Hydrocarbon Products Occluded within Zeolite Micropores Impose Transport Barriers that Regulate Brønsted Acid-Catalyzed Propene Oligomerization.

Brønsted acid zeolites catalyze alkene oligomerization to heavier hydrocarbon products of varied size and branching. Propene dimerization rates decrease monotonically with increasing crystallite size for MFI zeolites synthesized with fixed H+-site density, revealing the strong influence of intrazeolite transport limitations on measured rates, which has gone unrecognized in previous studies. Transient changes in dimerization rates upon step-changes in reactant pressure (150-470 kPa C3H6) or temperature (483-523 K) reveal that intrazeolite diffusion limitations become more severe under reaction conditions that favor the formation of heavier products. Together with effectiveness factor formalisms, these data reveal that product and reactant diffusion, and consequently oligomerization rates and selectivity, are governed by the composition of hydrocarbon products that accumulate within zeolitic micropores during alkene oligomerization. This occluded organic phase strongly influences rates and selectivities of alkene oligomerization on medium-pore zeolites (MFI, MEL, TON). Recognizing the coupled influences of kinetic factors and intrazeolite transport limitations imposed by occluded reaction products provides opportunities to competently tailor rates and selectivity in alkene oligomerization and other molecular chain-growth reactions through judicious selection of zeolite topology and reaction conditions.

Controlling Reaction Selectivity through the Surface Termination of Perovskite Catalysts.

Although perovskites have been widely used in catalysis, tuning of their surface termination to control reaction selectivity has not been well established. In this study, we employed multiple surface-sensitive techniques to characterize the surface termination (one aspect of surface reconstruction) of SrTiO3 (STO) after thermal pretreatment (Sr enrichment) and chemical etching (Ti enrichment). We show, by using the conversion of 2-propanol as a probe reaction, that the surface termination of STO can be controlled to greatly tune catalytic acid/base properties and consequently the reaction selectivity over a wide range, which is not possible with single-metal oxides, either SrO or TiO2 . Density functional theory (DFT) calculations explain well the selectivity tuning and reaction mechanism on STO with different surface termination. Similar catalytic tunability was also observed on BaZrO3 , thus highlighting the generality of the findings of this study.