Angewandte Chemie, Accepted Article.
Zeolite reactivity depends on the solvating environments of their micropores and the proximity of their Brønsted acid sites. Turnover rates (per H+) for methanol and ethanol dehydration increase with the fraction of H+ sites sharing six‐membered rings of chabazite (CHA) zeolites. DFT shows that activation barriers vary widely with the number and arrangement of Al (1‐5 per 36 T‐site unit cell), but cannot be described solely by Al–Al distance or density. Certain Al distributions yield rigid arrangements of anionic charge that stabilize cationic intermediates and transition states via H‐bonding to decrease barriers. This is a key feature of acid catalysis in zeolite solvents, which lack the isotropy of liquid solvents. The sensitivity of polar transition states to specific arrangements of charge in their solvating environments and the ability to position such charges in zeolite lattices with increasing precision herald rich catalytic diversity among zeolites of varying Al arrangement.