Active site requirements for bio-alcohol dehydration: Effect of chemical structure and site proximity

Synthesis-structure-activity relations are reported, describing how interzeolite conversion (IZC) allows synthesis of ZSM-5 (MFI framework) with fixed physicochemical properties, except the variable local acid site (Al) arrangement, by variation of the synthesis time. Local confinement and acidity effects are probed by applying both H-ZSM-5 and Na-ZSM-5 samples in alcohol dehydration. Pyridine and divalent cobalt ion probing are used to quantify the amount of accessible acid sites and of Al in close proximity. Al in close proximity shows a strong influence on n-butanol dehydration turnover rates. The turnover rates are also strongly dependent on local confinement: in Na-form, ZSM-5 synthesized with more Al present as isolated species is a factor of 3–7 times more active than Na-ZSM-5 with fewer isolated Al. However if the zeolites are in proton form, ZSM-5 with more proximate sites show a higher activity compared to ZSM-5 with more isolated sites. Linear butene selectivity increases in Na-ZSM-5 compared to H-ZSM-5, caused by a suppressed dibutyl ether formation. The selectivity towards 1-butene is enhanced to a greater extent on proximate sites, likely due to a local/steric constraint at the active site. Decomposition of DBE over Na-ZSM-5 is more active compared to n-butanol dehydration, independent of acid site proximity. Also for 2-propanol dehydration, Na-ZSM-5 is less active than H-ZSM-5, yet the activity difference is attenuated compared to n-butanol dehydration. Essentially, due to the intrinsic higher reactivity of 2-propanol, the acid site requirement is less stringent. These findings highlight the importance of local confinement and Al proximity in acid-catalyzed conversion of oxygenated compounds.