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Based on theoretical calculations of CO, NH 3 , and pyridine adsorption at different sites in MOR and MFI zeolites, we analyze how confinement effects influence the measurement of acidity based on the interaction of probe molecules with Brönsted acid sites. Weak bases, such as CO, form neutral ZH-CO adducts with a linear configuration that can be distorted by spatial restrictions associated with the dimensions of the pore, leading to weaker interaction, but can also be stabilized by dispersion forces if a tighter fitting with the channel void is allowed. Strong bases such as NH 3 and pyridine are readily protonated on Brönsted acid sites, and the experimentally determined adsorption enthalpies include not only the thermochemistry associated with the proton transfer process itself, but also the stabilization of the Z - -BH + ion pair formed upon protonation by multiple interactions with the surrounding framework oxygen atoms, leading in some cases to a heterogeneity of acidities within the same zeolite structure.

What Is Measured When Measuring Acidity in Zeolites with Probe Molecules?