Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol

Direct and selective production of C3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. Here, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde CC bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H2) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10–3 mol molY –1 s–1 vs 1.2 × 10–3 mol molZn –1 s–1). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.