Insight into Three‐Coordinate Aluminum Species on Ethanol‐to‐Olefin Conversion over ZSM‐5 Zeolites

Commercial bioethanol can be readily converted into ethylene by a dehydration process using solid acids, such as Brønsted acidic H‐ZSM‐5 zeolites, and thus, it is an ideal candidate to replace petroleum and coal for the sustainable production of ethylene. Now, strong Lewis acidic extra‐framework three‐coordinate Al3+ species were introduced into H‐ZSM‐5 zeolites to improve their catalytic activity. Remarkably, Al3+ species working with Brønsted acid sites can accelerate ethanol dehydration at a much lower reaction temperature and shorten the unsteady‐state period within 1–2 h, compared to >9 h for those without Al3+ species, which can significantly enhance the ethanol dehydration efficiency and reduce the cost. The reaction mechanism, studied by solid‐state NMR, shows that strong Lewis acidic EFAl‐Al3+ species can collaborate with Brønsted acid sites and promote ethanol dehydration either directly or indirectly via an aromatics‐based cycle to produce ethylene