Molecular-sized micropores of ZSM-5 zeolite catalysts provide spatial restrictions around catalytic sites that allow for shape-selective catalysis. However, the fact that ZSM-5 has two main pore systems with different geometries is relatively unexploited as a potential source of additional shape selectivity. Here, we use confocal laser-scanning microscopy to show that by changing the polarity of the solvent, the acid-catalyzed furfuryl alcohol oligomerization can be directed to selectively occur within either of two locations in the microporous network. This finding is confirmed for H-ZSM-5 particles with different Si/Al ratios and indicates a general trend for shape-selective catalytic reactions.
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