol to 1,3–butadiene conversion and selectivity. According to the results of detailed characterizations (e.g. CO/pyridine–DRIFTS, XPS, TEM, NH3–TPD, and 1H MAS NMR), it was found that the Ag–O–Si interfaces significantly enhanced the dehydrogenation of ethanol while the presence of ZrO2 improved the interaction between Ag and ZrO2/SiO2, creating more Agd+ active sites. The high dispersion of ZrO2 on SiO2 generated abundant Zr–O–Si interfaces with medium and weak Lewis acidity, promoting the condensation of acetaldehyde to crotonaldehyde. These Zr–O–Si interfaces in close interaction with Agd+ species played a critical role in the enhanced H transfer during the MPV reduction of crotonaldehyde to crotyl alcohol. The synergies among the interfaces resulted in retarded ethanol dehydration reactivity, balanced ethanol dehydrogenation and condensation reactions, and a subsequent high 1,3–butadiene yield.